http://pubs.acs.

org/journal/acsodf Review

Green Surfactants (Biosurfactants): A Petroleum-Free Substitute for

Sustainability�Comparison, Applications, Market, and Future
Prospects
Vaishnavi S. Nagtode,○ Clive Cardoza,○ Haya Khader Ahmad Yasin,*,○ Suraj N. Mali,*,○
Srushti M. Tambe, Pritish Roy, Kartikeya Singh, Antriksh Goel, Purnima D. Amin, Bapu R. Thorat,
Jorddy N. Cruz, and Amit P. Pratap*

Cite This: ACS Omega 2023, 8, 11674−11699 Read Online

ACCESS Metrics & More Article Recommendations

ABSTRACT: Surfactants are a group of amphiphilic molecules (i.e., having both

hydrophobic and hydrophilic domains) that are a vital part of nearly every
contemporary industrial process such as in agriculture, medicine, personal care, food,
and petroleum. In general surfactants can be derived from (i) petroleum-based sources
or (ii) microbial/plant origins. Petroleum-based surfactants are obvious results from
petroleum products, which lead to petroleum pollution and thus pose severe problems
to the environment leading to various ecological damages. Thus, newer techniques have
been suggested for deriving surfactant molecules and maintaining environmental
sustainability. Biosurfactants are surfactants of microbial or plant origins and offer
much added advantages such as high biodegradability, lesser toxicity, ease of raw
material availability, and easy applicability. Thus, they are also termed “green
surfactants”. In this regard, this review focused on the advantages of biosurfactants over
the synthetic surfactants produced from petroleum-based products along with their
potential applications in different industries. We also provided their market aspects and future directions that can be considered with
selections of biosurfactants. This would open up new avenues for surfactant research by overcoming the existing bottlenecks in this
field.

1. INTRODUCTION mental damage and toxicological problems.33,34 For example,

The term “surfactant” comes from “surface active agents”, which eutrophication is one of the direct effects on the environment
are molecules that adsorb on the water−surface interface and due to the use of synthetic surfactants that include
reduce water’s surface tension to enhance the cleaning of phosphates.35−38 Cleaning products and detergents with
surfaces.1,2 They are also known as amphiphiles because they phosphate surfactants are the principal sources of phosphate
have polar heads, also known as hydrophilic heads, that have an in aquatic systems.39 As a result, there is a high demand for
attraction for polar solvents, and nonpolar tails, also known as biodegradable products developed through green chemistry to
hydrophobic tails.2,3 The molecular structures of these prevent environmental pollution (the elimination of the use or
molecules help reduce the cohesive forces between water generation of hazardous substances in the design, manufacture,
molecules, resulting in the lowering of surface tension.1−5 They and application of chemical products worldwide). The growing
possess other qualities that allow them to be used in applications legal and societal pressures for these substances to be
other than lowering surface tension6,7 such as emulsifiers,8−11 biodegradable and produced in a sustainable manner have
foaming agents,12−16 corrosion inhibitors,17−21 and antistatic fueled research into new degradable surfactants of synthetic or
agents.22−25 Surfactants have been used in practically every biological origin.40 Also, diminishing petrochemical stocks and
industry because of their physicochemical characteristics.25 environmental degradation have created a drive toward the
These include paints,26 inks,27,28 coatings,29−31 adhesives, paper
and pulp, petroleum and oil, plastics, resins, textiles and fibers, Received: January 29, 2023
detergents, agricultural, food, cosmetics, pharmaceutical, and Accepted: March 9, 2023
various industrial applications.32 Originally, surfactants were Published: March 24, 2023
only created from renewable resources such as plant oils or
animal fat. The majority of surfactants in use today are either
only partly or slowly biodegradable, which results in environ-
© 2023 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsomega.3c00591
11674 ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

identification of novel renewable bioresources for efficient numbers of bactericidal and topical antiseptic properties in
surfactant production. Next-generation renewable surfactant various previous studies.55 Thereby, they are greatly used in the
inventions must be produced effectively, come from reliable and manufacturing of bathroom and hand sanitizers. Cationic
sustainable feedstocks, and have physicochemical characteristics surfactants are often used as fabric softeners, hydrophobic
that are on par with or better than those of petrochemical agents, hydrotropes, etc.55 The cationic head functionality of a
surfactants.41,42 All of these requirements must be met while CS tends to disrupt bacterial cell membranes, and therefore CSs
achieving a low manufacturing cost. The green surfactants are used as antibacterial agents.56,57 However, the use of CSs
currently in use come from two different sources: biosurfactants, should be within specific limits given by regulatory agencies.
which are produced by bacteria as they increase the availability Examples of CSs are methylbenzethonium and benzalkonium
of hydrocarbons, and oleo surfactants, which are sourced from QA (quaternary ammonium). These CSs include quaternary
feedstocks such oils and fats of plant and animal origins.43,44 ammonium compounds [QACs; R1R2R3R4N+X], esters of
Oleochemical-based surfactants are more biocompatible and QACs [RCO−O−CH2CH2−N(CH3)2], and derivatives of
easily biodegradable than petroleum-based ones.45 Fatty acids, pyridines and imidazolines [NC5H5]+·R1�C�N�(CH2)2�
fatty alcohols, fatty amines, and glycerol are the main N�R2+].
oleochemical feedstocks. The development of modern bio- 2.1.3. Zwitterionic Surfactants. Zwitterionic surfactants are
technology has made it feasible to generate many forms of also known as amphoteric surfactants and contain both cationic
biosurfactants from microbes and vegetable oils that are and anionic functionalities in the same molecule.58−60 The
biodegradable, have low toxicity, and behave similarly to anionic part can be varied, wherein the cationic functionality has
synthetic surfactants.46 primary, secondary, or tertiary amines or QACs. The behavior of
There are many negative environmental consequences of the cationic or anionic nature of such a surfactant is usually
using synthetic surfactants, including their high levels of toxicity prone to pH changes. Groups of such surfactants include
and poor biodegradability. These materials have a negative carboxylic acid/quaternary ammonium (e.g., lauryl-N,N-
impact on wastewater treatment as well as aquatic microbial (dimethylammonio)butyrate), sulfuric acid/quaternary ammo-
populations, fish and other aquatic life, and plant photochemical nium (e.g., surfactin), phosphoric acid/quaternary ammonium
energy conversion efficiency.46 With over 15 million tons of (e.g., miltefosine), phospholipids, and miscellaneous (e.g.,
surfactants used worldwide each year and an estimated 60% of lauryldimethylamine N-oxide).
them ending up in the aquatic environment, it is urgently 2.1.4. Nonionic Surfactants. Nonionic surfactants are
necessary to find substitutes that have fewer environmental surfactants which do not undergo ionization in aqueous
impacts.47−49 The origins and natural uses of biosurfactants are solutions. As they do not undergo ionization in aqueous
discussed, along with their benefits over synthetic alternatives, solution, they tend to retain higher stability and are less affected
such as their low toxicity and biodegradability. This review by or prone to strong electrolytes.61−64 They have been known
describes the current methods of surfactant production, the for their excellent compatibility with other surfactants and have
future trends, cleaner and sustainable production methods, and solubilities in both aqueous and organic solvents.64 The
an extensive comparison of performance parameters between inclusion of a polyethylene glycol chain, obtained through
green and petroleum-based surfactants. polycondensation of ethylene oxide, makes a high proportion of
these nonionic surfactants hydrophilic. As the strength of
2. CLASSIFICATION OF SURFACTANTS hydrogen bonds weakens with rising temperature, so do the
For better clarity and ease of understanding, surfactants can be water solubilities of nonionic surfactants. Nonionic surfactants
classified on the basis of their physicochemical properties, their are likely the most often employed in drug delivery
sources, and/or the hydrophilic and hydrophobic moieties applications.63 Polyol esters, polyoxyethylene esters, polox-
present in the molecule. amers, and Pluronics can all be used as nonionic surfactants. As
2.1. Classification of Surfactants According to the previously stated, nonionic surfactants have a unique feature
Charges of Their Headgroups. 2.1.1. Anionic Surfactants. known as a cloud point.64 The cloud point is the temperature at
Anionic surfactants are surfactants that have anionic function- which the nonionic surfactant begins to phase separate from the
alities at their heads. These anionic groups include phosphate, cleaning solution.64 The cleaning solution becomes cloudy as a
sulfate, sulfonate, and carboxylate. They tend to give negatively result of this. As a result, this cloud point is thought to be the
charged surfactant ions when dissolved in water.50−52 Such optimal temperature for detergency. Polyethylene glycol is a
surfactants are finding applicability in shampoos, laundering, significant component of polyoxyethylene esters (PEGs).64
dishwashing formulations, etc.50−52 One class of common soap Nonionic surfactants that are often used are ethers of fatty
surfactants is sodium stearates (comprise >50% of global alcohols. Nonionic surfactants aid in lowering the hardness
usage).53 Some examples of anionic surfactants are dioctyl sensitivity of the surfactant system. Alkylphenolethoxylates
sodium sulfosuccinate (DOSS; used as wetting agent in coatings, [RO(CH2CH2O)nH (R = alkylphenol group)], alcohol
toothpaste, etc.), linear alkylbenzene sulfonates (LASs; used in ethoxylates [CnH2+1(OCH2CH2)NOH], and nonylphenols are
laundry detergents, dishwasher detergents, etc.), and sodium noncharged hydrophilic parts of nonionic surfactants.
lauryl ether sulfate (SLES; used in shampoos, bath products, 2.2. Classification of Surfactants Based on Solubility.
etc.). Subtypes include (i) soaps (CnH2n+1COO−X), (ii) LASs Another way to classify surfactants is based on their solubility
(CnH2n+1SO3−X), (iii) alkyl ether sulfates (AESs; CnH2+1− profiles.65,66 For example, surfactants soluble in water would be
(OCH2CH2)n−OSO3X), and (iv) alcoholic sulfates (R−O− of “hydrophilic” nature, while those soluble in lipids can be
SO3X). It has been seen that anionic surfactants exhibit relatively termed “hydrophobic” (“lipophilic”) surfactants. In this
nontoxic characteristics.54 instance, ionic surfactants are hydrophilic in nature, while
2.1.2. Cationic Surfactants. Cationic surfactants (CSs) have nonionic surfactants can either be hydrophilic or hydrophobic.
positively charged heads and usually find application as good Such characteristics of nonionic surfactants are based on the
emulsifiers. These surfactants have also been reported for balance between the hydrophilic group and the lipophilic group.
11675 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Figure 1. Possible systematic modifications of sugar-based surfactants centered on octyl-β-D-glucoside. Adapted with permission from ref 70.
Copyright 2019 Elsevier.

This is usually quantified on the basis of the hydrophilic− Scheme 1. Synthesis of Sorbitan Esters by Intramolecular
lipophilic balance (HLB) scale. Other indicators are the cloud Dehydration of Sorbitol in the Presence of Acida
point for nonionic surfactants (the temperature at which the
mixture starts to phase separate and two phases appear, thus
becoming cloudy) and the Krafft point for ionic surfactants (the
Krafft point is the minimum temperature at which a surfactant
can form micelles).67
2.3. Sugar-Based Surfactants. Representing 95% of the
world’s biomass volume generated, carbohydrates are the most
abundant organic compounds worldwide.68 Although their
industrial-scale production has been relatively new, sugar-based
a
surfactants have been gaining increasing attention due to their RCOOH: fatty acids. Adapted with permission from ref 68.
advantages with respect to their performance, consumer health, Copyright 1999 John Wiley and Sons.
and environmental compatibility as compared to existing
surfactants.69 Sugar-based surfactants, such as sorbitan esters,
sucrose esters, alkyl polyglycosides, and fatty acid glucamides, derivatize sorbitan esters by reacting them with ethylene oxide to
are gaining popularity due to improvements in performance, form sorbitan ester ethoxylates. Commercially called “Tween”,
consumer health, and environmental compatibility over some polyethoxylated sorbitan monoesters are surfactants ideal for
traditional formulations. The very interesting review published creating oil-in-water emulsions due to their hydrophilicity.68,69
by Gaudin et al.70 describes the impact of the chemical structure Sorbitan esters mainly find use as emulsifiers in pharmaceut-
on amphiphilic properties of sugar-based surfactants. Sugar- icals, foods,3,71 cosmetic products,72−74 emulsion polymer-
based surfactants can also be classified based on their ization,75 explosives, and other specific applications. In contrast
stereochemistry. Figure 1 illustrates possible systematic to traditional nonionic surfactants, sucrose fatty acid esters’
modifications of sugar-based surfactants centered on octyl-β-D- hydrophilic−lipophilic balance (HLB) may be altered by
glucoside. switching from one to eight fatty acid residues attached to a
2.3.1. Sorbitan Esters. Sorbitan esters have been around since sucrose ring. It is quite intriguing to look at how the number of
1938, when the industrial processes to synthesize them were linked fatty acid residue affects the phase behavior and self-
established. There are two processes to manufacture them, one organized structures in a water/sucrose fatty acid ester system.
of which occurs in two steps. The process begins with the In comparison to ionic surfactants, nonionic surfactants have the
conversion of sorbitol into 1,4-sorbitan by dehydration, followed advantage of allowing anything to alter molecular structures,
by esterification with fatty acids of technical grade (Scheme 1).68 particularly the hydrophilic moiety, to produce surfactants with
These two steps can occur independently or simultaneously, a wide range of HLB. For nonionic surfactants of the
with both processes being used industrially to produce sorbitan polyoxyethylene type, the HLB is altered by varying the
esters.68,69 Sorbitan esters are known commercially as “Span” polymerization level of the polyoxyethylene group. Due to this
(e.g., Span 80 is a biodegradable surfactant based on a natural benefit, in water/polyoxyethylene-type surfactant systems, a
fatty acid (oleic acid) and sugar alcohol sorbitol). These esters wide range of surfactant aggregates, both with positive and
are relatively hydrophobic; hence they tend to find applications negative curvatures, are seen in a phase diagram as a function of
in the formation and formulation of water-in-oil emulsions. To the surfactant’s HLB number. The global sorbitan esters market
make these molecules more hydrophilic, it is common to is slated to top USD 756.4 million in 2021. Sales of sorbitan
11676 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

esters are expected to grow by 5.6% compound annual growth glycosides, and alkyl polyglycosides that results from both
rate (CAGR) between 2021 and 2031.76 synthesis methods depends on the proportion of glucose/fatty
2.3.2. Sucrose Esters. Sucrose is an organic compound alcohol used as reactants. The product’s surfactant properties are
abundantly produced and is available at high purity at low cost. determined by the length of the carbon chain and the average
Sucrose esters are primarily produced by combining the primary number of glucose units polymerized�the degree of polymer-
hydroxyl group of a nonreducing sugar moiety and a methyl ization.68 The primary attractiveness of APG is due to their
ester of a fatty acid.77 This is achieved using a transesterification environmental compatibility as they have high biodegradability
reaction between sucrose and the fatty acid ester, followed by and low aquatic toxicity. They also possess desirable
further purification to get the desired product (Scheme 2).2 A dermatological properties as they are mild to the skin and eye,
which have made this class of surfactants attractive to personal
Scheme 2. Synthesis of Sucrose Esters by Base Catalyzed care products.48 C12/C14 APGs have applications as liquid
Transesterification with Fatty Acid Methyl Esters dishwashing agents, personal care products, and detergents,
(R′COOMe)a while C8/C10 APGs are used as agrochemicals, hard surface
cleaners, and industrial and institutional cleaners.
Fatty acid glucamides, or N-methylglucamides (NMGAs),48
are an additional class of glucose-derived surfactants produced
industrially. The synthesis procedure involves reacting glucose
with methylamine under reductive conditions to form N-
methylglucamine, which is further converted with a fatty acid
a methyl ester to the respective fatty acid amide (Scheme 4).11 In
Adapted with permission from ref 68. Copyright 1999 John Wiley
and Sons.
comparison to APGs, NMGAs have only one carbohydrate
molecule attached to the chain. However, their physicochemical
properties are comparable to those of APGs.82 Currently,
large range of amphiphilic products can be obtained by NMGAs with C12/C14 and C16/C18 alkyl chains are exclusively
controlling the extent of esterification as well as the choice of used by The Procter & Gamble Company (P&G) in liquid
fatty acid used as the hydrophilic moiety. The most hydrophilic dishwashing agents and powdered and liquid detergents.
products are those with a high content of monoester, while the 2.3.4. Alkyl Polyglycoside (APG) Derivatives. APGs have
least hydrophilic products are those with a higher ratio of been employed as raw materials for the synthesis of specialty
multiple esterification products. This range of hydrophilicity, surfactants intending to slightly adjust the properties of APGs to
along with relatively low dermatological impact, provides this the desired impact due to the simplicity of procurement and
class of surfactants with a versatility that allows it to have a wide availability.78 Despite the fact that a wide variety of items can be
range of applications in personal care products, cosmetic care produced using straightforward techniques, only a small number
applications, food emulsifiers, and certain specialty detergent of goods�methyl glucoside esters and a number of specialized
products.2,48 The sucrose esters market size was valued at USD esters�have successfully entered the market.78
72 million in 2022 and is projected to reach USD 111.6 million By esterification of methyl glucoside with methyl esters of
by 2030, growing at a CAGR of 5.20% from 2023 to 2030.2 oleic or stearic acid, one can enhance the lipophilicity of the
2.3.3. Glucose-Derived Surfactants. Under the umbrella of molecule. Compared to APGs with the same chain length,
glucose-derived surfactants, there are two groups of compounds methyl glucoside esters are sparingly soluble in water and yet
which have been focused upon: alkyl polyglycosides (APGs) and show excellent emulsification properties. Methyl glucoside
alkyl glucamides (or fatty acid glucamides). esters have found applications as emollients, emulsifying and
There is currently an extremely strong interest in the synthesis moisturizing agents, and thickeners in cosmetic products and
of APGs, which is done by a direct reaction between glucose and formulations. The hydrocarbon chain length and degree of
a fatty alcohol, with the alcohol being in large excess to minimize substitution can be altered to obtain specific water-in-oil
and reduce sugar oligomerization and promoting the desired emulsification activity. The series of specialty esters, namely
product (Scheme 3).42 An alternate method is transacetalization citrates, tartrates, and sulfosuccinates, have applications in
between a short-chain alkyl glycoside and a long-chain fatty personal care products.68,78
alcohol.42 The mixture of alkyl oligoglycosides, alkyl mono- 2.4. Classification of Surfactants Based on Feedstocks.
2.4.1. Surfactants Manufactured Using Synthetic or Petro-
Scheme 3. Reaction of Glucose and Fatty Alcohol to Form chemical Feedstocks. Oil, gas, and chemical processing all offer
Alkyl Polyglycosides (APGs) Carrying Units of Glucosea synthetic or petrochemical feedstocks for surfactant manufactur-
ing. The resultant molecules, synthetic alcohols, can be further
processed or reacted to form a variety of surfactant molecules
(including those of alkylation, ethoxylation, or sulfation). Due to
their synthetic nature, the molecular structures of these
compounds may be adjusted during manufacturing to achieve
specialized physical and performance properties of surfactant
molecules. They are also chemically versatile, which allows them
to be compatible with a wide range of other chemicals and
substances. These include petroleum-based surfactants.79 A
recent review by Ng et al.79 summarizes recent advances of
a biosurfactants for waste and pollution bioremediation compared
Adapted with permission from ref 68. Copyright 1999 John Wiley
and Sons. with petroleum-based surfactants.
11677 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Scheme 4. Formation of Fatty Acid N-Methylglucamide with Two-Step Processa

a
Adapted with permission from ref 68. Copyright 1999 John Wiley and Sons.

Figure 2. Types of microbial surfactants: (a) mannosylerythritol lipid; (b) surfactin; (c) trehalose lipid; (d) sophorolipid; (e) rhamnolipid.

2.4.2. Surfactants Manufactured Using Renewable Feed- referred to as biosurfactants, lipoproteins and lipopolysacchar-
stocks. These surfactants are also known as “natural based” (also ide have high molecular weights and are usually referred to as
known as “biobased” or “oleo”) surfactants, as they have origins bioemulsifiers.80−84
in natural sources such as microbes, plants, and marine.80 To Glycolipids are the class of low molecular weight molecules
manufacture fatty alcohols, plant oils need to be chemically that have been the subject of the greatest research, with the most
processed (including esterification, hydrogenation, and distil- commonly known being the sophorolipids (sophorose lipids,
lation). Despite differing plant origins, these alcohols are SPLs), rhamnolipids (rhamnose lipids, RMLs), trehalose lipids,
comparable to their synthetic equivalents and hence go through and mannosylerythritol lipids (MELs).85−87 Glycolipids have
the same type of subsequent chemical processing steps to been reported to have wide ranges of applications in
produce the end surfactant. Natural feedstocks may be seen as pharmaceutical formulations.88−90
more environmentally sustainable; nevertheless, other factors Rhamnolipids are glycolipids that contain rhamnose (a
must be acknowledged when assessing sustainability, and all pentose monosaccharide, 6-deoxy-L-mannose) linked to a fatty
aspects of the surfactant life cycle must be examined. acid tail ranging from 8 to 16 carbon carbons in length, although
2.4.2.1. Microbial Surfactants. Microbial surfactants (Figure generally β-hydroxydecanoic acid (C10) is there.91 These
2), or second-generation biosurfactants, are surfactants which biosurfactants are well-known globally, and depending on the
are derived from microbial origins, harnessing the biosynthetic number of rhamnoses present in the molecule groups, their
machinery available in the biotic community to synthesize the architectures can be split into two groups: monorhamnolipids
desired molecule.80−84 Surfactants under this category are also and dirhamnolipids (one rhamnose group).91 The main method
termed “green surfactants” or “biosurfactants”. In contrast to of producing rhamnolipids uses the pathogenic Gram-negative
synthetically produced surfactants, which are typically catego- bacterium, Pseudomonas aeruginosa. Rhamnolipids are fre-
rized according to the characteristics of the polar groups they quently utilized in environmental processes including the
contain, biosurfactants are typically categorized according to the bioremediation of water and soils that have been contaminated
chemical compositions of their molecules and the microbes from by metals, petroleum, or other xenobiotic substances. Apart
which they originated.80−84 from bioremediation rhamnolipids are used in food processing,
With an average mass ranging from 500 to 1500 Da, protein folding, microbial fuel cells, and the creation of
biosurfactants are widely divided into low molecular mass and nanoparticles.92−100
high molecular mass biosurfactants.83 While larger molecular Sophorolipids are another type of glycolipidic biosurfactants
mass biosurfactants are better at stabilizing emulsions, smaller that have sophorose (a hydrophilic disaccharide consisting of
molecular mass biosurfactants are better at lowering surface or two glucose residues connected by a β-1,2 glycosidic linkage)
interfacial tension. While lipopeptides, glycolipids, and connected by a glycosidic linkage to a C16−C18 hydroxylated
phospholipids have low molecular weights and are commonly fatty acid which may or may not be acetylated.101 Sophorolipids
11678 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Figure 3. Types of amino acid based surfactant: (I) linear or single chain; (II) dimeric or gemini; (III) glycerolipid-like/glycolipid-like.

can be either acidic (containing a carboxyl group) or lactonic molecules with higher surfactant properties. Considering this,
(containing a cyclic ester). Yeasts are used for sophorolipid vast varieties of amino acid/peptide structures are available for
production, with strains such as Torulopsis bombicola and building amino acid/peptide based surfactants; one can regulate
Starmerella bombicola being mainly used.102 These molecules the surfactant properties of end molecules.116,117 Moreover,
often have applications in beauty and personal care products, such variety is also applicable due to the structural diversity
household cleaning products, and biopesticides.101−104 among chemical moieties, biological properties, and physico-
Mannosylerythritol lipids are among the biosurfactants with chemical properties. The amino acids and long aliphatic chains
the most exciting potential, as they are widely manufactured can be joined to synthesize three major structures of amino acid
from vegetable oils with the help of Pseudozyma antarctica.105 based surfactants: (1) linear or single chain, I; (2) dimeric or
These biosurfactants are characterized by mannose and gemini, II; and (3) glycerolipid-like structures, III116,117 (Figure
erythritol linked to a fatty acid and are further classified based 3). Linear structures (I) typically made up of an amino acid with
on the length of the hydrophobic fatty acid, degree of saturation, at least one hydrophobic tail. Gemini or dimeric (amphipathic)
and degree of acetylation (mono-, di-, or triacetylated). They are structures (II) consist of two polar heads (two amino acids) and
primarily used in the formulation of beauty and personal care two hydrophobic tails every molecule. Glycerolipid-like
products.105−109 structures (III) can be viewed as monoglyceride, diglyceride,
Trehalose lipids are made by species of the genera and phospholipid analogues. They are made up of one polar
Mycobacterium, Rhodococcus, Corynebacterium, and Nocardia head and one or two hydrophobic moieties that are joined
and consist of trehalose disaccharides coupled with a fatty acid, together by a glycerol skeleton. Natural α-amino acids are
primarily mycolic acid.110,111 The size, structure, degree of coupled by extensive aliphatic chains connected to the α-
unsaturation, and amount of carbon atoms in the trehalolipids COOH, α-amino, or side chains to form a linear, or single-chain,
produced by various organisms differ.111 amino acid surfactant. Hence, the fatty acids or alkyl halides are
The most well-known and well-known biosurfactant in the capable of reacting with the amino groups to yield the respective
lipopeptide family is surfactin, which is also one of the strongest N-acyl or N-alkyl derivatives. On the other hand, N-alkyl amides
biosurfactants ever discovered. This cyclic lipopeptide is made and esters can be created by condensing the carboxyl group of
by the species Bacillus subtilis and contains seven long-chain with alkyl amines or aliphatic alcohols.118−121
hydrophobic amino acids linked to a fatty acid chain by a lactone Gemini surfactants, which have two hydrophilic and two
bond. Due to its antibacterial, antimycoplasmal, antiviral, and hydrophobic groups in each molecule connected by a spacer
antitumoral characteristics, surfactin offers a wide range of chain, are an example of a particular kind of amphipathic
potential biological applications. In the food business, it can also chemicals.122 These molecules, which have good surface activity,
work well as a stabilizer, emulsifier, and surface modifier.112−114 can also be thought of as single-chain conventional surfactant
In 2021, the microbial biosurfactants market was around USD dimers.122,123 Gemini surfactants made of cysteine have been
16.1 million. It is estimated to increase at 3.9% CAGR through created to boost their effectiveness while lowering their
2032.115 environmental impact. Gemini surfactants have had large
2.4.2.2. Amino Acid/Peptide Based Surfactants. Amino numbers of biomedical and pharmaceutical applications
acids as raw materials for surfactant preparations have gained reported very recently.124−127
immense importance since the last century.116,117 Amino acid/ Glycerol-amino acids, a subclass of lipoamino acids that are
peptide based surfactants mostly have applications in the area of similar to mono- and diacylglycerides and phospholipids, are
life sciences and biomedicine as drug carriers, antiviral agents, amino acid glyceride conjugates. They consist of one or two
mediators in DNA, or DNA transfection and gene delivery aliphatic chains joined by ester bonds to the glycerol backbone,
agents in gene therapy.122,123 Previously, they were used for together with an amino acid serving as the polar head, and have
medicinal and cosmeceutical applications; however, they have biological applications, too.128−132
been thoroughly investigated nowadays for many of their As per previously published reports, this class of surfactants
surfactant applications. The chemical structure, length, and can be synthesized via (1) chemical methods, (2) enzymatic
number of fatty acid chains would be varied for nonpolar long- methods, or, usually, (3) a combination of both method-
chain compounds (hydrophobic moiety) coupled with polar ologies.132 Thus, saturated single-chain, double-chain, gemini,
amino acids/peptides (hydrophilic moiety) resulting in and amino acid glycerolipid conjugate surfactants formed from
11679 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Figure 4. Flowchart representing formation of petro-based surfactants from nonrenewable sources.

various ionic character amino acids have all been found to be “petro-based surfactants” and (II) surfactants derived from
highly biodegradable, with low toxicity, ecotoxicity, and irritant biological origins or “biosurfactants” or “green surfactants”.
effects.
The global amino acid based surfactants market size was 3. PETROLEUM-BASED SURFACTANTS
estimated at USD 528.58 million in 2021 and is projected to (PETRO-BASED SURFACTANTS): THEIR ORIGINS,
reach USD 1163.05 million by 2028, exhibiting a CAGR of ADVANTAGES, AND LIMITATIONS
11.92% during the forecast period.133 Oil, gas, and chemical processing are used to create synthetic or
2.4.2.3. Glycerol-Based Surfactants. Globally, the produc- petrochemical feedstocks (as shown in Figure 4). Through the
tion of emulsifiers is estimated to be of the order of 300 000 t.134 advancement of petrochemical processing, particularly petro-
Esters formed from glycerol and fatty acids are referred to as leum cracking, which yields unsaturated, short-chain hydro-
glycerides, more commonly known as acylglycerols. Glycerol has carbons, it was possible to obtain hydrophobic structures for
three hydroxyl functional groups, all of which can be esterified surfactant molecules through polymerization of these alkenes,
with one, two, or three fatty acids to form specific such as ethylene or propylene, which gives way to surfactants
monoglycerides, diglycerides, and triglycerides.134−136 Fats with C9−C18 carbon chains.138 The derived chemicals can be
and vegetable oils contain triglycerides which can be broken further processed or reacted to create a variety of other
down into monoglycerides and diglycerides (also called partial surfactant molecules, including through alkylation, ethoxylation,
glycerides) due to the activity of natural enzymes. and sulfation (Schemes 5−8 illustrate the chemical pathways
Pure partial glycerides are a type of nonionic surfactant which
show no charge. Pure monoglycerides and diglycerides have Scheme 5. Reaction Forming Alkylbenzene Sulfonic Acid
been proven to be efficient and effective surfactants and hence from Alkylbenzene
have multiple applications.134,136 Glycerol monostearate (GMS)
is a monoglyceride that has been used as a food additive as an
emulsifier, thickening agent, anticaking agent, and preservative;
as an emulsifier for oils and waxes; and as a control release agent
and solidifier for pharmaceutical agents. Magnesium stearate
(MG) and its derivatives make up 75% of the food emulsifiers that lead to the creation of petroleum-based surfactants).
used in the world.136 Because they are made of synthetic materials, manufacturers
Partial glycerides exist majorly in three crystalline forms: α, β, may manipulate the molecular structures to develop products
and β′. The α crystalline forms are the most functional and can with precisely defined physical and performance properties.
be converted into the β form, which are the most stable and They are also chemically adaptable, making a diverse variety of
moderately functional.135
Glycerol-based surfactants can be synthesized through either Scheme 6. Reaction Forming α-Olefin Sulfonates
direct esterification with glycerol and fatty acids or trans-
esterification with glycerol and natural fats/oils or fatty acid
methyl esters. Chemical syntheses of mono- and diglycerides are
done by glycerolysis of fats and oils under high temperatures
with inorganic catalysts.137 The global polyglycerol esters
market was valued at USD 9.8 billion in 2021 and is expected
to reach USD 15.24 billion by 2029, registering a CAGR of
5.60% during the forecast period of 2022−2029.137
Thus, herein this review shall be focusing on two major
categories of surfactants: (I) petroleum-based surfactants or
11680 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Scheme 7. Reaction Forming Alkane Sulfonates 3.1.2. Paraffin Sulfonates, Secondary n-Alkanesulfonates
(SASs). These are used largely in light-duty liquid home
detergents that are liquid (LDLs).143
The polymerization of vinyl polymers uses an SAS as an
emulsifier.47
It serves as an antistatic agent in a variety of polymers,
Scheme 8. Reaction Forming Monoester Sulfosuccinate including polyvinyl chloride (PVC) and polystyrene.47
The water solubility is desirable.47
Its aqueous liquids have low viscosities.47
SAS shows good compatibility with skin.
At low temperature it exhibits biodegradability.47
3.1.3. α-Olefin sulfonates (AOSs).144 AOSs are used in
variety of household, personal care soaps, and detergents.
They are stable over a wide range of pHs.
They are cold water and hard water compatible.
They are good foaming agents and are mild on skin.
They are sulfate free.
3.1.4. Sulfosuccinate Esters. Monoesters are used in
other chemicals and substances compatible with them. They can cosmetics and, when combined with other anionic surfactants,
thus be combined with various elements, such as other help to lessen the irritation that anionic surfactants can cause to
surfactants, to create a completed formulation whose qualities the skin and eyes.145,146
are adapted to the needs of certain applications. Table 1 Amide monoesters are among the anionic surfactants that are
highlights sources, properties, and application of some well- the least irritating to the eyes because they may be manufactured
known petrochemical surfactants. Due to their high toxicity, low electrolyte-free and are entirely soluble in organic sol-
biodegradability, and dependence on petroleum and its vents.145,146
derivatives for their synthesis, synthetic surfactants have come 3.2. Limitations of Petroleum-Based Surfactants.
under fire, particularly from environmental advocacy groups. Petroleum-based surfactants that have been chemically created
These synthetic compounds typically contain lengthy carbon degrade slowly when exposed to microbes. As a result, they
chains, branching, or aromatic groups, which impede biode- could bioaccumulate or produce byproducts that are harmful to
gradation and cause a host of environmental issues. the environment. Early in the 1960s, persistent foams began to
3.1. Advantages. Petro-based surfactants have been in use blanket numerous bodies of water, such as rivers and lakes that
for decades, and gradually, with increasing demand, their received wastewater from big towns, which led to an ecological
production has increased enormously with a huge extent of imbalance since the thick layer of foam inhibited photosynthesis
advancement in technology also. Despite extensive research in and oxygen dissolution.42 This was caused by inefficient
the field of biosurfactants, they are still struggling with the alkylbenzene sulfonates (ABSs). As a result, governments of
research and development stage of production. The actual part developed countries passed environmental laws to limit the use
of the study to infer applications of these surfactants is neglected, of ABSs in detergents around 1965. Because of this, less
due to which petroleum-based surfactants are major promising expensive surfactants like linear alkylbenzene sulfonates were
molecules to serve the demands of humankind. With continuous created. However, surfactants continue to be a concern of
advancements in research, scientists have come up with many sewage treatment facilities, as well as of freshwater resources like
biodegradable petroleum-derived surfactants such as LASs and lakes and rivers, in developing countries.79
paraffin sulfonates, which are used worldwide in various Another problem is the phosphate content in surfactants
industries giving satisfactory results. This type of surfactant is which is responsible for eutrophication. Eutrophication results
economical and has many upper edges compared with other in the abrupt and explosive growth of algae and other plankton
classes of surfactants.139 which consumes the oxygen dissolved in water, suffocating fish
The low shelf life and lack of supply of biosurfactants due to and other aquatic plant and animal life. This indirectly harms
low production yields are major concerns for their compatibility humans as many desirable aquatic species are at a loss or extinct.
in the surfactant industry.140 Decrease in species diversity, increase in plant and animal
Some specific advantages of petroleum-derived surfactants are biomass, increase in turbidity, increase in the rate of
given in sections 3.1.1−3.1.4. sedimentation, and shortening of the lifespan of the lake are
3.1.1. Linear Alkylbenzene Sulfonates (LASs). LASs have an adverse effects owing to eutrophication.79
advantage because of their low price ($2,400−2,800/MT) and Also, petro-based surfactants will soon start facing problems
their superior performance due to a low vapor pressure ((3−5) of raw material shortages due to the rapid depletion and
× 10−13 Pa), with a critical micelle concentration (CMC) of 0.1 exhaustion of petroleum and fossil fuels in the near future.
mg/L. They form clear solutions in water at concentrations up to Hence industries and researchers worldwide have shifted their
250 mg/L. Linear alkylbenzene sulfonic acid is among the most attention to biobased surfactants to tackle this issue.
widely used synthetic surfactants by volume.141 This chemical is Biosurfactants are also fully biodegradable and hence are a
biodegradable and environmentally friendly. better alternative to petroleum-based surfactants.
It has a low salt content and a good water solubility.142 Surfactant specific limitations are given in sections
It is completely compatible with hard water.142 3.2.1−3.2.3.
It is resistant to hydrolysis in hot acid or alkali. 3.2.1. Linear Alkylbenzene Sulfonates (LASs). With the
It is fully ionized; as a result, low pH has no effect on exception of alcohol, sodium alkylbenzene sulfonate (LAS) is
solubility.142 not soluble in organic solvents. The crucial quality for
11681 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Table 1. Properties, Advantages, and Sources of Some Well-Known Petroleum-Based Surfactants149−154

elimination in the environment is that LAS readily, quickly, and 3.2.2. Sulfosuccinate Esters. Acidic and hot alkaline solutions
fully degrades in aerobic environments. 147
However, under hydrolyze these surfactants. Dialkyl esters cause skin irritation
(monoesters do not).148
anaerobic conditions, LAS only experiences primary biode- 3.2.3. POE Alkylphenols, Alkylphenol “Ethoxylates” (APEs),
gradation. There has not been any proof that LAS completely RC6H4(OC2H4)nOH. The rates of biodegradation for APEs are
slower than those for other nonionic surfactants such as linear
biodegrades in anaerobic environments. LAS might irritate the alcohol ethoxylates, even though they are fully biodegradable in
skin. aerobic environments.140 Compared to the parent APE, the
11682 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Scheme 9. Different Routes to Form Fatty Alcohol Sulfates

intermediates of aerobic biodegradation are more hazardous to those that make use of the biosynthetic machinery of organisms
fish and other aquatic species.140 Although no evidence of APE of the biotic community (microbes, yeasts, plants, etc.) through
endocrine disrupting activity in actual environmental systems biological processes (biocatalysis or fermentation) to produce
has been established, there are reports that APEs may exhibit it the surfactants, from which the desired product is extracted and
in model systems in laboratory testing. purified (Figures 5−8 highlight downstream processes of some
popular microbial surfactants). Primarily examples of these
4. BIOSURFACTANTS: GREEN GENERATION OF biosurfactants are microbial surfactants such as glycolipids,
SPECIALTY CHEMICALS (ALSO TERMED “GREEN specifically rhamnolipids and sophorolipids, and lipopeptides,
SURFACTANTS”) specifically surfactin, produced in this way. The sources,
The shift from using petrochemicals to using renewable properties, and uses of a few well-known oleochemical-based
materials as starting raw materials for surfactant synthesis has surfactants are highlighted in Table 3.
been promoted by the concept of “going green” due to The structural characteristics of the product green surfactants
environmental concerns as well as legislation and government serve as the foundation for both the classification of these
restrictions over toxic detergents in products, resulting in what substances and the determination of their physicochemical
we now refer to as “green surfactants” as suitable substitutes.54 properties. As with any surfactant, they contain a hydrophobic
This new category of products is more biocompatible, and moiety (saturated, unsaturated, hydroxylated, or branched) and
biodegradable, and meets the rising consumer demand for a hydrophilic moiety (ester, carboxylate, hydroxyl group,
products which are “greener”, that is, milder, more effective, and phosphate, peptide, amino acid, or carbohydrate). As previously
less environmentally impactful. The term “green surfactants” mentioned, such products are considered extremely important
refers to biobased amphiphilic molecules that are either in the current scenario, due to their ecological soundness and
obtained naturally or can be synthesized from renewable raw low (or no) toxicity and high biodegradability. Such green
materials.54 They are also sometimes referred to as “bio- surfactants are also considered vastly versatile compounds due
surfactants”. First-generation biosurfactants are those directly to their applications in the petroleum, chemical, pharmaceutical,
extracted from animal-based or plant-based raw materials or food, metals, textiles, cosmetics, and agriculture industries.54
directly synthesized chemically. Multiple raw materials can be 4.1. Production/Synthesis and Extraction Methods of
used and chemically modified to yield green surfactants or Green Surfactants or Biosurfactants. In this section, we
biosurfactants.54 In particular, triglycerides, carbohydrate outline a few of the methods or routes available for the
sources, and certain organic acids have been extremely useful production of green surfactants or biosurfactants including their
as starting materials in green surfactant synthesis. Examples of biosyntheses.
surfactants produced through chemical synthesis are saponins, 4.1.1. Biosynthesis. The amphiphilic structure in biosurfac-
fatty alcohol sulfates (as shown in Scheme 9), fatty acid methyl tants consists of a long-chain fatty acid and the hydrophilic motif
ester sulfonates (as shown in Schemes 10 and 11), sugar esters, (which includes amino acid, carboxylic acid, phosphate,
etc.).155,156 The synthesis of their hydrophobic and hydrophilic
Scheme 10. Reaction to Form Fatty Acid Methylesters components is carried out by two primary metabolic pathways,
namely hydrocarbon and carbohydrate. The pathways for
synthesis of these two types of precursors are diversified and
rely on distinct sets of enzymes. Because the first enzymes
involved in the synthesis of these precursors are often regulatory
enzymes, there are some commonalities in their synthesis and
regulation. There are detailed descriptions of synthetic pathways
for these the major hydrophobic and hydrophilic motifs
Scheme 11. Reaction to Form Sucroesters available in the literature. However, a comprehensive summary
by Hommel and Ratledge155 may be handy to read. Per Syldatk
and Wagner,157 there are four possibilities which can exist for
synthesis of linkages and involved hydrophilic (HPL) and
hydrophobic (HB) moieties of biosurfactants:158
(1) HPL and HB moieties synthesized de novo by two
independent pathways
(2) HPL synthesized de novo and HB induced by substrate
(3) HB synthesized de novo and HPL substrate dependent
alkyl polyglucosides, and alkanolamines. Table 2 lists the (4) both HB and HPL substrate dependent
sources, properties, and uses of a few well-known oleochem- The chemical synthesis for a biosurfactant depends on the
ical-based surfactants. Second-generation biosurfactants refer to molecule and desired surfactant. Due to the vastness, there is no
11683 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

140

140

168

107
ref
enhanced oil recovery; cleanup of oil spills in aquatic media; proposed as concrete additives; in cosmetics

ethoxylated sophorolipids used as skin moisturizers; humectants in cosmetics; sophorolipid esters used in
lipstick and hair products; acidic forms of sophorose lipids used as agents for healing, desquamation, and
macrophage activation; release of bitumen from tar sands; improvement of oral hygiene by getting rid of

moisturizing property similar to those of ceramides; widely used in skin care industry as an antiaging and
detergents to remove tough stains like coffee and vegetable oils; also exhibit antifungal, antibacterial,

moisturizing agent having cytoprotective and antioxidant qualities; also exhibit antibacterial activity
in food industry as surface concentration (CMC) modifier, emulsifier, and stabilizer; incorporated in
bacterial biofilms or preventing growth of further bacterial cultures in the mouth
applications

and antimycoplasmal activities

against Gram-positive bacteria

Figure 5. Classification of biosurfactants based on molecular weight.

as promoters

overall generalization that can be made as each mechanism and

route will be different as suggested above.
4.1.2. Fermentation. Biosurfactants can be produced by a
Table 2. Properties, Advantages, and Sources of Some Well-Known Microbial Based Surfactants

variety of microorganisms such as bacteria, fungi, and yeasts and

are diverse. Their natures, chemical compositions, and amounts,
type of sophorolipid); CMC 82 mg/L; surface

reduces surface tension to 28−40 mN/m; CMCs

29 mN/m; good foaming and wetting abilities;

reduces surface tension from 72 to 27 mN/m low

depend on the microorganisms producing them.158,159 These

molecular weights 600−706 Da (depending on
CMC of 15 mg/L; reduce surface tension to
molecular weights in the range 500−650 Da;

organisms have the ability to use potentially noxious substrates

tension 37 mN/m; good wetting ability;
lactonic form inhibits growth of certain

as they have been isolated from contaminated soil, effluents, or

antibacterial and antiviral properties

wastewater sources. Hence, the possible substrates are vast and

can broadly be described as agro-industrial waste, industrial
properties

wastes of plant and animal origin, and other industrial wastes.

Agro-industrial waste refers to vegetable oils and oil wastes, oil
of (2−5) × 10−4 M

mill waste effluents (OMWE), and starchy waste materials such

as potato processing effluents. Industrial wastes of plant and
animal origins refer to waste such as dairy industry whey, animal
microbes

fat, molasses, and soy molasses. Other industrial wastes refer to

CMC

soap stock.158,159
Since such a process depends on microorganisms, culture
oil, animal
canola oil,

variables including agitation, pH, the concentration of metal

soybean oil,
sunflower
ery waste

vegetable
safflower
oil refin-

canola oil,
soybean
carbon
source
olive oil,

ions, temperature, dilution rate, and aeration, and the kinds of

sucrose,
fat

oil

oil

carbon and nitrogen sources affect the type, quality, and quantity
of biosurfactant production. By altering these conditions, the
Candida sphaerica, Starmerella
Pseudomonas aeruginosa, Pseu-

same microorganism can produce a different biosurfactant such

Pseudozyma antarctica, Ustila-
Bacillus subtilis, Bacillus neal-
bombicola, Cutaneotricho-

as by changing the substrate used. By closely studying them, one

can optimize the physicochemical properties of the desired
Pseudomonas spp.
microbe

biosurfactant, too.158,159
domonas cepacia,

sporonmucoides

4.1.3. Enzymatic Methods. Enzymes can be isolated,

immobilized, and used for producing base biosurfactants as
go nuda

well as used for processing or post-treatment to produce other

sonii

biosurfactants with modified properties. By using enzymes, one

can often find an alternate route for the synthesis of biobased
surfactants instead of using fermentation.85
mannosylerythritol
(sophorolipids)
sophorose lipids

The most well-known example of this is using immobilized

name
rhamnolipids

lipases to produce sugar esters. Solvent-free esterification of a

surfactin

simple APG by using fatty acid and Candida antarctica lipase has
been carried out under multiple conditions (molten fatty acid or
in various solvents) with different yields obtained.160 As such,
no.
1

other lipases or enzymes can be used to synthesize a whole range

11684 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Figure 6. Manufacturing process for rhamnolipids.

Figure 7. Manufacturing process for sophorolipids.

of biosurfactants, especially amino acid based esters and boundary layer, cellular membrane, and even the cytosol, by
amines.161 reducing the boundary layer thickness. Additionally, mass
4.1.4. Ultrasonication. Ultrasound refers to sounds inaudible transfer induced by ultrasonication can alter the active sites of
to the human ear and is subdivided into power ultrasound (20− enzymes and therefore alter the enzymatic activity.163 On the
100 kHz), high-frequency ultrasound (20 kHz−2 MHz), and contrary, high-intensity ultrasound can cause cellular membrane
diagnostic ultrasound (above 1 MHz). Practically, ultrasound is disruption and can damage vital macromolecules or even induce
used in two ranges: low-intensity (high-frequency 100 kHz−1 lysis. Hence, the utilization of mild ultrasound can stimulate and
MHz, low power of less than 1 W/cm2) and high-intensity (low-
control microorganism activity along with other processes such
frequency 2−100 kHz, high power of 10−1000 W/cm2).
as fermentation to increase efficiency and productivity.162
Depending on the intensity, the physical technology can have
4.1.5. Hydrodynamic Cavitation (HC). The fundamental
different biological impacts from beneficial to destructive.162
The primary effects are due to the phenomenon of cavitation, idea behind hydrodynamic cavitation is that when a liquid passes
which causes chemical and physical changes. It has been shown through a constriction or small opening, such as an orifice plate,
that ultrasonication increases cell permeability and, in turn, venturi, or throttling valve, the pressure of the liquid increases at
promotes or releases cellular metabolites and/or cells the expense of local pressure, and the pressure around the vena
themselves.162 Ultrasound can be employed in different stages, contracta falls below the threshold pressure, creating cavities.
via probes or bath ultrasound systems. A theory is that low- Due to the persistent pressure reduction, the eventual collapse of
intensity ultrasound promotes mass transfer through the these cavities releases a tremendous amount of energy and can
11685 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Figure 8. Manufacturing process for surfactin.

result in high-pressure shock waves and free radicals with 4.2. Advantages of Green Surfactants or Biosurfac-
temperatures up to 10 000 K.164 tants. Green surfactants or biosurfactants have lower
The extraction of integral molecules from natural products is toxicities.32,42
effectively done on an industrial scale by the use of efficient cell They have increased effectiveness at extreme temperatures or
disruption techniques such as cavitation. Even though ultra- pH values.
sound-based cavitation has wider applications, HC is a viable They have higher biodegradability; that is, compared to
option due to its efficiency and scale-up application. Depending chemical surfactants, biosurfactants are environmentally bene-
on the tools being used and the type of cell being disrupted, the ficial substances that break down quickly into simpler
mechanism of cell disruption varies. When compared to the metabolites. Different bioremediation and biosorption tech-
ultrasound-assisted approach, the lipid extraction percentage nologies have successfully utilized biosurfactants made from
from wet microalgae using venturi type HC is substantially marine microorganisms.32,42
greater.164,165 They improve hydrocarbon degradation: Biosurfactants, as
4.1.6. Microwave-Assisted Extraction (MAE). The extraction opposed to chemical surfactants, offer special qualities like low
method known as microwave-assisted extraction (MAE) toxicity and high biodegradability, selectivity, and surface
couples microwaves with conventional solvent extraction. By activity. They can also create more stable emulsions. These
applying microwaves for heating in the extraction process, one characteristics make them appealing for improved hydrocarbon
can expedite the kinetics of extraction and make it more recovery methods since they are maintained even at high
efficient.166 temperatures and a variety of pH and salinity ranges.32,42
Microwaves are nonionizing electromagnetic radiation with Biosurfactants have been discovered to be more effective and
frequencies in the range 0.3−300 GHz. The field simultaneously efficient than chemical surfactants in terms of their surface and
provides heating by two mechanisms: dipole rotation and ionic interfacial activities. Furthermore, the CMC values of
conduction. By doing so, one can cause changes in the cell biosurfactants are significantly lower than those of chemical
structure. The process’s acceleration and higher yield may be the surfactants.32,42
outcome of two transport phenomena, mass and heat transfer, 4.3. Limitations of Green Surfactants or Biosurfac-
which both work in the same direction, both from the inside to tants. Large-scale production of biosurfactants is complex and
the outside.167 One of the major benefits that modern MAE difficult.
offers is its solvent-free applications in extracting natural Some biosurfactants may be as toxic as synthetic bio-
products in an environmentally friendly green way. surfactants.
In MAE, extraction occurs by exposing the desired Biosurfactants may compete with the hydrocarbon as a
compounds and cells to the solvent through cell rupture. The preferred substrate.
free water molecules present in the cell matrix are heated, which Biosurfactant production is not economically viable.
results in the localized heating and expansion of the cell itself. As Many research groups are focusing on finding ways to produce
a result, the desired metabolites find it easier to flow out of the biosurfactants at lower costs by employing readily accessible and
cells.166 renewable bioresources as their primary raw materials.
Multiple parameters and factors may affect the MAE The biotechnological methods required in the synthesis of
extraction yield such as (i) extraction time and cycle, (ii) the biosurfactants are somewhat costly, and surfactant purification is
solvent system and solvent to feed ratio, (iii) contact surface area quite difficult. All biotechnology product costs are heavily
and water content, (iv) microwave power and extraction influenced by downstream processing. Different biosurfactants
temperature, and (v) stirring. By optimizing the conditions have been isolated, purified, and categorized using a wide variety
based on these parameters through detailed study and trial and of analytical techniques. There has been a significant amount of
error, one can achieve the best possible yield for MAE.167 research on upstream biosurfactant generation to improve
11686 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
 Table 3. Properties, Advantages, and Sources of Some Well-Known Oleo-Based Surfactants
no. name source properties applications ref
1 fatty alcohol tallow, palm kernels, coconut oil demonstrate strong emulsifying and dispersing abilities in hard water used in polymerization process as an emulsifying 169, 170
ACS Omega

sulfates agent and personal care and hygiene industry in

products such as toothpastes, cosmetics, and
synthetic soaps
2 fatty acid methyl waste palm oil exhibit high emulsifying and dispersing properties in hard water; moderate level of low interfacial tension for oil-in-water system and 171, 172
esters foaming environmentally safe nature, so find application in
(FAMEs) detergents containing no phosphates
3 sucroesters beet or cane sucrose, FAME from vegetable oil very low CMC values and higher esters provide more lipophilic surfactants that can help widely used in personal care and food industries 173
stabilize “water-in-oil” emulsions
4 alkyl polyglyco- fatty alcohols (palm kernel or coconut oil (C12−C14 carbon lessen the irritating effects of surfactant mixtures and have good compatibility with the widely used in cosmetic creams due to their effective 173
sides chain)) and rapeseed or palm oil (C16−18 carbon chain) skin, eyes, and mucous membranes emulsifying of water and oil
and glucose from wheat, corn starch, or potatoes
5 fatty acid gluca- glucose, derived from starches low potential for irritation due to polyol structure and synergistic effects with other glucamides with C16/18 and C12/14 alkyl chains are 173
mides types of surfactants; due to affinity for calcium ions and limited solubility, glucamides used in liquid dishwashing agents and powdered
have drawbacks and must always be mixed with sequestering agents to prevent and liquid
precipitation
6 sorbitan esters sorbitol (glucose derivative) HLB values of various sorbitan esters (such as laurates, oleates, or stearates) are used as emulsifiers and solubilizers in food,
typically in the range 1−8 medicinal, and cosmetic products
7 fatty amine fatty amides from coconut oil or palm kernel, or tallow; average molecular weight between 174 and 798 g/mol; length and level of ethoxylation used as lubricant agricultural adjuvants, antistatic 174, 175
ethoxylates ethoxylated fatty amines from coco, stearyl, oleyl, tallow, of fatty alcohol chain affect physical and chemical characteristics of fatty amine agent, detergents ingredient, and acid thickener
and lauryl amines (2−50 mol of EO/mol of amine ethoxylate
hydrophobe)
8 gemini surfac- palm oil fractions (cheap and abundant source) outperform traditional surfactants thanks to their outstanding surface activity recently discovered that gemini surfactants are very 121−124
tants characteristics; exhibit solubilizing, wetting, foaming, antibacterial, and lime soap intriguing as possible vehicles for transportation of
dispersion capabilities at incredibly low CMC levels bioactive compounds utilized in gene therapy

11687
http://pubs.acs.org/journal/acsodf
Review

ACS Omega 2023, 8, 11674−11699

https://doi.org/10.1021/acsomega.3c00591
ACS Omega http://pubs.acs.org/journal/acsodf Review

productivity and yield, but there has not been much done on lipids have been claimed to have the most uses in the cosmetic
downstream purification.176 industry. Chemically altered sophorolipid produced by
4.4. Properties of Biosurfactants. The properties of Torulopsis bombicola has been observed to contain a natural
biosurfactants are summarized in Figure 9.177 moisturizing component. Also, because of their antimicrobial
qualities, sophorolipids play an essential role in the treatment of
body odors, dandruff, and acne. Rhamnolipids find application
in toothpaste, nail care products, and deodorants and serve a
significant role as an antiwrinkle agent. Mannosylerythritol lipids
are utilized in antiaging skincare treatments.177
4.5.2. Applications of Biosurfactants in Contaminated
Soils. Heavy metals are contributing to serious environmental
issues. The most common heavy metals found in contaminated
soils are lead (Pb), mercury (Hg), arsenic (As), cadmium (Cd),
chromium (Cr), zinc (Zn), copper (Cu), and nickel (Ni), which
can cause a variety of health problems in humans, animals, and
plants. Biosurfactants derived from plants and microorganisms
have demonstrated superior performance in removing heavy
metals from contaminated soil.181 There are three major steps
involved in the extraction of heavy metals from soil via washing
with a biosurfactant solution. The sorption of biosurfactant
molecules at the interfaces between sludge (wet soil) and metal
in aqueous solution separates heavy metals adsorbed on the
surface of soil particles. The metal will then be absorbed by
biosurfactants and electrostatically trapped within the micelle.
Figure 9. General properties of biosurfactants. Ultimately, the biosurfactant can be retrieved with the use of the
membrane separation method.181−186
4.4.1. Interfacial Tension. Biosurfactants are more effective 4.5.3. Biosurfactants as Antimicrobial Agents. The rise in
than synthetic surfactants by a factor of 10−40. A study antibiotic resistance is driving research into novel antimicrobial
conducted on biosurfactant-mediated oil recovery by McIner- strategies.186−188 Antibiotic adjuvants or enhancers are com-
ney et al. showed that Bacillus mojavensis strain JF-2 bacteria, pounds that have little or no antimicrobial activity but improve
compared to average values of 28−29 mN/m, reduced antibiotic action or prevent resistance when used in conjunction
interfacial tension by almost 2 orders of magnitude.178 With with antibiotics. Because of their membrane-destabilizing
or without 2,3-butanediol (cosurfactant) present, raising the properties, biosurfactants are being considered as alternative
salinity enhanced the interfacial tension. The interfacial tension antimicrobial agents or as adjuvants for traditional antibiotics in
measured at the lowest point was 0.1 mN/m.178 the situation of increasing drug resistance in pathogenic bacteria
4.4.2. pH and Temperature. The pH and temperature of the and the necessity for new lines of therapy.189−192 A recent review
environment have little impact on the surface activity of many by De Giani et al.190 summarizes perspectives of biosurfactants
biosurfactants. Lichenysin, a biosurfactant produced from with antimicrobial activity.
Bacillus licheniformis JF-2, is unaffected with a pH range of 4.5.4. Biosurfactants in Agriculture. To fulfill the growing
4.5−9.0 and temperatures as high as 50 °C. Similarly, a demands of the human population and to accomplish
lipopeptide produced by B. subtilis LB5a maintained its surface sustainable agriculture, green surfactants are currently necessary.
activity for 6 months at a temperature of 121 °C and in a high salt Biosurfactants produced by bacteria, yeasts, and fungi are some
environment. The biosurfactant is stable at pH 4−10 and high possibilities for green surfactants. In agriculture, biosurfactants
temperatures up to 120 °C, and a NaCl content of up to 10% are employed to get rid of plant diseases and boost nutrient
(w/v) maintains emulsification action.179 bioavailability for helpful plant bacteria.177 The quality of
4.4.3. Biodegradability and Low Toxicity. The best agricultural soil may be significantly increased with biosurfactant
instrument for bioremediation without having any negative remediation. An estimated 0.2 million tons of surfactants are
effects on the environment is biosurfactants. They are far safer used annually in the formulation of crop protection and
than synthetic surfactants and more environmentally friendly. pesticides. The method of hydrophilization utilizing biosurfac-
Environmental bioremediation, enhanced oil recovery, pharma- tants results in good wettability, suppression of pesticide
ceuticals, and food processing have all seen a rise in the use of toxicants, and even dispersion of fertilizers in the soil. The
biosurfactants due to their special qualities, such as increased proliferation of Rhizobacteria in the rhizosphere is accelerated in
biodegradability and lower toxicity. A comparative study on several ways, aiding in the stimulation of plant growth. These
biosurfactants done by Muthusamy et al. between a synthetic biosurfactants enhance the soil’s quality and stimulate plant−
surfactant, Marlon A-350, and a biosurfactant produced by P. beneficial microbial interactions. These biosurfactants have
aeruginosa showed that the biosurfactant was nontoxic. In greater benefits than the synthetic surfactants currently
contrast, the synthetic surfactant was highly harmful in all assays employed in pesticides since they are environmentally safe, are
and its characteristics.180 inexpensive, and help the soil’s beneficial bacteria grow.177
4.5. Applications of Biosurfactants. 4.5.1. Applications 4.5.5. Biosurfactants in Bionanotechnology. Presently, the
in Cosmetics. In comparison to synthetic surfactants, the newly next generation of green chemistry or bioengineering nano-
created biosurfactants are biocompatible, nontoxic, biodegrad- catalyst sources is thought to be composed of biosurfactants
able, and milder on the skin and exhibit greater interfacial generated from microbes and nanoparticles.193 Environmental
activity. Sophorolipids, mannosylerythritol, and rhamnolipids remediation holds great promise for the production of
11688 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

Table 4. Antitumor Activities Reported for Some Biosurfactants

biosurfactant description activity ref
monoolein cervical cancer, leukemia cancer growth inhibition 195
serratamolide B-chronic lymphocytic leukemia apoptosis induction 196
viscosin metastatic prostate cancer migration inhibition 197
mannosylerythritol lipids (MELs) myelogenous leukemia growth inhibition, differentiation 198
sophorolipids promyelocytic leukemia interaction with plasma membrane 199
succinoyl trehalose lipids (STLs) promyelocytic leukemia growth inhibition, differentiation 200
surfactin or surfactin-like myelogenous leukemia growth inhibition 200, 201
biosurfactants
lipopeptides of Bacillus cancer cells killing and suppression of invasion 202
surfactin suppress proliferation of LoVo cells inducing proapoptotic activity and arresting the cell 203
cycle
human breast carcinoma cell line causing reactive oxygen species (ROS) generation 204
iturin alveolar adenocarcinoma A549; colon adenocarcinoma growth inhibition 205, 206
HCT-15
fengycin lung malignancy cell 95D growth inhibition 207
Bacillus subtilis fmbJ-derived fengycin colon cancer cell line HT29 inhibiting development and progression 208

nanoparticles by biosurfactant-mediated synthesis. The nano- makes biosurfactants potentially more useful and attractive than
particles produced with biosurfactant must, however, be traditionally used surfactants.213
commercially feasible. Biosurfactant microbes may stabilize 6.1. Critical Micelle Concentration (CMC). Biosurfactants
and reduce nanoparticle formation. Nanoparticles like gold, generally have CMC values ranging from 1 to 200 mg/L, which
silver, and titanium are produced by microorganisms.193 are on the lower side as compared to petroleum- and oleo-based
4.5.6. Biosurfactants in Cancer Therapeutics. Biosurfac- surfactants. One previous study showed the comparison of
tants have a crucial ability to regulate mammalian cell CMCs of biosurfactants derived from B. subtilis EG1 with
functionalities and, thus, would also be used in cancer traditional surfactants. Table 5 indicates the CMCs of given
therapeutics. These molecules have been reported for biosurfactants along with HLB values.
maintaining varieties of functionalities such as cell immune
responses and differentiations, signal transduction, etc. For Table 5. Critical Micelle Concentrations and Hydrophilic−
example, glycolipids were found to growth arrest and apoptosis Lipophilic Balances of the Different Commercial Surfactants
of melanoma B16 cells of mice. The potential applications of Assayed in a Previous Study213
such biosurfactants as antitumor agents have been detailed in
Table 4. Increase in reactive oxygen species (ROS) generation, surfactant CMC (g/L) HLB
suppressing Bcl-2 expression, promoting cytochrome c (Cyto-c) Glucopon 215 0.241 13
release, activation of caspase pathways, inhibiting 12-O- Glucopon 600 0.028 11.2
tetradecanoylphorbol-13-acetate (TPA) induced migration, Glucopon 650 0.073 11.9
colony formation, and invasion through MMP-9 regulation, Findet 10/15 0.152 9.6
apoptosis, DNA damage, etc. can be key pathways adopted by Findet 1214N/23 0.021 14.4
biosurfactants causing anticancer effects.194 Findet 9Q/21.5NF 0.034 12.8
LAS 1.018 −
5. REMEDIATION OF SURFACTANTS
Better management of surfactant usage and disposal has become The findings showed that B. subtilis EG1 producing
a necessity of the hour, at both the industrial and domestic levels. biosurfactant is significantly more effective than synthetic
Strict guidelines should be followed for properly remediating surfactants at reducing surface tension.213
surfactants before disposal. Oxidation-based approaches, photo- Additionally, biosurfactants have the ability to significantly
catalytic degradation, foam fractionation, electrochemical lower interfacial and surface tension. In comparison to synthetic
degradation, and microbial biodegradation are among the surfactants, they are even quite effective under adverse situations
techniques used to treat surfactants.209 In recent years, like high temperatures, acidic pH levels, and salinity.214,215
biosurfactants have attracted prospective interest for use in the 6.2. Emulsification. In applications that require low
environmental remediation of organic and inorganic contami- surfactant concentrations, biosurfactants may be appealing due
nants, particularly in the removal of heavy metals from soil and to their low CMC values and high exhibited emulsifying
water, cosmetics, and pharmaceutical products, as well as in abilities.213 The stabilities of the resulting water-in-oil emulsions
enhanced oil recovery.209−212 Biosurfactants have also applica- varied between the two surfactants, according to a comparison
tions as microbial-enhanced oil recovery (MEOR).210 between rhamnolipid biosurfactant and an amphiphilic
quaternary ammonium salt (containing 75 wt % diacetyl
dimethylammonium chloride in water−isopropanol solvent).
6. COMPARISON WITH ESTABLISHED PRODUCTS Rhamnolipid was 83% less efficient than the quaternary
WITH RESPECT TO PERFORMANCE AND COST ammonium salt at 0.01 wt %, and at 1.5 wt %, its emulsion
Green surfactants, i.e., biosurfactants, are known to have stability was half that of the quaternary ammonium salt (3 min
properties like self-assembly, reduction of surface and interfacial compared to 130 min).216
tension, emulsification, and adsorption which make them At greater concentrations, the emulsion stabilities of the two
applicable in various applications. Also, their low toxicity surfactants vary dramatically. Rhamnolipids stop the binding
11689 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

and aggregation of hydrate crystallites at concentrations of 80% of total production costs. A significant barrier to the
0.05% or higher. In comparison to SDS, rhamnolipid has also commercialization of biosurfactants is the economics of
demonstrated greater kerosene emulsification effectiveness in manufacturing.218
the pH range 6−9.
6.3. Toxicity. In general, biosurfactants have low toxicity. 7. SCREENING BIOSURFACTANT EFFICIENCIES
There is numerous research that has investigated the toxicities of
Biosurfactants can be screened with the use of methods such as
biosurfactants in aquatic life, plants, and human cell lines.
the hemolysis test, oil spreading test, drop collapse method,
According to a study, using biosurfactants made from Candida
emulsification index, hydrocarbon overlay agar method, and
lipolytica at concentrations 0.5−2 times the CMC had no impact
blue agar plate method (Figure 10).219
on plant root length or seed germination.81 In a recent study, the
toxicities of natural and synthetic biosurfactants were compared.
In aquatic habitats, both a naturally occurring monorhamnolipid 8. MARKET AND FUTURE PROSPECTS
and a synthetic monorhamnolipid had EC50 levels that were During the forecast period of 2021−2028, the global surfactants
“somewhat hazardous” according to the EPA. Additionally, a market is anticipated to expand at a CAGR of 4.9%, rising from
human cell line’s cytotoxicity and biodegradability (measured by $41.22 billion in 2021 to $57.81 billion in 2028. Surfactants are
the xCELLigence assay) were dependent on the stereochemistry produced by the industry at a rate of approximately 17 million
of the synthetic rhamnolipid.217 metric tons yearly, some of which come into direct contact with
6.4. Cost Analysis. Synthetic surfactants are substantially customers and most of which are eventually released as effluent.
less expensive than biosurfactants when comparing pricing (see In light of this volume, solving green issues is a crucial subject for
Table 6).217 a sector that is dealing with expanding regulation and customer
awareness.219 In 2020, the market for green surfactants was
Table 6. Market Prices of Some Popular Surfactants estimated to be worth close to USD 2.54 billion. The global
green surfactants market is projected to expand at a CAGR of
type of surfactant name of sufactant cost/kg222,223 5.7% from 2022 to 2027, reaching a value of $3.56 billion by
petro-based α-olefin sulfonates $1.00−$2.00 2026. The sector is expanding because of the growing demand
alkyl ether sulfates $0.8−$0.9 for green surfactants made from waste biomass and agricultural
linear alkylbenzene $1.4−$1.7 raw materials.220 The booming personal care sector is
alkyl phenol ethoxylates $2.19 contributing to the continuous rise of the market for green
oleochemical sorbitan monooleates (SPAN) $1.30−$1.50 surfactants. This industry is expanding as a result of the
polysorbate 80 (TWEEN) $1.60−$2.60 increased attention being paid to health, beauty, and personal
microbial surfactants rhamnolipids $25.00−$40.00 hygiene, which in turn is assisting the market for green
sophorolipids $30.00/L surfactants.221 Table 7 displays a list of companies that produce
novel green surfactants or use them in their products advancing
The prices of synthetic surfactants are significantly lower than sustainability in the process. Figure 11 demonstrates a typical
those of biosurfactants. The high cost of production is mainly comparison between synthetic surfactants and biosurfactants.177
due to the fermentation and product purification steps. This has led to a rise in the cultivation of natural oils, the origin
Rhamnolipids still cannot be recovered and purified on an of which, particularly tropical oils, is a major source of concern.
industrial scale using any downstream technique that is both Even though manufacturers have joined groups like the
cost-effective and compelling. For the manufacturing of Roundtable on Sustainable Palm Oil (RSPO), there is still
biosurfactants, downstream processing is responsible for 70− much disagreement over the true cradle-to-gate effects of using

Figure 10. Methods used to test biosurfactant efficiencies.

11690 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
 Table 7. Current Marketed Products Containing Green Surfactants
no. company product/surfactant description ref
1 Dow EcoSense SL-60 HA surfactant This is a special emulsifier and glycolipid surfactant for rinse-off and leave-on applications that is 100% bioderived. It is a biosurfactant and natural emulsifier made from sugar 223
ACS Omega

that has a high concentration of acid sophorolipid.

2 Dow EcoSense 3000 surfactant; It is a nonionic surfactant made from plants that is easily biodegradable and creates good to excellent stable foam for use in applications. It is comprised of 65% formulation 224
personal care grade water, and the remaining 35% solid content is considered derived naturally.
3 BASF BioToLife The component, which is based on sophorolipid, prevents the spread of several dangerous microbes. When used for skin, scalp, or oral hygiene, this promotes the development 225
of a balanced microecosystem.
4 BASF BASF APG Under the brand name Plantacare, BASF sells its APG range made entirely of plants. The all-purpose sugar surfactants have a great ecological and toxicological profile, a history 226
of being mild, and other useful properties.
5 Evonik REWOFERM RL 100 It has both primary and secondary surfactant functions. It has the ability to ease difficult formulations because of its special characteristics in terms of effectiveness, formulability, 227
and endurance.
6 Clariant Velsan SC It has reduced glucose from wheat or corn and the fatty acid from palm or coconut oil: sorbitan caprylate. It is entirely natural. It functions as a preservative booster, giving the 228
option to employ fewer preservatives while yet maintaining the safety of cosmetics. It also functions as an emulsifier or emollient at the same time.
7 Croda Arlasilk EFA; INCI Arlasilk EFA is a sunflower oil derived fatty acid carrier which not only acts as surfactant but also helps in countering irritation and also provide mildness. Due to its good 229
linoleamidopropyl compatibility with a variety of surfactants, it is increasingly used in rinse-off and leave-on skin care products.
PG-dimonium chloride
phosphate
8 Croda OleoCraft HP-33; INCI The ingredient is derived from vegetable and is a rheology modifier for high polarity liquids and water used in cosmetics and personal care products. It helps in forming a stable 230
polyamide-4 emulsion of oil in gelled water using polar organic liquids such as ethanol, butylene, and glycol without the help of surfactants.
9 Unilever Unilever’s Quix dishwashing The product uses a rhamnolipid, a type of biosurfactant which is mild on skin, 100% biobased, and biodegradable. Collaborating with Evonik, Unilever was able to deliver a 231
liquid sustainable and cleaner product with better performance. They believe in scaling up the innovation and exploring new technologies offering renewable and greener products.
10 Solvay Mirasoft SL L60 and Solvay introduced Mirasoft, a high-perfomance glycolipid biosurfactant developed from sugar and rapeseed oil, to suit broad applications in beauty care like shampoos, creams, 232
Mirasoft SL A60 face wash, and shower gels. These surfactants provide the same performance as synthetics and are biodegradable. This approach represents a dramatic shift in favor of
sustainability and makes sustainable beauty concepts a reality.
11 AGAE rhamnolipid biosurfactants The products can be used in pharmaceuticals, cosmetics, personal care products, bioremediation (in situ and ex situ), and enhanced oil recovery (EOR). 233

11691
Technologies,
USA
12 Fraunhofer IGB, glycolipid and cellobiose lipid These are used in cleaning products, dishwashing liquids, and pharmaceutical products (bioactive properties). 234
Germany biosurfactants
http://pubs.acs.org/journal/acsodf
Review

ACS Omega 2023, 8, 11674−11699

https://doi.org/10.1021/acsomega.3c00591
ACS Omega http://pubs.acs.org/journal/acsodf Review

sophorolipids is USD 34/kg as compared to sodium dodecyl

sulfate and amino acid surfactants that are priced at USD 1−4/
kg.237 But with technical advancements like integrated
separation, sophorolipid surfactants may be produced at a
lower operating cost of USD 2530/ton, making them
comparable in cost to other specialty surfactants.237 Increased
biosurfactant sustainability without noticeably greater perform-
ance is not well received since typical customers will not be
prepared to pay a premium for items made from biomaterials.
Therefore, improving biosurfactant manufacturing at a
reduced cost is crucial for achieving an economically viable
method and guaranteeing future market stability.237 Recently,
our group has also optimized various procedures pertaining to a
few biosurfactants with the ease of freely available raw
materials.238−243 The dependence of the demand for bio-
surfactants on the volatility and economic meltdown of
Figure 11. Comparison between synthetic surfactants and biosurfac- downstream end-user industries is another issue. The perform-
tants. ance of the overall macroeconomic environment is known to
have an impact on industries that are relevant for biosurfactant
land for renewable chemical feedstocks. It is interesting to note applications, including oil and gas, improved oil recovery, the
that Clariant introduced its GlucoPure Sense surfactant in 2017, food sector, construction, textiles, paints, pharmaceuticals, and
which utilizes European sunflower oil as opposed to oils from detergents. The coronavirus disease (COVID-19) pandemic
tropical regions. As an alternative to cocamidopropyl betaines also affects end-user industrial demand and raises concerns
generated from coconut oil, BASF has also developed about the sustainability of the raw material supply. The
amphoteric betaine surfactants for use in formulations for hair sustainability of raw materials is a significant issue since they
care.222 account for up to 50% of the cost of producing glycolipids and
Green surfactants provide a significant and expanding 10−30% of the price of other biosurfactant products. Of the cost
contribution to the business, albeit the extent of that of production, 60% goes in purification; however, this may be
contribution will depend on how people define what is natural, reduced when biosurfactants in their raw forms are used.
biobased, and sustainable. Additionally, even though different Additionally, a number of operational elements offer crucial
customer product and personal care companies have shown controls to reduce the expenses associated with the manufactur-
interest in 100% biobased surfactants, the market has not yet ing of biosurfactants. The fermentation and purification can be
evaluated whether consumers are prepared to pay premium improved with batch cycles’ optimization, which also aids in
pricing for them. A further factor driving the global market for shortening the time between two batches during production.
green surfactants is the strict government laws on the use of The most crucial element in the manufacturing economics of the
chemicals that may have a harmful impact on the environment. manufacture of biosurfactants at industrial sizes is productivity.
These rules are encouraging manufacturers to employ more eco- The most effective batch-sequencing campaign reduces the
friendly and sustainable goods. As businesses try to get away frequency of starting and shutdown to reduce production
from surfactants made from petroleum sources, green downtime and boost productivity. Last, but not least, the
surfactants are becoming more and more desirable. development of biosurfactant products will be hampered by
costly and time-consuming legal restrictions. Manufacturers of
9. INDUSTRIAL CHALLENGES OF BIOBASED biosurfactants pay a significant cost of compliance in addition to
SURFACTANTS the price of product development.
Many of the synthetic procedures required or involved in
biosurfactants’ production utilizes harsh conditions.235 It is 10. SUMMARY
interesting to note that several processes are still using hazardous
solvents, toxic acid catalysts, or toxic base catalysts. This The traditional usage of petroleum-based surfactants is a result
definitely has environmental issues regarding toxicities. Thus, of their inexpensive production costs, long shelf lives, wide-
one important challenge in synthesizing or purifying bio- spread availability, and improved performance at lower
surfactants is to have proper reaction optimizations for solvents temperatures. They also offer formula flexibility owing to their
or catalysts. Recent literature also demonstrates the usage of branching, odd, and even hydrocarbon chains. The necessity to
various enzymes in reaction optimizations, which definitely aids discover a renewable alternative that is safe for the environment
in sustainability.236 Enzymes’ primary disadvantages are their arises from their nonrenewability and environmental damage.
considerably greater costs as compared to chemical catalysts and The increasing interest of industries in developing environ-
their slower reaction rates. The requirement for sustainability mentally safe products has led to biotechnological advances
(reduced operating energy, less waste, and safer operating involving the synthesis of green surfactants. Biosurfactants and
conditions) is essential, nevertheless, as energy prices are oleo surfactants are examples of green surfactants gaining
predicted to increase. One other challenge includes the higher popularity and have been looked at as a breakthrough for the
pricing of biobased surfactants and biosurfactants; with this replacement of synthetic surfactants. There has been a rise in the
hurdle it is indeed difficult to meet the expectations of price- production of these surfactants over a decade, and they are likely
sensitive Asian customers. Further, the higher complexities and to touch the mark of 2.6 billion in 2023.52 However, the high
lower efficiencies of microbial surfactants also disappoint in their cost of production of these surfactants poses a problem for its
industrial production. For example, the average price of scale-up.
11692 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

The main obstacles to the manufacture of biosurfactants Author Contributions

○
include low productivity, extensive downstream processing, and V.S.N., C.C., H.K.A.Y., and S.N.M.: These authors made equal
a lack of adequate understanding of the bioreactor systems. contributions.
Although these problems are a cause of concern, there has Notes
been a substantial increase in the variety of manufacturing The authors declare no competing financial interest.
processes of these green surfactants. Also, chemical giants like
Dow, BASF, Croda, Evonik, and Clariant are investing heavily in
the research and development of these products and have
■ ACKNOWLEDGMENTS
The authors of this article are thankful to the Institute of
proved so by launching them in the market. We believe that in Chemical Technology, Mumbai, India. H.K.A.Y. would like to
thank the Deanship of Graduate Studies and Research, Ajman
the coming decades there will be a complete phasing out of University, UAE, for their support in providing assistance in
petroleum-based surfactants, giving rise to newer, greener, and article processing charges for this review.
sustainable surfactants.

■ AUTHOR INFORMATION
■ ABBREVIATIONS
APG, alkyl polyglycoside; LAS, linear alkylbenzene sulfonate;
Corresponding Authors SAS, secondary n-alkanesulfonate; AOS, α-olefin sulfonate;
Amit P. Pratap − Department of Oils, Oleochemicals and APE, alkylphenol “ethoxylate”; HC, hydrodynamic cavitation;
Surfactants Technology, Institute of Chemical Technology, MAE, microwave-assisted extraction; CMC, critical micelle
Mumbai 400019, India; Email: amitpratap2001@ concentration; DOSS, dioctyl sodium sulfosuccinate; LABSA,
gmail.com, [email protected] linear alkylbenzene sulfonic acid; SLES, sodium lauryl ether
Suraj N. Mali − Department of Pharmaceutical Sciences and sulfate; AES, alkyl ether sulfate; CS, cationic surfactant; QAC,
Technology, Birla Institute of Technology, Mesra 835215, quaternary ammonium compound; PEG, polyoxyethylene ester;
India; orcid.org/0000-0003-1995-136X; HLB, hydrophilic−lipophilic balance; CAGR, compound
Email: [email protected] annual growth rate; USD, U.S. dollar; APG, alkyl polyglycoside;
Haya Khader Ahmad Yasin − Department of Pharmaceutical NMGA, N-methylglucamide; P&G, The Procter & Gamble
Sciences, College of Pharmacy and Health Sciences, Ajman Company; SPL, sophorose lipid; RML, rhamnose lipid; MEL,
University, Ajman, United Arab Emirates; Center of Medical mannosylerythritol lipid; DNA, deoxyribonucleic acid; GMS,
and Bio-allied Health Sciences Research, Ajman University, glycerol monostearate; PVC, polyvinyl chloride; AMS, alkylaryl
Ajman, United Arab Emirates; Email: [email protected] monosulfonate; ADS, alkylaryl disulfonate; LAO, linear α-olefin;
MA, maleic anhydride; HPL, hydrophilic; HB, hydrophobic;
Authors OMWE, oil mill waste effluents; FAMEs, fatty acid methyl
Vaishnavi S. Nagtode − Department of Oils, Oleochemicals and esters; NaCl, sodium chloride; MMP-9, metalloproteinase-9;
Surfactants Technology, Institute of Chemical Technology, LoVo, cell line isolated in 1971 from the large intestine of a
Mumbai 400019, India white, 56-year-old, male with grade IV Dukes C colorectal
Clive Cardoza − Department of Oils, Oleochemicals and cancer; HCT-15, HCT-15 cells were isolated from the large
Surfactants Technology, Institute of Chemical Technology, intestine of a male with Dukes C colorectal cancer and can be
Mumbai 400019, India used for cancer and toxicology research; MEOR, microbial-
Srushti M. Tambe − Department of Pharmaceutical Sciences enhanced oil recovery; SDS, sodium dodecyl sulfate; COVID-
and Technology, Institute of Chemical Technology, Mumbai 19, coronavirus disease
400019, India
Pritish Roy − Department of Oils, Oleochemicals and
Surfactants Technology, Institute of Chemical Technology,
■ REFERENCES
(1) Ricardo, F.; Ruiz-Puentes, P.; Reyes, L. H.; Cruz, J. C.; Alvarez, O.;
Mumbai 400019, India Pradilla, D. Estimation and prediction of the air-water interfacial
Kartikeya Singh − Department of Oils, Oleochemicals and tension in conventional and peptide surface-active agents by random
Surfactants Technology, Institute of Chemical Technology, Forest regression. Chem. Eng. Sci. 2023, 265, 118208.
Mumbai 400019, India (2) De, S.; Malik, S.; Ghosh, A.; Saha, R.; Saha, B. A review on natural
Antriksh Goel − Department of Oils, Oleochemicals and surfactants. RSC Adv. 2015, 5 (81), 65757−65767.
Surfactants Technology, Institute of Chemical Technology, (3) Kralova, I.; Sjöblom, J. Surfactants Used in Food Industry: A
Mumbai 400019, India Review. J. Dispersion Sci. Technol. 2009, 30 (9), 1363−1383.
(4) Dias, M. A. M.; Nitschke, M. Bacterial-derived surfactants: an
Purnima D. Amin − Department of Pharmaceutical Sciences update on general aspects and forthcoming applications. Braz. J.
and Technology, Institute of Chemical Technology, Mumbai Microbiol. 2023, 54, 103−123.
400019, India (5) Kirtil, E.; Oztop, M. H. Mechanism of adsorption for design of
Bapu R. Thorat − Department of Chemistry, Government role-specific polymeric surfactants. Chem. Pap. 2023, DOI: 10.1007/
College of Arts and Science, Aurangabad, Maharashtra s11696-022-02636-9.
431001, India (6) Margaritis, A.; Zajic, J. E.; Gerson, D. F. Production and surface-
Jorddy N. Cruz − Laboratory of Modeling and Computational active properties of microbial surfactants. Biotechnol. Bioeng. 1979, 21
Chemistry, Department of Biological and Health Sciences, (7), 1151−1162.
Federal University of Amapá, Macapá 68902-280 Amapá, (7) Czajka, A.; Hazell, G.; Eastoe, J. Surfactants at the Design Limit.
Brazil; orcid.org/0000-0003-0529-3714 Langmuir 2015, 31 (30), 8205−8217.
(8) Tcholakova, S.; Denkov, N. D.; Lips, A. Comparison of solid
Complete contact information is available at: particles, globular proteins and surfactants as emulsifiers. Phys. Chem.
https://pubs.acs.org/10.1021/acsomega.3c00591 Chem. Phys. 2008, 10 (12), 1608−1627.

11693 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

(9) Ribeiro, H. M.; Morais, J. A.; Eccleston, G. M. Structure and (31) Wokosin, K. A.; Schell, E. L.; Faust, J. A. Emerging investigator
rheology of semisolid o/w creams containing cetyl alcohol/non-ionic series: surfactants, films, and coatings on atmospheric aerosol particles:
surfactant mixed emulsifier and different polymers. Int. J. Cosmet. Sci. a review. Environ. Sci. Atmos. 2022, 2 (5), 775−828.
2004, 26 (2), 47−59. (32) Tato, J. V.; Seijas, J. A.; Vázquez-Tato, M. P.; Meijide, F.; de
(10) Yan, N.; Ni, P.; Zhang, M. Preparation and properties of polyurea Frutos, S.; Jover, A.; Fraga, F.; Soto, V. H. Introduction to
microcapsules with non-ionic surfactant as emulsifier. J. Micro- Biosurfactants. Biosurfactants for a Sustainable Future 2021, 1−42.
encapsulation 1993, 10 (3), 375−383. (33) Rebello, S.; Asok, A. K.; Mundayoor, S.; Jisha, M. S. Surfactants:
(11) Rodríguez-López, L.; Rincón-Fontán, M.; Vecino, X.; Cruz, J. M.; Chemistry, Toxicity and Remediation. In Pollutant Diseases, Remedia-
Moldes, A. B. Biological Surfactants vs. Polysorbates: Comparison of tion and Recycling; Lichtfouse, E., Schwarzbauer, J., Robert, D., Eds.;
Their Emulsifier and Surfactant Properties. Tenside Surfactants Deterg. Springer International Publishing: 2013; pp 277−320.
2018, 55 (4), 273−280. (34) Henkel, M.; Müller, M. M.; Kügler, J. H.; Lovaglio, R. B.;
(12) Wang, H.; Guo, W.; Zheng, C.; Wang, D.; Zhan, H. Effect of Contiero, J.; Syldatk, C.; Hausmann, R. Rhamnolipids as biosurfactants
Temperature on Foaming Ability and Foam Stability of Typical from renewable resources: Concepts for next-generation rhamnolipid
Surfactants Used for Foaming Agent. J. Surfactants Deterg. 2017, 20 (3), production. Process Biochem. 2012, 47 (8), 1207−1219.
615−622. (35) Ostroumov, S. A. Inhibitory analysis of top-down control: new
(13) Bureiko, A.; Trybala, A.; Kovalchuk, N.; Starov, V. Current keys to studying eutrophication, algal blooms, and water self-
applications of foams formed from mixed surfactant-polymer solutions. purification. Hydrobiologia 2002, 469 (1), 117−129.
Adv. Colloid Interface Sci. 2015, 222, 670−677. (36) Ostroumov, S. A. The Synecological Approach to the Problem of
(14) Montufar, E. B.; Traykova, T.; Planell, J. A.; Ginebra, M.-P. Eutrophication. Dokl. Biol. Sci. 2001, 381 (1), 559−562.
Comparison of a low molecular weight and a macromolecular surfactant (37) Khan, M. N.; Mohammad, F. Eutrophication: Challenges and
as foaming agents for injectable self setting hydroxyapatite foams: Solutions. In Eutrophication: Causes, Consequences and Control; Ansari,
Polysorbate 80 versus gelatine. Mater. Sci. Eng., C 2011, 31 (7), 1498− A. A., Gill, S. S., Eds.; Springer Netherlands: 2014; Vol. 2, pp 1−15.
1504. (38) Phukan, M. M.; Sangma, S. R.; Kalita, D.; Pankaj, P. P.; Das, P. P.;
(15) Thompson, J. E. A Practical Guide to Contemporary Pharmacy Bora, P.; Saha, J.; Manoj, K.; Hazarika, N.; Kataki, R. Chapter 18 - Next-
Practice; Williams & Wilkins: 1998. generational biosurfactant and their practical application in the food
(16) Panda, A.; Kumar, A.; Mishra, S.; Mohapatra, S. S. Soapnut: A industry. In Applications of Next Generation Biosurfactants in the Food
replacement of synthetic surfactant for cosmetic and biomedical Sector; Inamuddin, Adetunji, C. O., Eds.; Academic Press: 2023; pp
applications. Sustain. Chem. Pharm. 2020, 17, 100297. 361−389.
(17) Zhu, Y.; Free, M. L.; Woollam, R.; Durnie, W. A review of (39) Dereszewska, A. K.; Cytawa, S.; Tomczak-Wandzel, R.;
surfactants as corrosion inhibitors and associated modeling. Prog. Medrzycka, K. The Effect of Anionic Surfactant Concentration on
Mater. Sci. 2017, 90, 159−223. Activated Sludge Condition and Phosphate Release in Biological
(18) Shalabi, K.; Helmy, A. M.; El-Askalany, A. H.; Shahba, M. M. Treatment Plant. Polym. J. Environ. Stud. 2015, 24 (1), 83−91.
New pyridinium bromide mono-cationic surfactant as corrosion (40) Tripathy, D. B.; Mishra, A.; Clark, J.; Farmer, T. Synthesis,
inhibitor for carbon steel during chemical cleaning: Experimental and chemistry, physicochemical properties and industrial applications of
theoretical studies. J. Mol. Liq. 2019, 293, 111480. amino acid surfactants: A review. C. R. Chim. 2018, 21 (2), 112−130.
(19) Osman, M. M.; El-Ghazawy, R. A.; Al-Sabagh, A. M. Corrosion (41) Tripathi, L.; Irorere, V. U.; Marchant, R.; Banat, I. M. Marine
inhibitor of some surfactants derived from maleic-oleic acid adduct on derived biosurfactants: a vast potential future resource. Biotechnol. Lett.
mild steel in 1 M H2SO4. Mater. Chem. Phys. 2003, 80 (1), 55−62. 2018, 40 (11), 1441−1457.
(20) Sliem, M. H.; Afifi, M.; Bahgat Radwan, A.; Fayyad, E. M.; Shibl, (42) Johnson, P.; Trybala, A.; Starov, V.; Pinfield, V. J. Effect of
M. F.; Heakal, F. E.-T.; Abdullah, A. M. AEO7 Surfactant as an Eco- synthetic surfactants on the environment and the potential for
Friendly Corrosion Inhibitor for Carbon Steel in HCl solution. Sci. Rep. substitution by biosurfactants. Adv. Colloid Interface Sci. 2021, 288,
2019, 9 (1), 2319. 102340.
(21) Deyab, M. A. Application of nonionic surfactant as a corrosion (43) Madeddu, S.; Ueckerdt, F.; Pehl, M.; Peterseim, J.; Lord, M.;
inhibitor for zinc in alkaline battery solution. J. Power Sources 2015, 292, Kumar, K. A.; Krüger, C.; Luderer, G. The CO2 reduction potential for
66−71. the European industry via direct electrification of heat supply (power-
(22) Zheng, A.; Xu, X.; Xiao, H.; Li, N.; Guan, Y.; Li, S. Antistatic to-heat). Environmental Research Letters 2020, 15 (12), 124004.
modification of polypropylene by incorporating Tween/modified (44) Santos, D. K. F.; Rufino, R. D.; Luna, J. M.; Santos, V. A.;
Tween. Appl. Surf. Sci. 2012, 258 (22), 8861−8866. Sarubbo, L. A. Biosurfactants: Multifunctional Biomolecules of the 21st
(23) Griffith, R. M. The effect of surfactants on the terminal velocity of Century. Int. J. Mol. Sci. 2016, 17 (3), 401.
drops and bubbles. Chem. Eng. Sci. 1962, 17 (12), 1057−1070. (45) Bhadani, A.; Kafle, A.; Ogura, T.; Akamatsu, M.; Sakai, K.; Sakai,
(24) Clint, J. H. Surfactants: applications in plastics. In Plastics H.; Abe, M. Current perspective of sustainable surfactants based on
Additives: An A-Z Reference; Pritchard, G., Ed.; Springer Netherlands: renewable building blocks. Curr. Opin. Colloid Interface Sci. 2020, 45,
1998; pp 604−612. 124−135.
(25) Joshi, T. A short history and preamble of surfactants. Int. J. Appl. (46) Sarubbo, L. A.; Silva, M. d. G. C.; Durval, I. J. B.; Bezerra, K. G.
Chem. 2017, 13, 283−292. O.; Ribeiro, B. G.; Silva, I. A.; Twigg, M. S.; Banat, I. M. Biosurfactants:
(26) Hellgren, A.-C.; Weissenborn, P.; Holmberg, K. Surfactants in Production, properties, applications, trends, and general perspectives.
water-borne paints. Prog. Org. Coat. 1999, 35 (1), 79−87. Biochem. Eng. J. 2022, 181, 108377.
(27) Deng, Y.; Zheng, X.; Bai, Y.; Wang, Q.; Zhao, J.; Huang, J. (47) Rosen, M. J.; Kunjappu, J. T. Surfactants and Interfacial
Surfactant-controlled ink drying enables high-speed deposition of Phenomena; John Wiley & Sons: 2012.
perovskite films for efficient photovoltaic modules. Nat. Energy 2018, 3 (48) Ortiz, M. S.; Alvarado, J. G.; Zambrano, F.; Marquez, R.
(7), 560−566. Surfactants produced from carbohydrate derivatives: A review of the
(28) Zhmud, B.; Tiberg, F. Surfactants in ink-jet inks. In Surfactants in biobased building blocks used in their synthesis. J. Surfactants Deterg.
Polymers, Coatings, Inks and Adhesives; Blackwell: 2020; pp 211−244. 2022, 25 (2), 147−183.
(29) Swarup, S.; Schoff, C. K. A survey of surfactants in coatings (49) Cserháti, T.; Forgács, E.; Oros, G. Biological activity and
technology. Prog. Org. Coat. 1993, 23 (1), 1−22. environmental impact of anionic surfactants. Environ. Int. 2002, 28 (5),
(30) Trier, X.; Granby, K.; Christensen, J. H. Polyfluorinated 337−348.
surfactants (PFS) in paper and board coatings for food packaging. (50) Zhang, L.; Liu, X.; Zhang, M.; Wang, T.; Tang, H.; Jia, Y. The
Environ. Sci. Pollut. Res. 2011, 18 (7), 1108−1120. effect of pH/PAC on the coagulation of anionic surfactant wastewater

11694 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

generated in the cosmetic production. J. Environ. Chem. Eng. 2023, 11 (72) Final Report on the Safety Assessment of Sorbitan Caprylate,
(2), 109312. Sorbitan Cocoate, Sorbitan Diisostearate, Sorbitan Dioleate, Sorbitan
(51) Bazel, Y. R.; Antal, I. P.; Lavra, V. M.; Kormosh, Z. A. Methods Distearate, Sorbitan Isostearate, Sorbitan Olivate, Sorbitan Sesquiisos-
for the determination of anionic surfactants. J. Anal. Chem. 2014, 69 tearate, Sorbitan Sesquistearate, and Sorbitan Triisostearate. Int. J.
(3), 211−236. Toxicol. 2002, 21, 93−112..
(52) Bartnik, F. G. Interaction of anionic surfactants with proteins, (73) Moldes, A. B.; Rodríguez-López, L.; Rincón-Fontán, M.; López-
enzymes, and membranes. In Anionic Surfactants: Biochemistry, Prieto, A.; Vecino, X.; Cruz, J. M. Synthetic and Bio-Derived
Toxicology, Dermatology; Gloxhuber, C., Klunstler, K., Eds.; Surface Surfactants Versus Microbial Biosurfactants in the Cosmetic Industry:
Science Series 43; Marcel Dekker: 1992; p 1. An Overview. Int. J. Mol. Sci. 2021, 22 (5), 2371.
(53) Lin, B.; McCormick, A. V.; Davis, H. T.; Strey, R. Solubility of (74) Final Report on the Safety Assessment of PEG-6, -8, and -20
sodium soaps in aqueous salt solutions. J. Colloid Interface Sci. 2005, 291 Sorbitan Beeswax. Int. J. Toxicol. 2001, 20, 27−38..
(2), 543−549. (75) Zhang, Y.; Dubé, M. A. Green Emulsion Polymerization
(54) Rebello, S.; Asok, A. K.; Mundayoor, S.; Jisha, M. S. Surfactants: Technology. In Polymer Reaction Engineering of Dispersed Systems;
toxicity, remediation and green surfactants. Environ. Chem. Lett. 2014, Pauer, W., Ed.; Springer International Publishing, 2018; Vol. I, pp 65−
12 (2), 275−287. 100.
(55) Zakharova, L. Y.; Pashirova, T. N.; Doktorovova, S.; Fernandes, (76) Sorbitan Esters Market Outlook (2023−2033). FMI, March 2023.
A. R.; Sanchez-Lopez, E.; Silva, A. M.; Souto, S. B.; Souto, E. B. Cationic https://www.futuremarketinsights.com/reports/sorbitan-esters-
Surfactants: Self-Assembly, Structure-Activity Correlation and Their market (accessed 2022-10-19).
Biological Applications. Int. J. Mol. Sci. 2019, 20 (22), 5534. (77) Szű ts, A.; Szabó-Révész, P. Sucrose esters as natural surfactants in
(56) Mynacik, D.; Devinsky, F.; Lacko, I. Influence of counterions on drug delivery systems�A mini-review. Int. J. Pharm. 2012, 433 (1), 1−
antimicrobial activity of quaternary ammonium salts. Eur. J. Pharm. Sci. 9.
1996, 4 (4), S191. (78) Geetha, D.; Tyagi, R. Alkyl Poly Glucosides (APGs) Surfactants
(57) Chen, A.; Karanastasis, A.; Casey, K. R.; Necelis, M.; Carone, B. and Their Properties: A Review. Tenside Surfactants Deterg. 2012, 49
R.; Caputo, G. A.; Palermo, E. F. Cationic Molecular Umbrellas as (5), 417−427.
Antibacterial Agents with Remarkable Cell-Type Selectivity. ACS Appl. (79) Ng, Y. J.; Lim, H. R.; Khoo, K. S.; Chew, K. W.; Chan, D. J. C.;
Mater. Interfaces 2020, 12 (19), 21270−21282. Bilal, M.; Munawaroh, H. S. H.; Show, P. L. Recent advances of
(58) Zhou, M.; Li, S.; Zhang, Z.; Wang, C.; Luo, G.; Zhao, J. Progress biosurfactant for waste and pollution bioremediation: Substitutions of
in the Synthesis of Zwitterionic Gemini Surfactants. J. Surfactants petroleum-based surfactants. Environ. Res. 2022, 212, 113126.
Deterg. 2017, 20 (6), 1243−1254. (80) Kapadia, S. G.; Yagnik, B. Current trend and potential for
(59) FernLey, G. W. Zwitterionic surfactants: Structure and microbial biosurfactants. Asian J. Exp. Biol. Sci. 2013, 4 (1), 1−8.
(81) Banat, I. M.; Franzetti, A.; Gandolfi, I.; Bestetti, G.; Martinotti,
performance. J. Am. Oil Chem. Soc. 1978, 55 (1), 98−103.
M. G.; Fracchia, L.; Smyth, T. J.; Marchant, R. Microbial biosurfactants
(60) Gerola, A. P.; Costa, P. F. A.; Quina, F. H.; Fiedler, H. D.; Nome,
production, applications and future potential. Appl. Microbiol.
F. Zwitterionic surfactants in ion binding and catalysis. Curr. Opin.
Biotechnol. 2010, 87 (2), 427−444.
Colloid Interface Sci. 2017, 32, 39−47.
(82) Marchant, R.; Banat, I. M. Microbial biosurfactants: challenges
(61) Jiao, J. Polyoxyethylated nonionic surfactants and their
and opportunities for future exploitation. Trends Biotechnol. 2012, 30
applications in topical ocular drug delivery. Adv. Drug Delivery Rev.
(11), 558−565.
2008, 60 (15), 1663−1673.
(83) Naughton, P. J.; Marchant, R.; Naughton, V.; Banat, I. M.
(62) Cserháti, T. Alkyl Ethoxylated and Alkylphenol Ethoxylated
Microbial biosurfactants: current trends and applications in agricultural
Nonionic Surfactants: Interaction with Bioactive Compounds and and biomedical industries. J. Appl. Microbiol. 2019, 127 (1), 12−28.
Biological Effects. Environ. Health Perspect. 1995, 103 (4), 358−364. (84) Lang, S. Biological amphiphiles (microbial biosurfactants). Curr.
(63) Kumar, G. P.; Rajeshwarrao, P. Nonionic surfactant vesicular Opin. Colloid Interface Sci. 2002, 7 (1), 12−20.
systems for effective drug delivery�an overview. Acta Pharm. Sin. B (85) Grüninger, J.; Delavault, A.; Ochsenreither, K. Enzymatic
2011, 1 (4), 208−219. glycolipid surfactant synthesis from renewables. Process Biochem. 2019,
(64) Lindman, B.; Medronho, B.; Karlström, G. Clouding of nonionic 87, 45−54.
surfactants. Curr. Opin. Colloid Interface Sci. 2016, 22, 23−29. (86) Sałek, K.; Euston, S. R.; Janek, T. Phase Behaviour, Functionality,
(65) Bou-Chacra, N.; Melo, K. J. C.; Morales, I. A. C.; Stippler, E. S.; and Physicochemical Characteristics of Glycolipid Surfactants of
Kesisoglou, F.; Yazdanian, M.; Löbenberg, R. Evolution of Choice of Microbial Origin. Front. Bioeng. Biotechnol. 2022, 10, 816613.
Solubility and Dissolution Media After Two Decades of Biopharma- (87) Kitamoto, D.; Morita, T.; Fukuoka, T.; Konishi, M.-a.; Imura, T.
ceutical Classification System. AAPS Journal 2017, 19 (4), 989−1001. Self-assembling properties of glycolipid biosurfactants and their
(66) de Guertechin, L. O. Classification of surfactants. In Handbook of potential applications. Curr. Opin. Colloid Interface Sci. 2009, 14 (5),
Cosmetic Science and Technology; Barel, A. O., Maibach, H. I., Eds.; CRC 315−328.
Press: 2001; pp 431−450. (88) Cortés-Sánchez, A. d. J.; Hernández-Sánchez, H.; Jaramillo-
(67) Nishikido, N.; Kobayashi, H.; Tanaka, M. Pressure effect on the Flores, M. E. Biological activity of glycolipids produced by micro-
Krafft points of ionic surfactants. J. Phys. Chem. 1982, 86 (16), 3170− organisms: New trends and possible therapeutic alternatives. Microbiol.
3172. Res. 2013, 168 (1), 22−32.
(68) Hill, K.; Rhode, O. Sugar-based surfactants for consumer (89) Pöhnlein, M.; Hausmann, R.; Lang, S.; Syldatk, C. Enzymatic
products and technical applications. Lipid/Fett 1999, 101 (1), 25−33. synthesis and modification of surface-active glycolipids. Eur. J. Lipid Sci.
(69) Allen, D. K.; Tao, B. Y. Carbohydrate-alkyl ester derivatives as Technol. 2015, 117 (2), 145−155.
biosurfactants. J. Surfactants Deterg. 1999, 2 (3), 383−390. (90) Dusane, D. H.; Pawar, V. S.; Nancharaiah, Y. V.; Venugopalan, V.
(70) Gaudin, T.; Lu, H.; Fayet, G.; Berthauld-Drelich, A.; Rotureau, P.; Kumar, A. R.; Zinjarde, S. S. Anti-biofilm potential of a glycolipid
P.; Pourceau, G.; Wadouachi, A.; Van Hecke, E.; Nesterenko, A.; surfactant produced by a tropical marine strain of Serratia marcescens.
Pezron, I. Impact of the chemical structure on amphiphilic properties of Biofouling 2011, 27 (6), 645−654.
sugar-based surfactants: A literature overview. Adv. Colloid Interface Sci. (91) Soberón-Chávez, G.; Lépine, F.; Déziel, E. Production of
2019, 270, 87−100. rhamnolipids by Pseudomonas aeruginosa. Appl. Microbiol. Biotechnol.
(71) González-Peña, M. A.; Ortega-Regules, A. E.; Anaya de Parrodi, 2005, 68 (6), 718−725.
C.; Lozada-Ramírez, J. D. Chemistry, Occurrence, Properties, (92) Kumar, R.; Das, A. J. Application of Rhamnolipids in Medical
Applications, and Encapsulation of Carotenoids�A Review. Plants Sciences. In Rhamnolipid Biosurfactant: Recent Trends in Production and
2023, 12 (2), 313. Application; Springer Singapore: 2018; pp 79−87.

11695 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

(93) Jiang, L.; Shen, C.; Long, X.; Zhang, G.; Meng, Q. Rhamnolipids (111) Franzetti, A.; Gandolfi, I.; Bestetti, G.; Smyth, T. J. P.; Banat, I.
elicit the same cytotoxic sensitivity between cancer cell and normal cell M. Production and applications of trehalose lipid biosurfactants. Eur. J.
by reducing surface tension of culture medium. Appl. Microbiol. Lipid Sci. Technol. 2010, 112 (6), 617−627.
Biotechnol. 2014, 98 (24), 10187−10196. (112) Falardeau, J.; Wise, C.; Novitsky, L.; Avis, T. J. Ecological and
(94) Elshikh, M.; Funston, S.; Chebbi, A.; Ahmed, S.; Marchant, R.; Mechanistic Insights Into the Direct and Indirect Antimicrobial
Banat, I. M. Rhamnolipids from non-pathogenic Burkholderia Properties of Bacillus subtilis Lipopeptides on Plant Pathogens. J.
thailandensis E264: Physicochemical characterization, antimicrobial Chem. Ecol. 2013, 39 (7), 869−878.
and antibiofilm efficacy against oral hygiene related pathogens. New (113) Meena, K. R.; Kanwar, S. S. Lipopeptides as the Antifungal and
Biotechnology 2017, 36, 26−36. Antibacterial Agents: Applications in Food Safety and Therapeutics.
(95) Yi, G.; Son, J.; Yoo, J.; Park, C.; Koo, H. Rhamnolipid Biomed Res. Int. 2015, 2015, 473050.
nanoparticles for in vivo drug delivery and photodynamic therapy. (114) Shaligram, N. S.; Singhal, R. S. Surfactin-a review on
Nanomedicine: Nanotechnology, Biology and Medicine 2019, 19, 12−21. biosynthesis, fermentation, purification and applications. Food Sci.
(96) Pratap, A.; Wadekar, S.; Kale, S.; Lali, A.; Bhowmick, D. N. Non- Biotechnol. 2010, 48 (2), 119−134.
traditional Oils as Newer Feedstock for Rhamnolipids Production by (115) Microbial Biosurfactants Market (2022−2032). Fact.MR.
Pseudomonas aeruginosa (ATCC 10145). J. Am. Oil Chem. Soc. 2011, https://www.factmr.com/report/microbial-biosurfactants-market (ac-
88 (12), 1935−1943. cessed 2023-10-19).
(97) Oluwaseun, A. C.; Phazang, P.; Sarin, N. B. Significance of (116) Morán, M. C.; Pinazo, A.; Pérez, L.; Clapés, P.; Angelet, M.;
rhamnolipids as a biological control agent in the management of crops/ García, M. T.; Vinardell, M. P.; Infante, M. R. “Green” amino acid-
plant pathogens. Curr. Trends biomed. Eng. Biosci. 2017, 10 (3), 555788. based surfactants. Green Chem. 2004, 6 (5), 233−240.
(98) Bayee, P.; Amani, H.; Najafpour, G. D.; Kariminezhad, H. (117) Chandra, N.; Tyagi, V. K. Synthesis, Properties, and
Experimental Investigations on Behaviour of Rhamnolipid Biosurfac- Applications of Amino Acids Based Surfactants: A Review. J. Dispersion
tant as a Green Stabilizer for the Biological Synthesis of Gold Sci. Technol. 2013, 34 (6), 800−808.
Nanoparticles. Int. J. Eng. 2020, 33 (6), 1054−1060. (118) Dunuweera, S. P.; Rajapakse, R. M. S. I.; Rajapakshe, R. B. S. D.;
(99) Moussa, Z.; Chebl, M.; Patra, D. Interaction of curcumin with Wijekoon, S. H. D. P.; Nirodha Thilakarathna, M. G. G. S.; Rajapakse,
1,2-dioctadecanoyl-sn-glycero-3-phosphocholine liposomes: Intercala- R. M. G. Review on Targeted Drug Delivery Carriers Used in
tion of rhamnolipids enhances membrane fluidity, permeability and Nanobiomedical Applications. Curr. Nanosci. 2019, 15 (4), 382−397.
stability of drug molecule. Colloids Surf., B 2017, 149, 30−37. (119) Gayen, K.; Basu, K.; Bairagi, D.; Castelletto, V.; Hamley, I. W.;
(100) Bordas, F.; Lafrance, P.; Villemur, R. Conditions for effective Banerjee, A. Amino-Acid-Based Metallo-Hydrogel That Acts Like an
removal of pyrene from an artificially contaminated soil using Esterase. ACS Appl. Bio Mater. 2018, 1 (5), 1717−1724.
Pseudomonas aeruginosa 57SJ rhamnolipids. Environ. Pollut. 2005, (120) Infante, M. R.; Pérez, L.; Pinazo, A.; Clapés, P.; Morán, M. C.;
138 (1), 69−76. Angelet, M.; García, M. T.; Vinardell, M. P. Amino acid-based
(101) Intasit, R.; Soontorngun, N. Enhanced palm oil-derived
surfactants. C. R. Chim. 2004, 7 (6), 583−592.
sophorolipid production from yeast to generate biodegradable plastic (121) Menger, F. M.; Keiper, J. S. Gemini Surfactants. Angew. Chem.,
precursors. Ind. Crops Prod. 2023, 192, 116091.
Int. Ed. 2000, 39 (11), 1906−1920.
(102) Xu, R.-Q.; Ma, L.; Chen, T.; Zhang, W.-X.; Chang, K.; Wang, J.
(122) Menger, F. M.; Littau, C. A. Gemini-surfactants: synthesis and
Sophorolipid inhibits histamine-induced itch by decreasing PLC/IP3R
properties. J. Am. Chem. Soc. 1991, 113 (4), 1451−1452.
signaling pathway activation and modulating TRPV1 activity. Research
(123) Zhou, G.; Wang, Q.; Li, S.; Huang, Q.; Liu, Z. Effect of a newly
Square, January 5, 2023, ver. 1. DOI: 10.21203/rs.3.rs-2427024/v1.
synthesized anionic Gemini surfactant composite fracturing system on
(103) Zhang, X.; Wang, Y.; Lu, J.; Liu, M.; Tan, W.; Cheng, Y.; Tao,
the wettability of coking coal. Process Saf. Environ. Prot. 2023, 169, 13−
Y.; Du, J.; Wang, H. Biosurfactant promoted enzymatic saccharification
23.
of alkali-pretreated reed straw. Bioresour. Technol. 2023, 372, 128665.
(124) Lu, Z.; Zongjie, G.; Qianyu, Z.; Xueyan, L.; Kexin, W.; Baoyan,
(104) Nascimento, M. F.; Keković, P.; Ribeiro, I. A. C.; Faria, N. T.;
Ferreira, F. C. Novel Organic Solvent Nanofiltration Approaches for C.; Ran, T.; Fang, R.; Hui, H.; Huali, C. Preparation and
Microbial Biosurfactants Downstream Processing. Membranes 2023, 13 characterization of a gemini surfactant-based biomimetic complex for
(1), 81. gene delivery. Eur. J. Pharm. Biopharm. 2023, 182, 92−102.
(105) Matosinhos, R. D.; Cesca, K.; Carciofi, B. A. M.; de Oliveira, D.; (125) Akram, M.; Osama, M.; Lal, H.; Salim, M.; Hashmi, M. A.; Din,
de Andrade, C. J. Mannosylerythritol lipids as green pesticides and plant K.-u. Biophysical investigation of the interaction between NSAID
biostimulants. J. Sci. Food Agric. 2023, 103 (1), 37−47. ibuprofen and cationic biodegradable Cm-E2O2-Cm gemini surfac-
(106) Yang, Q.; Shen, L.; Yu, F.; Zhao, M.; Jin, M.; Deng, S.; Long, X. tants. J. Mol. Liq. 2023, 370, 120972.
Enhanced fermentation of biosurfactant mannosylerythritol lipids on (126) Ansari, F.; Lal, H.; Osama, M.; Akram, M.; Kabir-ud-Din.
the pilot scale under efficient foam control with addition of soybean oil. Solution Behavior of Bovine Skin Gelatin in the Presence of Cationic
Food Bioprod. Process. 2023, 138, 60−69. Gemini Surfactants. ChemistrySelect 2023, 8 (3), No. e202202080.
(107) Mawani, J. S.; Mali, S. N.; Pratap, A. P. Formulation and (127) Pavlov, R. V.; Gaynanova, G. A.; Kuznetsov, D. M.; Ivanov, Y.
evaluation of antidandruff shampoo using mannosylerythritol lipid A.; Amerkhanova, S. K.; Lyubina, A. P.; Voloshina, A. D.; Zakharova, L.
(MEL) as a bio-surfactant. Tenside Surfactants Deterg. 2023, 60 (1), Y. A study involving PC-3 cancer cells and novel carbamate gemini
44−53. surfactants: Is zeta potential the key to control adhesion to cells? Smart
(108) de Oliveira Schmidt, V. K.; de Vasconscelos, G. M. D.; Vicente, Mater. Struct. 2023, 4, 123−133.
R.; de Souza Carvalho, J.; Della-Flora, I. K.; Degang, L.; de Oliveira, D.; (128) Varka, E. M.; Coutouli-Argyropoulou, E.; Infante, M. R.;
de Andrade, C. J. Cassava wastewater valorization for the production of Pegiadou, S. Synthesis, characterization, and surface properties of
biosurfactants: surfactin, rhamnolipids, and mannosileritritol lipids. phenylalanine-glycerol ether surfactants. J. Surfactants Deterg. 2004, 7
World J. Microbiol. Biotechnol. 2023, 39 (2), 65. (4), 409−414.
(109) Khalafi, H.; Ahmadi, S. A comparative study of Mannosyler- (129) Lozano, N.; Pérez, L.; Pons, R.; Pinazo, A. Diacyl glycerol
ythritol lipids (MELs) surfactant adsorption upon the Al12N12 and arginine-based surfactants: biological and physicochemical properties
B12N12 nano-cages as potential candidates for detecting MELs. J. of catanionic formulations. Amino Acids 2011, 40 (2), 721−729.
Indian Chem. Soc. 2023, 100 (1), 100805. (130) Benavides, T.; Martınez, V.; Mitjans, M.; Infante, M. a. R.;
(110) Selva Filho, A. A. P.; Converti, A.; Soares da Silva, R. d. C. F.; Moran, C.; Clapés, P.; Clothier, R.; Vinardell, M. a. P. Assessment of the
Sarubbo, L. A. Biosurfactants as Multifunctional Remediation Agents of potential irritation and photoirritation of novel amino acid-based
Environmental Pollutants Generated by the Petroleum Industry. surfactants by in vitro methods as alternative to the animal tests.
Energies 2023, 16 (3), 1209. Toxicology 2004, 201 (1), 87−93.

11696 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

(131) Infante, M. R.; Pérez, L.; Morán, M. C.; Pons, R.; Mitjans, M.; category: Alkyl sulfates, primary alkane sulfonates, and α-olefin
Vinardell, M. P.; Garcia, M. T.; Pinazo, A. Biocompatible surfactants sulfonates. Ecotoxicol. Environ. Saf. 2011, 74 (5), 1089−1106.
from renewable hydrophiles. Eur. J. Lipid Sci. Technol. 2010, 112 (1), (152) Bajpai, D.; Tyagi, V. K. Laundry Detergents: An Overview. J.
110−121. Oleo Sci. 2007, 56 (7), 327−340.
(132) Adlercreutz, P.; Hatti-Kaul, R. Synthesis of surfactants using (153) Adam, R. Skin Care of the Diaper Area. Pediatr. Dermatol. 2008,
enzymes. In Surfactants from Renewable Resources; Kjellin, M., 25 (4), 427−433.
Johansson, I., Eds.; Wiley: 2010; p 143.. (154) DeLeo, P. C.; Huynh, C.; Pattanayek, M.; Schmid, K. C.;
(133) Amino Acid based Surfactants Market Trends, Size, Share, Top Pechacek, N. Assessment of ecological hazards and environmental fate
Players, Opportunities, Revenue, Regional Analysis, Future Growth by of disinfectant quaternary ammonium compounds. Ecotoxicol. Environ.
2022−2028. Digital Journal. August 30, 2022. https://www. Saf. 2020, 206, 111116.
digitaljournal.com/pr/amino-acid-based-surfactants-market-trends- (155) Hommel, R. K., Ratledge, C. Biosynthetic mechanisms of low
size-share-top-players-opportunities-revenue-regional-analysis-future- molecular weight surfactants and their precursor molecules; Bio-
growth-by-2022-2028. surfactants: Production, Properties, Applications; Kosaric, N., Ed.; Marcel
(134) Johansson, I.; Svensson, M. Surfactants based on fatty acids and Dekker: 1993; pp 3−63.
other natural hydrophobes. Curr. Opin. Colloid Interface Sci. 2001, 6 (2), (156) Desai, J.; Desai, A. Production of Biosurfactants. In
178−188. Biosurfactants: Production, Properties, Applications, Kosaric, N., Ed.;
(135) Sharma, K.; Negi, S.; Thakur, N.; Kishore, K. Partial glycerides- Marcel Dekker: 1993; pp 65−97.
an important nonionic surfactant for industrial applications: an (157) Syldatk, C.; Wagner, F. Production of Biosurfactants. In
overview. J. Biol. Chem. Chron. 2017, 3 (1), 10−19. Biosurfactants and Biotechnology; Kosaric, N., Ed.; Marcel Dekker, 1987;
(136) Hasenhuettl, G. L. Analysis of Food Emulsifiers. In Food pp 89−120.
Emulsifiers and Their Applications, 2nd ed.; Hasenhuettl, G. L., Hartel, R. (158) Desai, J. D.; Banat, I. M. Microbial production of surfactants and
W., Eds.; Springer: 2008; pp 39−62. their commercial potential. Microbiol. Mol. Biol. Rev. 1997, 61 (1), 47−
(137) Polyglycerol Esters Market Players, Report, Statistics, Trends, 64.
Research, Drivers, & Forecast Analysis By 2029. Data Bridge Market (159) Saharan, B.; Sahu, R.; Sharma, D. A review on biosurfactants:
Research.https://www.databridgemarketresearch.com/reports/ fermentation, applications, current. Genet. Eng. Biotechnol. J. 2011, 29,
global-polyglycerol-esters-market (accessed 2022-10-19). 1−42.
(138) Farias, C. B. B.; Almeida, F. C. G.; Silva, I. A.; Souza, T. C.; (160) Neta, N. S.; Teixeira, J. A.; Rodrigues, L. R. Sugar Ester
Meira, H. M.; Soares da Silva, R. d. C. F.; Luna, J. M.; Santos, V. A.; Surfactants: Enzymatic Synthesis and Applications in Food Industry.
Converti, A.; Banat, I. M.; et al. Production of green surfactants: Market Crit. Rev. Food Sci. Nutr. 2015, 55 (5), 595−610.
prospects. Electron. J. Biotechnol. 2021, 51, 28−39. (161) Clapés, P.; Rosa Infante, M. Amino Acid-based Surfactants:
(139) Piispanen, P.Synthesis and Characterization of Surfactants Enzymatic Synthesis, Properties and Potential Applications. Biocatal.
Based on Natural Products. B.Sc. Thesis, Kungl Tekniska Högskolan, Biotransform. 2002, 20 (4), 215−233.
Stockholm, 2002. (162) Behzadnia, A.; Moosavi-Nasab, M.; Ojha, S.; Tiwari, B. K.
(140) Ivanković, T.; Hrenović, J. Surfactants in the environment. Arh. Exploitation of Ultrasound Technique for Enhancement of Microbial
Hig. Rada Toksikol. 2010, 61 (1), 95−109. Metabolites Production. Molecules 2020, 25 (22), 5473.
(141) Mungray, A. K.; Kumar, P. Fate of linear alkylbenzene (163) Behzadnia, A.; Moosavi-Nasab, M.; Tiwari, B. K.; Setoodeh, P.
sulfonates in the environment: A review. Int. Biodeterior. Biodegrad. Lactobacillus plantarum-derived biosurfactant: Ultrasound-induced
2009, 63 (8), 981−987. production and characterization. Ultrason. Sonochem. 2020, 65, 105037.
(142) Stamatelatou, K.; Pakou, C.; Lyberator, G. Occurrence, toxicity, (164) Panda, D.; Saharan, V. K.; Manickam, S. Controlled
and biodegradation of selected emerging priority pollutants in Hydrodynamic Cavitation: A Review of Recent Advances and
municipal sewage sludge. In Comprehensive Biotechnology; Elsevier: Perspectives for Greener Processing. Processes 2020, 8 (2), 220.
2011; Vol. 6, pp 473−484. (165) Rocha e Silva, F. C. P.; Rocha e Silva, N. M. P.; Luna, J. M.;
(143) Fekarcha, L.; Tazerouti, A. Surface Activities, Foam Properties, Rufino, R. D.; Santos, V. A.; Sarubbo, L. A. Dissolved air flotation
HLB, and Krafft Point of Some n-Alkanesulfonates (C14-C18) with combined to biosurfactants: a clean and efficient alternative to treat
Different Isomeric Distributions. J. Surfactants Deterg. 2012, 15 (4), industrial oily water. Rev. Environ. Sci. Biotechnol. 2018, 17 (4), 591−
419−431. 602.
(144) Adami, I. Production of linear alkylbenzene sulfonate and α- (166) Delazar, A.; Nahar, L.; Hamedeyazdan, S.; Sarker, S. D.
olefin sulfonates. In Handbook of Detergents, Part F: Production; Taylor Microwave-Assisted Extraction in Natural Products Isolation. In
& Francis: 2009; pp 83−115. Natural Products Isolation; Sarker, S. D., Nahar, L., Eds.; Humana
(145) Caryl, C. R. Sulfosuccinic Esters. Structure and Wetting Power. Press: 2012; pp 89−115.
Ind. Eng. Chem. Res. 1941, 33 (6), 731−737. (167) Veggi, P. C.; Martinez, J.; Meireles, M. A. A. Fundamentals of
(146) Deepika; Tyagi, V. K. Sulfosuccinates as Mild Surfactants. J. Microwave Extraction. In Microwave-Assisted Extraction for Bioactive
Oleo Sci. 2006, 55 (9), 429−439. Compounds: Theory and Practice; Chemat, F., Cravotto, G., Eds.;
(147) Jensen, J. Fate and effects of linear alkylbenzene sulphonates Springer US: 2013; pp 15−52.
(LAS) in the terrestrial environment. Sci. Total Environ. 1999, 226 (2), (168) Chen, X.; Lu, Y.; Shan, M.; Zhao, H.; Lu, Z.; Lu, Y. A mini-
93−111. review: mechanism of antimicrobial action and application of surfactin.
(148) Hulzebos, E. M.; Maslankiewicz, L.; Walker, J. D. Verification of World J. Microbiol. Biotechnol. 2022, 38 (8), 143.
literature-derived SARs for skin irritation and corrosion. QSAR & (169) Johansson, I.; Somasundaran, P. Handbook for Cleaning/
Combinatorial Science 2003, 22 (3), 351−363. Decontamination of Surfaces; Elsevier: 2007.
(149) Luan, H.; Gong, L.; Yue, X.; Nie, X.; Chen, Q.; Guan, D.; Que, (170) Hill, K. Industrial development and application of biobased
T.; Liao, G.; Su, X.; Feng, Y. Micellar Aggregation Behavior of Alkylaryl oleochemicals. Pure Appl. Chem. 2007, 79 (11), 1999−2011.
Sulfonate Surfactants for Enhanced Oil Recovery. Molecules 2019, 24 (171) Rabiu, A.; Elias, S.; Oyekola, O. Oleochemicals from palm oil for
(23), 4325. the petroleum industry. In Palm Oil; Waisundara, V., Ed.; InTechOpen:
(150) Penteado, J. C. P.; El Seoud, O. A.; Carvalho, L. R. Linear 2018. DOI: 10.5772/intechopen.76771.
alkylbenzene sulfonates: chemistry, environmental impact and analysis. (172) Jin, Y.; Tian, S.; Guo, J.; Ren, X.; Li, X.; Gao, S. Synthesis,
Quim. Nova 2006, 29, 1038−1046. Characterization and Exploratory Application of Anionic Surfactant
(151) Wibbertmann, A.; Mangelsdorf, I.; Gamon, K.; Sedlak, R. Fatty Acid Methyl Ester Sulfonate from Waste Cooking Oil. J.
Toxicological properties and risk assessment of the anionic surfactants Surfactants Deterg. 2016, 19 (3), 467−475.

11697 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

(173) Benvegnu, T.; Plusquellec, D.; Lemiègre, L. Chapter 7 - (192) Rout, S.; Tambe, S.; Deshmukh, R. K.; Mali, S.; Cruz, J.;
Surfactants from Renewable Sources: Synthesis and Applications. In Srivastav, P. P.; Amin, P. D.; Gaikwad, K. K.; Andrade, E. H. d. A.;
Monomers, Polymers and Composites from Renewable Resources; Oliveira, M. S. d. Recent trends in the application of essential oils: The
Belgacem, M. N., Gandini, A., Eds.; Elsevier: 2008; pp 153−178. next generation of food preservation and food packaging. Trends Food
(174) Hayes, D. G. Chapter 11 - Fatty Acids-Based Surfactants and Sci. Technol. 2022, 129, 421−439.
Their Uses. In Fatty Acids; Ahmad, M. U., Ed.; AOCS Press: 2017; pp (193) Jimoh, A. A.; Lin, J. Biosurfactant: A new frontier for greener
355−384. technology and environmental sustainability. Ecotoxicol. Environ. Saf.
(175) Lang, R. F.; Parra-Diaz, D.; Jacobs, D. Analysis of ethoxylated 2019, 184, 109607.
fatty amines. Comparison of methods for the determination of (194) Rofeal, M.; El-Malek, F. A. Valorization of Lipopeptides
molecular weight. J. Surfactants Deterg. 1999, 2 (4), 503−513. Biosurfactants as Anticancer Agents. Int. J. Pept. Res. Ther. 2021, 27 (1),
(176) Manga, E. B.; Celik, P. A.; Cabuk, A.; Banat, I. M. 447−455.
Biosurfactants: Opportunities for the development of a sustainable (195) Chiewpattanakul, P.; Phonnok, S.; Durand, A.; Marie, E.;
future. Curr. Opin. Colloid Interface Sci. 2021, 56, 101514. Thanomsub, B. W. Bioproduction and anticancer activity of
(177) Gayathiri, E.; Prakash, P.; Karmegam, N.; Varjani, S.; Awasthi, biosurfactant produced by the dematiaceous fungus Exophiala
M. K.; Ravindran, B. Biosurfactants: Potential and Eco-Friendly dermatitidis SK80. J. Microbiol. Biotechnol. 2010, 20 (12), 1664−1671.
Material for Sustainable Agriculture and Environmental Safety�A (196) Escobar-Díaz, E.; López-Martín, E. M.; Hernández del Cerro,
Review. Agronomy 2022, 12 (3), 662. M.; Puig-Kroger, A.; Soto-Cerrato, V.; Montaner, B.; Giralt, E.; García-
(178) McInerney, M. J.; Maudgalya, S.; Knapp, R.; Folmsbee, M. Marco, J. A.; Pérez-Tomás, R.; Garcia-Pardo, A. AT514, a cyclic
Development of Biosurfactant-Mediated Oil Recovery in Model Porous depsipeptide from Serratia marcescens, induces apoptosis of B-chronic
Systems and Computer Simulations of Biosurfactant-Mediated Oil lymphocytic leukemia cells: interference with the Akt/NF-κB survival
Recovery; University of Oklahoma: 2004. pathway. Leukemia 2005, 19 (4), 572−579.
(179) Purwasena, I. A.; Astuti, D. I.; Syukron, M.; Amaniyah, M.; (197) Saini, H. S.; Barragán-Huerta, B. E.; Lebrón-Paler, A.;
Sugai, Y. Stability test of biosurfactant produced by Bacillus Pemberton, J. E.; Vázquez, R. R.; Burns, A. M.; Marron, M. T.;
licheniformis DS1 using experimental design and its application for Seliga, C. J.; Gunatilaka, A. A. L.; Maier, R. M. Efficient Purification of
MEOR. J. Pet. Sci. Eng. 2019, 183, 106383. the Biosurfactant Viscosin from Pseudomonas libanensis Strain M9−3
(180) Muthusamy, K.; Gopalakrishnan, S.; Ravi, T. K.; and Its Physicochemical and Biological Properties. J. Nat. Prod. 2008,
Sivachidambaram, P. Biosurfactants: Properties, commercial produc- 71 (6), 1011−1015.
tion and application. Curr. Sci. 2008, 94 (6), 736−747. (198) Isoda, H.; Nakahara, T. Mannosylerythritol lipid induces
(181) Adamu, C. I.; Nganje, T. N.; Edet, A. Heavy metal granulocytic differentiation and inhibits the tyrosine phosphorylation of
contamination and health risk assessment associated with abandoned human myelogenous leukemia cell line K562. Cytotechnology 1997, 25
Barite mines in Cross River State, southeastern Nigeria. Environ. (1), 191−195.
Nanotechnol. Monit. Manag. 2015, 3, 10−21. (199) Isoda, H.; Kitamoto, D.; Shinmoto, H.; Matsumura, M.;
(182) Guan, R.; Yuan, X.; Wu, Z.; Wang, H.; Jiang, L.; Li, Y.; Zeng, G. Nakahara, T. Microbial Extracellular Glycolipid Induction of Differ-
Functionality of surfactants in waste-activated sludge treatment: A entiation and Inhibition of the Protein Kinase C Activity of Human
review. Sci. Total Environ. 2017, 609, 1433−1442. Promyelocytic Leukemia Cell Line HL60. Int. J. Pept. Res. Ther. 1997,
(183) Ibrahim, W. M.; Hassan, A. F.; Azab, Y. A. Biosorption of toxic 61 (4), 609−614.
heavy metals from aqueous solution by Ulva lactuca activated carbon. (200) Sudo, T.; Zhao, X.; Wakamatsu, Y.; Shibahara, M.; Nomura, N.;
Egypt. J. Basic Appl. Sci. 2016, 3 (3), 241−249. Nakahara, T.; Suzuki, A.; Kobayashi, Y.; Jin, C.; Murata, T.; et al.
(184) Tang, J.; He, J.; Liu, T.; Xin, X. Removal of heavy metals with Induction of the differentiation of human HL-60 promyelocytic
sequential sludge washing techniques using saponin: optimization leukemia cell line by succinoyl trehalose lipids. Cytotechnology 2000,
conditions, kinetics, removal effectiveness, binding intensity, mobility 33 (1), 259−264.
and mechanism. RSC Adv. 2017, 7 (53), 33385−33401. (201) Cao, X.; Wang, A. H.; Jiao, R. Z.; Wang, C. L.; Mao, D. Z.; Yan,
(185) da Rosa, C. F. C.; Freire, D. M. G.; Ferraz, H. C. Biosurfactant L.; Zeng, B. Surfactin Induces Apoptosis and G2/M Arrest in Human
microfoam: Application in the removal of pollutants from soil. J. Breast Cancer MCF-7 Cells Through Cell Cycle Factor Regulation. Cell
Environ. Chem. Eng. 2015, 3 (1), 89−94. Biochem. Biophys. 2009, 55 (3), 163.
(186) Mali, S. N.; Thorat, B. R.; Gupta, D. R.; Pandey, A. Mini-Review (202) Wang, C. L.; Ng, T. B.; Yuan, F.; Liu, Z. K.; Liu, F. Induction of
of the Importance of Hydrazides and Their Derivatives�Synthesis and apoptosis in human leukemia K562 cells by cyclic lipopeptide from
Biological Activity. Eng. Proc. 2021, 11 (1), 21. Bacillus subtilis natto T-2. Peptides 2007, 28 (7), 1344−1350.
(187) Desale, V. J.; Mali, S. N.; Thorat, B. R.; Yamgar, R. S. Synthesis, (203) Park, S. Y.; Kim, J.-H.; Lee, Y. J.; Lee, S. J.; Kim, Y. Surfactin
admetSAR Predictions, DPPH Radical Scavenging Activity, and Potent suppresses TPA-induced breast cancer cell invasion through the
Anti-mycobacterial Studies of Hydrazones of Substituted 4-(anilino inhibition of MMP-9 expression. Int. J. Oncol. 2013, 42 (1), 287−296.
methyl) benzohydrazides (Part 2). Current Computer - Aided Drug (204) Cao, X.-h.; Wang, A.-h.; Wang, C.-l.; Mao, D.-z.; Lu, M.-f.; Cui,
Design 2021, 17 (4), 493−503. Y.-q.; Jiao, R.-z. Surfactin induces apoptosis in human breast cancer
(188) Thorat, B. R.; Mali, S. N.; Rani, D.; Yamgar, R. S. Synthesis, In MCF-7 cells through a ROS/JNK-mediated mitochondrial/caspase
silico and In vitro Analysis of Hydrazones as Potential Antituberculosis pathway. Chem. Biol. Interact. 2010, 183 (3), 357−362.
Agents. Current Computer - Aided Drug Design 2021, 17 (2), 294−306. (205) Dey, G.; Bharti, R.; Dhanarajan, G.; Das, S.; Dey, K. K.; Kumar,
(189) Rodrigues, L.; Banat, I. M.; Teixeira, J.; Oliveira, R. B.; Sen, R.; Mandal, M. Marine lipopeptide Iturin A inhibits Akt
Biosurfactants: potential applications in medicine. J. Antimicrob. mediated GSK3β and FoxO3a signaling and triggers apoptosis in breast
Chemother. 2006, 57 (4), 609−618. cancer. Sci. Rep. 2015, 5 (1), 10316.
(190) De Giani, A.; Zampolli, J.; Di Gennaro, P. Recent Trends on (206) Hajare, S. N.; Subramanian, M.; Gautam, S.; Sharma, A.
Biosurfactants With Antimicrobial Activity Produced by Bacteria Induction of apoptosis in human cancer cells by a Bacillus lipopeptide
Associated With Human Health: Different Perspectives on Their bacillomycin D. Biochimie 2013, 95 (9), 1722−1731.
Properties, Challenges, and Potential Applications. Front. Microbiol. (207) Yin, H.; Guo, C.; Wang, Y.; Liu, D.; Lv, Y.; Lv, F.; Lu, Z.
2021, 12, 655150. Fengycin inhibits the growth of the human lung cancer cell line 95D
(191) Rossi, C. C.; Santos-Gandelman, J. F.; Barros, E. M.; Alvarez, V. through reactive oxygen species production and mitochondria-
M.; Laport, M. S.; Giambiagi-deMarval, M. Staphylococcus haemoly- dependent apoptosis. Anti-Cancer Drugs 2013, 24 (6), 587−598.
ticus as a potential producer of biosurfactants with antimicrobial, anti- (208) Cheng, W.; Feng, Y.; Ren, J.; Jing, D.; Wang, C. Anti-tumor role
adhesive and synergistic properties. Lett. Appl. Microbiol. 2016, 63 (3), of Bacillus subtilis fmbJ-derived fengycin on human colon cancer HT29
215−221. cell line. Neoplasma 2016, 63 (2), 215−222.

11698 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699
ACS Omega http://pubs.acs.org/journal/acsodf Review

(209) Singh, P.; Cameotra, S. S. Enhancement of metal and New Insights; Kumar Dutta, A., Ed.; IntechOpen: 2022.
bioremediation by use of microbial surfactants. Biochem. Biophys. Res. DOI: 10.5772/intechopen.100542.
Commun. 2004, 319 (2), 291−297. (236) Rodríguez-López, L.; Rincón-Fontán, M.; Vecino, X.; Cruz, J.
(210) Mohanty, S.; Jasmine, J.; Mukherji, S. Practical Considerations M.; Moldes, A. B. Extraction, separation and characterization of
and Challenges Involved in Surfactant Enhanced Bioremediation of Oil. lipopeptides and phospholipids from corn steep water. Sep. Purif.
Biomed Res. Int. 2013, 2013, 328608. Technol. 2020, 248, 117076.
(211) Churchill, P. F.; Dudley, R. J.; Churchill, S. A. Surfactant- (237) Roelants, S.; Van Renterghem, L.; Maes, K.; Everaert, B.;
enhanced bioremediation. Waste Manage. (Oxford) 1995, 15 (5), 371− Redant, E.; Vanlerberghe, B.; Demaeseneire, S. L.; Soetaert,
377. W.Microbial biosurfactants: from lab to market. In Microbial
(212) Franzetti, A.; Di Gennaro, P.; Bestetti, G.; Lasagni, M.; Pitea, Biosurfactants and their Environmental and Industrial Applications;
D.; Collina, E. Selection of surfactants for enhancing diesel hydro- Banat, I. M., Thavasi, R., Eds.; CRC Press: 2019; pp 340−362.
carbons-contaminated media bioremediation. J. Hazard. Mater. 2008, DOI: 10.1201/b21950-13.
152 (3), 1309−1316. (238) Pal, Y.; Mali, S. N.; Kale, S. B.; Pratap, A. P. Improved adsorptive
(213) Vaz, D. A.; Gudiña, E. J.; Alameda, E. J.; Teixeira, J. A.; purification and effective separation of acidic and lactonic sophorolipid
Rodrigues, L. R. Performance of a biosurfactant produced by a Bacillus biosurfactant. J. Indian Chem. Soc. 2022, 99 (11), 100776.
subtilis strain isolated from crude oil samples as compared to (239) Pal, Y.; Mali, S. N.; Pratap, A. P. Optimization of the primary
purification process of extracting sphorolipid from the fermentation
commercial chemical surfactants. Colloids Surf., B 2012, 89, 167−174.
broth to achieve a higher yield and purity. Tenside Surfactants Deterg.
(214) Hung, H.-c.; Shreve, G. S. Effect of the Hydrocarbon Phase on
2022, 59 (5), 441−449.
Interfacial and Thermodynamic Properties of Two Anionic Glycolipid
(240) Bhangale, A. P.; Wadekar, S. D.; Kale, S. B.; Mali, S. N.; Pratap,
Biosurfactants in Hydrocarbon/Water Systems. J. Phys. Chem. B 2001,
A. P. Non-traditional oils with water-soluble substrate as cell growth
105 (50), 12596−12600. booster for the production of mannosylerythritol lipids by Pseudozyma
(215) Nitschke, M.; Costa, S. G. V. A. O.; Contiero, J. Rhamnolipids antarctica (ATCC 32657) with their antimicrobial activity. Tenside
and PHAs: Recent reports on Pseudomonas-derived molecules of Surfactants Deterg. 2022, 59 (2), 122−133.
increasing industrial interest. Process Biochem. 2011, 46 (3), 621−630. (241) Sivagiri, S. D.; Mali, S. N.; Pratap, A. P. Improved synthesis of
(216) Lovaglio, R. B.; dos Santos, F. J.; Jafelicci, M.; Contiero, J. sophorolipid biosurfactants using industrial by-products and their
Rhamnolipid emulsifying activity and emulsion stability: pH rules. practical application. Tenside Surfactants Deterg. 2022, 59 (1), 17−30.
Colloids Surf., B 2011, 85 (2), 301−305. (242) Pratap, A. P.; Mestri, R. S.; Mali, S. N. Waste derived-green and
(217) Hogan, D. E.; Tian, F.; Malm, S. W.; Olivares, C.; Palos sustainable production of Sophorolipid. Curr. Opin. Green Sustain.
Pacheco, R.; Simonich, M. T.; Hunjan, A. S.; Tanguay, R. L.; Klimecki, Chem. 2021, 4, 100209.
W. T.; Polt, R.; et al. Biodegradability and toxicity of monorhamnolipid (243) Singh, P.; Mali, S.; Sangale, N.; Pratap, A. P. Synthesis of (2-
biosurfactant diastereomers. J. Hazard. Mater. 2019, 364, 600−607. hydroxyl-3-butoxyl) propyl-succinyl-chitosan (HBP-SCCHS)-an
(218) Sekhon Randhawa, K. K.; Rahman, P. K. S. M. Rhamnolipid amino sugar anionic surfactant under Microwave Irradiation and its
biosurfactants�past, present, and future scenario of global market. application. Thai J. Pharm. Sci. 2021, 45 (6), 461−469.
Front. Microbiol. 2014, 5, 454.
(219) Almansoory, A. F.; Idris, M.; Abdullah, S. R. S.; Anuar, N.
Screening for potential biosurfactant producing bacteria from hydro-
carbon-degrading isolates. Adv. Environ. Biol. 2014, 639−648.
(220) Green Surfactants Market Size, Share, Price Analysis 2022−2027.
Expert Market Research. https://www.expertmarketresearch.com/
reports/green-surfactants-market (accessed 2022-08-19).
(221) Kandasamy, R.; Rajasekaran, M.; Venkatesan, S. K.; Uddin, M.
New Trends in the Biomanufacturing of Green Surfactants: Biobased
Surfactants and Biosurfactants. In Next Generation Biomanufacturing
Technologies; Rathinam, N. K., Sani, R. K., Eds.; ACS Symposium Series
1329; American Chemical Society, 2019; pp 243−260..
(222) Bland, A. Assessing the sustainability and performance of green
surfactants. IHS Markit, March 4, 2020. https://ihsmarkit.com/
research-analysis/assessing-sustainability-and-performance-of-green-
surfactants.html (accessed 2022-08-19).
(223) EcoSenseTM SL-60 HA Surfactant.
(224) EcoSenseTM 3000 Surfactant - Personal Care grade.
(225) BioToLife Postbiotic Rebalance Mouthwash.
(226) BASF announces 25th anniversary of APG production at
Düsseldorf site.
(227) Entering a new era of surfactants - Evonik Industries.
(228) Velsan SC preservative booster for cosmetics.
(229) ArlasilkTM EFA|Personal Care.
(230) OleoCraftTM HP-33|Personal Care.
(231) Unilever and Evonik partner to launch green cleaning
ingredient.
(232) Solvay launches new biosurfactants for carbon-neutral and
circular beauty care products.
(233) AGAE|AGAE Technologies.
(234) Fraunhofer IGB - Wir verbinden Biologie and Technik -
Fraunhofer IGB.
(235) Ismail, N. L.; Shahruddin, S.; Othman, J. Perspective Chapter:
Overview of Bio-Based Surfactant�Recent Development, Industrial
Challenge, and Future Outlook. In Surfactants and Detergents: Updates

11699 https://doi.org/10.1021/acsomega.3c00591
ACS Omega 2023, 8, 11674−11699