Unsaponifiable, a source of active ingredients for cosmetics

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1 Unsaponifiable, a source of active ingredients for cosmetics Dr Florent JOFFRE Professional Training Manager Analytic Development Manager ITERG f.joffre@iterg.com

2 Oils from seeds and fruits Nutrition Non food Cosmetic

3 a wide diversity of chemical compounds Aliphatic - Fatty alcohols - Hydrocarbons - Wax esters Triglyceride 90-95% Fatty acid 95-99% 3-5% 0,1 à 2%-10% Glycerin Unsaponifiable Terpenic - Sterols - Tocopherols - Terpenics acids - Carotenoids OIL 1-5% Naturals 0,1-0,2% Polar lipids - Phospholipids - Sphyngolipids - Glycolipids 1-5% Minor compounds ppb-ppm Degradation - Hydrolyse - Oxidation - Isomerisation - Dimerisation - Cyclisation Undesired - water - Impurities - Proteins - Copper/Iron ppb-ppm Contaminants - Pesticides - HAP - MOSH/MOAH - MCPDs - Phthalates...

4 What is an Unsaponifiable? The "unsaponifiable" or unsaponifiable fraction include all of the components that after an alkaline hydrolysis (saponification) are barely soluble in aqueous solutions, but are soluble in organic solvents (hexane, ether). In summarize, unsaponifiable is the lipid fraction that cannot be transformed into soap. Quantity in oil: 0,5 to 2% for common oils except for avocado oil (10%), shea butter (5-12%), plant waxes (30-60%) Major lipid classes of the unsaponifiable : sterols, tocopherols, wax, hydrocarbons such as squalene, carotenoid, ubiquinone Quality and composition of the unsaponifiable depend on the origin of the seeds (or fruits), storage, process using for oil extraction, refining and concentration/extraction of unsaponifiable

5 Determination of unsaponifiable matter DEFINITION Unsaponifiable matter is determined gravimetrically after saponification of the sample with KOH in ethanol and liquid-liquid extraction with diethyl ether or hexane METHODS NF EN ISO 3596 : LLE with diethyl ether NF EN ISO : LLE with hexane AOCS Official Method Ca 6a-40 : Unsaponifiable Matter in Fats and Oils, Except Marine Oils AOCS Official Method Ca 6b-53 : Unsaponifiable Matter in Fats and Oils, High Level Method. This method is especially suited for marine oils, but is also applicable to vegetable oil deodorizer distillates and sludges. Limits of NF EN ISO methods These methods are not suitable 1/ for fats and oils containing an excessive amount of unsaponifiable matter and 2/ waxes

6 NF EN ISO 3596 & NF EN ISO ml water Diethy ether or Hexane g of oil 50 ml KOH/EtOH Saponification (1h) Extraction & washing 40 C Solvent evaporation gg Weight of the residue "If it is considered that a correction of the free fatty acids is necessary, titrate with a standard solution of potassium hydroxide and correct the mass of the residue not mandatory but may impact results Internal reference : mean without correction : 1,07% and with correction : 0,91%

7 Unsaponifiable matter Diethyl ether > Hexane Hexane Diethyl ether D Refined palm oil 0,25 ± 0,03 0,29 ± 0, % Crude sunflower oil 0,59 ± 0,03 0,73 ± 0, % Virgin Olive oil 0,83 ± 0,06 0,86 ± 0,05 + 4% Hazelnut oil 0,29 ± 0,02 0,38 ± 0, % Camelina oil 0,65 ± 0,06 0,74 ± 0, % Crude soyabean oil 0,57 ± 0,04 0,80 ± 0, % Refined peanut oil 0,33 ± 0,04 0,47 ± 0, % Cocoa butter 0,40 ± 0,02 0,55 ± 0, % Sweet almond oil 0,40 ± 0,04 0,49 ± 0, % Refined rapeseed oil 0,79 ± 0,05 1,00 ± 0, % Source :BIPEA 2016/2017

8 Unsaponifiable & cosmetic interest Total UnSap (waxes, hydrocarbons, vitamin ) Anti-wrinkle Restructuring of the micro-relief Activation of the synthesis of cutaneous lipids (ceramide and collagen) Moisturizer Promotes the barrier function of the skin Total UnSap (waxes, hydrocarbons, vitamin ) Sterols and triterpene alcohols Anti-inflammatory Antioxidant activity (vit E) Free radical scavengers (pro-vit A) vite, carotene, CoQ10

(lignan), karitene (specific hydrocarbon).

9 a wide diversity of molecules Aliphatic compounds Unsaponifiable Terpenic compounds And a lot of specific lipids depending of the sourcing: alkylfuran (avocado), alcenylphenol (cashew nut), cafestol (diterpene of green coffee), sesamin and sesamolin (lignan), karitene (specific hydrocarbon). Hydrocarbons R-CH 3, n impair, C11 à C35 Fatty alcohols R-CH 2 OH, C16-C20 Waxes C40-C50 Pseudo-cyclic Cyclic Squalene triterpene, C 30 H 50, 5-10 % of US Lycopene C 40 H 56 Triterpenes : Sterols Tocopherols Carotenoids

10 Aliphatic compounds : hydrocarbons Hydrocarbons are the least polar compounds of the unsaponifiable matter of vegetable oils and the profile of n-alkane is specific for each oil. The n-alkanes are thought to be endogenous to a plant, they are formed as a result of the decarboxylation of long-chain fatty acids (crude vegetable oil) or may be formed during the refining (stigmastadiene for example). mg/kg Sunflower VOO Sesame Peanut Safflower C15-C22 1,6 2,7 1,1 1,6 10,3 C23 0,2 18,5 0,5 0,2 2,9 C24 0,2 9,5 0,3 0,4 1,2 C25 1,5 18,0 1,1 0,8 2,8 C26 0,4 2,0 0,6 0,4 1,2 C27 11,2 15,7 6,3 3,4 13,5 C28 2,4 1,8 1,6 0,8 2,1 C29 49,6 12,4 18,5 12,7 27,1 C30 5,5 1,7 0,8 2,0 C31 48,0 9,4 14,2 6,2 15,2 C32 1,8 1,5 1,4 0,4 0,9 C33 3,6 5,7 6,6 0,9 1,5

11 Aliphatic compounds : waxes «True» waxes are esters of long chain fatty acids with long chain fatty alcohols A beewax is not a wax but a complex mixture containing waxes, free fatty acids, free fatty alcohols, hydrocarbons

Aliphatic compounds : vegetable waxes Esters 80-85 %

+ C22:1 Candelilla wax Hard wax, bright and fragrant

12 Aliphatic compounds : vegetable waxes Esters % Acids C24-C28 Alcohols C24-C34 Carnauba wax hard wax, brittle, shiny Esters 20 % Acids C30 C34 AlcoholsC20 C32 Esters 98% Acids C20:1 AlcoholsC20:1 + C22:1 Candelilla wax Hard wax, bright and fragrant (terpenes) rich in hydrocarbons Jojoba oil Liquid wax emolliant

13 Terpenic lipid in plant : a complex LEGO world Geranyl-PP Isopentenyl (IPP) Number of unit (n) Number of carbons Monoterpene Sesquiterpene Di- Terpenes 1 1, Geranyl-PP Farnesyl-PP Triterpenes Tetraterpenes Geranylgeranyl-PP

14 Terpenic lipid in plant: a complex LEGO world More than 4,000 different structures MVA pathway (mevalonate) Isopentenyl (IPP) MEP pathway (methylerythritol phosphate) Geranyl-PP Farnesyl-PP Squalene Sterols Polyprenols CoQs Geranyl-PP Diterpenes Carotenoids (vit A) Tocopherols (vit E) Phylloquinones (vit K) Chlorophylls

15 Terpenic pseudo cyclic compounds Squalene (C30H50) Precursor of triterpenic alcohols such as sterols Skin properties: emollient, hydration Oils (mg/kg) Almond Avocado Olive Sunflower

16 Terpenic pseudo cyclic compounds Lycopene (C40H56)

17 Terpenic pentacyclic PENTACYCLIC Specific of plants Main molecules : lupeol, amyrine, uvaol, erythrodiol lupeol uvaol erythrodiol b amyrine

18 Terpenic tetracyclic : sterols (>100 structures) A convenient way to describe phytosterols is to divide them into three groups : 4-Dimethylsterols : 2 CH 3 esterified on C4 (ex. Cycloartenol, Butyrospermol) 4-monomethylsterols : 1 CH 3 esterified on C4 (ex. Gramisterol) 4-desmethyl phytosterols : 0 CH 3 esterified on C4 (end-products) total carbons: C27, C28 or C29 double bond in the D5 or D7 Cycloartenol 70-80% of UnSap v Gramisterol Cholesterol D5 C27 Campesterol D5 C28 Sitosterol D5 C29 D7 Stigmasterol D7 C29

19 Terpenic tetracyclic : conjugated sterols

Phytosterols in vegetable oils Pharmaceutical applications: anti-inflammatory, treatment of erythema, treatment of solar burns (same action as cortisone, without side effects) Cosmetic applications:

20 Phytosterols in vegetable oils Pharmaceutical applications: anti-inflammatory, treatment of erythema, treatment of solar burns (same action as cortisone, without side effects) Cosmetic applications: emulsifier for lotion, creams, body milks. Good tolerance of the skin, recovery of skin barrier function, improved skin elasticity and decreased skin roughness, Increased collagen and hyaluronic acid production, protective effect of the hair, reduction of the electrostatic effect, Nutrition : reduce the absorption of cholesterol in the gut mg sterols / 100 g oil Palm Olive / Hazelnut Walnut Soya / Grapeseed Sunflower Rapeseed / wheat germ Corn germ

21 Phytosterols: a marker of adulteration Peanut Rapeseed Corn Soya Sunflower Hazelnut Cholesterol ND-1 ND-1.3 ND-1 ND-1 ND-0.4 ND-0.4 b-sitosterol Campesterol Stigmasterol 8-11 ND <2 D7-stigmasterol ND-1 ND-1 ND <0,5 D7-campesterol - ND ,7 <0,5 D5-avenasterol D7-avenasterol 1-2 ND-1 ND <0,5 Brassicasterol <0,4 Others ND

22 Terpenic cyclic compounds : vitamin E -tocopherol : C 29 H 50 O 2 PM = 431 g/mol % of UnSap. Synthesize by the plant Free or esterified forms The profile of isomers is specific for each vegetable oils : marker of fraud or mix

23 Terpenic cyclic compounds : vitamin E Olive Peanut Rapeseed Soya Sunflower Wheat Corn -tocopherol b-tocopherol tocopherol tocopherol Content (mg/kg)

anti-lipoperoxidation of membrane of lipoprotein and cells :

24 Biological activity versus Antioxidant activity -tocopherol is the most bioavailable isomer; so -tocopherol can play a role in the anti-lipoperoxidation of membrane of lipoprotein and cells : Prevention of skin aging isomers + -tocopherol : antioxidant in oils and formulated products

25 Terpenic cyclic compounds : carotenoids Plant pigments : carotenoids and xanthophylls Carotenoids: tetraterpene mainly trans b and carotene (C40H56), sometimes included in the «hydrocarbon terpenic family» Xanthophylls: carotenoids with OH substitution (zeaxanthin, lutein ) high antioxidant activity of carotenoids as singlet oxygen traps (Free radical scavengers) carotenoids are precursors of vitamin A after chemical modification under light (UV)

26 Pro-vitamin A activity of the carotenoids Trans-b-carotene 100 % 9 cis-b-carotene 38 % 13 cis-b-carotene 53 % Trans- -carotene 52 % 9 cis- -carotene 13 % Trans- -carotene % Cis- -carotene 19 % b-zeacarotene % Lycopene 0 % 1 ER = 1 µg retinol = 6 µg β-carotene (= 3,3 UI) Vitamin A is involved in vision, epithelial integrity, growth, resistance to infections, cellular detoxification Vitamin A deficiency can cause skin dryness

C H 3 Ubiquinone (IUPAC, 1975), Coenzym Q All cells of your body contain it > 1000s of scientific

27 Ubiquinone or CoEnzyme Q10 and 9 2,3-dimethoxy, 5-methyl, 6-polyisoprenyl parabenzoquinone O Isoprene Chain H 3 C O CH 3 Functional group Benzoquinone Ring H 3 CO H Linkage on membrane cells O C H 3 Ubiquinone (IUPAC, 1975), Coenzym Q All cells of your body contain it > 1000s of scientific and clinical studies 1 Nobel Price (Dr. Peter Mitchell) n n= 9 (sunflower) or 10 (soyabean and rapeseed oil)

28 Ubiquinone or CoEnzyme Q10 and 9 O OH H 3 CO CH 3 + 2H + + 2e - H 3 CO CH 3 H 3 CO O CH 3 H n - 2H + - 2e - H 3 CO OH CH 3 n H CoQ10 - Ubiquinone (oxidized form) CoQ10H 2 - Ubiquinol (reduced form) Active form as antioxidant is the reduced form (ubiquinol) Protection against oxidative modifications of LDL, Essential in vitamin E regeneration, Protective effect on lipids, proteins, and DNA, Protection against endogenous produced radicals in the mitochondria Active form as energy metabolic is the oxidized form (Ubiquinone) Required for energy production in the cell (95% of all ATP production (oxidative phosphorylation process)

29 Occurrence of CoQ10 Body synthesis Complex pathway content when statin treatment Food content Meat, eggs and fish 1 to 280 mg/kg fresh wt Oil (rapeseed, soybean) 75 to 250 mg/kg Average daily intake: 5-10 mg but absorption of CoQ10 is poor and limited Blood concentration : 1 µg/ml (safe) 2 µg/ml (disease) Health claim support 30 mg/day for antioxidant function or supports energy production 100 mg/d maintenance of heart health

30 Composition of the Unsaponifable fraction of edible common oils Oil % UnSap Sterols Tocopherols Squalene Hydrocarb. Triterpenic alcohols Soyabean < 20 < 5 < 20 Sunflower < 20 < 5 - Corn < 20 < 40 < 100 Rapeseed < 20 < Wheat germ < 20 < 40 - Cotonseed < Peanut Coprah < 10 < Virgin Olive Palm > 100 (3) < 20 < 120 Carotènes Source: Piccirelli (unpublished) All data are expressed in mg/100g

31 Sourcing of the unsaponifiable Vegetable oils : Crushing < hexane extraction and refining %Unsap. Deodistillates Composition Vegetable oils DoD from chemical refining DoD from physical refining % TAG > 97 < 5 < 5 % MAG/DAG < 1 < 20 < 15 % FFA < > 70 % unsaponifiable < 5 % sterols < < 1 % tocopherols < < 1 % others (1) < < 4 (1) hydrocarbons, squalene, volatils compounds, contaminants, Source: Piccirelli (unpublished)

32 Special thanks to Mme Anne Rossignol-Castera (OLEOS), Mr Antoine Piccirelli (OLVEA Green technology) and to my colleagues Florence Lacoste and Franck Dejean for their help to prepare this lecture Thanks for your attention

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