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Introduction: The Indian cosmetic market, which comprises of skin care, hair care, color cosmetics, fragrances and

oral care categories, has outperformed worlds leading cosmetic markets in terms of growth in the recent past. The Indian cosmetic market has started witnessing rampant growth driven by improved spending power and rising consumer awareness about cosmetic products amid growing beauty consciousness. Cosmetics in general are classified as substances that are used to groom and beautify the body, to contribute to a persons sense of well-being and to enhance their feelings of attractiveness. Since ancient times mankind has explored ways of beautifying the body, including face painting and wearing ornate headress and jewellery. In this module, we will focus on the cosmetics that help us clean and beautify the skin, hair, nails and teeth. Cosmetics are manufactured in a chemical process, either on a small scale or large scale, and the production has to be carefully monitored. The manufacture of skin cream, moisturisers and other skin treatments, particularly face creams, are often carried out in clean-room conditions so that no bacteria enter the cream and there is little or no risk of an adverse skin reaction. Staff entering the clean room wear protective clothing and a face mask at all times and the air conditions are controlled in the room. This may explain why some womens face creams are so expensive. Skincare involves an entire range of washing products, including soaps, perfumed soaps, shower gels and lotions. Haircare has a tremendous store of treatments, including shampoos and conditioners and then branching out to including a multitude of dye products from full colour treatments to highlights. Nailcare has become a big business in Ireland in the last few years, with nail extensions of many types replacing the more traditional manicures and nail varnishes. Teethcare has entered the realm of cosmetic surgery, besides toothpaste there is mouth washes, tooth polishes and whitening pastes. The end result Transition Year Science 6 is that young people are more aware of the need to present themselves clean and well groomed. New markets have been created, for example, the BodyShop has entered a new market, producing smaller quantities and a more environmentally friendly product (www.the-body-shop.com). This new consciousness about the origin of the cosmetics, whether or not they are tested on animals and where they are originating from has led to a new debate. While this unit will not seek to cover all the possible debates it suggests that you get the scientific knowledge first and foremost so that your debate is based on facts. You will be aware of the black and white attitude taken by many people with regard to chemicals, the thinking that chemicals are either all bad or all good for you, when in fact neither statement is in fact correct. You can search for the chemistry underlying the products by looking closely at the labels and doing a website search for more information. Use of Nanotechnology in Cosmetics : The applications of nanotechnology and nanomaterials can be found in many cosmetic products including moisturisers, hair care products, make up and sunscreen. Almost all the major cosmetic manufacturers use nanomaterials in their products. LOral has a number of nanotechnology-related products in the market and ranks 6th in US in the number of nanotech related patents in US1. The European Commission estimated in 2006, that 5 % of cosmetic products contained nanoparticles. The application of nanomaterials in cosmetic products has been the subject of continuous discussion in the media, scientific circles and among policy makers for the past few years. Toxicity issues have been raised due to conflicting research papers about the safety of nanomaterials and lack of agreement between researchers on whether the nanomaterials are safe for dermal use. There are a number of classes of nanoparticles used, or proposed for use, in cosmetic applications. In cosmetics there are currently two main uses for nanotechnology. The first of these is the use of nanoparticles as UV filters. Titanium dioxide (TiO2) and zinc oxide (ZnO) are the main compounds used in these applications. Organic alternatives to these have also been developed. The second use is nanotechnology for delivery.

Liposomes and niosomes are used in the cosmetic industry as delivery vehicles. Newer structures such as solid lipid nanoparticles (SLN) and nanostructured lipid carriers (NLC) have been found to be better performers than liposomes. In particular, NLCs have been identified as a potential next generation cosmetic delivery agent that can provide enhanced skin hydration, bioavailability, stability of the agent and controlled occlusion. Encapsulation techniques have been proposed for carrying cosmetic actives. Nanocrystals and nanoemulsions are also being investigated for cosmetic applications. Patents have been filed for the application of dendrimers in the cosmetics industry. Other novel materials, such as fullerene, have also appeared in a small number of beauty products. This report looks into some of the nanotechnologies used in the cosmetic industry and provides an overview of current activity in this area. Unit 1 SKIN Soap Soap is a product when used with water decreases surface tension, loosens unwanted particles and th absorbs dirt and grease into a foam which can be washed away. Soap bars are a 19 century invention, with soaps used in the textile industry been around for the last 5000 years. Bathing was popular in Roman times and a soap factory was found in the ruins of Pompeii, a city destroyed by the eruption of Mount Vesuvius in 79 A.D. People who made soaps for personal use tended also to make candles since the same raw materials are used in both products. In the 19th century a new process, using sodium hydroxide, was found making a hard product and making soap bars that were affordable. Soap results from a chemical reaction between an acid and a base, that causes saponification to occur. The acid part of the soap comes from a fat, either an animal or vegetable fat. The soap molecule is made up of a fat-loving tail and a water-loving head. It removes dirt by emulsifying the oil on the skin making it miscible with water. Animal fats have to be rendered and purified before been used in soap making. Soaps, made from vegetable oils, like Castile soap in Spain, are regarded as superior to those made from lard. The vegetable fats includes olive oil, coconut oil and other oils such as jojoba, almond and avocado. The base or alkali part, is either made from ashes (lye water from potash) or sodium hydroxide. Sodium hydroxide is corrosive and requires careful handling, including safety goggles and gloves. It was introduced into the soapmaking industry by the French chemist Nicolas Leblanc (1742 1806) and improved Transition Year Science10by the Belgian chemist, Ernest Solvay (1836-1922). The soap bars produced from sodium hydroxide were hard and easy to ship and to store. During the chemical reaction the base reacts with the fat or oil, fatty acids get separated from the glycerin part and they bond with the sodium or potassium part of the alkali. The product formed, is the sodium or potassium salt, so that technically soap is a salt, for example, sodium hexadecanoate. The sodium salts of long chain carboxylic acids are soaps. A carboxylic acid has a COOH grouping. The sodium displases the hydrogen in the process and a typical soap molecule is formed.The long chain part of the hydrocarbon molecule, tends to dissolve in non-polar solvents while the other end of the molecule, the COONa part is hydrophobic and dissolves in water. The end product has a neutral pH and will not burn the skin. Additives get added to soaps including fragrances and additives that will extend the shelf life and enhance colour and odour. The effectiveness of soap is reduced in areas with hard water i.e. water rich in calcium or magnesium salts. Unit 2 HAIR The detergent action of hair shampoo, removes dirt from the hair and scalp, as well as enough sebum to keep the Transition Year Science 14hair looking clean, but not so much as to remove all the oil. The action of the detergent lauryl sulphates accomplishes this tightrope act very well. Other shampoo ingredients are added to give the shampoo a pleasant viscosity, to adjust the pH and to act as

preservatives. The acidity of the shampoo plays a part in the production of a good shine, a slightly acidic cuticle reflects light better, thus giving the hair a better shine.Hair has two natural pigments, melanin, the dark brown pigment of the skin and phaeomelanin, a red-brown or yellow-brown pigment similar to melanin. The colour of hair depends on the amount of these two pigments within the hair strand. Their absence produces white or grey hair. Changing the colour of hair nowadays occurs through the action of complex synthetic organic chemicals. Dyes without bleach darken the hair, while hair is lightened in colour with bleaches. Hair is the protein keratin, and the protein molecules are held together by disulphide linkages -S-S- . If hair is to be made either wavy, or straight the disulphide linkages have first to be broken and their positions changed. This happens when hair is washed, and heated rollers and other methods are used to change the shape of the hair as it dries. Unit 3 TEETH Toothpastes have antibacterial agents as well as cleaning agents. Fluoride is added to toothpaste to help strengthen the enamel. Fluorides in toothpaste are found in the form of: stannous fluouride ( SnF ) sodium monofluorophosphate (Na PO F) and sodium fluoride (NaF). Toothpaste typically contains water, glycerol (retains water), calcium phosphate (abrasive), sodium-N-lauryl sarcoinate (surfactant), carrageenan (thinkening agent) and fluorides (enamel hardener). Good dental hygiene is essential for our health and well being. It is recommended that you change your toothbrush every three months, you brush your teeth regularly twice a day and you use a mouth wash. New:The global market for skincare and color cosmetics exceeded 53 billion dollars in 2002. The number of new products brought to market continues to expand exponentially. Cosmetic chemists are always looking for interesting and exotic ingredients that improve skin's appearance and health. A vast array of compounds is required to supply these products. The latest edition of the Cosmetics Toiletries and Fragrance Association (CTFA) Dictionary lists more than 10,000 raw materials. Every year hundreds of new ingredients are added to the list of those that have been used for centuries. Some materials used today can be traced to 11,000 B.C.E. in the animal drawings from the caves of Altimira. History :The appearance of skin care formulation dates to around 3000 B.C.E. in ancient Egypt. Most concoctions were prepared from natural materials. Cleopatra is said to have bathed in donkeys' milk to keep her skin smooth and supple. One naturally occurring material used by the ancients was red ochre, or iron oxide. Lumps of red ore were formed when iron oxidized or rusted. The red iron oxide was found in burial tombs in ceremonial lip tints and rouge preparations. It was also used to draw the ancient cave pictures of animals, as seen in Altimira, and is still used in many makeup formulations

Figure 1. Phosphatidylcholine (PC). today. Eye paints have also been found at ancient gravesites. These paints consisted primarily of a copper-based green ore called malachite that was mined from nearby quarries. Animal fat was combined with fragrant substances such as frankincense and myrrh to produce early skin ointments. More sophisticated creams and lotions were fine tuned through trial and error and passed down over many generations. Emulsions :The majority of creams and lotions are emulsions. An emulsion can be defined simply as two immiscible fluids in which one liquid is dispersed as fine droplets in the other. Homogenized milk is an example of a typical oil-in-water (o/w) emulsion. Milk fat (oil) is dispersed in water as fine droplets by the homogenization process. The reason the fat does not float to the top immediately is due to the presence of emulsifiers; in this case, a milk protein called sodium caseinate as well as several phopholipids. In the case of water-in-oil (w/o) emulsions, water is dispersed as droplets and suspended in the oil phase. The nondispersed liquid or external suspending phase is also called the continuous phase. Mayonnaise, vinegar water dispersed as fine droplets in a continuous phase of soybean oil, is an example of a waterin-oil emulsion. Lecithin from eggs stabilizes the mayonnaise emulsion. Surfactants :Most emulsifiers can be considered surfactants or surface-active agents. These materials are able to reduce the surface tension of water. What makes an emulsifier surface active is related to its HLB, or hydrophile-lipophile balance. HLB is determined by the size of the hydrophilic (water-loving or polar) portion of a molecule as compared to the size of the lipophilic (oilloving or nonpolar) portion. The HLB system was created to rank the relative polarity of materials. The most polar, water soluble, materials are at the top of the twenty-point scale with more non-polar, oil soluble, materials closer to zero. The HLB of sodium caseinate is assigned a value of around fourteen because of it's high solubility in water.

Lecithin, being poorly soluble in water, has an HLB value of about six. Both have polar groups. The polar group in the milk protein is sodium. Lecithin's surface-active component is a molecule called phosphotidylcholine or PC (See Figure 1). The polar, or water soluble part of PC is the phosphate functional group. The emulsifiers' polar groups orient toward the polar water phase. Their lipophilic, nonpolar groups oriented toward the oil phase to form micelles (see Figure 2). These spherical structures provide stability to the emulsion through Hydrogen bonding and weak electrical forces.

Figure 2. Surfactant. Skin-care emulsifiers can be divided into two groups based on ionic charge (See Figure 3). Materials that can dissociate into charged species are considered ionic while those that do not are called nonionic. Ionic emulsifiers can be further classified by type of charge. Anionics are negatively charged when solvated as in sodium stearate or soap. When fatty acids are reacted with alkali they form soaps. The process of soap formation is called saponification. The negatively charged stearic acid group is the main emulsifying unit of the soap, giving it the anionic classification. Positively charged emulsifiers are called cationic. Quarternium24's emulsifying unit dissociates into the positively charged ammonium group. Amphoterics are compounds that express both negative and positive charges. Nonionic emulsifiers are often used in skin-care emulsion for their safety and low reactivity. They are generally classified by chemical similarity. Glycerin, commonly added to cosmetic emulsions for its humectant properties, is the backbone of a class of emulsifiers called Glyceryl esters . Glyceryl monostearate, or GMS, is called a monoester because of its sole ester linkage (see Figure 4). The diester is prepared by esterifying two molecules of stearic acid for every molecule of glycerin. Glyceryl mono- and diesters are very effective emulsifiers because they contain both polar hydroxyl (OH) groups as well as

non-polar fatty acids. If all three of Glycerin's hydroxyl groups are reacted, the resulting triester will have little emulsifying capability. Stearic acid is called C18 fatty acid. The fatty acids, present in fats and oils, are classified according to their carbon-chain lengths. Because stearic acid is a major component of many of the fats and oils used in beauty treatments, stearate-based emulsifiers are particularly useful. Fatty acids are key components of many cosmetic emulsifiers due their miscibility in a variety of natural and synthetic oils.

Figure 3. Structures of emulsifiers.

Figure 4. Direct esterification of glycerine.

Esters polyethylene glycol or ethylene glycol are called PEG esters. A PEG ester's solubility is determined by the number of PEG molecules reacted per molecule of acid. PEG 6 oleate for instance has six molecules of PEG reacted with one molecule of oleic acid. As the number of polar, PEG molecules per acid molecule increases the water solubility/HLB is increased; PEG 8 oleate is more soluble than PEG 6 oleate. The cosmetic chemist will often use blends of glyceryl esters and a PEG ester with high and low HLB values to determine the required polarity to emulsify various fats and oils. The many types of emulsifiers are too numerous to list here, however McCutcheon's Emulsifiers and Detergents is an excellent source for a more complete listing. Emollients :The majority of emollients used in personal care and beauty items are fats and oils, also called lipids. Animal fat or tallow is composed primarily of stearic and palmitic acids with carbon chains lengths of 18 and 16 respectively. Many of the major cosmetic companies are moving away from animalbased materials like tallow to renewable vegetable-based materials. Coconut oil and palm kernel oil are often used. Some of the key characteristics required in good emollients are good spreading properties, low toxicity/skin irritation and good oxidative stability. Oleic acid, a major constituent of olive oil has poor oxidative stability due to the presence of its double bond. Fats and oils are considered saturated if they do not have double bonds. Unsaturated oils like olive oil have double bonds that can react with oxygen, especially when heated. The oxidation process can produce off colors and odors in lipids causing them to go rancid and unusable. Petroleum-based emollients such as petroleum jelly and mineral oil are found in many formulations because they do not contain double bonds or reactive functional groups. Silicone oils such as cyclomethicone, dimethicone are often added to increase slip and emolliency (See Figure 5). Oils that contain high levels of essential fatty acids, EFAs, are prized for their ability to replenish lipids (oils) that are found naturally within the skin layers. Linoleic acid is an example of an EFA. Long-chain alcohols, also called fatty alcohols, are useful as emollients and emulsion stabilizers. Their polar hydroxyl groups orient to the water phase with their fatty chains oriented towards the oil phase. Esters of fatty alcohols and fatty acids make excellent emollients because of their low reactivity and good stability. Lanolin, derived from sheep's wool, is often called wool grease. Lanolin has been used for centuries due to it's unique composition of complex sterols, fatty alcohols, and fatty acids. Cholesterol, a cyclic molecule called

Figure 5. Dimethicone and cyclomethicone. a sterol, is a major component. The polar hydroxyl groups of sterols and alcohols enable the grease to absorb and hold water. Skin is primarily composed of water, countless oils and emollients are used to nourish and protect it. Moisturizers :The main distinction between moisturizers and emollients is their solubility in water. Healthy skin requires moisture. Moisturizers are generally polar materials that are hygroscopic in nature; they hold onto water. An important tool to assess the efficiency of moisturizers is the high scope. It measures transepidermal water loss or TEWL. After a moisturizer is applied to the skin, the moisture level is recorded. After several minutes the moisture level will be reduced due to the natural tendency of the skin to release moisture over time. Ingredients that can maintain a high level of moisture in the upper layers of the skin for several hours can reduce the rate at which water is lost. Glycerin is a very costeffective ingredient used to help reduce TEWL. Sorbitol, sucrose, glucose, and other sugars are also commonly used to hydrate the skin. Aloe, which contains a mixture of polysaccharides, carbohydrates, and minerals, is an excellent moisturizer. As skin becomes drier in the winter months, it may be necessary to incorporate materials that better seal the moisture in the skin. Waxes :Waxes are composed primarily of long-chain esters that are solid at room temperature. Anyone who has ever dipped a finger in molten wax has experienced its sealing properties. Some common waxes used in cosmetics are beeswax, candelilla, carnauba, polyethylene, and paraffin. The melting points of waxes vary widely depending on their unique composition and chain lengths. Commonly used in lip balms and sticks, waxes function as structuring agents, giving the stick enough rigidity to stand up on its own, as well as barrier properties. By combining waxes with different properties such as high shine, flexibility, and brittleness, optimal cosmetic performance can be achieved. Often waxes are combined with compatible

oils to achieve the desired softness. Compatibility is generally determined by gauging the turbidity and degree of separation of two materials mixed together above their melt points. Waxes are particularly useful in hand creams and mascara emulsions for their thickening and waterproofing properties. Thickeners :By incorporating enough wax into a thin lotion, a thick cream can be formed. Many thickeners are polymers. Cellulose, a fine powder polymer of repeating

Figure 6. Cellulose and carbopol. D-glucose units, swells in hot water creating a gel network. Carbopol, a polyacrylic acid, swells when neutralized (See Figure 6). Bentone clays swell when their structure, resembling a stack of cards, is opened up through mechanical shear. Carrageenan, pectin, and locust bean gum are all examples of cosmetic thickeners that are also used in some of our favorite foods such as jellies, salad dressings, and pie fillings. Active Ingredients :Materials that work physiologically within the skin or aid in protecting the skin from insult are also called active ingredients. The term "cosmeceuticals" coined by famed dermatologist Dr. Albert Kligman, refers to a product that is in-between a cosmetic and a drug. Although a cosmetic, by legal definition, can only serve to beautify and protect the surface of the skin, many cosmetic products can be shown to penetrate the dermal layers of the skin to exact a physiological change. Fruit acids are an example of an active material. Also called alpha hydroxyacids or AHAs, they have the ability to penetrate the skin, where they can increase the production of collagen, elastin, and intracellular substances thus improving the appearance of the skin. Thousands of cosmetic actives are used to affect the skin in a variety of ways. They are used to lighten, tighten, and firm the skin. They can be used to suppress perspiration as in the case of aluminum chlorohydrate. Salicylic acid and benzoyl peroxide are

important ingredients because of their anti-acne activity (See Figure 7). Some active materials are added to skin treatments to protect the skin from the environment. Dimethicone and petrolatum are examples of skin protectants. Sunscreens :Sunscreens are a class of compounds that protect the skin from ultraviolet radiation. Wavelengths between 290nm and 400nm are particularly damaging to the skin. Sunscreens' ability to absorb or reflect these damaging wavelengths are rated by their SPF or sun-protection factor. For instance a person protected with a factor-15 sunscreen will be able to stay in the sun fifteen times longer than if unprotected. Octyl methoxycinnamate, octyl salycilate, titanium dioxide, and avobenzone are some important topical sunscreens. They can be classified as either UVA or UVB sunscreens depending the wavelengths they absorb. Benzophenone 4, a water-soluble UV filter, is commonly used to protect the color of cosmetic products.

Figure 7. Structure of Benzoyl peroxide. Color :Pigments and dyes are used in products to impart a color. Titanium dioxide (TiO 2 ) is a white pigment that is mined. In combination with natural mined and synthetic iron oxides, which range in color from red, yellow, black and brown, depending upon the degree of oxidation and hydration, a range of color can be produced that will be suitable for almost every skin tone. Face powders are produced by blending inorganic oxides and fillers. Fillers are inert, generally inexpensive materials such as kaolin, talc, silica, and mica that are used to extend and fully develop colors. Pressed powders like eyeshadows and blushers are prepared by blending additional binding ingredients such as oils and zinc stearate and pressing the mixture into pans. Eyeshadows and lipsticks often contain pearlescent pigments commonly called pearls. Pearls sparkle and reflect light to produce a multitude of colors. They are prepared by precipitating a thin layer of color on

thin platelets of mica. Varying the thickness of the color deposited changes the angle of light refracted though the composite, creating different colors. Organic pigments are used to color lipsticks and eyeshadows. When organics are precipitated on a substrate they are called lake pigments. The term lake refers to the laking or precipitating of the organic salt onto a metal substrate such as aluminum, calcium, or barium. They are called D&C (drug and cosmetic) and FD&C (food, drug and cosmetic) colors. Some examples are D&C Red#7 calcium lake and FD&C Yellow #5 aluminum lake. Dyes such as FD&C Blue#1 and D&C Yellow #10 are readily soluble as opposed to pigments, which are insoluble. Dyes are useful in providing tints for lotions, oils, and shampoos. Preservatives :Most cosmetic products require the addition of preservative to prevent microbial contamination and rancidity. Parabens and ester of parabenzoic acid are by far the most commonly used because of their effectiveness against gram-positive bacteria. Phenoxyethanol is used to protect against gramnegative strains. The cosmetic chemist will generally employ a mixture of preservatives to protect against different bacterial strains as well as yeasts and molds. Antioxidants such as tocopherol (vitamin E) and BHT are also added to prevent oxidation of sensitive ingredients as well as protect the skin from free-radical damage. Conclusion :As long as society continues to puts great emphasis on looking young and beautiful cosmetic chemistry will continue to flourish. A good understanding of the fundamentals of emulsion chemistry and skin physiology are prerequisites, when formulating personal care products. A good cosmetic chemist must be able to combine science and art to create products with the feel and look that consumers desire.

6.3.5 Dendrimers and hyperbranched polymers Dendrimers and hyperbranched polymers have also been considered for use in the cosmetic industry. Dendrimers are unimolecular, monodisperse, micellar nanostructures, around 20 nm in size, with a well-defined, regularly branched symmetrical structure and a high density of functional end groups at their periphery. They are known to be robust, covalently fixed, threedimensional structures possessing both a solvent-filled interior core (nanoscale container) as well as a homogenous, mathematically defined, exterior surface functionality (nano-scaffold) 36. They are prepared in a step-wise fashion, with an architecture like a tree branching out from a central point. Hyperbranched polymers are effectively disorganised, unsymmetrical dendrimers that are prepared in a single synthetic polymerisation step, making them much

more cost-effective than dendrimers. The large number of external groups suitable for multifunctionalisation which is a requirement for its use as a cosmetic agent carrier. LOral have a patent for a formulation containing hyperbranched polymers or dendrimers which form a thin film when deposited on a substrate 37. This formulation could be used for a wide variety of cosmetics e.g. mascara or nail polish. A problem of current polymers is that films are formed too soon after deposition. The new formulations will form highly adherent, water washable films only upon oxidation, usually by exposure to air. It is also possible to incorporate cosmetic agents into the medium to help form films for different applications. They have also developed a formulation comprising of a tanning agent and dendrimers for artificial skin tanning38. Unilever have a patent for hydroxylfunctionalised dendrimers from polyester units to create formulations for use in sprays, gels orlotions39. Several patents have been filed for the application of dendrimers in hair care, skin care and nail care products40,41.

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