1 s2.0 S0144861722010475 Main
1 s2.0 S0144861722010475 Main
Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol
Review
A R T I C L E I N F O A B S T R A C T
Keywords: Chitin is the most abundant natural amino polysaccharide, showing various practical applications owing to its
Chitin functional properties. However, there are barriers in the development due to the difficulty of chitin extraction
Extraction and purification, regarding its high crystallinity and low solubility. In recent years, some novel technologies such
Biomaterial
as microbial fermentation, ionic liquid, electrochemical extraction have emerged for the green extraction of
Functional foods
Application
chitin from new sources. Furthermore, nanotechnology, dissolution systems and chemical modification were
applied to develop a variety of chitin-based biomaterials. Remarkably, chitin was used in delivering active in
gredients and developing functional foods for weight loss, lipid reduction, gastrointestinal health, and anti-aging.
Moreover, the application of chitin-based materials was expanded into medicine, energy and the environment.
This review outlined the emerging extraction methods and processing routes of different chitin sources and
advances in applying chitin-based materials. We aimed to provide some direction for the multi-disciplinary
production and application of chitin.
* Correspondence to: Z. Jiang, Key Laboratory of Food Bioengineering (China National Light Industry), College of Food Science and Nutritional Engineering, China
Agricultural University, Beijing, China.
** Correspondence to: X. Fu, College of Food Science and Technology, Huazhong Agricultural University, Wuhan, Hubei Province, China.
E-mail addresses: [email protected] (Z. Jiang), [email protected] (X. Fu).
https://doi.org/10.1016/j.carbpol.2022.120142
Received 8 July 2022; Received in revised form 19 September 2022; Accepted 19 September 2022
Available online 22 September 2022
0144-8617/© 2022 Elsevier Ltd. All rights reserved.
J. Lv et al. Carbohydrate Polymers 299 (2023) 120142
In addition to chitin’s original non-toxic, antibacterial and biocom structure highly similar to cellulose and molecular weights ranging from
patible properties, chitin-based biomaterials have enhanced mechanical hundreds of thousands to millions (Martau et al., 2019). The presence of
strength and chemical resistance, resulting in unique properties for hydrogen bonds in the structure of chitin facilitates the formation of
many applications. For example, novel chitinous biomaterials were used crystalline states and their transformation into new derivatives. Its
to develop degradable biomedical materials such as wound dressings, molecular chain is rich in hydroxyl groups (C-3 and C-6), acetamides,
bio-scaffolds and drug carriers (Yang et al., 2020). Moreover, there are and a small number of amino groups capable of various chemical re
new advances in functional materials made of chitin in areas sur actions. The crystalline form of chitin can be classified into α-chitin,
rounding nutrition and health, energy and environment, and diagnostics β-chitin and γ-chitin according to the arrangement of the molecular
and testing. Chitin-based emulsions and nanomaterials are being chains (Fig. 1).
developed to deliver functional food additives and bioactive ingredients Chitin is found in the shells of crustaceans and insects, the cell walls
(Lee et al., 2021a; Saeb et al., 2022). Chitin and its composites are of fungi, and the cartilage of mollusks. Crustaceans (shrimps and crabs)
widely used to develop sewage adsorbents, biofuels and microbial fuel are the most critical source of chitin and usually contain protein (30–40
cells to play an environmentally friendly role (Peter et al., 2021). %), CaCO3 (30–50 %), chitin (20–30 %) and small amounts of lipids,
Furthermore, chitin has been used indirectly for fungal detection and astaxanthin and other mineral salts (Yadav et al., 2019). Insects are the
disease diagnosis (Subramanyam et al., 2010; Xu et al., 2017). most diverse and abundant organisms in the animal kingdom. They
In recent years, several reviews on the extraction and utilization of contain >30 % of chitin in their exoskeletons and can be an alternative
chitin from different sources have been reported (Hossin et al., 2021; source of chitin (Khajavian et al., 2022).
Iber et al., 2022; Khajavian et al., 2022; Shamshina, 2019; Shamshina However, animals are often subject to seasonal variations, with
et al., 2019; Sharma et al., 2021). However, a systematic overview of the variability and low reproducibility disadvantages. The extraction of
various extraction and processing methods is still lacking. Most of the chitin from fungi can effectively overcome the limitations of seasonal
applications of chitin are focused on biology and medicine but less on rhythms, and the extraction process is relatively simple, inexpensive and
functional food (Ahmad et al., 2020; Azuma et al., 2014; Satitsri & more stable (Tan et al., 2020). For this reason, fungal chitin has been
Muanprasat, 2020). Thus, this review focused on the multifaceted green extensively studied as an excellent alternative to animal sources during
extraction and synthesis pathways of different sources of chitin bio the past few decades. An increasing number of organisms have been
materials, highlighting the promising applications of chitin (especially found to contain chitin. In addition to the most studied marine shellfish
emulsions and nanomaterials) among the emerging fields. Meanwhile, products and fungi, corals and marine sponge organisms have also been
feasible suggestions based on the limitations were presented, aiming to suggested as potential sources of chitin (Iber et al., 2022).
provide a reference for chitin’s development and multifunctional
applications. 3. Extraction of chitin
2. The origin and structure of chitin Chitin is generally extracted by single or combined chemical, bio
logical and physical methods, with physical methods commonly used to
Chitin is a natural polymer insoluble in water consisting of N-acetyl- aid extraction. Many novel extraction approaches, such as green sol
D-glucosamine linked by β-1,4-glycosidic bonds, with a chemical vents (ILs, DESs, EDTA) and electrochemical technology, have emerged
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J. Lv et al. Carbohydrate Polymers 299 (2023) 120142
in recent years, overcoming the potential drawbacks of acid-base 2014). Ultrasound can also be used to improve the efficiency of decol
methods (Fig. 2). orization. Chitin prepared by conventional chemical methods may
contain residual acids or bases, making it unsuitable for producing
3.1. Chemical extraction method related food products. However, it can be used to develop adsorbents
and batteries for environmental and energy applications.
Typically, chitin can be extracted by demineralization, deproteini
zation, and decolorization. Shrimps and crabs are the primary animal 3.2. Biological extraction method
seafood sources of chitin, and mineral salts and proteins are the main
components other than chitin (Yadav et al., 2019). Therefore, chitin is Although the chemical method is efficient, the extraction requires
extracted mainly to remove minerals (CaCO3) and proteins. Chemical large amounts of acid and alkali, which do not fit the green develop
extraction methods are very economical and efficient and have been ment. In contrast, the eco-friendly biological method has advantages in
used in industry. maintaining chitin structure and improving resource utilization. More
Various chemical reagents have been reported for deproteinization, over, the removed nutrients, such as proteins and mineral salts, can be
e.g., bases of medium strength or higher such as NaOH, KOH, Ca(OH)2, reused by humans and animals. However, extraction time and costs are
and alkaline salt solutions such as Na2CO3, Na3PO4, Na2S (Rahayu et al., taken into account for industrial production. Biological methods such as
2022). Currently, NaOH is the reagent of choice for deproteinization enzymatic hydrolysis and microbial fermentation can be combined with
with an industrial dose of about 2–5 % (Dayakar et al., 2021; Dhana chemical reagents aiming to increase efficiency with minimal chemical
balan et al., 2021). A mild chemical method can be used to extract chitin treatment (Hamed et al., 2016).
from fungi. For example, a low NaOH concentration (2 %) was used to In recent years, microbial fermentation for chitin extraction has
treat the residue of Hericium erinaceus at 85 ◦ C for 3 h, and purity of the emerged as a green alternative to the chemical method. The main
extracted chitin was 97.88 % (Liao & Huang, 2020). Most previous principle is fermented by unique bacteria or fungi, consequently pro
studies used HCl for demineralization, while different types of acid so ducing proteases and organic acids to remove proteins and CaCO3.
lutions impacted chitin quality. Rahayu et al. (2022) compared the ef Fermentation of cooked shellfish waste using halophilic archaea
fect of HCl, HNO3, H2SO4 and CH3COOH, indicating that the three removed 98 % of the proteins and produced chitin with minimal
inorganic acid solutions were more effective than CH3COOH. However, chemical treatment (Dayakar et al., 2021). Zhang et al. (2021) isolated
CH3COOH has the advantage being safe and environmentally friendly. 18 % (wt%) chitin from shrimp shells using co-fermentation of Aceto
In addition, the combination of physical technologies such as ultrasound bacter pasteurianus and Bacillus subtilis. The process achieved a demin
and microwave further optimize the extraction rate of chitin. With ul eralization and deproteinization rate of over 90 %. In addition to
trasonic technology, the demineralization rate of shrimp shells reached bacterial fermentation, the complex fungal fermentation of shrimp shell
89.47 % (Xu et al., 2019). waste to produce chitin is also a hot topic of research. Mucor circi
Furthermore, crustaceans and insects contain high levels of pig nelloides were fermented to secrete proteases that can be used for
ments, resulting in a rather dark color of the extracted chitin, which deproteinization. The amino acids released during fermentation
compromises its application and commercial value. Therefore, the decreased the medium pH and further demineralized the shells (Tan
decolorization process is necessary to produce high-quality chitin. et al., 2020). The chitin extracted by fermentation displayed good
Decolorization is mainly carried out by organic solvents (ethanol, quality, and the degree of deacetylation was comparable to commercial
acetone) and strong oxidants (KMnO4, H2O2 and NaClO) (Tan et al., products. The biological extraction process is green and safe, and the
Fig. 2. Flow chart of various extraction processes of chitin. The extraction methods for chitin include chemical extraction, biological extraction, green solvent
extraction and electrochemical extraction. Physical methods are often used as a secondary method to improve extraction efficiency.
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J. Lv et al. Carbohydrate Polymers 299 (2023) 120142
extracted high-purity chitin is advantageous in the food industry. action. In practice, the viscosity can be reduced by adding water,
Moreover, enzymatic deproteinization was successfully used to changing the percentage of acidic solvent, controlling the reaction time
extract chitin. The alkaline protease treatment of crab shells (Portunus and temperature.
segni) resulted in 85 % protein removal, preparing high-quality chitin
(Hamdi et al., 2017). Recycle of chitin from shrimp shell waste using 3.3.1.3. Other solvents. EDTA is representative of metal chelators and
lactic and acetic acid demineralization and protease-assisted deprotei can be used to demineralize chitin in place of hydrochloric acid. This
nization was also reported. It was found that enzyme-assisted produc reaction process has a low impact on the chitin molecular chain, and
tion of chitin has a higher degree of acetylation and better retention of EDTA can be recovered or recycled. The crayfish powder was dissolved
crystal structure than chemical extraction (Hongkulsup et al., 2016). in 18 % EDTA, sonicated at 30 ◦ C for 45 min, and decolorized by H2O2.
The degree of enzymatic hydrolysis affected the polymeric characteris The obtained chitin extracts were white in color, high in purity, and low
tics of chitin. The polymer quality of chitin obtained by enzymatic hy in ash content (0.13 %) and nitrogen content (3.51 %) (Dou et al., 2014).
drolysis of shrimp shell residue was higher than that of chemical Moreover, the yield of chitin from shrimp shells was 47.32 % using
extraction (Dhanabalan et al., 2021). Thus, the enzymatic method ultrasound-assisted citric acid for demineralization, with reverse mi
combined with chemical extraction can reduce environmental pollution celles extraction technology for protein removal and 30 % H2O2 for color
and improve chitin quality. Nevertheless, fermentation parameters for removal (Zhong & Jia-xin, 2017). This method made a lower chitin yield
enzyme and microbial growth, pH and temperature could affect the than the chemical method but much higher than the enzymatic method.
quality and yield of chitin. To expand production, it is essential to focus It significantly saved reaction time and reduced environmental pollu
on the factors such as suitable bioreactors, highly skilled operations and tion. Demineralization with organic reagents often leads to changes in
energy consumption (Mohan et al., 2022). the physicochemical properties of chitin, resulting in a decrease in
quality. CO2 gas and cationic salt reaction systems were used to
demineralize crayfish shells (Panulirus argus) to solve the problem
3.3. Other novel extraction methods (Ramírez et al., 2017). The ash content of chitin (1.3 %) is similar to the
EDTA method but with a high DA, crystallinity and thermal stability.
3.3.1. Green solvents The purity is greatly improved using green organic reagents instead of
chemical reagents. Further processing can be applied in the biomedical
3.3.1.1. ILs. In recent years, some green processes for chitin extraction field.
have been developed to meet sustainable development. ILs are generally
composed of specific organic cations and organic or inorganic anions, 3.3.2. Electrochemistry
which can dissolve chitin under appropriate conditions, and the poly In addition to green solvents, the less explored electrochemistry is
mers will not degrade during extraction. The standard ILs are imidaz also gaining attention. A research treated shrimp shells with 1 % acidic
oles, pyrroles, morpholines, quaternary ammonium salts, quaternary and alkaline electrolytic water at 20 V for 6 h (Xiao-mei et al., 2019).
phosphonium salts, etc. (Morais et al., 2020). In previous studies, The minerals and proteins were entirely removed, and 19.46 % of
imidazole-based ionic liquids have been used extensively in the pro extraction ratio was obtained. Different electrolytes such as Na2SO4 and
duction and modification of chitin. In particular, the crab shell was NaCl have also been used to extract chitin from marine sponges (Now
solubilized by 1-allyl-3-methylimidazolium bromide ([AMIM][Br]) to acki, Stępniak, Langer, et al., 2020). The physicochemical properties of
produce chitin with a yield of 12.6 % and 93 % acetylation (Setoguchi chitin extracted by electrochemical methods are essentially the same as
et al., 2012). Another new ammonium-based ionic liquid was used to those of traditional chemical methods. The electrochemical extraction
recycle 13.4 % medium molecular weight chitin from shrimp shell waste process is efficient with low reagent usage. It can be an environmentally
(Tolesa et al., 2019). In addition, the pretreatment of fungal chitin by friendly alternative to chemical methods. However, the preparation
combining IL with steam explosion technology transformed the biomass process is not mature enough, and constant experimentation is needed to
into value-added products (Ma et al., 2021). determine the optimal amount of chemical reagents to obtain good
IL-based extraction of chitin is costly, even with potential safety purity and chitin yield (Nowacki, Stępniak, Machałowski, et al., 2020).
risks. Therefore, this method may not be the best choice for producing In order to save costs, electrode materials that can replace the platinum,
functional chitin substrate and should be tested for toxicity when such as nanostructured carbon electrodes, could be sought in practical
applied in the food industry. In the future, it is necessary to develop applications.
more green and economic processes for ILs and DESs, and further Table 1 shows the recent sources, extraction methods, and yields
explore the toxicity and recycling of ionic liquid. from chitin in crustaceans, insects, sponges, mollusks, and other species.
To assure a green and cost-effective chitin extraction procedure, we need
3.3.1.2. DESs. DESs are binary and ternary systems consisting of to investigate more creative approaches and improve process
hydrogen bond acceptors (HBA) and hydrogen bond donors (HBD) in technology.
specific molar ratios, which have similar properties to ILs (Sun et al.,
2022). This system contains many hydrogen bonds and free H+, so it is 4. Development of chitin-based biomaterials
highly soluble in natural polymers such as chitin, cellulose and lignin
(Khajavian et al., 2022). Lobster shells treated with a mixed system of Chitin is insoluble in water and common solvents, which signifi
choline chloride-malonic acid (1:2) yielded high-purity chitin, with a cantly limits the development and application in industry. Notably,
higher yield (20.63 %) than the chemical method (16.53 %) (Zhu et al., nanotechnology, new solubilization systems, and chemical modification
2017). Furthermore, microwave-assisted extraction of chitin signifi methods have primarily improved chitin’s inherent limitations (e.g.,
cantly improves the deproteinization rate (88 %) and retains a high high degree of polymerization or dense crystal structure) and facilitated
degree of acetylation (DA) (>91 %) (Zhao et al., 2019). Compared with the development of biomaterials. The typical processing methods and
traditional heating methods, microwaves significantly increase the re chitin based functional materials are shown in Fig. 3.
action rate, shorten the reaction time, and are often used to enhance the
green chemical production of chitin. Moreover, steam explosion, ultra
sound and other mechanical means are used to assist in chitin extraction 4.1. Nanometerization of chitin
can provide more possibilities for industrial production.
Notably, the high viscosity is a drawback of DES, which hinders the Nano-sized chitin particles can be uniformly dispersed in water with
interaction between solvent and chitin and reduces the efficiency of a high specific surface area, low density, and excellent forming (Sun
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Table 1
Extraction and yield of chitin from organisms of different origins.
Sources Organisms Method Yield (%) References
Crustaceans Acetes NaOH, HCl, alkaline protease 4.22 (Dhanabalan et al., 2021)
Callinectes amnicola HCl, NaOH 19.36 (Olafadehan et al., 2020)
Litopenaeus vannamei Alcaligenes faecalis S3, Bacillus coagulans L2 25.40 (Rakshit et al., 2021)
B. amyloliquefaciens (BA01), L. rhamnoides 19.6 (Liu et al., 2020)
Shrimp shells [DIPEA][Ac], aqueous citric acid 5.5–14.8 (Tolesa et al., 2019)
Insects Brachytrupes portentosus NaOH, oxalic acid, NaClO 4.3–7.1 (Ibitoye et al., 2018)
Cicada orni HCl, NaOH, NaClO 42.8 (Poerio et al., 2020)
Bombyx eri NaOH, HCl, ethanol and acetone 45 (Huet et al., 2020)
Polyphylla fullo HCl, NaOH, chloroform-methanol-water (1:2:4, v/v) 11.3 (Kabalak et al., 2020)
Lucanus cervus 10.9
Gryllotalpa gryllotalpa 10.1
Bradyporus (C.) sureyai 9.8
Fungi Aspergillus niger NaOH, ethanol 38.50 (Vallejo et al., 2021)
Hericium erinaceus HCl, NaOH, NaClO 16.30 (Liao & Huang, 2020)
Agaricus bisporus NaOH, acetic acid 19.7 (Hassainia et al., 2018)
Sponges Aplysina aerophoba Na2SO4(electrolyte), catholyte, anolyte NA (Nowacki, Stępniak, Machałowski, et al., 2020)
Mycale euplectellioides CH3COOH, NaOH, HF NA (Zółtowska-Aksamitowska et al., 2018)
Aplysina archeri Microwave, NaOH, CH3COOH, H2O2 5 (Klinger et al., 2019)
Pseudoceratina purpurea CH3COOH, NaOH, HF NA (Żółtowska-Aksamitowska et al., 2018)
Mollusks and others Cirrhipathes sp. Na2SO4(electrolyte), catholyte, anolyte NA (Nowacki, Stępniak, Langer, et al., 2020)
Chiton HCl, NaOH, acetone 4.3 (Rasti et al., 2017)
Snail HCl, NaOH NA (Akpan et al., 2018)
et al., 2016). The two main types of chitin nanoparticles include chitin structure (Tran et al., 2019; Yang et al., 2020). Chitin can be converted
nanocrystals (ChNCs) and chitin nanofibers (ChNFs). Based on the directly into ChNFs by ball milling, and the product can be mixed with
unique external form and internal properties, chitin nanoparticles are polylactic acid to produce nanocomposites (Tran et al., 2019). Sala
valuable in developing multifunctional nanocomposites and hybrid berria, Diaz, et al. (2015a) and Salaberria, Fernandes, et al. (2015)
nanomaterials (Salaberria, Diaz, et al., 2015b). In recent years, ChNCs prepared α- ChNFs (5–10 μm in length and 80–100 nm in width) and
and ChNFs have been produced from a wide range of chitin-derived ChNCs (300 nm in size and 60 nm in average diameter) from yellow
organisms using both ‘top-down’ and ‘bottom-up’ approaches with lobster waste using dynamic high-pressure homogenization and hydro
great potential for innovation (Ngasotter et al., 2022). chloric acid hydrolysis, respectively. Subsequently, they developed
For the ‘top-down’ approach, acid hydrolysis and mechanical treat composite packaging films with heat-resistant and antibacterial prop
ment are the main traditional methods for preparing nano-sized chitin erties using ChNCs as nanofillers. TEMPO oxidation is also a typical
(Larbi et al., 2018). Acid digestion is used to prepare ChNCs with high “top-down” method for preparing chitin nanoparticles. Amphoteric
crystallinity and rod-like morphology. Meanwhile, mechanical treat ChNFs with homogeneous and stable dispersion under alkaline and
ment usually yields ChNFs with a high aspect ratio and fibrous network acidic conditions can be trained in the TEMPO/NaClO2/NaClO system,
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J. Lv et al. Carbohydrate Polymers 299 (2023) 120142
which is expected to be used as stabilizers for Pickering emulsions (Pang 5. Application in functional foods
et al., 2017).
Another way to prepare nano-sized chitin is “bottom-up,” where 5.1. Use as a functional ingredient
chitin is dissolved in some special solvents and then regenerated by
electrostatic spinning, self-assembly with the addition of water or As the second most abundant natural polysaccharide, chitin’s bene
methanol (Naghdi et al., 2020; Sun et al., 2016). Barber et al. (2013) ficial effects on human health include anticancer, immune-boosting,
prepared ChNFs by dissolving shrimp shells in 1-ethyl-3-methylimida gastrointestinal regulation, weight loss and fat reduction (Fig. 4).
zole acetate solution and combined microwave and electrostatic spin Chitin added to food can confer specific functional effects that
ning technologies. In addition, ChNFs (50 nm diameter) prepared by contribute to human health. Therefore, chitin resources will have many
dissolving chitin in concentrated phosphoric acid and deionized water application prospects in human health or the functional food field.
can be synthesized into emulsion gels for further applications in the food
industry (Zhang et al., 2015). 5.1.1. Weight loss and fat reduction
Obesity has become a global health problem that affects people’s
4.2. Dissolution of chitin daily lives and increases the incidence of cancer and a range of meta
bolic diseases. The natural polymer chitin has a positive charge that
Acid hydrolysis is not easy to control, and yields are low. At the same binds to negatively charged bile acids and bile salts in the human body.
time, oxidation requires expensive chemicals, both of which have a It can also reduce lipase activity and inhibit adipocyte differentiation
safety risk when utilized in food industry. Therefore, there have been (Tzoumaki et al., 2013). Therefore, addition of chitin to food can reduce
some studies for new solvent systems to dissolve chitin. The NaOH/urea the synthesis of cholesterol and fat, which has a lipid-lowering and anti-
system was often used to construct chitin microspheres and chitin obesity effect.
composite hydrogels, which showed great potential for antibacterial Huang, Wu, et al. (2020) who treated the obese rats with different
materials and cellular microcarriers (Xu et al., 2021). The dissolved concentrations of chitin solutions, found that chitin reduced body
chitin in such systems was mixed with carbon nanotubes to form novel weight, blood lipid levels and the risk of aortic atherosclerosis, improved
composites with both electrical conductivity and biocompatibility for liver function and alleviated obesity-induced hepatic steatosis. Dysbiosis
neural regeneration and repair therapy (Niu & Zhang, 2020). of the human gut flora also increases the risk of obesity. Chitin as a
A wide range of chitin-based biomaterials can also be prepared from specific food supplement to regulate gut microbes can significantly
chitin dissolved in green solvent systems, such as ILs and DESs (Kha reduce the prevalence of non-communicable diseases (Wang et al.,
javian et al., 2022). Choline chloride-ZnCl (1:2 molar ratio) has been 2021). Saeb et al. (2022) observed changes in the composition of in
reported as a green dissolution/catalytic system to produce functional testinal flora of obese rats by feeding insect cuticles (a source of chitin).
ChNCs (Hong et al., 2019). King et al. (2017) synthesized chitin films It was found that rats fed 3 % insect cuticles had a significant increase in
using regenerated chitin (2.5 wt%) obtained by dissolving in [EMIm] Lactobacillaceae and Actinobacteria, but a significant decrease in lipid
[OAc] for the delivery of drugs such as caffeine and the development of accumulation. Thus, chitin cuticles can be added to foods as a functional
food packaging materials. In addition, composite hydrogel materials material to treat people suffering from obesity or metabolic disorders.
prepared using a mixture (1 wt%) consisting of IL-chitin and cellulose In addition, carboxymethyl-chitin inhibited the differentiation and
dissolved in a dimethyl sulfoxide/IL system can be used as environ lipid accumulation of 3T3-L1 adipocytes by modulating adipogenesis-
mentally friendly electrolyte components (Kasprzak & Galiński, 2021). related elements, thus exerting an anti-obesity effect (Kong et al.,
The chemicals used in the above reactions are all potentially toxic. 2011). Chitin nanomaterials are being deliberately added to some food
Although the chemicals have been removed from the products, further products to improve their functional properties. Pickering emulsions
toxicity and toxicological assessments are required in the food industry. stabilized by ChNFs have been shown to increase stomach satiety or
control lipid digestion and calorie intake (Tzoumaki et al., 2013). The
4.3. Modification of chitin gastrointestinal effects of chitin nanoparticles on functional foods were
studied using in vitro digestion models. Natural ChNCs could delay the
The functional chitin derivatives can be prepared by introducing digestion of lipids in food emulsions, and somehow reduced the bio
different groups or molecular chains for potential applications. The accessibility of β-carotene and vitamins (Zhou et al., 2021). Therefore,
chemical modification of chitin includes deacylation, hydroxylation, when developing edible nano-chitin as a functional ingredient for
carboxylation, quaternary amination and graft modification (Sun et al., weight loss, it is important to consider its reduction in food nutritional
2016). For example, chitin was readily deacetylated in aqueous alkali/ value.
urea solutions to obtain modified chitin with a DA of 33.2 %, which was
easier to be processed and more versatile than before (Li et al., 2021). 5.1.2. Gastrointestinal health
Carboxymethyl chitin was prepared by mixing chitin in monochloro Polysaccharides and other macromolecular constitute a large part of
acetic acid solution under alkaline conditions, and its addition to food people’s daily diet. Chitin neutralized gastric juices by releasing
has anti-obesity properties (Kong et al., 2011). Both the carboxyl and glucosamine, which reduces gastric acid irritation at the injury site, thus
amino-modified chitin can be used to develop amphoteric adsorbents effectively preventing gastric ulcers (Anandan et al., 2010). As a type of
(El-Shishtawy et al., 2021). The chitin modified by quaternary ammo insoluble dietary fiber, chitin can promote gastrointestinal motility and
nium salts has many positive charges and significantly high solubility. It stabilize intestinal flora, consequently improving human immunity
can be loaded with adriamycin for rapid drug release into cancer cells (Ngasotter et al., 2022). In particular, chitin has been repeatedly re
because it self-assembles with hydrophobic cetyl groups to produce new ported to improve gastrointestinal health and alleviate metabolic syn
micelles (Peng et al., 2019). In addition, nano-chitin can be structurally drome associated with diabetes and cardiovascular disease (Wang et al.,
modified to achieve more functional effects. Allyl modification of graf 2021). The dextran-chitin complex improved metabolic disorders and
ted hydrocarbon chains on the surface of ChNCs and ChNFs and covalent also increased the number of Bifidobacterium and the metabolites in a rat
crosslinking with thiolated polyethylene glycols can prepare organo-gels model (Rodriguez et al., 2020). Therefore, chitin can be added to
(Kiliona et al., 2020). This kind of gel was effective in removing metal healthy foods as a probiotic compound to promote digestion and
ions and organic pollutants. improve intestinal disorders.
In addition, fibrillated nano-chitin has been extensively studied.
ChNFs had anti-inflammatory and anti-fibrotic effects and prevented
tissue damage caused by sodium dextran sulfate-induced acute colitis
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(Azuma et al., 2012). Chitin also acted as an excellent barrier and anti- inhibition by affecting the expression of oncogenic proteins (Libreros
inflammatory to DSS-induced acute colitis (Liberti et al., 2018). Oral et al., 2012).
administration of ChNFs effectively inhibited anticancer drug-induced Furthermore, a variety of chitin composites have been used to inhibit
mucositis and reduced liver injury and oxidative stress in rats (Koi cancer development. Metal (silver, copper) composites containing chitin
zumi et al., 2017). In summary, chitin is expected to be a functional nanoparticles exhibited significant targeting toxic effects on human
ingredient in the food industry to alleviate gastrointestinal inflamma breast cancer cells (MCF-7) (Solairaj et al., 2017). Chitin benzoates
tion, mainly by regulating the balance of intestinal microorganisms and inhibited the proliferation of cancer cells by inducing apoptosis of HeLa
immune cytokines. (human cervical adenocarcinoma cells) through stimulation of exo-
pathway receptors (Karagozlu et al., 2014). Chitin-dextran-aldol-
5.1.3. Age-delaying quercetin couples are more potent than the free form in terms of anti
The global phenomenon of aging is becoming more and more severe. oxidant activity, and are highly detrimental to macrophage cancer cell
People are constantly exposed to many free radicals from the body and lines (Singh et al., 2018). These chitin complexes are expected to be used
the external environment daily. Chitin acts as an antioxidant by scav as anticancer drugs or functional materials in the food or pharmaceutical
enging free radicals to protect the body from damage (Sharma et al., industry.
2021). Thus, it is expected to be used as a dietary supplement or med Shellfish is the primary source of chitin, and seafood allergies are
icine to slow aging, regarding its ability to enhance immunity and common worldwide (Ngasotter et al., 2022). Thus, chitin and its nano
health. materials have the potential to cause allergic reactions when used as
The introduction of quaternary amine groups into chitin has functional food ingredients. The limitation of chitin could be the po
improved its solubility and ability to chelate free radicals, further tential toxicity in the human respiratory tract, and the side effects
enhancing its antioxidant activity (Zhang et al., 2012). The most depend on the route of exposure (Satitsri & Muanprasat, 2020). How
apparent cosmetic manifestation of aging is skin changes. When a ever, the effect of biopolymer on human metabolic pathways and
complex of beta-glucan (MEB) and ChNCs was administered topically physiological functions remains to be further validated.
and orally to healthy subjects with aging skin, the clinical effect was
significantly higher than with MEB alone, as evidenced by a reduction in
5.2. For the stabilization, encapsulation and delivery of functional
wrinkles and age spots (Morganti et al., 2012). Notably, ChNFs can be
ingredients
used as active ingredients in functional foods and anti-aging agents and
as active tissue carriers to delay human aging in cosmetics such as masks
Compared to surfactants, chitin particles are widely available,
and lotions (Morganti et al., 2019).
environmentally compatible and highly stable. These non-toxic poly
meric biopolymers act as solid particles to stabilize food-grade Pickering
5.1.4. Anticancer and anti-tumor
emulsions. ChNCs, ChNFs, combinations of the two and blends with
The incidence of various cancers is increasing every year due to the
other substances compose the primary chitin micro/nanoparticles for
changing lifestyles of modern society. Chitin and its derivatives have
stabilizing Pickering emulsions (Fig. 5). Traditional edible oil emulsions
been reported to enhance the proliferation of immune lymphocytes and
are poorly stabilized and prone to oxidative degradation, which shortens
have inhibitory effects on various types of cancer cell lines (Satitsri &
the product’s cargo holiday and reduces its nutritional value and sensory
Muanprasat, 2020). Among them, chitin exhibited cytotoxic and dose-
quality (Dai et al., 2020). The O/W Pickering emulsions (30:70, v:v)
dependent inhibitory effects on both Hep2 and RD human cancer cell
prepared from chitin-dextran nanofibers and palm oil are stable over a
lines (Bouhenna et al., 2015). In addition to directly inhibiting cancer
wide pH range (Xiao et al., 2020). They are not affected by ionic
cells, chitin can also indirectly enhance the targeting process of cancer
strength, which can significantly improve the stability of edible oils. In
7
J. Lv et al. Carbohydrate Polymers 299 (2023) 120142
Fig. 5. Chitin-based emulsion systems stabilized by different nanoparticles. ChNCs (A), ChNFs (B), combinations of ChNCs and ChNFs (C), and mixed particles
composed with other biomass (D).
addition to stabilizing edible oils, chitin-based emulsions can be used for to about 2 months (Lee et al., 2021a). Therefore, emulsion systems
stabilizing and delivering plant antimicrobial essential oils (EOs). For prepared from various stabilizers have an excellent encapsulation effect
example, Pickering emulsions prepared from ChNFs (partially deacety on functional components. They can be used as suitable carriers to
lated) and cinnamon oil exhibited good emulsion stability and extended protect and deliver bioactive substances in food systems.
antibacterial activity against E. coli (Huang, Liu, et al., 2020). This study Unlike chitin-based emulsions, chitin-based microspheres and gel
will be a guide for future Pickering emulsion delivery EOs. materials were less commonly investigated in food science. Studies
In addition, the incorporation of different types of nanoparticles and showed that chitin has strong hydrogen bonding and hydrophobic in
biomass can modulate the functional and physicochemical properties of teractions with polyphenols and that porous chitin microspheres can
Pickering emulsions, contributing to the shelf life and stability of adsorb large amounts of anthocyanins as their delivery carriers (Wang
emulsion-based products. Polysaccharide particles consisting of posi et al., 2017). This system protected anthocyanins from damage during
tively charged ChNCs and negatively charged fucoidan were used to processing, increased bioaccessibility and enabled colon-targeted de
extend Pickering emulsion’s stability (Liu et al., 2021). Tannins livery. More interestingly, the short-chain fatty acids produced by the
combining with chitin enhanced the antioxidant properties of stabilized degradation of dietary fiber (e.g., chitin) act synergistically with an
oil phase (Yang et al., 2021). Complexes consisting of 0.2 % ChNFs and thocyanins in the colon to promote human health (Quirós-Sauceda et al.,
1 % starch nanoparticles (SNPs) showed more stable physical properties 2014). Furthermore, a delivery system can be used to increase the sur
and environmental tolerance than the single stabilized 10 % soybean oil vival rate of probiotics during transit through the gastrointestinal tract
(Lee et al., 2021b). This phenomenon is probably due to the synergistic and fully realize their health effects on the body. The composite
effect of the two stabilizers. Afterward, it was found that the retention of hydrogel prepared by mixing chitin with xanthan gum as an encapsu
curcumin was significantly improved when the concentration of both lation/delivery system for probiotics improved the survival of live pro
solid nanoparticles was doubled, and the shelf life was further extended biotic cells in the intestinal tract, entirely using the health functions
8
J. Lv et al. Carbohydrate Polymers 299 (2023) 120142
(Argin et al., 2014). major component of fungal cell walls but is not found in high-level
Sustainability is a development theme in today’s world. Both plants and vertebrates. Therefore, scientists can determine food
academia and industries are increasingly interested in the chitin of contamination by measuring the level of chitin on the surface of pro
biological origin. Chitin and its nanomaterials are not only functional cessed products or ingredients. For example, fungal contamination in
ingredients, but also useful deliveries, which may further improve the processed tomatoes can be assessed by measuring lectins (FITC-labeled)
utilization and bioaccessibility of functional substances to promote that selectively bind to chitin and are more accurate than Howard mold
human health. Although some studies are still at the laboratory scale, count and visual inspection methods (Potts et al., 2002). In addition to
these findings herald the practical feasibility of chitin and its derived ingestion, people exposed to a humid environment for a long time and
materials in food-related fields. poor resistance and personal hygiene are susceptible to fungal in
fections. In vitro, chitin-binding proteins (99mTc-labeled) bind specif
6. Application in other fields ically to chitin to help one distinguish between bacterial and fungal
infections (Siaens et al., 2006). Similarly, gold nanoparticles readily
Chitin and chitin-based biomaterials have been widely used to interacted with the external chitin layer of the fungus and achieved
develop functional foods. Moreover, they also have potential applica specific screening and sensitive detection within 30 min (Xu et al.,
tions in other fields such as biodegradable biomedical materials, testing 2017).
and diagnostics, environment and energy (Fig. 6). Chitin can also help people with disease diagnoses. Subramanyam
et al. (2010) used 1 % chitin dissolved in 5 % sulphuric acid to treat
6.1. Biomedical materials sputum specimens. The combination was found to completely lyse the
sputum and control the growth of normal flora within 30 min, facili
Traditional wound dressings often have the disadvantage being tating the subsequent isolation and detection of the Mycobacterium
ineffective and irritating. Recently, natural chitin biopolymers are tuberculosis. Moreover, chitin is often used to develop biosensors as a
becoming one of the most concerning materials due to their anti- degradable and low-cost biomaterial. The self-powered haptic sensor
inflammatory and antibacterial properties. Jung et al. (2018) reported and internet optical sensing platform developed based on ChNF pro
a net of β-ChNFs made by electrospinning technology for wound healing vided intelligent services for the medical testing industry and our daily
experiments in rats. They found that the material accelerated collagen lives (Naghdi et al., 2020).
deposition and promoted wound healing. Notably, the degree of acety
lation (DA) of ChNFs may affect wound recovery. In a rat skin defect 6.3. Environmental protection
model, chitin nonwoven fabrics with DA values of 42 %, 60 %, 71 % and
90 % displayed better performance than gauze during wound healing Heavy metals and organic pollutants (dyes, microplastics) in waste
(He et al., 2021). water are significant sources of contaminants that enter the food chain
Chitin-based composites can be used as an anticancer drug carrier to and cause severe damage to human health, posing a serious threat to
control the release of drugs and reduce side effects in humans (Peng environmental safety (Peter et al., 2021). The application of chitin in the
et al., 2019). The α-chitin-based hydrogel significantly enhanced the environmental field has received much attention due to its good
penetration of drugs into the skin. It shortened the duration of action of adsorption properties and low cost. Chitin-based nanocomposite mi
drugs on cancer cells, facilitating the treatment of all types of skin cancer crospheres with a layered structure effectively removed methylene blue
(Nair et al., 2021). In addition, chitin-hydroxyapatite collagen com from wastewater, with a highly stable adsorption/desorption process
posite scaffolds and chitin-based nerve grafts showed good defect repair and low raw material costs (Xu et al., 2018). In general, amphoteric
results when used for bone and nerve tissue regeneration treatments, chitin is more effective in decolorizing anionic and cationic dyes in
respectively (Wang et al., 2022; Xing et al., 2021). Therefore, chitin- wastewater (El-Shishtawy et al., 2021). Chitin nanomaterials are also
based biomaterials can be a new option for constructing biological able to adsorb heavy metals effectively. Yan et al. (2019) used a ChNFs
scaffolds such as bone scaffolds and nerve scaffolds. filtration membrane to purify oil and water and found that it separated
oil/water emulsion while removing heavy metal ions.
6.2. Rapid detection and diagnosis Not only organic dyes, but up to 350 million tonnes of plastic
packaging waste are also produced from food, cosmetics and industry
The toxic metabolites produced by moldy cereals affect human each year (Ye et al., 2020). Various microplastics (MPs, <5 mm) are
health, leading to cancer and organ failure in severe cases. Chitin is a widely distributed in aquatic systems, posing a severe threat to
9
J. Lv et al. Carbohydrate Polymers 299 (2023) 120142
organisms and human health. Chitin-based sponge material removed up provide some reference value for the future development and applica
to 71.6–92.1 % of three modified styrene microplastics in an alkaline tion of chitin in multiple fields.
environment. It had an excellent removal capacity for MPs of different
functional groups (Sun et al., 2021). Interestingly, the sponge material is Declaration of competing interest
both reusable and easily degradable by soil microorganisms, meeting the
need for economic and environmental protection. The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
6.4. Green energy the work reported in this paper.
As world reserves of fossil fuels are being depleted, the introduction Data availability
of biofuels can help alleviate the tension. Currently, biofuels are pro
duced from traditional energy crops, biomass straw and forestry waste. The authors do not have permission to share data.
The production process takes up large land and costs much money, time
and feed value. Chitin is a new economical, biological source for biofuel Acknowledgments
production. Many microorganisms such as yeasts and molds can use N-
acetylglucosamine as a carbon source to produce ethanol, but few or This research was supported by the National Natural Science Foun
ganisms can ferment unprocessed chitin to produce ethanol (Sur dation of China (32072158), and we also appreciated China-Korea
yawanshi & Eswari, 2022). Mucor circinelloides NBRC 6746 created 0.11 Young Researcher Exchange Program.
g/L of ethanol using chitin powder as a substrate, while ethanol pro
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