Primer on Formulating

NATURAL
Products
Primer on Formulating
NATURAL
Products
 Primer on Formulating Natural Products

ISBN: 978-1-937235-07-9

Copyright 2012, by Allured Business Media. All Rights Reserved.

Publisher: Marian Raney

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rapid change, it is difficult to ensure that all information provided is entirely accurate and up-
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0911
 Table of Contents
Chapter 1 Building Natural Products

Chapter 2 Organic and Natural: Caveat Emptor

Chapter 3 Skin Care

Chapter 4 Hair Care

Chapter 5 Green Formulations: Not All Components

Are Equal

Chapter 6 Navigating the Challenges of Formulating

With Naturals
 INTRODUCTION
One of the hottest areas in cosmetic formulations is the development
of products that are considered “natural” by consumers, marketers, and
regulators. Whether you are just starting out or are a seasoned formulator,
getting a handle on the formulation of natural products is critical to your
continued success. Traditional formulation techniques have focused on
creating the best performing products at the lowest cost. Little regard
has been given to the source of the starting raw materials. However,
issues of sustainability, consumer desires and regulatory pressures
have led to the need for the development of cosmetics using primarily
plant-based, renewable resourced raw materials. This presents a special
challenge to formulators as the starting materials often do not work as
well as traditional synthetic ingredients.
In this short book, we have gathered experts to write chapters on the most
important topics in the area of natural formulation. The book starts with
a chapter on what it means to be a natural formulation and reviews some
specific formulations that are touted as natural. The second chapter provides a
thorough review of the various worldwide natural standards and gives direction
on what type of ingredients can be included. The third and fourth chapters
are written by naturals expert Art Georgalas and focus specifically on natural
formulation types for skin care and hair care, respectively. The skin chapter
focuses on creating natural emulsions, while hair topics include shampoos,
conditioners, and styling aids.
The final two chapters explore the future challenges cosmetic chemists can
expect to face as they continue to create natural formulations. The difficulty
of proving the effectiveness and “naturalness” of ingredients is the subject of
the fifth chapter. The sixth and final chapter details specific problems related
to natural formulating and provides suggested solutions. This primer on
natural formulations is meant as a starting point that will guide cosmetic
chemists to a future world where petroleum derivatives are rarely used, and
renewable, plant-based formulations are the norm.
We hope you find it useful.

All the best,

Perry Romanowski
 CHAPTER 1

Building Natural
Products
Eric S. Abrutyn

Based on previously published studies and consumer articles, it appears

that consumer interest in natural and organic products is growing. The
question is: What does this mean? Are consumers actually interested
in products that contain natural materials, or are they really interested
in products that are safer and whose production or use have a minimal
impact on the planet (i.e., they are renewable)? The key to meeting
consumer demand is to understand what natural means in order to
produce formulations that meet expectations.
Since the cosmetics and personal care industry is not regulated,
various organizations have offered conflicting positions on standardized
guidelines for natural and organic claims. To improve communication
on this topic, it will therefore become important to dissociate claims
regarding the naturalness of ingredients from the perception of safety.
Safety is inherent in the raw materials used for formulating, regardless
of their origin and in the synergies among ingredients—for more than
50 years, the industry has worked hard to monitor the safety of products
on the market, supported by the US Food and Drug Administration
(FDA). And recently, more governmental agencies such as the FDA,
the US Department of Agriculture (USDA) and the Council of
Europe’s Committee of Experts on Cosmetic Products have taken a
proactive role in sorting out the meanings of natural and organic for
the cosmetics and personal care industry. Such organizations act as a
clearer scientific focal point in deciding what ingredients are safe for
use in cosmetic products. In addition, several organizations currently
are monitoring the safety of cosmetics and personal care ingredients,
such as the Cosmetic Ingredient Review (CIR) panel.
1
2
Building Natural Products

General Formula Standards

As noted, an ever-growing list of organizations with standardized
guidelines exists that measures the naturalness of a product formula.
The definition for natural in chemicals legislation was introduced in
1981, and in 2000, the Council of Europe’s Committee of Experts on
Cosmetic Products issued guidelines for natural cosmetic products.
Only as recently as 2008, however, did the USDA and the European
Cosmetic Standards Working Group (COSMOS)1 provide additional
guidance for formulating to meet natural claims. Nongovernmental,
for-profit organizations offering organic and/or natural certification
for cosmetic products include: Quality Assurance International,2 the
National Science Foundation,3 ECOCERT,4 OASIS,5 Nature,6 the Soil
Association, Guaranteed Organic Certification Agency,7 BDIH,8 the
Natural Products Association,9 and Certech10—to name a few. However,
organic and natural certifications Formula 1. Burt’s Bees
for cosmetics are not backed by beeswax lip balm
specific legislation, such as in the
foods industry. Beeswax qs
Coconut oil 2.05–5.0%
Formulas 1–5 are examples of Sunflower oil 2.5–5.0
natural products on the market, Tocopheryl acetate 0.5–1.0
taken from sources of public Tocopherol (vitamin E) 0.5–1.0
domain and including estimates Lanolin 0.5–1.0
Peppermint oil < 0.25
of the ingredient percentages Comfrey root extract < 0.1
used and/or their function in the Rosemary extract < 0.1
formula, to provide readers
with a starting point for Formula 2. Tom’s of
their own formulation Maine lemongrass natural
work. It is suggested that deodorant body bar
readers perform a patent
Soaps of coconut and palm qs
search to ensure they are Sage extract < 0.1%
not infringing on any Rosemary extract < 0.1%
existing and protected Ascorbyl palmitate < 0.1%
Lemongrass oil < 0.25%
technologies. In addition,
two supplier-submitted Note: These vegetable-based soaps include
examples of natur al a blend of rosemary and vitamin C for
preservation, and of sage and lemongrass
formulas are provided, for for their reported natural odor-fighting
properties.
reader consideration.
 3
Chapter 1

Formula 3.
Green By Nature mint green tea hand cream
Water (aqua) Carrier
Butyrospermum parkii (shea butter) Emollient/moisturizer
Sesamum indicum (sesame) seed oil Emollient
Beeswax Structurant
Prunus persica (peach) kernel extract Emollient
Pistacia vera seed oil (pistachio oil) Emollient
Glycine soja (soybean) seed extract Emollient
Chamomilla recutita (matricaria) flower extract Emollient
Stearic acid Emulsifier
Aloe barbadensis leaf extract Skin calming
Camellia oleifera leaf extract (green tea extract) Claim support
Yogurt powder Co-emulsifier
Rosa moschata seed oil (rose hip oil) Claim support
Sorbitan olivate Emulsifier
Tocopherol (vitamin E) Antioxidant
Citrus grandis (grapefruit) seed extract Skin calming
Mentha piperita (peppermint) oil Skin calming
DMDM hydantoin Preservative
Iodopropynyl butylcarbamate Preservative
Citrus aurantium amara (bitter orange) fruit extract Skin calming/aroma
Ascorbic acid (vitamin C) Antioxidant
Citric acid pH Adjuster
Malic acid pH Adjuster
Glycerin Humectant

Most natural products launched consist of at least 90% naturally

derived materials and they omit certain ingredients construed as
being unsafe, such as parabens. Cosmetic products meeting organic
standards tend to follow USDA food standards, where no chemical
fertilizers, herbicides, pesticides or other toxins were used to grow the
non-hybridized plant sources from which the raw materials are derived.
The most common denominators among formulas that meet claims
for natural standards include:
• Ingredients based on environmentally conscious and ecologically
sound practices that are socially responsible with regard to the
use of resources, and that impart minimum human impact on
the environment;
4
Building Natural Products

• Water is considered a basic ingredient; therefore, it is not included

in the calculation for total percentage of natural or organic
ingredients;
• At least 90% of the formula composition, sans water, is based
on renewable feedstock and ingredients with neutral carbon
footprints;
• Incidental ingredients such as preservatives, chelating agents and
antioxidants do not have to be included in the calculation so long
as they represent less than 1% of the non-water portion of the
composition, and there are no renewable resource alternatives;
and
• All raw materials used should represent the best approach to safe
exposure to humans; safety measurements are based on scientific
studies demonstrating their long-term safety to humans.

Formula 4. All natural styling gel*

A. Dehydroxanthan gum (AMAZE XT polymer, Azko Nobel) 0.85% w/w
B. Deionized water (aqua) 50.00
C. Tapioca starch (Naviance Tapioca certified organic biopolymer,
Azko Nobel) 2.50
D. Deionized water (aqua) 44.95
Glycerin (vegetable grade) 0.25
E. Sodium benzoate 1.00
Benzyl alcohol 0.25
Hydrolyzed wheat protein (and) hydrolyzed wheat starch (and)
water (aqua) 0.20
100.00

Procedure: Without heat, slowly sift A into B with good agitation (700 rpm),
until completely dispersed. Reduce mixing speed to 400 rpm and mix for 15
min to completely hydrate. In a separate mixing vessel, sift C into D with good
agitation (~ 400 rpm) and mix until completely dispersed. Slowly add CD to
AB. Continue mixing at ~ 400 rpm and heat to 80°C. Hold for 25 min. Cool to
45°C before adding E in order. Mix until homogenous. Fill containers. Viscos-
ity: 15,000–20,000 cps; Brkfld Heliopath Spindle #T-C /10 rpm; pH 5.0–7.0

*Note: Formula provided courtesy of Akzo Nobel; naturally derived ingredients in

this styling gel provide moderate stiffness with humidity resistance and a pleasant
aesthetic feel. Tapioca starch offers texture and hold with excellent aesthetics while
dehydroxanthan gum polymer yields rheology and high humidity hold.

In general, the key to formulating natural products is to choose safe

and effective raw materials of as natural an origin as possible. Their
 5
Chapter 1

renewability also should be incorporated into the product development

process, to result in the smallest possible negative footprint on the
environment. However, for product developers to meet the specific
requirements of a given standard, it is important to fully understand
the requirements since they can vary as to how the percentage of
natural ingredients is calculated, or the degree of modification allowed
to a natural source material. This is important because some natural
ingredients are either not functionally suitable to create good aesthetics,
are not stable, or are not sufficiently pure—odorless and colorless.

Formula 5. All natural sunscreen lotion*

A. Deionized water (aqua) qs
Zinc oxide 10.00% w/w
B. Glycerin 2.50
Xantham gum 0.50
C. Cetearyl alcohol (and) coco glucoside 3.00
Sorbitan sesquioleate 0.75
White beeswax 1.50
Butyrospermum parkii (shea butter) 1.50
Simmondsia chinensis (jojoba) seed oil) 1.00
Prunus amygdalus dulcis (sweet almond) oil 0.50
Sesamum indicum (sesame) oil 0.50
Tocopheryl acetate (vitamin E acetate) 0.50
Bisabolol nat. 0.20
Procedure: Combine A, mix well and heat to 75–80°C. Premix B and add to A
at 75°C while homogenizing. Separately combine C, heat to 75°C and add C to
AB at 75°C, homogenizing until batch is uniform. Transfer batch to sweep mix-
ing and cool to 40°C. Add D in order and mix until room temperature. Homog-
enize at slow to medium speed till batch uniform, then stop.

*Note: Formula provided courtesy of BASF.

Conclusions
The continued market demand for natural products is growing, and
while the definition of natural remains an ongoing discussion, there
is a definite push toward eliminating classical, “chemical-sounding”
ingredients, even if they are proven safe and have little or no impact on
the planet. Since the concept of natural and how it is positioned in the
marketplace is still a moving target with minimal legal standardization,
it will take some time to provide formulators with a clear idea of how
to find and utilize the right materials that support this market claim.
6
Building Natural Products

Current standards are dependent upon the marketing division

within individual companies and their legal department. For now, it is
best for formulators to work with their company’s legal, regulatory and
marketing groups to agree on how natural will be defined and stay true
to the course. Then it will be easier to work with raw material suppliers
to document and match to these specification requirements.
Various organizations including those previously listed, whose Web
sites may be found in the concluding references to this chapter, have
developed a list of acceptable and unacceptable renewable ingredients
that would meet their standards for natural and organic claims. Also, a
number of raw material suppliers have published prototype formulations
for use as starting points for natural product formulations.
The development of personal care products for this market requires
clear communication regarding whether said products will be positioned
as natural—meaning either containing natural ingredients or being
safer for the environment; organic and thus meeting a set of specified
standards; or renewable, referencing low impact on resources in the
environment. In addition, such products should outline the source of
feedstock from which their ingredients derived, as well as the renewability
and greenness of the source; and safety assurance based on reliable,
peer-reviewed science and scientific organizations.
The personal care industry must take a leadership role, as it has
for the past 50 years with other issues, to control the misleading
association of terms such as natural and organic with the consumer’s
expectation of implied safety; the industry must continue in its defense
of ingredients with established safety.

References
1. www.cosmos-standard.org
2. www.qai-inc.com
3. www.nsf.gov
4. www.ecocert.com
5. www.oasisseal.org
6. www.natrue.org
7. www.goca.ws/organic-certification
8. www.kontrollierte-naturkosmetik.de/e/bdih.htm
9. www.naturalproductsassoc.org
10. www.certechregistration.com/1_organic_certification.htm
 CHAPTER 2

Organic and Natural:

Caveat Emptor
David C. Steinberg

Every once in a while, readers ask how topics are selected for this column.
This time, the idea came from an e-mail inquiring what COSMOS
standards are. Previous columns have discussed Canadian Natural
Health Products regulations but have steered clear of the natural and
organic debate, although this author previously published an article1 that
debates animal versus vegetable ingredients, in which he explains that
a chemical is a chemical regardless of its origin; a molecule of glycerin
is just that, whether from natural sources like animal or vegetable fat,
or from petroleum or biodiesel sources.
COSMOS is the European Union’s (EU) newest effort to outline
organic and natural standards, with draft guidelines published in
November 2008. But how is it different than other standards? This
calls for a review of the various natural and organic standards for the
personal care industry and how they have evolved.

What is Natural?
According to the author, when he first began to learn during the Dark
Ages, the elements of earth, air, fire and water were understood to be
natural; thus everything made from them was considered natural. Later,
industry expert Ken Klein stated that anything made from the first
92 elements of the periodic table are natural, and that no man-made
elements should be used in products claiming to be natural; however,
this philosophy did not seem a sufficient answer for what marketers
where claiming.

7
8
Organic and Natural: Caveat Emptor

An Internet investigation retrieved several meanings for the term

natural, among which were: being present in or produced by nature; i.e.,
a natural pearl; being inherent or not acquired; not being produced or
changed artificially; and not being altered, treated or disguised.
The US Food and Drug Administration (FDA) does not define
natural in the Food, Drug and Cosmetic Act or any other FDA
regulation; the closest definition2 for natural personal care products was
established in Canada as a regulated category called Natural Health
Products. This regulation, which went into effect on Jan. 1, 2004,
defines natural health products (NHPs) as: vitamins and minerals,
herbal remedies, homeopathic medicines, traditional medicine such
as traditional Chinese medicine, probiotics, and other products like
amino acids and essential fatty acids.
While these materials are found in nature, Canada took it a step
further to describe acceptable substances as being synthetic duplicates
of those materials listed above. Synthetic duplicates are substances that
share identical chemical structures and pharmacological properties
with their natural counterparts; an example of such is vitamin E and
dl alpha-tocopherol.
A semi-synthetic substance may also be acceptable as an NHP,
provided that it shares identical chemical structures and pharmacological
properties with its natural counterpart. Semi-synthetic substances are
produced by processes that chemically change a related starting material
that has been extracted or isolated from a plant or a plant material,
an alga, a fungus or a non-human animal material. An example of
such is ginsenosides, which are produced from the starting compound
betulafolienetriol.
In the end, whatever marketing deems natural is natural; the critical
inference is that consumers believe products marketed as natural are safer
than products that are not marketed as natural. This has given rise to
an increase in use of the word organic within the cosmetic industry.

Organic
Recalling studies from his youth, the author notes that the term organic
originally referred to the chemistry of the carbon atom. Then in 1973,
an organization called the California Certified Organic Farmer was
formed to promote organic farming in California, instilling in the
 9
Chapter 2

public a new sense of the word organic. This group became one of the
first to certify products with an organic seal of approval on the label.
In 1979, the state made the organic labeling of foods a law subject to
their controls.
In 1980, the US Department of Agriculture (USDA) published its
“Report and Recommendations on Organic Farming,”3 in which organic
farming was described as a “production system that avoids or largely
excludes the use of synthetically compounded fertilizers, pesticides,
growth regulators and livestock feed additives. To the maximum
extent feasible, organic farming systems rely upon crop rotations, crop
residues, animal manures, legumes, green manures, off-farm organic
wastes, mechanical cultivation, mineral-bearing rocks and aspects of
biological pest control to maintain soil productivity and tilth, to supply
plant nutrients and to control insects, weeds and other pests.”4
Reasons for interest in this system included:
• Increased cost and uncertain availability of energy and
chemicals;
• Increased resistance of weeds and insects to pesticides;
• Decline in soil productivity from erosion and accompanying loss
of organic matter and plant nutrients;
• Pollution of surface waters with agricultural chemicals and
sediment;
• Destruction of wildlife, bees and beneficial insects by
pesticides;
• Hazards to human and animal health from pesticides and feed
additives;
• Detrimental effects of agricultural chemicals on food quality;
• Depletion of finite reserves of concentrated plant nutrients (e.g.,
phosphate rock); and
• Decrease in numbers of farms, particularly family-type farms, and
disappearance of localized and direct marketing systems.5
By the late 1980s, a number of private and state-run certifying
bodies were operating in the United States. Standards varied among
these entities, causing trouble in commerce. Certifiers often refused to
recognize products certified as organic by other agents, which was a
problem particularly for organic livestock producers seeking feed, and
10
Organic and Natural: Caveat Emptor

for processors trying to source ingredients. In addition, a number of

well-publicized incidents of fraud began to undermine the credibility
of the organic industry.
In an effort to curb these problems, the organic community pursued
federal legislation. The result was the Organic Foods Production Act of
1990, which mandated the creation of the National Organic Program
(NOP) and the passage of uniform organic standards. These standards
were incorporated into NOP regulations.6 Implementation of the
regulations began on April 21, 2001, and all organic certifiers, producers,
processors and handlers were required to be in full compliance by Oct.
21, 2002.7
Beyond federal legislation, the California Organic Products Act
(COPA) was signed into law in 2003, and beginning Jan. 1, 2003, all
products sold in California containing a total of less than 70% organic
ingredients were no longer allowed to use the word organic on the
front labeling panel. Later in 2003, the State Assembly repealed the
non-food provision of the COPA but in the end, cosmetics remained
a part of the Act.
With the growth of nationwide food stores based on certified organic
foods, interest in the organic market has spread to cosmetics and other
personal care products. From this interest, several groups have emerged
with varying standards for organic certification; most use a seal that
appears on product labels to indicate organic certification. Following
are some of the major bodies, as well as their requirements. This is not
a comprehensive list but it will provide an overview.
National Organic Program (NOP, United States): Within this
program are four levels of organic claims for foods. The NOP defines
the claims that can be used for agricultural products by their content,
excluding water and salt.
100% Organic: For this claim,
100% of the ingredients in the
product must be certified organic
products and in this case, the
USDA Organic seal may be used
(see Figure 1).
Organic: To make this claim,
95% of the materials in the product Figure 1. USDA Organic seal
 11
Chapter 2

must be certified organic products; the same USDA Organic seal may
be used in this instance.
Made with organic ingredients: For this label claim, 70% to 94.99%
of the product’s ingredients must be certified organic; in this case, use
of the USDA Organic seal is not permitted.
Contains organic: This label claim requires less than 70% of certified
organic ingredients in a product and also cannot bear the USDA
Organic seal.
Natural Products Association (NPA, United States): This
organization was founded in 1936 and was principally concerned
with dietary supplements. The
group represents more than 10,000
retailers, manufacturers, wholesalers
and distributors of natural products,
including foods,dietary supplements,
and health and beauty aids. On
May 1, 2008, the group issued its
certification program for personal
care products. In order to display the
NPA seal (see Figure 2), a product Figure 2. NPA seal
must meet the following requirements:
• Contain at least 95% truly natural ingredients or ingredients that
are derived from natural sources;
• Contain no ingredients linked with potentially suspected human
health risks;
• Not be processed in ways that significantly or adversely alter the
purity of its natural ingredients;
• Include ingredients derived from a purposeful, renewable/plentiful
source found in nature (flora, fauna, mineral);
• Be minimally processed and avoid the use of synthetic or harsh
chemicals so as not to dilute the material’s purity; and
• Should contain non-natural ingredients only where viable natural
alternative ingredients are unavailable, and only when they pose
absolutely no potentially suspected human health risks.
The Natural Products Association also has published8 a list including
839 ingredients that it considers meets these requirements.
12
Organic and Natural: Caveat Emptor

Cosmetics Organic and Natural Standard (COSMOS, EU): As

noted above, COSMOS is one of the EU’s newest efforts, with its
draft published in November 2008. This standard was developed from
collaborations between working groups including: the Instituto per la
Certificazione Etica e Ambientale (ICEA in Italy); the Federation of
German Industries and Trading Firms for Pharmaceuticals, Health
Care Goods, Dietary Supplements and Personal Hygiene products
(BDIH in Germany); Bioforum in Belgium; the French Professional
Association of the Ecological and Organic Cosmetics, and a French
certification organization (Cosmebio/Ecocert in France); and an
environmental charity promoting sustainable, organic farming and
championing human health (The Soil Association in the UK). The
COSMOS draft is available at www.cosmos-standard.org.
These standards describe five categories of ingredients: water,
minerals, physically processed agro-ingredients, chemically processed
agro-ingredients and synthetic materials.The draft details what materials
are and are not allowed. It is interesting to note the chemical reactions
that are and are not allowed (see COSMOS Chemical Reactions).
Under Appendix II of the COSMOS standard, the following
synthetic ingredients are allowed: benzoic acid, benzyl alcohol,
dehydroacetic acid, denatonium benzoate, heliotropine, salicylic acid,
sorbic acid and tetrasodium glutamate diacetate. The second part
of Appendix II lists the mineral origin products allowed—which
contradicts the initial five categories of organic ingredients listed since
“mineral” is included one of the organic ingredient categories.
California Organic Program (United States): Products sold in
California must comply with the 2003 COPA Act10 to be labeled organic.
These products also must be at least 70% organic, not including water
and salt content. Like the USDA program, this program attempts to
apply a food law to cosmetics. All organic ingredients used in organic
products must be certified by one of the organizations listed by the
USDA. There are additional registration fees and other labeling
requirements.
Organic and Sustainable Industry Standards (OASIS, United States):
OASIS was developed and is observed by major cosmetic companies
in the United States such as L’Oréal and Estée Lauder. This standard
certifies products at two levels—organic or made with organic. The made
 13
Chapter 2

COSMOS Chemical Reactions

Allowed physical processes:
• Extractions must use natural materials with any form of water or
with a third solvent of plant origin such as ethyl alcohol, glycerin,
vegetable oils and CO2 absorption (on an inert support that
conforms to these standards);
• Bleaching or deodorization (on an inert support conforming to
these standards);
• Grinding, centrifuging (solid/liquid separation, spin-drying);
• Settling, decanting, desiccation or drying (progressive or not by
evaporation/natural under sun);
• Deterpenation (if fractionated distillation with steam);
• Distillation, expression or extraction (steam);
• Filtration and purification (ultra filtration, dialysis, crystallization
and ion exchange);
• Lyophilization, blending, percolation, cold pressure and hot
pressure (depending on the fluidity of the fatty acids to be
extracted);
• Sterilization with thermal treatments (according to a temperature
respectful of the active substances); and
• Sifting, maceration and ultrasound

Allowed chemical processes:

• Alkylation, amidation, calcination of plant residues and
carbonization (resins, fatty organic oils);
• Condensation/addition, esterification, etherification and
fermentation (natural/biotechnological);
• Hydration, hydrogenation, hydrolysis and neutralization (to obtain
Na, Ca, Mg and K salts);
• Oxidation/reduction processes for the manufacture of amphoterics;
and
• Saponification, sulphation and roasting

Unallowed processes:
Any other processes that are not listed above are not allowed,
including but not limited to:
• Bleaching or deodorization (on a support of animal origin);
• Use of enzymes derived from GMOs;
• Deterpenation (other than with beam);
• Ethoxylation, irradiation and sulphonation (as the main
reaction);
14
Organic and Natural: Caveat Emptor

• Techniques employing genetic engineering;

• Treatments with ethylene oxide or using mercury (mercurial soda);
• Use of petrochemical solvents (hexane, toluene, benzene, etc.); or
• Propoxylation.9

with organic designation requires

70% minimum organic content with
additional criteria for the remaining
30% of ingredients.The organic label
claim will require a minimum of
85% organic content until January
2010, at which time it will increase
to a requirement of 90% minimum
organic content; the minimum
requirement will increase a third Figure 3. OASIS seal
time to 95% by 2012. Products that
cannot achieve a 95% organic level, such as soap, must use the made
with organic claim.
This interval approach takes into consideration the fact that at least
two years are necessary for surfactant and emulsifier manufacturers
to put enough products into the commercial stream to supply the
industry with organic versions of functional ingredients. Since one
of the goals of OASIS is to promote the development of more raw
materials developed from organic starting materials, this approach
works with chemical manufacturers to achieve these goals.11
Whole Foods—Premium Body Care Seal (United States): One of the
major retail outlets for organic products is the Whole Foods supermarket
chain. This group has established its own rules and symbol. As of press
time, the author has not been able to obtain the rules or the symbol. The
group lists more than 250 ingredients that are not allowed, and also does
not allow animal testing or organic UV filters. The group is aligned with
the Environmental Working Group (EWG).
Organic Consumers Association (United States): This final group
was established in 1998 in opposition to the USDA’s NOP program,
and deals primarily with the food area. It has been involved in litigation
with other standards.12
 15
Chapter 2

Comments
What chaos. Why are there so many different organizations, standards,
symbols—and now, lawsuits? There is only one answer: marketing. One
may question whether the companies selling cosmetics stamped with
these symbols care about anything more than selling products. The
underlying message is that consumers have been misled to believe that
these products are safer than non-natural or non-organic cosmetics.
These organizations’ definitions are contradictory and in some ways,
amusing. One set of rules states that water found in the Aloe barbadensis
leaf is organic while water from the faucet is not. Water is water is
water. Also, natural minerals are allowed as colorants but they cannot
be processed; as a minor point, this means that with the exception of
mica, none of these natural minerals would be permitted in cosmetics.
Natural iron oxides, for example, would be in violation of FDA, EU
and Japanese standards since ground iron oxide ores have enough lead,
mercury, arsenic, cadmium, etc., in them to keep Proposition 65 lawyers
in California busy filing lawsuits forever.
Natural does not mean safe. In fact, the NPA’s list of permitted
“safe ingredients” includes 15 of the EU’s 26 listed fragrance allergens.
Perhaps natural allergens are better, then? And while one firm stands
behind the EWG and proclaims that synthetic UV filters are dangerous,
only permitting ZnO and TiO2, the International Agency for Research
on Cancer has in the meantime declared TiO2 to be a known human
carcinogen; plus, synthetic ZnO is the only ZnO used since its natural
ore only exists with lead.
How far can this go?13 Do natural or organic cosmetics impart real
benefits or are they just another marketing fad? As the economy in
the United States declines, it appears that consumers are still spending
money for organic foods but are foregoing higher priced organic personal
care products.
This column is titled “Caveat Emptor,” which means “let the buyer
beware.” This column also calls to mind a quote by David Hannum,
among others, that states: “There’s a sucker born every minute.” In
this author’s opinion, that is what keeps these products on the store
shelf.
16
Organic and Natural: Caveat Emptor

References
1. DC Steinberg, Ingredient Review: Animal vs. Vegetable, A Continuing Controversy, Skin Inc.
11(3) 58–62 (Apr 1999)
2. Natural Health Products Regulations, Health Canada Web site, available at www.hc-sc.gc.ca/
dhp-mps/prodnatur/legislation/acts-lois/prodnatur/index-eng.php (Accessed Feb 4, 2009)
3. Report and Recommendations on Organic Farming, USDA Web site, available at http://nal.
usda.gov/afsic/pubs/USDAOrgFarmRpt.pdf (Accessed Feb 4, 2009)
4. Ibid Ref 3, pp 13
5. Ibid Ref 3, pp 16–17
6. National Organic Program, USDA Web site, available at www.ams.usda.gov/nop (Accessed
Feb 4, 2009)
7. ATTRA Web site, National Sustainable Agriculture Information Service, available at www.
attra.org (Accessed Feb 4, 2009)
8. Illustrative “Positive List” of Ingredients, Natural Products Association Web site, available at
www.naturalproductsassoc.org/site/DocServer/Natural_Ingredients_List.pdf?docID=7341
(Accessed Feb 4, 2009)
9. OASIS draft document, available at: www.oasisseal.org (Accessed Feb 4, 2009)
10. California Organic Products Act of 2003, California Department of Food and Agriculture
Web site, available at www.cdfa.ca.gov/is/docs/copa2003.pdf (Accessed Feb 4, 2009)
11. Ibid Ref 9
12. Round One Legal Victory for Organic Consumers and Dr. Bronner’s against “Organic
Cheater” Personal Care Brands and Certifiers, Organic Consumers Association Web site,
available at www.organicconsumers.org/articles/article_15126.cfm (Accessed Feb 4, 2009)
13. 100 Percent Pure Web Site, available at www.100percentpure.com/fruitpigmentedintro.
html (Accessed Feb 4, 2009)
 CHAPTER 3

Skin Care
Art Georgalas

When formulating skin care with natural ingredients the first question
to ask is: With which definition of natural will the product conform?
The definition might be significantly different for the general public
than for consumers following lifestyles of health and sustainability
(LOHAS) philosophies. However, one may wonder what even these
purist consumers know about the myriad of natural and organic
certifications out there.This author would venture that most consumers’
identification for natural products would be analogous to Chief Justice
Stewart’s definition of obscenity—i.e., “I know it when I see it.”
While market research firms specialized in this market have
undoubtedly conducted surveys to understand what consumers view
as natural, the current picture is likely quite variable. When, if ever,
consumers come to a general consensus and accept one or more of
the various competing natural and organic standards, formulators can
follow those standards; but right now there are simply too many.

Approaches to Natural
Should the formulator choose ingredients from the multitude given
the Ecocert imprimatur, or choose those on the Natural Products
Association’s list of 800+ acceptable materials? Or should the formulator
instead avoid ingredients found on the Whole Foods list of nearly
400 unacceptable ingredients? Then there are the criteria set forth by
NaTrue or the National Sanitation Foundation/American National
Standards Institute (NSF/ANSI);1 the European cosmetics standards
working group, also known as the COSMOS consortium;2 as well as
the Organic and Sustainable Industry Standards (OASIS) industry
group in the United States.3 Formulators may just want to follow

17
18
Skin Care

the guidance of renowned expert Ken Klein and use only materials
composed of the first 92 naturally occurring elements. Again, who
defines what’s natural?
Further, official governing bodies provide little more guidance. For
example, the US Food and Drug Administration (FDA) gives no formal
definition for natural except to state that natural ingredients come
from natural sources. Regarding foods, the “FDA has not developed a
definition for use of the term ‘natural’ or its derivatives,”4 but a product
is considered a natural food when it contains no artificial or synthetic
ingredients and is only minimally processed according to the 2005
food labeling guidelines.
Verbiage in the European Union’s (EU) REACH regulation states,
“A naturally occurring substance is such [that is] unprocessed, or
processed by manual, mechanical gravitational means; by dissolution
in water; by flotation; by extraction with water; by steam distillation;
or by heating solely to remove water, or which is extracted from air
by any means.”5
The International Organization for Standardization (ISO) has issued
vocabulary for natural aromatic substances in ISO 9235:1997, developed
by the essential oil technical committee (TC) 54, and is currently
working on ISO/NP 16128, “Cosmetics—Technical definitions and
criteria for ‘natural’ and ‘organic’ ingredients and products,” which is at
the approved new project stage for ISO TC 217: Cosmetics. Perhaps
this is what Julie Tyrrell of NaTrue is referring to on the group’s website
when she says, “The criteria for ‘natural’ claims should be finalized in
the second half of 2011 and become operational from 2012 based on
legislation in EU Parliament Article 20 that restricts false claims for
cosmetics.”6

At the Bench: Lipids and Proteins

When formulators finally get to the bench to begin building natural
skin care products, they can begin with the basic ingredients for
emulsions: emollients, emulsifiers, humectants, thickeners, preservatives
and other stabilizers, colors and fragrance. By focusing on these key
components, one can identify candidates from their compendium of
natural ingredients. Skin care emollients are generally easy since there
are many to choose from, although they consist primarily of the natural
 19
Chapter 3

triglycerides—i.e., fatty oils and butters. Add to this jojoba oil, strictly
speaking a liquid wax ester, and squalene, a triterpene precursor of the
sterol backbone distilled from olive oil as the major unsaponifiable
liquid lipid and the basic ingredient list is all but exhausted.
Oxidatively unstable squalene becomes the elegant branched chain
natural hydrocarbon squalane upon hydrogenation, a chemical process
that is allowed in many certification schemes. Of course the question then
arises: Is this truly natural? Other, lighter hydrocarbon components can
be extracted by fractional distillation from natural oils, allowing for the
adjustment of feel with mixtures of these oils, butters and other lipids.
In general, lower molecular weight and less polar oils with branching
and unsaturation give a lighter feel. Unsaturated oils may be challenged
by oxidation leading to potential rancidity.
Considering the emulsification mechanism itself, the formulator
might ask: What does nature do? How are stable oil and water systems
established in nature? Nature works at a molecular level to produce the
results observed macroscopically. Tiny, subcellular nanofactories churn
chemicals out one molecule at a time that are then harvested by industry
in bushel baskets and stainless steel vats. For instance, the olive oil that
consumers serve at the dinner table begins as single triglycerides produced
by the olive tree’s lipid synthesis pathway.
The stabilization of these two-phase systems in nature usually involves
complex combinations of lipids and proteins. Some commercially
available natural emulsions include oleosomes—lipid bodies in oil seeds
such as safflower that stabilize vegetable oil droplets for seed storage
by coating them in oleosin protein. Mammalian milk is also stabilized
by proteins, among which are caseins—one of the major milk protein
groups present as micelles that disperse milk fat.7
In addition, plant latex, found in more than 20,000 species including
guayule,milkweed,poinsettia and many Euphorbiaceae and other botanical
families, is stabilized in laticiferous (milk-forming) systems with the help
of proteins plus polar lecithin lipids and other components. Studies8 of
the Hevea species, the chief rubber-producing plant, show an adsorbed
sheath of protein on the surface, stabilizing the particles of isoprenoid
oils that comprise rubber’s source hydrocarbons. This protein gives the
oil droplets electrophoretic mobility, i.e. a zeta potential, and stabilizes
them via surface electrostatic charges. In fact, many proteins are known
20
Skin Care

to have surfactant properties based on the relative hydrophobicity of their

amino acid side chains and ionizable groups, a major factor in governing
their tertiary structure. Even relatively small hydrolyzed proteins have
surface activity that can contribute to emulsion stabilization. Formulators
should look both inside and outside of the cosmetic buyer’s guide for
proteins to assist in the natural stabilization of dispersed systems.9
If one allows for simple kitchen chemistry processes such as
saponification in the development of natural products, a range of soap
surfactants based on vegetable oils are also available, most commonly
coconut, palm kernel and soy. Use of the strongly alkaline amino acid
arginine in the free base form can be an unusual natural alternative to
simple mineral alkali or ammonia for neutralization, replacing the much
maligned triethanolamine (TEA).10 In addition, waxes such as beeswax
and candellila can supply naturally occurring free fatty acids for soap
formation since both have acid values near 20; in fact, one company
reports that a certified organic emulsion can be prepared using the US
Department of Agriculture’s (USDA) NOP beeswax.11
Other natural amphiphiles that can be combined or used individually
include the phospholipid lecithins and lanolin, the wool wax-based
mixture of sterol esters, plant sterols and saponins, as well as a range
of commercial plant sterol and triterpenoid glycosides extracted from
soapwort and agave.
Formulators should note that lecithins can have a varied hydrophilic-
lipophilic balance (HLB), depending on the degree of hydrolysis
and extraction methods, which can be useful for both o/w and w/o
emulsions. Unmodified sterols are exclusively w/o stabilizers whereas
the saponin glycosides, as their name implies, act like soaps and are
used more for foam generation.

Carbohydrates
Natural thickeners and stabilizers from the carbohydrate group of
polymers include many of the plant gums of microbial, algal and vascular
plant origin. These gums modify the texture and flow properties of
emulsions and add to their physical stability. Xanthan gum is a mainstay
of food emulsion preparation and is one of the few ingredients named
in the USDA’s list of allowed additives to organic-certified processed
foods. It imparts the shear thinning rheology with significant yield
 21
Chapter 3

value necessary to give creams and lotions shelf stability with desired
feel at acceptably low use levels of a few tenths percent.
Additional vegetable gums having varying degrees of emulsification,
stabilization and viscosity control include tragacanth, scleroglucans,
guar, locust bean, carageenan and the alginates, many of which
demonstrate synergy, suggesting trials of varying mixtures. Simple
insoluble cellulose itself also has been used in the form of citrus fibers
and microcrystalline cellulose. Another soluble complex carbohydrate
for dispersion enhancement and reduced, more homogeneous emulsion
particle sizes is galactoarabinan from the Larch tree. Further, naturals
of the mineral variety including swellable clays such as bentonite are
useful for their water-structuring ability, forming a hydrated “house
of cards” on high shear dispersion. They are also especially effective in
combination with natural gums.

Emulsion Construction
The three primary plant metabolite groups described, i.e. lipids,
proteins and carbohydrates, provide the scaffold and building blocks
for emulsion construction. Some of the starting materials for these
polymers also function as humectants in finished products, notably
glycerol and amino acids such as pyrrolidone carboxylic acid (PCA)
and sugar alcohols such as sorbitol. From the range of secondary plant
metabolites identified, mostly polyphenols and terpenoids, the ancillary
components of emulsions—colors, fragrances and preservatives as well
as some botanical actives, are sourced; botanical actives will be addressed
in a future column.
When nature-derived materials are difficult to obtain, nature-
identical compounds can be synthesized that function virtually the
same—as long as they are not chiral compounds and they are sufficiently
purified. The NaTrue organization, for one, goes to great lengths to
identify the nature-equivalent preservatives they allow,12 including
such organic acids as sorbic, benzoic, salicylic and dehydroacetic and
their salts as well as benzyl alcohol.
Allowed organic cosmetic colorants, as listed in the US Code of
Federal Regulations (CFR) 21, part 73, include annatto orange-red
and beta-carotene, both yellow-orange, oil-soluble carotenoids, as well
as carmine, the red polyphenol pigment derived from carminic acid
22
Skin Care

from the cochineal bug. It should be noted that many nature-derived

food colorants such as beet extract are only specifically approved for
foods, not cosmetics.
To fragrance the emulsion, numerous natural flower and fruit
scents are available. From this author’s limited experience in fragrance,
chamomile essential oil is suggested as a good starting scent since
it works at low levels to mask many base odors with a pleasant and
persistent floral note. Natural fragrancing is an art that requires an
expert to achieve the right result but suffice it to say it is quite possible
to naturally fragrance most products the formulator may envision.

Conclusion
Overall, formulators may limit their range by choosing to go truly
natural; however, with some background information and a good
deal of experimentation, a variety of effective and aesthetic skin care
emulsions can be formulated. When the ingredient range is expanded
to naturally derived and nature-identical compounds, the formulator’s
palette expands to an even greater variety. In either case, hopefully these
strictures placed on formulators will engender innovation rather than
stifle creativity in the development of natural products with greater
benefits for the end user.

Lab Practical: Using Naturals

• Natural materials have more • Naturals can be more heat/
microbes, and microbial limits for processing sensitive. Formulators
food products are sometimes higher should be aware of how heat,
than cosmetics. Be sure to check shear and order of addition affect
and control the microbe content. the final result and formula
reproducibility.
• Natural materials have a wider
variability. Specifications should
be set and supplies should be
screened critically.
• Naturals have more natural color
and odor. This should be considered
when setting formulated product
specifications and choosing
fragrances and masking agents.
 23
Chapter 3

References
1. www.nsf.org/business/newsroom/articles/0903_n3_nsf305.asp
2. www.cosmos-standard.org/docs/COSMOS-standard-final-jan-10.pdf
3. www.oasisseal.org/OASIS_Standard_100_draft.pdf
4. www.fda.gov/AboutFDA/Transparency/Basics/ucm214868.htm
5. http://guidance.echa.europa.eu/docs/guidance_document substance_id_en.pdf
6. www.natrue.org/articles-news/read/article/new-legislation-in-europe-to-set-an-end-
togreenwashing/
7. Food Chemistry, 3rd edn, H-D Belitz, W Grosch, P Schieberle, eds, Springer-Verlag: Berlin
(2004) pp 515
8. J Bonner and AW Galston, The Physiology and Biochemistry of Rubber Formation in
Plants, The Botanical Review XIII(10) 543–596 (Dec 1947)
9. XQ Han, Natural raw materials and enzymatic modification of agricultural by-products for
protein-based surfactants, in Protein Based Surfactants, ch 2, I Nanna and J Xia, eds,
Marcel Dekker, New York (2001) pp 35–36
10. Arginine, company data sheet, www.ajiaminoscience.com/products/manufactured_
products/l-amino_acids/L-Arginine.aspx (2007)
11. 90% Organic cream formulation, company website, www.kosterkeunen.com
12. www.natrue.org/fileadmin/natrue/downloads/Criteria_EN_1.9_FINAL.pdf
(All websites accessed Dec 7, 2010)
 CHAPTER 4

Hair Care
Art Georgalas

Today, hair care formulators aiming to formulate for the natural market
are in a quandary as the performance of modern products is driven
more and more by the use of innovative new synthetic materials.
The bench chemist witnesses the weekly arrival of new iterations as
manufacturers graft one functionality onto another to try to outdo
the competition. Cosmetic chemists cannot seem to get enough of
different silicone copolymers, acrylate cross polymers, quaterniums,
polyquaterniums and syndets—and whatever hybrids the organic
chemists can create—since high performance is generally imagined
to require high-tech ingredients.
However, some formulators march to the beat of a different
drummer, guided by a more natural rhythm, so their ingredient choices
may be more restricted. Of the raw materials essential for advanced
hair formulas, the two major types that are problematic for natural
recipes are polymers and surfactants. This is not because they do not
exist in nature but because formulators constrain themselves within
the boundaries of what is viewed as acceptable in formulas labeled as
natural. Regardless of which certifying organization is used to guide
formulating choices, performance should not be sacrificed for a natural
certification. This dictum from marketing and management holds sway
in most companies unless a product line raison d’etre overrides it.

Naturals Guidance
While the industry is not yet at the point where one certifying body
has come to the forefront, there seems to be a consensus of do’s and
don’ts among them. Lists of acceptable and unacceptable materials are
generated based on safety and environmental concerns. In addition,

25
26
Hair Care

certain chemical and physical processes may be given the imprimatur

of that organization in order to display their logo. Under all natural
and organic cosmetic standards, the agricultural practices of irradiation
for sterilization and the use of sewage sludge fertilizer, or employment
of genetically modified organisms, are as universally forbidden as they
are with the original farm products. Further, some chemical processes
including ethoxylation are universally restricted, while some processes
such as hydrogenation and esterification are generally accepted.
Ecocert: Many formulators and raw material suppliers have jumped
on the Ecocert bandwagon. This may be because Ecocert led the way
initially, thus the volume of materials available to formulators under
this certification standard is significantly larger than others. But even
when Ecocert-approved cosmetics reach store shelves, many consumers,
including those familiar with natural and organic certifications, will
scratch their heads and wonder how many of the “chemical-sounding”
ingredients listed on the label are natural.To paraphrase another cliché or
platitude, natural is in the mind of the beholder. It’s all about perception;
consumers are put off by chemical names, and INCI nomenclature does
not always help in this respect—in some cases, baffling even chemists
about what chemicals are actually contained in the product.
COSMOS: The Cosmetics Organic Standard (COSMOS)1
in Europe arose as a consensus among six national organizations,
including Ecocert. This group published a final rule in January 2010
that accommodates different levels of ecotoxicology for different
degrees of biodegradability—a fairly rational way to measure relative
environmental risk. The greater the aquatic toxicity, up to a maximum,
the more completely the compound must biodegrade. Conversely,
the lower the toxicity, the less biodegradable the compound must be,
within limits. Restricted compounds that persist in the environment,
that are not biodegradable, or that are bioaccumulative, i.e., retained
in an organism’s tissues, are prohibited.
NaTrue: NaTrue, another European natural products certifier,
recently announced2 it will form a harmonized natural standard in
collaboration with NSF International,brokered by the Quality Assurance
International (QAI) organization.3 QAI has taken a lead in promoting
the NSF/ANSI 305 standards that it administers and is proactive in
providing education for these standards. NaTrue’s standard states that
 27
Chapter 4

any detergent surfactants used must be completely biodegradable in

accordance with the European Commission’s Regulation on Detergents;
however, other materials were not specifically addressed as recently as
early February 2011.4
USDA: In the United States, natural product guidance was recently
complicated by the addition of the new US Department of Agriculture
(USDA) category of “biopreferred,” i.e. biobased fabricated and
formulated products.
Such products are distinctly different from products certified as
organic at one of the four levels by the National Organic Program
(NOP). Both of these certifications were promulgated by the USDA.
The latter, USDA Organic, was developed to certify agricultural
products, clearly the domain of USDA, while the former was initially
developed to drive federal procurement practices in a more sustainable
direction. This more recent biopreferred standard now anoints a wide
variety of consumer products, including personal care items such as
hand cleansers, sanitizers, lip products and more recently, hair care, as
presumably more sustainable for the environment.
To be designated as biobased, a consumer product must simply
meet the requirement for what portion of its content is derived from
a biological origin. Percentages for each consumer category varies
extensively: carpets 7%, towels 12%, glass cleaners 49%, lip products
82%, shampoos 66%, conditioners 78%, etc.5 The jurisdiction here
appears to span several agencies including the US Food and Drug
Administration (FDA), the US Environmental Protection Agency,
and the US Consumer Product Safety Commission. With this new
biopreferred standard, the USDA likely does not imagine it could be
opening another Pandora’s box as it did with the NOP certification
since this standard was developed for farm and derivative food products
and is therefore difficult to apply to personal care ingredients and
products—hence the promulgation of the aforementioned NSF/
ANSI 305 standards for personal care products containing organic
ingredients.
The personal care industry is aching for ways to market its products as
green—whether they are truly sustainable, milder to the skin, or simply
derived from natural origins. Therefore, the new biopreferred standard
presents marketers with a unique product positioning especially if there
28
Hair Care

is a government agency that sanctions the claim because even with the
continued antigovernment rhetoric in the media, consumers still trust
government agencies as a credible arbiter of advertising claims.

At the Bench
From a pragmatic perspective, this column aims to address what materials
consumers may accept and product developers can use to formulate
natural hair care products. Most hair care products fit into what could
be considered a holistic product paradigm, meaning the whole product
itself delivers consumer benefits.This is different from the drug delivery
paradigm for personal care formulas, wherein a defined set of actives
such as sunscreens, antioxidants, anti-acne and anti-aging materials,
etc., deliver the desired benefits. Antidandruff shampoos as well as,
arguably, permanent waves or hair colorants also fall into this latter
category. In this paradigm, the active ingredients perform a function
and the surrounding product is an optimized vehicle or package that
carries those goods to the “address” on the label—i.e., the skin, scalp
or hair shaft—to deliver the desired benefits. The presumed benefits
that accrue from the product feature, in this case the feature of being
natural, are enhanced safety or mildness.
These two product development paradigms are, in a sense, arbitrary
distinctions, with the lines blurred for many products but they do provide
some direction as to the strategies for both goal-directed formulating
on the front end and claim substantiation testing on the back end. By
examining traditional hair care categories for their critical performance
ingredients, formulators can determine what functionality is potentially
available from the use of natural ingredients. Some benefits may be
more difficult than others to provide through natural ingredients since
they were designed into the synthetic molecules in a structure-function
approach.
Shampoos: Shampoos, for all their ancillary benefits, are primarily
meant to cleanse the hair.While the actual amount and type of surfactant
necessary to promote the roll-up mechanism of soil and oil removal
from fibers is quite minimal, the current consumer is looking for copious
foam; in fact, it has been observed that many Asian consumers seek
products whose foam density gives a “white glove” appearance on the
hands during use. Therefore, the industry is compelled to come up
 29
Chapter 4

with natural dense and high foamers. One type of natural surfactant
found in a few plant varieties is the saponins, steroidal glycosides that
readily generate foam in water. They work well for beverages where
they are generally recognized as safe (GRAS) and impart copious foam
to frothy drinks. However, in personal care, the do not impart a lather
as rich as consumers expect from their shampoos at conventional use
levels of less than 1%.
Of course, formulators could hark back to the old fashioned
technology of liquid soaps by using unsaturated vegetable oil fatty acids,
as some pioneers in natural products still do. Soaps made with oils
from unsaturated fatty acids, such as olive, the traditional castile soap
in Renaissaince Spain, or hemp oil, can remain clear in a concentrated
solution. Mixed with coconut to enhance the lather, these liquid soaps
do cleanse well but they experience solubility problems in hard water.
One suggestion would be to add natural chelating agents such as phytate
salts or inositol hexaphosphate to chelate with the divalent calcium
and magnesium ions. However, pH effects may limit the usefulness of
such techniques. Some such commercial agricultural sources include
rice and soy.
If natural certification by bodies such as Ecocert is the standard
followed, the surfactant choice becomes much wider, encompassing
anionics such as acyl glutamates, acyl hydrolyzed protein salts
and even alkyl sulfates and sulfosuccinates; amphoterics like the
cocoamphoacetates; and nonionics in the alkyl glucoside family. Ranges
of mild, high-foaming products can be formulated but the biggest
concern is how to thicken these shampoos effectively and cheaply.
Formulators cannot get away with the conventional salt-thickening
method used in many mass market, dollar-a-bottle shampoo variants
but there are some natural polymers, such as xanthan gum, that can
successfully be used. Work has also been done using magnesium sulfate
(Epsom salts) in combination with fatty amphiphiles such as glyceryl
laurate to thicken glutamate cleansers by building surfactant association
structures akin to those using the cheaper monovalent salts.
Hair conditioners: Hair conditioners deliver the eponymous benefit
of hair conditioning, but what exactly does this mean? Looking at
how one actually tests hair conditioning—i.e., via tress testing and
half-head salon testing—can provide formulators with answers. In
30
Hair Care

answer to these tests, key conditioner benefits would therefore include

reducing the force necessary to comb through wet and dry hair fibers
as well as reducing the surface charge on hair fibers, in this case excess
negative energy, to reduce electrostatic repulsion and the macroscopic
appearance of fly-away. And what better way to impart these effects than
applying a species that has both a positive charge and a long molecular
chain of low intermolecular attractive forces, such as hydrocarbon or
silicone polymers. In the conditioner arena, these would be cationic
surfactants, exemplified by quaternary ammonium salts or quats, but
these are severely restricted by most private natural certifiers.
However, formulators can look to amino acid derivatives as a way
out of this dilemma. Two examples are PCA ethyl cocoyl arginate and
brassicyl isoleucinate esylate, which can provide hair conditioning. Like
their parent compounds, i.e. proteins and amino acids, they are naturally
amphoteric. Thus, the pH of the system governs their functionality, as
dictated by their isoionic points. Although not promoted as heavily as in
the past, the acyl derivatives of amino acids and proteins may eventually
be the shining light of naturals for hair treatments—both for cleansing
and conditioning. Combinations of vegetable oils and jojoba oil and
other emollients also find their way into hair conditioners, as well as
lecithin, usually of soy origin, all of which are available in NOP organic
versions. These materials have some substantivity to the hair cuticle,
virgin hair more than damaged, and can serve as a friction-reducing
film on the hair shaft. These ingredients are also seen in conditioning
shampoos and body washes, although most of their conditioning effects
are washed down the drain.
It is important to remember that when looking at natural derivatives,
some simple naturals can be derived via synthetic routes. Glycine, the
smallest amino acid, for example, is abundant in nature but it is difficult
to distinguish the natural from the synthetic; having no substituent on
the carbon between the carboxyl and amine groups, it does not have
positive and negative optical isomers as all the other proteogenic amino
acids do. One cannot tell the feedstock source simply because it is not
chiral. The same is also true for glycerol-based derivatives; there are
both synthetic and naturally derived versions from vegetable oils and
fats, as well as natural biological building blocks of animal origin, so
formulators may want to ask their suppliers to certify the source.
 31
Chapter 4

Further, the same can also be an issue also with preservatives and
fragrances. Some nature-identical preservatives are allowed under
certain certification systems, e.g. NaTrue, but are only allowed under
NSF/ANSI 305 if they are derived from non-petrochemcial feedstocks.
Fragrance also can have natural roots, and many flavor and fragrance
houses can provide natural fragrances. Combinations of related essential
oils, many available as NOP Organic, can form pleasant compositions
but professionally developed natural fragrances are better suited to most
products. Aromatic extracts of fruits and flowers are also available if
that is the chosen marketing direction.
There are, however, severe limitations in relation to color since many
colors extracted from plants are not approved for cosmetic use, even
if they are approved for food and drug use. The soluble dyes that can
be used include caramel, annatto, beta-carotene and carmine from the
Mexican cochineal insect.6 Formulators are not likely to use inorganic
pigments such as titanium dioxide, iron oxides or chrome oxides, which
go into color cosmetics, in hair care. There is also the unique copper
chelate disodium EDTA-copper, which is only approved for use as a
shampoo colorant but unfortunately it is not natural.
Styling aids: Styling aids and hair sprays depend upon the film-
forming or simple adhesive properties of their dry residues. Fiber bundles
typically are either coated with a solution of polymer or sprayed with
a mist of droplets that “spot-welds” the fibers together, as numerous
hair chemists have metaphorically quipped, to affect the style and
freeze it in place. Such polymers can come from natural sources–either
carbohydrate-or protein-based. The drawback here is their reduced
humidity resistance. Proteins such as corn zein and carbohydrates such
as plant gums, e.g. acacia or Arabic gum and pectin, currently are used.
In addition, a unique thickening combination of xanthan and konjac
mannan carbohydrates reportedly yields clear gels, and potentially
could be one alternate to the synthetic polyacrylate carbomer in making
clear gels.7 Finally, to modify flexibility and reduce flaking, glycerol
may be considered as a universal plasticizer and other glycols, such as
fermentation-sourced 1,3 propylene glycol, can be used.
In addition, besides being a good cosolvent in water-based products,
ethanol at >15% can be a fail-safe preservative in hair sprays but readers
should note the importance of microbial challenge testing the final
32
Hair Care

formula in all cases. The formula pH and water activity can also provide
strategies to aid in preservation with low pH levels where feasible.
The use of water activity control as a strategy has been suggested by
Steinberg,8 as water activity can have significant bacteristatic effects
in highly concentrated systems like shampoos but yeast and mold will
still be problematic. An instrumental determination of water activity
is therefore essential.

Conclusions
A full compendium of natural ingredients for hair care would be difficult
to compile at any point in time as more materials are being invented
or their utility in personal care discovered every day. Many will gain
approval by Ecocert, QAI, NaTrue or the Natural Products Association
and become additions to the natural formulators’ palette. A complete
volume would be too extensive to catalog here but if product developers
simply want to work with Mother Nature as she provides, the palette
will be limited to nature-made metabolite, e.g. proteins, lipids and
carbohydrates that were found on farms, in fields and in oceans before
the advent of organic synthetic chemistry. Otherwise formulators can
choose a natural certifier and consistently apply their guidelines.
The future will unfold with new ingredients for natural formulations
as green chemistry advances yield new functional ingredients. This
consumer need for natural and sustainable technologies will not
stifle creativity but instead add a new direction to innovation. The
bench chemist should monitor activity in the regulatory arena as the
overlap between the FDA, USDA and Federal Trade Commission
jurisdiction is worked out; in fact, the Personal Care Products Council
has established an Organic/Natural Committee to keep abreast of these
developments.9 In addition, on both the domestic and international
fronts, formulators should follow the non-governmental organizations
that are promulgating natural standards as these are evolving as well.
Good luck!
 33
Chapter 4

References
1. www.cosmos-standard.org
2. www.natrue.org/articles-news/read/ article/nsf-international-partners-with-natrue-to-
develop-first-american-national-standard-for-natural-cosme/?no_cache=1
3. www.qai-inc.com
4. www.natrue.org/fileadmin/natrue/downloads/ Criteria_English_Version_2.pdf
5. www.biopreferred.gov
6. www.accessdata.fda.gov/scripts cdrh/cfdocs/ cfcfr/CFRSearch.cfm?CFRPart=73&showFR
=17
7. PA Williams et.al. Fluid gels based on natural polymers for cosmetic applications, in
Polymers: The Pathway to Versatile Technology, A.J. O’Lenick Jr, ed, Allured Books, Carol
Stream, IL USA (2011)
8. www.cosmeticsandtoiletries.com/formulating/ ingredient/preservatives/112901129.html
9. www.personalcarecouncil.org/newsroom/20100608
(All websites accessed on Feb 23, 2011)
 CHAPTER 5

Green Formulations:
Not All Components
Are Equal
A. Cristoni, G. Maramaldi and C. Artaria

Nature has always been a generous source of wellness for mankind.

Since ancient times, the healing properties of various plants have
represented the first medicines and cosmetics. The study of tribal and
native traditions has many times laid the foundation to successfully
isolate new and effective cosmetic active ingredients.
Modern functional cosmetics represent valid alternatives to
dermatological treatments for preventing the signs of aging, and the
plant kingdom can provide many active compounds to counteract those
signs, including: skin tone and elasticity loss,1 wrinkle formation,2,3
capillary fragility,4 and increased skin sensitivity.5
However, natural ingredients require specific expertise not only in
their research, but also in their analysis and formulation. The quality
of botanical extracts, which needs to be standardized, is a crucial point
for the quality of the final formulation, among others.

Standardized Extracts
To demonstrate the efficacy and reproducibility of a botanical active’s
variables in a cosmetic formulation, the consistency of the natural extract
is a key factor. Reproducibility is also important when considering
regulatory aspects aimed to assess the toxicity and tolerability of a
cosmetic ingredient.

35
36
Green Formulations: Not All Components Are Equal

The consistency of a botanical extract is relatively achievable when dealing

with a pure product such as escin or esculin from Aesculus hippocastanum;
glycyrrhetinic acid from Glycyrrhiza glabra; or with a dry extract highly
purified up to the isolation of a unique class of molecules such as triterpenes
from Centella asiatica, flavolignans from Silybum marianum, polyphenols
from Vitis vinifera and anthocyanins from Vaccinum myrtillus.
In some cases it is convenient to purify a unique active principle
up to 80–90%, whereas in other cases a complete extract of numerous
different compounds may be more active than the single isolated
molecules. Research in this field is complex and involves not only the
identification of the active principle, it also aims to investigate the
interactions between the active ingredients and other molecules present
in the phytocomplex.6
Different technologies or manufacturing methods may be necessary
for different types of extracts but the main parameters include:
composition constancy, stability, microbe counting and the limitation
of residual solvents and pesticides.These parameters should be carefully
monitored as required by health authorities.
The crucial stages of the process include, as a rule of thumb, choosing
the raw material first, followed by extraction and purification. While
the choice of extraction solvents in the preparation of standardized
extracts is an important factor for the finished product quality, the
choice of the raw material is pivotal.
From a practical point of view, the botanical source must be
thoroughly checked before extraction, as far as botanical and chemical
aspects are concerned (see Table 1).
The next phase is the preparation of the extract in standardized
conditions, which requires the steps described in Table 2.
Extracts prepared according to the criteria in Tables 1 and 2 can be
classified as standardized. Although some of these parameters appear
obvious, they can be difficult to achieve. For instance, all the botanical
materials must be gathered within in a short, specific time period then
stored after analysis to avoid the degradation of the active ingredients.
In some cases, crops from homogeneous, genetically selected strains
of plantules or seeds are grown in controlled agrochemical conditions.
Cultivation can be a solution for plants whose harvesting in the wild
could endanger the species’ survival.
 37
Chapter 5

Table 1. Raw material characteristics and preliminary

analysis
Parameter Action to control the parameter
Part of plant Botanical identification, macro and
microscopic analysis, control of
sophisticant and contaminant presence
Harvesting Careful selection and control of the region,
area and harvesting period
Storage Control of harvesting, drying and storage
conditions
Active principle content Chemical analysis in order to adequately
mix different batches
Heavy metals and pesticides Chemical analysis in order to discard the
polluted batches

Table 2. Standardization and analysis

Parameter Action to control the parameter
Extraction Follow a defined method, with specified
grinding, solvent, temperature, pressure
Concentration (if necessary) Follow defined procedures, with analysis at the
key steps of production
Chemical analysis Control of the content in active principles, and
control of the presence of impurities, heavy
metal, pesticides and residue solvents
Microbiologic analysis Control of the microbial presence and of
pathogen absence
Stability Periodical analysis, in order to confirm the
extract quality

Safety Issues
From a safety standpoint, the quality of a botanical extract needs to be
carefully evaluated both on the raw material itself and within the final
formulation—whether it is intended as a topical or oral cosmetic.
Recent evaluations6 have in fact demonstrated that, besides labelling
claims, only a small percentage of commercial products had chemical
profiles that complied with their declared content.This research focused
38
Green Formulations: Not All Components Are Equal

on the commercial preparation of

bilberry extract purchased from
different countries.
The HPLC method developed
and validated in Indena research
laboratories was optimized to
analyze the content of anthocyanins,
the polyphenols that bestow
beneficial properties to bilberry
extracts. (see Figure 1). Figure 1. Case study: Bilberry

Bilberry: A Case Study

Chemical and pharmacological studies of bilberry extract have identified
anthocyanosides, also known as anthocyanins, as the major components
responsible for the biological properties of bilberry. They have been
demonstrated to possess a broad range of activities, including: antioxidant
activity,7,8 antiplatelet aggregation,9 phosphodiesterase inhibition,10
interaction with collagen, phospholipids and proteoglycans,11 a
relaxing effect on vascular smooth muscle,12 and arteriolar vasomotion
stimulation.13
Bilberry is exploited for its capacity of reinforcing the blood vessel
wall: it strengthens capillary walls by linking with the endothelial
cell membranes, thus increasing their resistance and reducing
capillary permeability by stimulating the synthesis of perivascular
tissue constituents. In topical applications, these properties are
particularly useful in case of heavy legs or couperose, where
microcirculation improvement and capillary tone are crucial to the
relief of disorders.
According to Indena research, 6 40 different preparations
containing bilberry, marketed under 24 different brands, were
collected in four different countries for analysis. The samples came
from the United States, Italy, Japan and Malaysia. The labels indicated
three different types of preparations:
• bilberry extracts with a 36% anthocyanin content;
• bilberry extracts with a 25% anthocyandin content; and
• bilberry extract without content indication.
 39
Chapter 5

The analytical work based on HPLC revealed that 25% of the

tested products had a different profile from a typical bilberry profile
of either an anthocyanins content at 36%, or anthocyanidin at 25%. In
fact, 10% did not even contain the active anthocyanins molecules and
only 15% were found to possess a sufficient quantity of anthocyanins
to be effective, as proven by clinical trials.
The fact also emerged that only 65% of the tested commercial
products sold in the United States contained a quantity of ingredients
matching the label claim.
Regarding the issue of appropriate labelling, a recent review14 of the
described analytical work highlighted some of the confusing information
provided to the final consumer. For instance, the identity of the botanical
species Vaccinium myrtillus, the only species with a sound tradition of
medicinal use and well-documented by the scientific literature, is reported
in 60% of labels, whereas the genus Vaccinium comprises over 450 species
and the part of the plant is indicated on 70% of labels.
It needs to be taken into consideration that different parts of the same
plant may have different biological properties.Bilberry leaves,for instance,
have been traditionally used as a remedy for diabetes.This is not surprising
since bilberry leaves, although they contain few anthocyanosides, are rich
in tannins. The active ingredients are not defined on the labels, making
it difficult for the consumer to understand the differences between the
products. The quantity it contains in either milligrams or as a percentage
concentration also is not listed.

Conclusions
Callaghan observed15 that when the cosmetic industry wants to
demonstrate how supplements can benefit the skin, it needs to
be innovative and address questions relating to safety, toxicity,
bioavailability, molecule interactions that control biological function,
and age-related physiology.
The commercial preparations that have been analyzed recently
highlight differences in content and variations between labelling and
actual concentration, revealing a scenario of the herbal preparations
that require the development of reliable analytical methods to analyze
finished formulations.
40
Green Formulations: Not All Components Are Equal

It is important for formulators to be aware of the different qualities

of natural extracts that may, by all means, affect the quality of the final
formulations.

References
1. FR Maffei, M Carini, R Stefani, G Aldini and
L Saibene, Anti-elastase and anti-hyaluronidase
activities of saponins and Sapogenins form Hedera helix, Aesculus hippocastanum
and Ruscus aculeatus: Factors contributing to their efficacy in the treatment of venous
insufficiency, Arch Pharm 328 720–724 (1995)
2. RF Maffei, M Carini, G Aldini, R Stefani,
E Bombardelli and P Morazzoni, Free radical scavenging action and anti-enzyme activity
of proanthocyanidine A2, a new polyphenol from Aesculus hippocastanum L., 18th IFSCC
Congress, Venezia, Italy (Oct 3–6, 1994)
3. E Bombardelli, M Spelta, LR Della, S Sosa and A Tubaro, Aging skin: Protective effect of
silymarin phytosome, Fitoterapia vol LXII
2 115–122 (1991)
4. E Bombardelli, P Morazzoni and A Griffini, Aesculus hyppocastanum L., Fitoterapia vol.
LXVII 6 483–511 (1996)
5. A Cristoni, F Di Pierro, G Guglielmini, A Giori and P Morazzoni, Soothing activity of
terpenoid fraction of Ginkgo biloba and of its phospholipidic complex, proceedings of 22nd
IFSCC Congress, Edinburgh (2002)
6. C Cassanese, E De Combarieu, M Falzoni,
N Fuzzati and R Pace R, New liquid chromatography method with UV detection for analysis
in anthocyanins and anthocyanidins in Vaccinum myrtillus fruit dry extracts and commercial
preparations, J AOAC Int 90 4 911–919 (2007)
7. R Salvare, P Braquet, Th Perruchot and
L Douste-blazy, in Flavonoids and Bioflavonoids 1981, L Farkas, M Gabòr, F Kàllay and H
Wagner, eds, Elsevier: Amsterdam, Oxford, New York (1982) pp 437–442
8. P Morazzoni and S Malandrino, Anthocyanosides and their aglycons as scavengers of free
radicals and antilipoperoxidant agents, Pharmacol Res Comm 20 suppl 2 254 (1988)
9. P Morazzoni and MJ Magistretti, Activity of myrtocyan, an anthocyanoside complex from
Vaccinum myrtillus (VMA) on platelet aggregation and adhesivness, Fitoterapia 61 13 (1990)
10. C Ferretti, M Blengio, S Malandrino and
G Pifferi, Effect of Vaccinum myrtillus on some phosphodiesterase isoforms, XI Internat Symp on
Medicinal Chem, Jerusalem, Israel (Sep 2–7, 1990)
11. E Bombardelli and SB Curri, Antocianosidi, sostanza fondamentale del connettivo e correlazioni
istangiche, Terapia angiologia 32 117 (1976)
12. V Bettini, F Mayellaro, E Patron, P Ton and
V Terribile Wiel Marin, Fitoterapia 55, 323 (1984)
13. A Colantuoni, S Bertuglia, MJ Magistretti and
L Donato, Effects on Vaccinum myrtillus anthocyanosides on arteriolar vasomotion, Arzneim
Forsch 41 905 (1991)
14. C Artaria, R Pace, G Maramaldi and G Appendino,
Different brands of bilberry extract—A comparison of selected components, Nutrafoods
(2007) 6 (4), pp 5–10
15. T Callaghan, Challenges, opportunities in clinical evaluations of oral beauty supplements,
Cosm & Toil 120 9 (Sep 2005)
 CHAPTER 6

Navigating the
Challenges of Formulating
With Naturals
Lakshmi Prakash, Ph.D., and Muhammed Majeed, Ph.D.

A judicious blend of art and science is critical to creating natural

cosmeceuticals for use in personal care products. The major challenge
is finding ingredients that are compatible with existing formulations.
Aesthetics is a particularly important concern. For example, while
there is much interest in using natural botanical extracts in cosmetic
preparations, a too-dark color, a gritty texture, ingredient instability,
poor absorption of actives, or dispersibility problems could render the
“healthy and natural” ingredient unattractive. Additionally, the safety
and efficacy of natural ingredients need to be established in order to
enable their use in finished personal care products.

Challenges in Innovating
Color issues: Natural ingredients for antiaging skin care are prepared
from botanicals with a long history of traditional cosmeceutical use,
such as skin lightening, skin smoothing and antimicrobial applications,
although the term itself is of recent origin. Botanicals are rich in
phenolic and other pigments including carotenoids, flavonoids
and related compounds, and often some of the healthful properties
of these natural materials reside in the pigments themselves. An
example is turmeric, a culinary spice with a tradition of topical use in
South Asia. The active compounds in this case are the yellow
curcuminoids that also are used as a natural colorant. This brilliant

41
42
Navigating the Challenges of Formulating with Naturals

yellow color, however, does not blend well with currently manufactured
personal care products.The end user is concerned about the unappealing
yellow color staining the skin.
Scientific developments such as extraction processes and
derivatization techniques have enabled a method to extract the mixture
of biologically active curcuminoids from turmeric roots and convert
them into colorless biologically active tetrahydrocurcuminoids. Such
a composition finds versatile applications in personal care products,
particularly in the antiaging category.
Tetrahydrocurcuminoids have been found to efficiently inhibit
protein cross-linking and provide skin-lightening action as well as
provide antioxidant and bioprotectant properties. This discovery is the
subject of a recently granted U.S. patent.1
Tetrahydrocurcuminoids offer additional functional antioxidant
benefits in protecting fat-based compositions from oxidation. In
laboratory studies,2 tetrahydrocurcuminoids were found to quench free
radicals more efficiently than the commonly used synthetic antioxidant,
butylated hydroxytoluene (BHT).
From a safety point of view, the bioprotectant role of
tetrahydrocurcuminoids is further enhanced by its low toxicity, (oral
LD50 is 5000 mg/kg) with a 0.00 irritation score in a skin patch test.3
Turmeric root, the source of tetrahydrocurcuminoids, is listed by the
U.S. Food and Drug Administration (FDA) as an herb generally
recognized as safe (GRAS) for its intended use as a spice, seasoning
and flavoring agent.4
Dispersibility: Botanicals often are difficult to use in formulations
because of their poor solubility or dispersibility in acceptable solvents.
In such cases, the formulator faces a challenging task that sometimes
requires modifications to the formulation process itself. The order of
addition of ingredients, the type of solvents used, temperature and pH
conditions, the nature of the mixing process and several other factors
influence dispersibility.
Boswellia serrata, for example, has been used in the ayurvedic system
of medicine to manage inflammatory conditions (see Boswellia Serrata
in Antiaging).
 43
Chapter 6

Boswellia serrata in Antiaging

Olibanum, the resin from the Boswellia species, has been used as
incense for centuries. Its major use today is as a fixative in perfumes,
soaps, creams lotions and detergents. In India, the gum resin
exudates of Boswellia serrata and has been used in the ayurvedic
system of medicine in the management of several inflammatory
conditions.
Inflammation is considered to be the prime cause in aging, an
inflamed site forming a micro-scar that over time develops into a
wrinkle or blemish. Inflammatory mediators such as leukotrienes and
prostaglandins, cytokines and growth factors target skin texture,
integrity and tone. Containing inflammation at its roots is therefore an
effective antiaging strategy.

The active boswellic acids reside in the gum resin from the tree,which is
a difficult material to formulate, and the gum constituents may irritate the
skin. Natural extract manufacturers have developed efficient extraction
processes that produce a composition rich in boswellic acids in a powder
form. Such an ingredient can be conveniently used in formulations for
soaps, lotions and cosmetic creams as an anti-inflammatory ingredient
(see Formula 1)—however, the powder must be dispersed well during
the formulation process. Optimal proprietary methods for formulation
have been developed after extensive experimentation.
Products tested containing 5% of a standardized extract from the
gum resina did not produce any irritation or sensitization in standard
patch tests.5
Stability issues: Retaining the biological activity of natural ingredients
through raw material preparation, processing, extraction, packaging
and storage presents a myriad of challenges.
Nutrients in natural materials such as vitamins, growth factors,
amino acids, flavonoids, pigments and essential oils are susceptible
to degradation on contact with oxygen or exposure to suboptimal
temperature and pH conditions.
An example is young or “green” coconut water—a reservoir of
nutrients and growth factors. Green coconut water is the liquid
a
Boswellin (INCI: Boswellia serrata extract) is a registered trademark of Sabinsa Corp.
44
Navigating the Challenges of Formulating with Naturals

endosperm of coconut (Cocos nucifera L), which is a refreshing natural

drink in the tropics and traditionally used as a health and beauty aid.
Natural coconut water is rich in proteins, amino acids, sugars, vitamins,
minerals and growth hormones that are essential to promote tissue
growth. Laboratory researchers use the material as a supplement in
media for the growth of plant tissue cultures.

Formula 1.
Cream formulation with Boswellia serrata extract
A. Water (aqua) 59%–60%
Carbomer 0.25%–0.27%
B. Glycerin 4.0 Methylparaben 0.2
Edetate sodium 0.01
C. Cetyl alcohol 3.5
D. Stearyl alcohol 3.5
Stearic acid 6.5
Glyceryl stearate 2.5
PEG-100 stearate 2.5
Isopropyl palmitate 6.0
Vitamin E acetate 1.0
Dimethicone 0.1
Propylparaben 0.1
Vitamin A palmitate 0.1
Ascorbyl palmitate 0.2
E. Boswellia serrata extract 5.0
F. Water (aqua) 2.0
Triethanolamine 0.4
G. Imidazolidinyl urea 0.3
Water (aqua) 1.0

Procedure: Mix A under propeller agitation until dissolved. Add B to A and

blend. Begin heating to 72°C–77°C and continue mixing until completely
dissolved. In a separate container, charge C and add D to C in order. Heat CD
to 72°C–77°C until dissolved. Mix CD with AB, maintaining 72°C–77°C. Add
E to batch under propeller agitation. In a separate container, combine F until
dissolved and mix with batch. Keep mixing until completely dissolved while
maintaining 72°C–77°C. In a separate container, combine G until dissolved and
add to the main batch. Mix and cool to 35°C–40°C and package.

Coconut water is useful in hair care formulations and in topical

preparations to rejuvenate, nourish, condition, soothe and moisturize
the tissues. However, its short shelf life and sensitive nature of the
inherent actives make it difficult to use the material in cosmetic
formulations. A freeze-drying process has been developed to retain
 45
Chapter 6

the activity of coconut water components. The process produced a

light tan-colored powder consisting of coconut water solids that
readily blends into cosmetic preparations. In in vitro irritection
studies, a product formulated with the ingredientb was found to
be non-irritating.
Skin permeation: The efficacy of actives depends upon their skin
permeation capabilities. Selective nutrient absorption by the skin is an
important physical property of the skin. This selective process begins
with the stratum corneum (SC). The function of this barrier is related
to the unique composition of the lipid moiety in the epidermis. The
intercellular lipids mediate transdermal delivery of both lipophilic
and hydrophilic molecules. Research shows that regulating the
composition of intracellular lipids in the skin can increase or decrease
the bioavailability of nutrients.6
Besides the modification of skin lipid composition, there are several
strategies to improve topical nutrient bioavailability. Improvement
can be accomplished by supersaturation of the delivered ingredient.
The delivery formulation also may contain ingredients that decrease the
diffusional (electrostatic) resistance of the lipid bilayer to the passing
molecule. Topical liposome preparations are effective penetration
enhancers for the delivery of biological compounds, probably due to
their role in increasing cell membrane fluidity. In addition, an increase
in blood supply to the skin can enhance absorption of delivered
nutrients.
Historically, a number of chemical-penetration enhancers have been
used to enhance the uptake of actives. These include: solvents such as
dimethyl sulfoxide (DMSO), ethanol and other alcohols; glycols such
as propylene glycol; fatty acids such as oleic acid; and detergents such
as sodium lauryl sulfate, polyoxyethylene lauryl ethers, and chaotropic
agents such as thioglycolate, urea, and mercaptoethanol.
As such, they also have the potential to cause damage to the SC and
to increase the probability of irritation. Most of these agents work by
perturbation of the intercellular lipid bilayers present in the SC.
Therefore, there is a need for compounds of natural origin with
low irritancy and minimal side effects that can be efficiently combined
b
Cococin (INCI: Cocos nucifera (coconut) fruit juice) is a registered trademark of
Sabinsa Corp.
46
Navigating the Challenges of Formulating with Naturals

with nutrients to enhance the uptake and utilization of such active

molecules.
An innovation in enhancing topical delivery of natural actives is
available in the form of a proprietary extract obtained from black pepper
fruitsc, a common culinary spice.
When added in small amounts (0.01%–0.1%) to cosmetic
formulations, tetrahydropiperine, the active principle, enhances
the uptake and delivery of other actives in the formulation. Poorly
absorbed botanicals, therefore, can be made more “bioavailable” with
this ingredient.7
Quality, safety and eff icacy: Herbal raw materials available
commercially as powders and extracts often do not meet global standards
of quality, efficacy and safety.To preserve the authenticity and credibility
of such products, it is important that the ingredients therein contain
adequate amounts of biologically active principles that manifest the
desired biological functions.
Plant materials pose several challenges in standardization. Natural
products are complex matrices with a number of active principles varying
widely in content and type, based on geographical origin, cultivation and
collection practices, and processing and storage conditions. This often
leads to variations in potency, label ambiguity and related problems
in finished cosmetics.
Compositional consistency of botanical extracts in terms of active
principles is the key factor in ensuring potency and sustaining consumer
confidence. Marker compounds are chemicals proven to be characteristic
of botanicals and endowed with validated health benefits. Chemical
fingerprints using chromatography and spectrophotometric methods,
in combination with bioassays, are the accepted methods to ensure the
presence of marker compounds in botanical materials.
A botanical’s active principle may concentrate in a specific location in
the plant and manufacturers often use combinations of plant materials
in preparing finished extracts. Contaminant levels, including heavy
metals, pesticide residues, extraneous matter and genetic modification
aspects also need to be considered. The complexity of these challenges
is exacerbated by mislabeling in the commercial marketplace.
c
Cosmoperine (INCI: Tetrahydropiperine) is a registered trademark of Sabinsa Corp.
 47
Chapter 6

Organic vs. Natural

According to the U.S. Department of Agriculture’s (USDA)
National Organic Program (NOP), the term organic may be used on
product labels when certain conditions are met.1
100% organic:
• This designation may be used for agricultural products that are
composed of a single ingredient such as raw, organically produced
fruits and vegetables and products composed of two or more
organically produced ingredients, provided that the individual
ingredients are, themselves, wholly organic and produced without
any nonorganic ingredients or additives. (Only processing aids
that are, themselves, organically produced, may be used in the
production of these products.)
Organic:
• Products labeled or represented as organic must contain, by weight
(excluding water and salt), at least 95% organically produced raw
or processed agricultural product.
• Up to 5% of the ingredients may be nonagricultural substances and,
if not commercially available in organic form, nonorganic agricultural
products and ingredients in minor amounts (i.e., spices, flavors,
colorings, oils, vitamins, minerals, accessory nutrients, incidental
food additives).
Made with organic ingredients:
• Multiingredient products containing by weight or fluid volume
(excluding water and salt) between 70%-95% organic agricultural
ingredients may be designated as "made with organic [specified
ingredients or food group(s)]." Up to three organically produced
ingredients or food groups may be named in the phrase.

The term natural, according to the National Consumer’s League

(NCL), is not regulated by the FDA as far as the use of the word on
personal care or cosmetic products.2 The FDA’s Office of Cosmetics
and Colors has, however, produced consumer information
regarding the natural claim for personal care products. Products
claiming to be all natural or plant-derived may include more than
just natural ingredients or plant products.

1. Source: National Organic Program (NOP) Web site. Available at: www.ams.usda.
gov/nop/NOP/standards/LabelPre.html. (Accessed Jan. 23, 2006.)

2. Source: Naturally misleading: Consumers’ understanding of “natural” and “plant-

derived” labeling claims, National Consumers League (NCL) Web site. Available at:
www.nclnet.org/naturalsreport.htm#_ednref5. (Accessed Jan. 23, 2006.)
48
Navigating the Challenges of Formulating with Naturals

Authentication of plant materials used to manufacture cosmetic

ingredients is critical. Selecting appropriate extraction and purification
processes is important as this reflects heavily on the quality of finished
extracts. To avoid skin irritation and sensitization, solvent residues and
other contaminant levels in finished extracts should be minimized.

Meeting These Challenges

In the rapidly growing market for natural antiaging cosmetics,
application-oriented product development goes a long way in facilitating
the introduction of traditionally used botanicals into conventional
formulations. The initial challenge is to innovatively transform plant
materials into safe and efficacious ingredients for functional cosmetics.
Once this is achieved, the next step is to comprehensively address
global regulatory issues and nurture consumer confidence through
consistent quality management. Furthermore, in vitro testing methods
for safety and efficacy need to be optimized to facilitate cruelty-free
product development.
Nature provides a plethora of options to support healthy aging.
Blending traditional knowledge with modern science results in
innovative approaches to the effective use of plant-based materials in
contemporary personal care formulations.

References
1. US Patent 6,653,327, Cross-regulin composition of tumeric-derived
tetrahydrocurcuminoids for skin lightening and protection against UVB rays
2. Research Reports 8–13, Sabinsa Corp. (1999)
3. Research Report, Sabinsa (1999)
4. Code of Federal Regulations Title 21, 100.0, 182.10, 182.20
5. Research Report, Sabinsa Corp. (Feb. 2000)
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