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Antimicrobial used as preservatives in cosmetics
By – Mahendra Kumar Prajapati
Ph.D. Scholar
Institute of Chemical Technology, Mumbai
Cosmetics, containing water and organic/inorganic compounds, require preservation against
microbial contamination to guarantee consumer’s safety against potentially pathogenic
microorganisms and to increase their shelf-life.
Preservation strategies:
Chemical
Physical
or Physicochemical.
The most common strategy is based on the application of antimicrobial agents,
Ex: parabens, isothiasolinone, organic acids, formaldehyde releasers, triclosan, and
chlorhexidine.
These chemical agents have different mechanisms of antimicrobial action, depending on their
chemical structure and functional group’s reactivity. Their high concentrations are more
effective from the preservation viewpoint but can be toxic for the consumer, whereas at low
concentrations microbial resistance can develop.
Modification of cosmetic products is due to
➢ Presence of microorganisms (need antimicrobial preservatives-act on microorganisms)
➢ Exposure to atmospheric oxygen (need antioxidant preservatives- suppressing oxidation
and formation of free radicals)
A preservative is a substance of natural or synthetic origin intended to inhibit the development
of microorganisms. Preservatives should have broad spectrum of activity against
microorganism and should be effective for long time (longer than product shelf life and usage
time).
Antimicrobials should prevent microorganism’s adaptation and development of resistance. The
cosmetic products are a nutrient-rich medium that favors microorganism’s growth, which,
thereafter, influences the efficacy of the preservatives.
Amount of antimicrobial agent to be used in a cosmetic is dependent on its role; As active used
in high concentrations (antimicrobial cosmetics) and as preservatives in low concentrations
(most cosmetics)
Other strategies
➢ water activity
➢ pH control
➢ use of multifunctional ingredients
Overview of Cosmetics and Their Microbiological Safety
Definition of Cosmetics
any substance or mixture intended to be placed in contact with the external parts of the human
body (epidermis, hair system, nails, lips, and external genital organs) or with the teeth and the
mucous membranes of the oral cavity with a view exclusively or mainly to cleaning them,
perfuming them, changing their appearance, protecting them, keeping them in good
condition, or correcting body odours”
(1) Cosmetics for personal cleansing (soaps, deodorants, shampoos)
(2) Cosmetics for the skin, hair, and integument care (toothpastes, products for external
intimate care)
(3) Cosmetics for embellishment (perfumes, lip colors)
(4) Protective cosmetics (solar products, anti-wrinkle products)
(5) Corrective cosmetics (beauty masks, hair dyes)
(6) Maintenance cosmetics (shaving cream, moisturizing creams)
(7) Active cosmetics (fluoridated toothpastes, antiseptics)
Cosmeceuticals
Cosmetics + Pharmaceuticals
e.g., retinol, certain bleaching agents, etc have a beneficial effect on skin, also have a clear
biological therapeutic effect.
Cosmetic products with antimicrobial effect
Cosmetic products with antimicrobial effect can be described as preparations with the ability to
provide consumer’s protection against the presence of antimicrobial compounds, having
bactericidal effect.
Products like mouthwashes, skin disinfectants or antibacterial soaps.
The difference between a cosmetic product and a drug lies in the concentration of the active
ingredient in the product (e.g., mouthwash). There is also an unclear distinction between the
definition of cosmetic and dermatological treatment (e.g., acne treatment).
Microbiological Safety of Cosmetic Products
An ideal preservation system (intrinsic or extrinsic) should protect the product from microbial
degradation, both in its original closed packaging until use, and in an open container
throughout its use.
Most frequent microorganisms found in cosmetics comprise Pseudomonas aeruginosa,
Staphylococcus aureus, Escherichia coli, Candida albicans, and other bacteria, fungi and
yeasts. The skin and mucous membranes are protected against microorganisms; however, their
presence in these products can increase the risk of microbial infection.
Microbial contamination may occur during manufacture (primary contamination) and/or
during consumer use (secondary contamination).
All potential sources of contamination must be identified and monitored. In order to do so, four
steps must be considered: (1) inspection and control of raw materials; (2) manufacturing process;
(3) delivery of the final product and; finally; (4) its use by the consumer.
Preservation Strategies
The term preservation refers to the use of synthetic and natural chemical preservatives.
However, self-preservation is a preservation without the use of an additional chemical
ingredient. The microbial preservation strategies range from the first stages of manufacture
to consumption, in order to minimize the risk of microbial contamination.
To achieve a good protection of cosmetic products against microbial contamination, the industry
provides two stages of preservation: primary and secondary. The strategy of primary preservation
occurs during manufacturing and is based on the application of GMP. The secondary preservation,
which takes place after manufacture, uses chemical, physical, or physicochemical ways to attain
an efficient protection.
Secondary Preservation Strategy
Physical Secondary Preservation
Use of primary packaging where a physical barrier exists to prevent microbial contamination. The
shape and characteristics of primary packaging influence in the potential for microbial
contamination. These characteristics include not only the physical configuration of the
packaging (boxes, jars, bottles, flasks, sachets, tubes, aerosol propellants, etc.), but also the
nature and composition of the used materials (polymers, glass, etc.). For example, jars and
bottles are more likely to cause microbial contamination, whereas closed system
configurations are less accessible to contamination. Aerosol pumping systems and tubes
containing narrow openings provide a good protection to the product. Moreover, the risk of
contamination of shampoos and shower gels from contaminated bath water from during use is
greatly diminished by the use of containers with a narrow opening. Additionally, the use of re-
closable systems can reduce the potential for microbial risk. Beyond this, the sizes of the
packaging and the delivery holes may also have an effect on exposure and microbial risks.
However, the primary packaging system can influence the effectiveness of chemical
preservatives by migration or adsorption phenomena. In the last decade, active packaging
technology (packaging incorporated with antimicrobial agents) has been transferred from food to
the cosmetic.
Physicochemical Secondary Preservation
Water Activity
Usually, water is the major constituent of cosmetics, but it is an ideal growth factor for
microorganisms. To solve this problem, certain substances can reduce the water activity, such as
polyols (sorbitol, glycerol, ethoxydiglycol, etc.), protein hydrolysates, amino acids, and
hydrocolloids (xanthan gum, guar gum, etc.), glyceryl polyacrylate gel, sodium polyacrylate
and sodium chloride. The choice of these substances depends on their aspect, their toxic effect,
and also the nature of the cosmetics.
Emulsion Form
Water-in-oil (W/O) emulsions can minimize the risk of microbial contamination more than oil-in-
water (O/W) emulsions. The size of the emulsions droplets can improve the cosmetics
effectiveness. In many cases, the decrease in the size of the emulsion droplets increases the
antimicrobial activity. However, the antimicrobial activity depends also of the oil phase chemical
composition, namely the type of phenolic compounds, their concentration, and chemical structure.
pH Control
The optimum pH for microorganism’s growth in cosmetic products is between 5 to 8, meaning
that any pH outside this range induces unfavourable conditions, thus decreasing their growth
rate. The acidic pH of cationic hair conditioners (pH = 4, approximately) can inhibit the growth
of microorganisms, such as products containing salicylic acid and aluminium compounds in
antiperspirants (pH ranging from 3.5 to 4.5). Liquid soaps having an alkaline pH (pH 9.5 to 10.5)
inhibit microorganism growth of (e.g., destabilizing their membrane), due to the effects fatty acids
and NaOH.
Chemical Secondary Preservation
Synthetic Chemical Preservatives
Generally, preservative selection is based on three criteria (plus the regulatory criterion): (1) very
good antimicrobial efficacy; (2) non-toxic; and (3) compatible with the other ingredients of the
cosmetic formulation.
Currently, preservatives used in combination to increase antimicrobial activity, broadening the
spectrum of activity, reducing the resistance of microorganisms and the risk of toxicity.
Natural Chemical Preservatives
Plant extracts and essential oils are mainly added to cosmetic preparations due to their well-
recognized properties, such as: antioxidant anti-inflammatory and antimicrobial, emollients,
dyes, humectants, wound healing, anti-mutagens, anti-aging, protective agents against UV-
B damage, and reducing skin discoloration. Their application as antimicrobials in cosmetic
preparations is often discouraged due to their volatility and lipophilic aspects (essential oils), and
strong odor (essential oils), which can be highly inadequate/undesirable for some kind of product.
Multifunctional Ingredients
Each ingredient is added to the cosmetic formulation for a well-defined function, but it can,
simultaneously, contribute to another effect (such as antimicrobial activity), thus acting as a
multifunctional ingredient. In the sense of self-preservation, these ingredients have been used as
antimicrobial preservatives by replacing conventional preservatives.
Chelating agents, surfactants, humectants, and phenolic compounds are examples of
multifunctional ingredients. Chelating agents (e.g., EDTA, glutamic acid, N,N-diacetic acid, lactic
acid, citric acid, and phytic acid) increase the permeability of cell membranes and make them more
sensitive to antimicrobial agents.
Chelating agents block the iron required for metabolism and microbial growth, and can enhance
the antimicrobial efficacy of the used preservatives.
Surfactants with antimicrobial properties are the 1,2-diols (from butanediol to octane diol, mainly
caprylyl glycol) due to their amphiphilic character and average molecular size, exhibit viscosity
modulation properties that complement their antimicrobial properties.
In a dental cream, a mixture of sorbitol and glycerin, at 10% to 12% levels. High concentration of
glycerin, beyond having an influence on the appearance of the product, it could also present an
effect on the microbial growth.
The primary function of phenolic antioxidants is to delay the self-oxidation of unsaturated oils that
could influence the color and odor of the product. Beyond that, compounds as propylic gallate,
caffeic acid, coumaric acid, ferulic acid, citric acid, and tartaric acid have also demonstrated
antimicrobial activity.
Synthetic Chemical Preservatives
These are nitrogen compounds, formaldehyde releasers, isothiazolinones, and the quaternary
ammonium Compounds etc. The nitrogen compounds used as preservatives according to zinc
pyrithione, triclocarban, piroctone olamine, chloroacetamide, hexamidine, dibromohexamidine
isethionate, dimethyloxazolidine, climbazole, iodopropynyl butylcarbamate, 7-
ethylbicyclooxazolidine, and ethyl lauroyl arginate hydrochloric acid [4].
Currently, the cosmetic industry suffers from a considerable lack of less-toxic preservatives, with
regulations updating the limits of their use periodically. For this reason, there is considerable
interest in finding effective and safe alternative preservatives. Future alternatives seek a broad
spectrum against microorganisms with a better safety profile. Compounds with good antimicrobial
properties and low toxicity, such as plant extracts, are interesting future alternatives. In addition,
the development of preservative-free products is also of particular interest today.
Organic Acids
The organic acids are active if the carbon number of the alkyl chains is high, however, decreasing
their solubility in water. pH is considered to be a major determinant of the organic acids’
effectiveness because it affects the concentration of formed undissociated acids. Uncharged
molecules are those forms that enable the penetration of organic acids into the cell, however, the
antimicrobial efficacy of most organic acids is presented by their dissociated form.
The acidic pKa of these preservatives should be controlled since a pH change of 1.5 or more
above the neutrality may cause the progressive loss of antimicrobial activity.
The most important organic acids: benzoic acid, propionic acid, salicylic acid, sorbic acid,
dehydroacetic acid, formic acid, undecylenic acid, citric acid, and sodium hydroxy methyl
amino acetate.
Alcohols and Phenols
The preservatives of this class, which are included in the positive list, are: parabens (0.14%),
triclosan, chlorobutanol, o-phenylphenol, chlorocresol, chloroxylenol, phenoxypropanol,
benzylhemiformal, phenoxyethanol, dichlorobenzyl alcohol, benzyl alcohol, o-cym-5-ol,
chlorophene, chlorphenesin, and bromochlorophene.
Triclosan to a maximum concentration of 0.2% in mouthwashes and 0.3% in special cosmetic
products, such as toothpaste, hand soaps, body soaps, and face powders.
In these amendments, five parabens were added to the prohibited substances list in cosmetic
products described in Annex II: isopropylparaben, isobutylparaben, phenylparaben,
benzylparaben, and pentylparaben.
Furthermore, hydroxybenzoic acid and its salts and esters—other than the esters mentioned
above—are limited to a maximum concentration of 0.4% as acid for a single ester, and 0.8%
for mixtures of esters.
Aldehydes and Formaldehyde Releasers
Formaldehyde is a preservative used in shampoos, shower gels, and liquid soaps.
Formaldehyde donors slowly release formaldehyde by degradation or decomposition under use
conditions. The antimicrobial activity of these preservatives probably results from formaldehyde
released by hydrolysis in the presence of water. Formaldehyde releasers are regulated on the basis
of their formaldehyde release content. Formaldehyde release is dependent on the matrix, pH,
storage time and temperature.
Ex: formaldehyde and paraformaldehyde, glutaral, imidazolidinyl urea, diazolidinyl urea,
quaternium-15, DMDM hydantoin, bronopol, bronidox, hexetidine, and methenamine.
Isothiazolinones
The isothiasolinone activity is related with the thiol and amine groups of their structures. Their
usage is being diminished due to the large number of allergic reactions reported by dermatologists
Maximum authorized concentration of methylisothiazolinone was greatly reduced in rinse-off
products (0.0015%).
Biguanides
The biguanides are a family of compounds known for their antimicrobial activities; they are used
not only as antiseptics but also as preservatives activity.
Biguanides against the human oral flora. Chlorhexidine and polyaminopropyl biguanide.
Quaternary Ammonium Compounds (QAC)
Quaternary ammonium compounds (QACs) mainly represent cationic surfactants. They are the
most used antiseptics and disinfectants. The optimum activity against Gram-positive. bacteria and
yeast is obtained with chain lengths of 12 to 14 alkyls, while optimum activity against Gram-
negative bacteria is obtained with chain lengths of 14–16 alkyls. Compounds with N-alkyl chain
lengths <4 or >18 are virtually inactive.
The European directive Annex V, includes the following quaternary ammonium compounds:
Alkyl (C12-22) trimethyl ammonium bromide and chloride (behentrimonium chloride,
Cetrimonium bromide, Cetrimonium chloride, laurtrimonium bromide, laurtrimonium chloride,
steartrimonium bromide, steartrimonium chloride), and benzalkonium chloride.
Nitrogen Compounds
alkyl amides and amines Zinc pyrithione.
Gram-positive bacteria are more sensitive than Gram-negative.
Considering the ethyl lauroyl arginate HCl, in mouthwashes allowed to a maximum concentration
of 0.4%.
Heavy Metal Derivatives
Metal derivatives of mercury and silver are used as preservatives in cosmetics (thimerosal and
phenylmercuric salts as organomercury compounds and silver chloride, Among the most
important characteristics of metals is their ability to take part in redox reactions. The heavy metals
are toxic. They react with the proteins by complexing with the thiol groups (-SH), thus causing
their inactivation.
Inorganic Compounds
This class is represented by inorganic sulfites and bisulphites. The most important factor that
affects the antimicrobial activity of sulfites is pH. Sulfur dioxide and its associated salts exist as a
pH-dependent mixture during aqueous dissolution.
Factors affecting action of preservatives
1. Molecular structure: Molecular structure affects the effectiveness of preservative. Out of
parabens (p-hydroxy benzoic acid), m-hydroxy benzoic acid and benzoic acid; benzoic acid is
more effective than parabens. Esterification of parabens leads to formation of much effective
preservatives. So depending upon the requirement, the type of the preservatives can be used.
2. Position of Double Bond: Double bond in a compound in its cis form is more effective than in
trans form. For example sorbic acid (CH3CH=CH-CH=CHCOOH) a 2, 4- hexadecenoic acid is a
strong anti-microbial agent since position of double bond is in cis form. With change in position
of double bond to trans form the sorbic acid becomes less effective than cis form. Sorbic acid is
the safest preservative as it undergoes ß- oxidation and changes to pyruvic acid.
3. Presence or absence of double bond: With the increase in degree of unsaturation, the
effectiveness of preservative is increased.
4. Presence or absence of side chain: Straight chain molecules are more effective preservatives
than the branched chain molecules.
5. pH of the medium: Acidic pH increases the effectiveness of preservative. For example, benzoic
acid at pH 3.5 is 10 times effective than at pH 7. At low pH of 2, the effectiveness is 100 times
because at low pH, the un-dissociated molecules of the acid are more and it is the unassociated
molecules with create the effect.
6. Solubility: Some of the preservatives are insoluble in their natural form but when converted to
their sodium salts, becomes more effective. For example sodium benzoate in place of benzoic acid.
Demerits
1. Types of preservatives • Natural – not very effective • Synthetic – many different kinds
• Parabens – recently banned in France, disrupt endocrines • Formaldehyde – present
in shampoos, linked to cancer and allergic reactions • Hydroquinone – found in skin
lighteners, linked to cancer and organ-system toxicity
2. Coal tar – found in shampoos, derived from burning coal, known carcinogen •
Triclosan – used in soaps, suspected of endocrine disruption, emergence of resistant
bacteria • Heavy metals (lead, arsenic, aluminum) – found in lip products, toothpaste,
eyeliner, foundation, etc. Accumulation in the body can be dangerous.
3. Are preservatives dangerous? • Only found in very small amounts in products •
Multiple products are used, chemicals can stack – «The cocktail effect » • Not enough
research done yet • Can cause allergies, irritation, side effects • People should
research what is in their cosmetics
4. Conclusion • Preservatives are used in almost all kinds of cosmetics • They are often
untested and potentially dangerous • Care should be taken to avoid health issues •
Companies should work to find safer alternatives
5. Stay safe!
Merits:

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Antimicribial used as preservatives their merits and demerits

  • 1. Antimicrobial used as preservatives in cosmetics By – Mahendra Kumar Prajapati Ph.D. Scholar Institute of Chemical Technology, Mumbai Cosmetics, containing water and organic/inorganic compounds, require preservation against microbial contamination to guarantee consumer’s safety against potentially pathogenic microorganisms and to increase their shelf-life. Preservation strategies: Chemical Physical or Physicochemical. The most common strategy is based on the application of antimicrobial agents, Ex: parabens, isothiasolinone, organic acids, formaldehyde releasers, triclosan, and chlorhexidine. These chemical agents have different mechanisms of antimicrobial action, depending on their chemical structure and functional group’s reactivity. Their high concentrations are more effective from the preservation viewpoint but can be toxic for the consumer, whereas at low concentrations microbial resistance can develop. Modification of cosmetic products is due to ➢ Presence of microorganisms (need antimicrobial preservatives-act on microorganisms) ➢ Exposure to atmospheric oxygen (need antioxidant preservatives- suppressing oxidation and formation of free radicals) A preservative is a substance of natural or synthetic origin intended to inhibit the development of microorganisms. Preservatives should have broad spectrum of activity against microorganism and should be effective for long time (longer than product shelf life and usage time).
  • 2. Antimicrobials should prevent microorganism’s adaptation and development of resistance. The cosmetic products are a nutrient-rich medium that favors microorganism’s growth, which, thereafter, influences the efficacy of the preservatives. Amount of antimicrobial agent to be used in a cosmetic is dependent on its role; As active used in high concentrations (antimicrobial cosmetics) and as preservatives in low concentrations (most cosmetics) Other strategies ➢ water activity ➢ pH control ➢ use of multifunctional ingredients Overview of Cosmetics and Their Microbiological Safety Definition of Cosmetics any substance or mixture intended to be placed in contact with the external parts of the human body (epidermis, hair system, nails, lips, and external genital organs) or with the teeth and the mucous membranes of the oral cavity with a view exclusively or mainly to cleaning them, perfuming them, changing their appearance, protecting them, keeping them in good condition, or correcting body odours” (1) Cosmetics for personal cleansing (soaps, deodorants, shampoos) (2) Cosmetics for the skin, hair, and integument care (toothpastes, products for external intimate care) (3) Cosmetics for embellishment (perfumes, lip colors) (4) Protective cosmetics (solar products, anti-wrinkle products) (5) Corrective cosmetics (beauty masks, hair dyes) (6) Maintenance cosmetics (shaving cream, moisturizing creams) (7) Active cosmetics (fluoridated toothpastes, antiseptics) Cosmeceuticals Cosmetics + Pharmaceuticals
  • 3. e.g., retinol, certain bleaching agents, etc have a beneficial effect on skin, also have a clear biological therapeutic effect. Cosmetic products with antimicrobial effect Cosmetic products with antimicrobial effect can be described as preparations with the ability to provide consumer’s protection against the presence of antimicrobial compounds, having bactericidal effect. Products like mouthwashes, skin disinfectants or antibacterial soaps. The difference between a cosmetic product and a drug lies in the concentration of the active ingredient in the product (e.g., mouthwash). There is also an unclear distinction between the definition of cosmetic and dermatological treatment (e.g., acne treatment). Microbiological Safety of Cosmetic Products An ideal preservation system (intrinsic or extrinsic) should protect the product from microbial degradation, both in its original closed packaging until use, and in an open container throughout its use. Most frequent microorganisms found in cosmetics comprise Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli, Candida albicans, and other bacteria, fungi and yeasts. The skin and mucous membranes are protected against microorganisms; however, their presence in these products can increase the risk of microbial infection. Microbial contamination may occur during manufacture (primary contamination) and/or during consumer use (secondary contamination). All potential sources of contamination must be identified and monitored. In order to do so, four steps must be considered: (1) inspection and control of raw materials; (2) manufacturing process; (3) delivery of the final product and; finally; (4) its use by the consumer. Preservation Strategies The term preservation refers to the use of synthetic and natural chemical preservatives. However, self-preservation is a preservation without the use of an additional chemical
  • 4. ingredient. The microbial preservation strategies range from the first stages of manufacture to consumption, in order to minimize the risk of microbial contamination. To achieve a good protection of cosmetic products against microbial contamination, the industry provides two stages of preservation: primary and secondary. The strategy of primary preservation occurs during manufacturing and is based on the application of GMP. The secondary preservation, which takes place after manufacture, uses chemical, physical, or physicochemical ways to attain an efficient protection. Secondary Preservation Strategy Physical Secondary Preservation Use of primary packaging where a physical barrier exists to prevent microbial contamination. The shape and characteristics of primary packaging influence in the potential for microbial contamination. These characteristics include not only the physical configuration of the packaging (boxes, jars, bottles, flasks, sachets, tubes, aerosol propellants, etc.), but also the nature and composition of the used materials (polymers, glass, etc.). For example, jars and bottles are more likely to cause microbial contamination, whereas closed system configurations are less accessible to contamination. Aerosol pumping systems and tubes containing narrow openings provide a good protection to the product. Moreover, the risk of contamination of shampoos and shower gels from contaminated bath water from during use is greatly diminished by the use of containers with a narrow opening. Additionally, the use of re- closable systems can reduce the potential for microbial risk. Beyond this, the sizes of the packaging and the delivery holes may also have an effect on exposure and microbial risks. However, the primary packaging system can influence the effectiveness of chemical preservatives by migration or adsorption phenomena. In the last decade, active packaging technology (packaging incorporated with antimicrobial agents) has been transferred from food to the cosmetic. Physicochemical Secondary Preservation Water Activity Usually, water is the major constituent of cosmetics, but it is an ideal growth factor for microorganisms. To solve this problem, certain substances can reduce the water activity, such as polyols (sorbitol, glycerol, ethoxydiglycol, etc.), protein hydrolysates, amino acids, and hydrocolloids (xanthan gum, guar gum, etc.), glyceryl polyacrylate gel, sodium polyacrylate
  • 5. and sodium chloride. The choice of these substances depends on their aspect, their toxic effect, and also the nature of the cosmetics. Emulsion Form Water-in-oil (W/O) emulsions can minimize the risk of microbial contamination more than oil-in- water (O/W) emulsions. The size of the emulsions droplets can improve the cosmetics effectiveness. In many cases, the decrease in the size of the emulsion droplets increases the antimicrobial activity. However, the antimicrobial activity depends also of the oil phase chemical composition, namely the type of phenolic compounds, their concentration, and chemical structure. pH Control The optimum pH for microorganism’s growth in cosmetic products is between 5 to 8, meaning that any pH outside this range induces unfavourable conditions, thus decreasing their growth rate. The acidic pH of cationic hair conditioners (pH = 4, approximately) can inhibit the growth of microorganisms, such as products containing salicylic acid and aluminium compounds in antiperspirants (pH ranging from 3.5 to 4.5). Liquid soaps having an alkaline pH (pH 9.5 to 10.5) inhibit microorganism growth of (e.g., destabilizing their membrane), due to the effects fatty acids and NaOH. Chemical Secondary Preservation Synthetic Chemical Preservatives Generally, preservative selection is based on three criteria (plus the regulatory criterion): (1) very good antimicrobial efficacy; (2) non-toxic; and (3) compatible with the other ingredients of the cosmetic formulation. Currently, preservatives used in combination to increase antimicrobial activity, broadening the spectrum of activity, reducing the resistance of microorganisms and the risk of toxicity. Natural Chemical Preservatives
  • 6. Plant extracts and essential oils are mainly added to cosmetic preparations due to their well- recognized properties, such as: antioxidant anti-inflammatory and antimicrobial, emollients, dyes, humectants, wound healing, anti-mutagens, anti-aging, protective agents against UV- B damage, and reducing skin discoloration. Their application as antimicrobials in cosmetic preparations is often discouraged due to their volatility and lipophilic aspects (essential oils), and strong odor (essential oils), which can be highly inadequate/undesirable for some kind of product. Multifunctional Ingredients Each ingredient is added to the cosmetic formulation for a well-defined function, but it can, simultaneously, contribute to another effect (such as antimicrobial activity), thus acting as a multifunctional ingredient. In the sense of self-preservation, these ingredients have been used as antimicrobial preservatives by replacing conventional preservatives. Chelating agents, surfactants, humectants, and phenolic compounds are examples of multifunctional ingredients. Chelating agents (e.g., EDTA, glutamic acid, N,N-diacetic acid, lactic acid, citric acid, and phytic acid) increase the permeability of cell membranes and make them more sensitive to antimicrobial agents. Chelating agents block the iron required for metabolism and microbial growth, and can enhance the antimicrobial efficacy of the used preservatives. Surfactants with antimicrobial properties are the 1,2-diols (from butanediol to octane diol, mainly caprylyl glycol) due to their amphiphilic character and average molecular size, exhibit viscosity modulation properties that complement their antimicrobial properties. In a dental cream, a mixture of sorbitol and glycerin, at 10% to 12% levels. High concentration of glycerin, beyond having an influence on the appearance of the product, it could also present an effect on the microbial growth. The primary function of phenolic antioxidants is to delay the self-oxidation of unsaturated oils that could influence the color and odor of the product. Beyond that, compounds as propylic gallate, caffeic acid, coumaric acid, ferulic acid, citric acid, and tartaric acid have also demonstrated antimicrobial activity. Synthetic Chemical Preservatives These are nitrogen compounds, formaldehyde releasers, isothiazolinones, and the quaternary ammonium Compounds etc. The nitrogen compounds used as preservatives according to zinc
  • 7. pyrithione, triclocarban, piroctone olamine, chloroacetamide, hexamidine, dibromohexamidine isethionate, dimethyloxazolidine, climbazole, iodopropynyl butylcarbamate, 7- ethylbicyclooxazolidine, and ethyl lauroyl arginate hydrochloric acid [4]. Currently, the cosmetic industry suffers from a considerable lack of less-toxic preservatives, with regulations updating the limits of their use periodically. For this reason, there is considerable interest in finding effective and safe alternative preservatives. Future alternatives seek a broad spectrum against microorganisms with a better safety profile. Compounds with good antimicrobial properties and low toxicity, such as plant extracts, are interesting future alternatives. In addition, the development of preservative-free products is also of particular interest today. Organic Acids The organic acids are active if the carbon number of the alkyl chains is high, however, decreasing their solubility in water. pH is considered to be a major determinant of the organic acids’ effectiveness because it affects the concentration of formed undissociated acids. Uncharged molecules are those forms that enable the penetration of organic acids into the cell, however, the antimicrobial efficacy of most organic acids is presented by their dissociated form. The acidic pKa of these preservatives should be controlled since a pH change of 1.5 or more above the neutrality may cause the progressive loss of antimicrobial activity. The most important organic acids: benzoic acid, propionic acid, salicylic acid, sorbic acid, dehydroacetic acid, formic acid, undecylenic acid, citric acid, and sodium hydroxy methyl amino acetate. Alcohols and Phenols The preservatives of this class, which are included in the positive list, are: parabens (0.14%), triclosan, chlorobutanol, o-phenylphenol, chlorocresol, chloroxylenol, phenoxypropanol, benzylhemiformal, phenoxyethanol, dichlorobenzyl alcohol, benzyl alcohol, o-cym-5-ol, chlorophene, chlorphenesin, and bromochlorophene.
  • 8. Triclosan to a maximum concentration of 0.2% in mouthwashes and 0.3% in special cosmetic products, such as toothpaste, hand soaps, body soaps, and face powders. In these amendments, five parabens were added to the prohibited substances list in cosmetic products described in Annex II: isopropylparaben, isobutylparaben, phenylparaben, benzylparaben, and pentylparaben. Furthermore, hydroxybenzoic acid and its salts and esters—other than the esters mentioned above—are limited to a maximum concentration of 0.4% as acid for a single ester, and 0.8% for mixtures of esters. Aldehydes and Formaldehyde Releasers Formaldehyde is a preservative used in shampoos, shower gels, and liquid soaps. Formaldehyde donors slowly release formaldehyde by degradation or decomposition under use conditions. The antimicrobial activity of these preservatives probably results from formaldehyde released by hydrolysis in the presence of water. Formaldehyde releasers are regulated on the basis of their formaldehyde release content. Formaldehyde release is dependent on the matrix, pH, storage time and temperature. Ex: formaldehyde and paraformaldehyde, glutaral, imidazolidinyl urea, diazolidinyl urea, quaternium-15, DMDM hydantoin, bronopol, bronidox, hexetidine, and methenamine. Isothiazolinones The isothiasolinone activity is related with the thiol and amine groups of their structures. Their usage is being diminished due to the large number of allergic reactions reported by dermatologists Maximum authorized concentration of methylisothiazolinone was greatly reduced in rinse-off products (0.0015%). Biguanides The biguanides are a family of compounds known for their antimicrobial activities; they are used not only as antiseptics but also as preservatives activity. Biguanides against the human oral flora. Chlorhexidine and polyaminopropyl biguanide. Quaternary Ammonium Compounds (QAC)
  • 9. Quaternary ammonium compounds (QACs) mainly represent cationic surfactants. They are the most used antiseptics and disinfectants. The optimum activity against Gram-positive. bacteria and yeast is obtained with chain lengths of 12 to 14 alkyls, while optimum activity against Gram- negative bacteria is obtained with chain lengths of 14–16 alkyls. Compounds with N-alkyl chain lengths <4 or >18 are virtually inactive. The European directive Annex V, includes the following quaternary ammonium compounds: Alkyl (C12-22) trimethyl ammonium bromide and chloride (behentrimonium chloride, Cetrimonium bromide, Cetrimonium chloride, laurtrimonium bromide, laurtrimonium chloride, steartrimonium bromide, steartrimonium chloride), and benzalkonium chloride. Nitrogen Compounds alkyl amides and amines Zinc pyrithione. Gram-positive bacteria are more sensitive than Gram-negative. Considering the ethyl lauroyl arginate HCl, in mouthwashes allowed to a maximum concentration of 0.4%. Heavy Metal Derivatives Metal derivatives of mercury and silver are used as preservatives in cosmetics (thimerosal and phenylmercuric salts as organomercury compounds and silver chloride, Among the most important characteristics of metals is their ability to take part in redox reactions. The heavy metals are toxic. They react with the proteins by complexing with the thiol groups (-SH), thus causing their inactivation. Inorganic Compounds This class is represented by inorganic sulfites and bisulphites. The most important factor that affects the antimicrobial activity of sulfites is pH. Sulfur dioxide and its associated salts exist as a pH-dependent mixture during aqueous dissolution.
  • 10. Factors affecting action of preservatives 1. Molecular structure: Molecular structure affects the effectiveness of preservative. Out of parabens (p-hydroxy benzoic acid), m-hydroxy benzoic acid and benzoic acid; benzoic acid is more effective than parabens. Esterification of parabens leads to formation of much effective preservatives. So depending upon the requirement, the type of the preservatives can be used. 2. Position of Double Bond: Double bond in a compound in its cis form is more effective than in trans form. For example sorbic acid (CH3CH=CH-CH=CHCOOH) a 2, 4- hexadecenoic acid is a
  • 11. strong anti-microbial agent since position of double bond is in cis form. With change in position of double bond to trans form the sorbic acid becomes less effective than cis form. Sorbic acid is the safest preservative as it undergoes ß- oxidation and changes to pyruvic acid. 3. Presence or absence of double bond: With the increase in degree of unsaturation, the effectiveness of preservative is increased. 4. Presence or absence of side chain: Straight chain molecules are more effective preservatives than the branched chain molecules. 5. pH of the medium: Acidic pH increases the effectiveness of preservative. For example, benzoic acid at pH 3.5 is 10 times effective than at pH 7. At low pH of 2, the effectiveness is 100 times because at low pH, the un-dissociated molecules of the acid are more and it is the unassociated molecules with create the effect. 6. Solubility: Some of the preservatives are insoluble in their natural form but when converted to their sodium salts, becomes more effective. For example sodium benzoate in place of benzoic acid. Demerits 1. Types of preservatives • Natural – not very effective • Synthetic – many different kinds • Parabens – recently banned in France, disrupt endocrines • Formaldehyde – present in shampoos, linked to cancer and allergic reactions • Hydroquinone – found in skin lighteners, linked to cancer and organ-system toxicity 2. Coal tar – found in shampoos, derived from burning coal, known carcinogen • Triclosan – used in soaps, suspected of endocrine disruption, emergence of resistant bacteria • Heavy metals (lead, arsenic, aluminum) – found in lip products, toothpaste, eyeliner, foundation, etc. Accumulation in the body can be dangerous. 3. Are preservatives dangerous? • Only found in very small amounts in products • Multiple products are used, chemicals can stack – «The cocktail effect » • Not enough
  • 12. research done yet • Can cause allergies, irritation, side effects • People should research what is in their cosmetics 4. Conclusion • Preservatives are used in almost all kinds of cosmetics • They are often untested and potentially dangerous • Care should be taken to avoid health issues • Companies should work to find safer alternatives 5. Stay safe!