Moving on to GREENer Pastures

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Moving on to GREENer Pastures?

• Facing the Challenges of Natural Formulating

Christopher Johnson - Kinetik Technologies Midwest
Holistic Symposium March 17, 2009
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What is Natural?
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What is natural? some analogies
bad
good is to
black
white
hot
cold
non-organic (Agriculture)
organic
inorganic (Chemistry)
natural
unnatural
chemical
synthetic
supernatural
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natural

• Adjective
• existing in or formed by nature (opposed to
  artificial)
• based on the state of things in nature
  constituted by nature
• in a state of nature uncultivated, as land

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Is this natural?
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Is this natural?
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Is this natural?
Genetically Modified
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What is natural?
Definition Perception
Physical world, including living organisms
excluding manufactured objects from human
interaction
Nature
unnatural
natural
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What is natural?
Definition Perception
Coming from nature gtgt harvest, collection
Natural
Natural
Synthetic
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Why Natural Personal Care?
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Why Natural Personal Care?

• Growing concerns regarding the fate of our planet
  (Global Warming, Pollution, Fuel Crisis, etc.)
• Increased demand for alternative fuel sources,
  organic foods and sustainable business practices
  (reduced carbon footprint)
• Increased consumer awareness is resulting in
  rapid growth (15 in 2005) of natural personal
  care
• Signifies major shift in consumer culture

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Challenges of Natural Personal Care

• No official definition for natural personal care
• Limited formulatory access to ingredients or
  unethical behavior leading to natural products
  with conventional ingredients
• Limited knowledge of consumers makes it easier to
  make natural claims as a marketing tool without
  corresponding formulating effort

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Challenges of Natural Personal Care

• Consumers believe ingredients used in
• natural personal care are
• Safer to use on themselves and their families
• Promoting overall health well-being
• Better for the environment

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Challenges of Natural Personal Care

• The reality is
• Natural ingredients are not always safe
• Finished products are costly to create
• Often inferior in performance
• Challenging to formulate
• Problems with large scale manufacturing

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Going GREEN?
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GREEN Chemistrydefinition

• a chemical philosophy encouraging the design of
  products and processes that reduce or eliminate
  the use and generation of hazardous substances

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GREEN Chemistrya holistic approach

• Raw materials considered GREEN should be
• Natural made up of building blocks and
  produced using environmentally sound processes
• Efficient Run chemical reactions at ambient
  temperature and pressures to reduce energy waste
• Safe should not be suspected of causing human
  health or environmental risk
• Sustainable biodegradable and derived from
  renewal vegetal feed stocks
• Responsible no animal testing in its development
  (unique to cosmetics)

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Going GREEN a starting point

• Natural Products Association Standard and
  Certification for Personal Care Products
• a set of guidelines to help define the term
  natural as it applies to personal care

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Going GREEN

• All products that are labeled or branded natural
  must
• Be made with at least 95 all natural ingredients
• Contain only synthetic ingredients specifically
  allowed under this standard and
  environmentally-friendly products that are
  nurturing to us and as harmless as possible to
  the earth

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Going GREEN

• What is natural?
• Ingredients that come or are made from a
  renewable resource found in nature (flora, fauna,
  mineral), with absolutely no petroleum compounds.
  

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Going GREEN

• Ingredients that are prohibited
• Have suspected human health risks as indicated by
  peer-reviewed third-party scientific literature
• Incorporate synthetic silicone or petroleum
  compounds
• Parabens Synthetic preservatives that are
  potential endocrine disrupters
• Sodium Lauryl Sulfate Harsh cleansing agent
• Petrolatum/Mineral Oil/Paraffin Non-renewable
  byproducts of crude oil
• Chemical Sunscreens (Avobenzone/Oxybenzone)
  Synthetic sunscreens
• Glycols Petroleum derived synthetic chemicals

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Going GREEN

• Phthalates Synthetic fragrance components that
  are potential toxins
• Ethoxylated Ingredients - Ingredients that are
  made in part with ethylene oxide
• Ethanolamines Foam and viscosity boosting
  ingredients that can interact with other
  ingredients to form nitrosamines, a known
  carcinogen(37)
• Synthetic polymers (PVP/Acrylates) - may contain
  residual hydrocarbons - widespread organic
  pollutants
• Formaldehyde Donors (DMDM Hydantoin/ Diazolidinyl
  Urea/ Methylisothiazolinone) Preservatives that
  work by releasing formaldehyde

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Going GREEN

• Allowed synthetic ingredients those temporarily
  allowed in the initial phase of this standard
• Non-paraben, non-formaldehyde-donating synthetic
  preservatives
• Non-phthalate, non-irritating synthetic
  fragrances
• Quaternary anti-static hair conditioners
• Coco Betaine

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Going GREEN

• Prohibited ingredients
• Ammonium Lauryl Sulfate
• Amodimethicone
• Behentrimonium Methosulfate
• Butylene glycol
• Carbomer
• Ceteareth-20
• Cetrimonium Chloride
• Coco DEA
• Cocoamidopropyl Betaine
• Cyclopentasiloxane
• Diazolidinyl Urea
• Dimethicone
• Disodium Cocoamphodiacetate
• EDTA
• EthylHexylGlycerin
• Glycereth-7 Cocoate
• Isoceteth 20
• Isopropyl Palmitate

• Prohibited ingredients
• Methoxycinnamate
• Olefin Sulfonate
• Oleyl Betaine
• Parabens (methyl, propyl, butyl, etc.)
• PEG-150 Distearate
• PEG-7 Glyceryl Cocoate
• Polyquaternium 10
• Propylene Glycol
• Sodium Cocoyl Sarcosinate
• Sodium Hydroxymethylglycinate
• Sodium Laureth Sulfate
• Sodium Lauroyl Sarcosinate
• Sodium Lauryl Carboxylate
• Sodium Lauryl Sulfate
• Sodium Lauryl Sulfoacetate
• Sodium Myreth Sulfate
• Sodium PCA or Na PCA (pyrrolidone carbonic acid)
  
• Soyamidopropalkonium Chloride

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Going GREEN
INCI Purified Water, Aloe Barbadensis Leaf
Juice, Sodium Lauryglucosides Hydroxypropylsulfona
te, Cocamidopropyl Betaine, Decyl Glucoside,
Glycerin, Guar Hydroxypropyltrimonium Chloride,
Panthenol, Allantoin, Simmondsia Chinensis
(Jojoba) Seed Oil(2), Helianthus Annuus
(Sunflower) Seed Oil(3), Olea Europaea (Olive)
Fruit Oil(3), Linum Usitatissimum (Linseed) Seed
Oil(4), Borago Officinalis Seed Oil(3), Vitis
Vinifera (Grape) Seed Oil(4), Rosa Canina Fruit
Oil(4), Citric Acid, Polysorbate 20, Sodium
Benzoate, Potassium Sorbate, Ethylhexylglycerin.
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Going GREEN

• List of Allowed Ecological Processes
• Saponification of vegetable oils to make soap
• Hydrolysis of Proteins into Amino Acids
• Fat-Splitting of vegetable oils to produce
  glycerin and fatty acids
• Hydrogenation of oils
• Hydrogenolysis of methyl esters to products fatty
  alcohols
• Glucosidation of fatty alcohols and glucose
• Sulfation of fatty alcohol
• Protein fragment acylation
• Etherificiation of glycerin making polyglycerol
• Esterification or Transesterification to produce
  esters

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GREEN Preservation
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Consumer Perception
Background - Parabens have been found in breast
cancer cells (Darbre, J. et al Appl. Toxicology,
24, (2004),1.) - Parabens might facilitate
skin ageing (Ishiwatari et al, Proc.
IFSCC Conf. (2005), 129-135.)
- Without parabens
- Without preservatives
- Natural
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Consumer Perception
- Without parabens
Background The consumer relates preservatives
to negative effects like skin irritation allergic
reactions cancer causing, etc.
- Without preservatives
- Natural
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Consumer Perception
- Without parabens

• Background
• - Natural is considered by the consumer to be
  the opposite of chemical
• Natural is associated by the consumer with
  attributes such as safe and gentle

- Without preservatives
- Natural
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GREEN Preservation

• Natural organic acids
• Natural surface active materials

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GREEN Preservationthe organic acids
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GREEN PreservationIntroducing natural Levulinic
Acid
Access to levulinic acid from sustainable
starting material
Mineral Acid
Vegetable Starch
Levulinic Acid
- Levulinic acid has an infinite water solubility
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Natural Levulinic Acid
Challenge test 0.3 levulinic acid in water
- Levulinic acid has broad antibacterial efficacy
- Unlike other organic acids it shows no weakness
against Pseudomonas
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Natural Levulinic Acid
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GREEN PreservationIntroducing natural Anisic Acid
O2 /
H2O2 / NaOH
trans-Anethol
Natural Anisic Acid
p-anisic acid is accessible in gt 99 purity in a
patented process by oxygenation of trans-anethole
which is readily available from star anise oil or
basil oil
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Natural Anisic Acid
Challenge Test 0.2 anisic acid as a fungicidal
component in a natural O/W Emulsion pH 5.25
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Natural Anisic Acid
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GREEN Preservationthe organic acids

• Organic acids should be added to the aqueous
  phase
• When using Anisic Acid, a pre-solution with small
  amounts of sodium hydroxide is often recommended
• Levulinic Acid can be added to the aqueous phase
  or used to adjust the pH of the finished
  formulation
• The pH of the formulation should not exceed 5.5
  in order to provide sufficient antimicrobial
  activity
• Specific incompatibilities of the acids with
  other natural raw materials have not been
  reported

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GREEN Preservationthe organic acids
Each organic acid dissociates in an aqueous medium
Base


HA
A-
Bases can be water, salts (e.g. citrate,
lactate, hydroxide)
Acids and base form a dynamic and pH-dependent
equilibrium
pH pK log cA- / cHA
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Organic Acidshow they work
pH pK log cA- / cHA
pH
Water Phase
O
H
C
O
3
O-
pH pK
O
H
C
O
3
O
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Organic Acidshow they work
After dissociation only the unpolar acid can
penetrate the membrane. The salt remains in the
medium and is inactive.
The energy consumption and continuously low pH
lead to the death of the microorganism.
Within the cell the acid dissociates, disturbs
the pH-equilibrium in the plasma and inhibts
enzyme activity.
The cell struggles to maintain the pH by pumping
H into the medium with concurrent intake of Na.
This process consumes energy (ATP)
Bacterium
pH
pH
Lipid membrane
Medium
Oil Phase
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Organic Acidshow they work
Summary
Acids which are capable of penetrating the cell
membrane of microorganisms affect the
intracellular pH equilibirium and thereby the
metabolism of the cell.
In order to re-establish the physiological pH the
cell actively pumps out H thereby burning cell
fuel ATP. Continious efforts to maintain the
pH-level of the cytosol finally leads to an
exhaustion of cellular energy reserves.

• A sufficient efficacy of an organic acid
  requires
• A sufficient number of uncharged acid molecules,
  which is related to the pH and the pK of the
  organic acid
• A sufficient total concentration of the organic
  acid

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Organic Acidshow they work
pH pK log cA- / cHA
Anisic acid comparison of 0.06 at pH 5.0 with
0.5 at pH 6.0
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GREEN Preservationthe organic acids

• Levulinic Acid and Anisic Acid are two
  antimicrobially active natural organic acids
• These organic acids are accepted for use by
  several natural organizations including OASIS
  (USA), BDIH (Germany), Organic Soil Association
  (UK) and Ecocert (France)
• The antimicrobial efficacy of these acids is
  complementary, providing broad spectrum
  protection
• Limitation formulation pH should be lt5.5

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GREEN Preservationthe surface active materials
the glyceryl monoesters
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GREEN Preservationthe glyceryl monoesters
Glyceryl Caprylate
Glyceryl Caprate
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GREEN Preservationthe glyceryl monoesters
Access to naturally derived glyceryl monoesters
Coconut or Palm Oil as a natural source of
shorter chain fatty acids
Distillation
Distilled Acids
Cocofatty acids
Esterification
Coconut Oil
Hydrolysis
Glycerol
Glyceryl monoester
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GREEN Preservationthe glyceryl monoesters
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Natural Glyceryl Caprylate
Challenge Test 0.7 Glyceryl Caprylate in a
natural O/W Emulsion pH 5.1
Glyceryl Caprylate has strong efficacy against
bacteria and yeast but only limited activity
against fungi
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GREEN Preservationthe glyceryl monoesters
Glyceryl Caprylate is a good basic component for
alternative preservation Glyceryl Caprate is a
good deodorant active (gram bacteria)
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Glyceryl Monoestershow they work
The active compounds are not used up and remain
active in the formula.
The high surface activity and incompatible size
of the molecules destabilizes the membrane
The active compounds are small amphiphilic
molecules, that exchange membrane lipids.
Cell
Oil Phase
Water Phase
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Glyceryl Monoestershow they work
Treatment of negatively stained Chlamydia
trachomatis with 1 mM of Glyceryl Caprate

• Lit. Bergsson, G., Arnfinnsson, J, Karlsson,
  S.M., Steingrimsson, Ó, Thormar, H., In Vitro
  Inactivation of Chlamydia trachomatis by Fatty
  Acids and Monoglycerides, Antimicrob. Agents
  Chemother. 42 (1998) 2290-2294.

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Formulating with Glyceryl Monoesters
Surface active materials, like Glyceryl
Caprylate, can penetrate the interphase between
oil phase and water phase
Oil Phase
Water Phase
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Formulating with Glyceryl Monoesters
At elevated concentrations, the high surface
activity of the anti-microbial surfactant may
result in a destabilization of the emulsion
Oil Phase
Water Phase
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Formulating with Glyceryl Monoesters
Using mixtures of non-ionic and anionic
emulsifiers can efficiently lead to a
stabilization of the emulsion
A suitable systems is
Polyglyceryl-3 Stearate
Sodium Stearoyl Lactylate
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Formulating with Glyceryl Monoesters
Using ionic emulsifiers leads to an additional
layer of organized water molecules at the
interphase
- Na
Oil Phase
- Na
- Na
- Na
- Na
- Na
- Na
- Na
- Na
- Na
- Na
- Na
- Na
- Na
- Na
- Na
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GREEN Preservation Summary 1
The organic acids are a good choice for
alternative preservation without any change of
the characteristics of a given formula if pH is
suitable.
In some cases the performance in emulsions needs
to be enhanced.
Antimicrobial surfactants can be formulated at a
wider pH range but may have an impact on the
viscosity or the stability of emulsions. The use
of blends of non-ionic and anionic emulsifiers
can improve the stability of emulsion based
products.
In rinse-off products inactivation can sometimes
be observed due to theformation of micelles.
The efficacy of some antimicrobial surfactants
alone against fungi is limited and additional
combinations should be explored.
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GREEN PreservationNew Developments!!!

• a synergy between the organic acids (Levulinic
  Acid, Anisic Acid) and the surface active
  materials (Glyceryl Caprylate) has been
  discovered!!
• boosts antimicrobial performance

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Natural O/W EmulsionChallenge Study
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Natural O/W EmulsionChallenge Study
European Pharmacopoeia Criteria
EP Criteria
Aspergillus Niger
A
Candida Albicans
A
Escherichia Coli
A
Pseudomonas Aeruginosa
A
Staphylococcus Aureus
A
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Natural O/W EmulsionChallenge Study
Levulinic Acid 0.7
Standard O/W, pH 5.3
EP Criteria
Aspergillus Niger
B
Candida Albicans
NF
Escherichia Coli
B
Pseudomonas Aeruginosa
B
Staphylococcus Aureus
A
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Natural O/W EmulsionChallenge Study
Levulinic Acid 0.7 Anisic Acid 0.2
Standard O/W, pH 5.3
EP Criteria
Aspergillus Niger
B
Candida Albicans
F
Escherichia Coli
A
Pseudomonas Aeruginosa
A
Staphylococcus Aureus
A
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Natural O/W EmulsionChallenge Study
Glyceryl Caprylate 0.7
Standard O/W, pH 5.3
EP Criteria
Aspergillus Niger
B
Candida Albicans
A
Escherichia Coli
A
Pseudomonas Aeruginosa
A
Staphylococcus Aureus
A
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GREEN Preservationsynergies
Glyceryl Caprylate 0.7 Anisic Acid 0.2
Standard O/W, pH 5.3
EP Criteria
Aspergillus Niger
A
Candida Albicans
A
Escherichia Coli
A
Pseudomonas Aeruginosa
A
Staphylococcus Aureus
A
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GREEN Preservationsynergies
Glyceryl Caprylate 0.5 Levulinic Acid 0.3
Standard O/W, pH 5.3
EP Criteria
Aspergillus Niger
B
Candida Albicans
A
Escherichia Coli
A
Pseudomonas Aeruginosa
A
Staphylococcus Aureus
A
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GREEN Preservationsynergies
Glyceryl Caprylate 0.5 Levulinic Acid 0.3
Anisic Acid 0.2
Standard O/W, pH 5.3
EP Criteria
Aspergillus Niger
A
Candida Albicans
A
Escherichia Coli
A
Pseudomonas Aeruginosa
A
Staphylococcus Aureus
A
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GREEN Preservationsynergies

• The antimicrobial efficacy of organic acids at pH
  5.3 could be increased significantly in
  combination with surface active antimicrobial
  materials like Glyceyrl Caprylate
• Can we use this synergy to extend the scope of
  the organic acids to high pH values?

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GREEN Preservationsynergies
O/W Test Emulsion, pH 6.5 challenge tests
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GREEN Preservationsynergies
Standard O/W, pH 6.5
Levulinic Acid 0.7 Anisic Acid 0.4
EP Criteria
Aspergillus Niger
A
Candida Albicans
F
Escherichia Coli
B
Pseudomonas Aeruginosa
A
Staphylococcus Aureus
A
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GREEN Preservationsynergies
Standard O/W, pH 6.5
Levulinic Acid 0.7 Anisic Acid 0.4 Glyceryl
Caprylate 0.3
EP Criteria
Aspergillus Niger
A
Candida Albicans
A
Escherichia Coli
A
Pseudomonas Aeruginosa
A
Staphylococcus Aureus
A
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GREEN Preservationsynergies
Standard O/W, pH 6.5
Anisic Acid 0.4 Glyceryl Caprylate 0.7
EP Criteria
Aspergillus Niger
A
Candida Albicans
A
Escherichia Coli
A
Pseudomonas Aeruginosa
A
Staphylococcus Aureus
A
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GREEN Preservationsynergies
The acid molecules can penetrate more easily to
unfold their activity within the cell.
Surface active species penetrate the cell
membrane and destabilize the structure of the
membrane
The surfactants cause a higher permeability by
forming pores in the membrane.
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GREEN PreservationSummary
Organic acids and surface active substances are
versatile options for the alternative
preservation of cosmetics.
Interesting synergistic effects are observed when
organic acids and surface active substances are
combined.
By combining with surface active substances the
scope of application for organic acids can be
extended to higher pH values (up to 6.5).
Depending on the type of formulation, the amount
of surface active substances can be significantly
lowered in synergistic combinations to avoid
stability problems.
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THANK YOU!!!