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  1. Topic : GMO
    http://www.cosmeticsinfo.org/genetically-modified-organisms-gmos

    What Are Genetically Modified Organisms?
    Genetically Modified Organisms are plants and other living organisms derived from modern molecular biotechnology techniques that alter the genetics of the organism. Humans have indirectly changed traits in plants and animals since prehistoric times, but new techniques of molecular biotechnology have resulted in the ability to target specific traits for alteration. Biotechnology has allowed the introduction of proteins, for example, that are not native to a given species. The United States Department of Agriculture defines biotechnology as “the use of biological processes of microbes, and of plants and animal cells for the benefit of humans.” Genetically modified foods were first introduced in 1996. A large portion of the food supply in North and South America is now produced with this technology. In the United States, over one-half of the soybean crop and a large percentage of corn and cotton are genetically modified and have been since the late 1990s. No adverse health effects associated with the consumption of Genetically Modified Organisms have been demonstrated, and these crops may have important benefits to farmers and consumers. For example, plants have been modified to produce soybeans with less saturated fat than conventional soybeans, offer significant consumer health benefits.

    Why are ingredients from Genetically Modified Organisms used in cosmetic and personal care products?
    Plant-derived (botanical) ingredients were among the very first cosmetics, and, as noted above, large percentages of many agricultural commodities have been genetically modified. This use of biotechnology in agriculture has occurred largely to assist farmers in the production of crops for food and other uses. In some cases, however, Genetically Modified Organisms have been developed to assist in the production of cosmetic ingredients. For example, canola has been modified to produce high levels of lauric acid, a key ingredient in soaps and detergents, at a reduced cost to consumers. Cosmetic ingredients potentially derived from Genetically Modified Organisms include ingredients such as corn oil, corn flour, soybean oil, lecithin and proteins produced by yeast.

    Are ingredients from Genetically Modified Organisms safe in cosmetic and personal care products?
    The FDA has concluded there is no evidence that bioengineered food or plant ingredients are less safe than those produced through conventional methods. Similarly, ingredients derived from Genetically Modified Organisms that are now found in cosmetic and personal care products are considered to be as safe as those produced through conventional means.

    More Information:
    Find out more about Genetically Modified Organisms. FDA: Are bioengineered foods safe? http://www.cfsan.fda.gov/~dms/fdbioeng.html UK Health and Safety Executive: Genetically modified organisms. Genetically Modified Organisms (Contained Use) – health and safety at work: http://www.hse.gov.uk/biosafety/gmo/index.htm New Scientist bibliography of publications. Special Report on GM Organisms – New Scientist: http://www.newscientist.com/channel/opinion/gm-food

    – See more at: http://www.cosmeticsinfo.org/genetically-modified-organisms-gmos#sthash.BdKRjYUG.dpuf

  2. Trans Fats in Cosmetics?

    Background
    http://www.cosmeticsandtoiletries.com/formulating/function/moisturizer/126610168.html

    It is common practice in cosmetic chemistry to be interested in achieving different types of aesthetics. As natural personal care products rise in demand, altering feels and physical properties of natural oils and fats through cosmetic chemistry become paramount.

    A popular approach has been altering the physical properties of natural oils or fats to achieve butters that are spreadable on skin. These butters posses attributes that are different from traditional solids and liquids in that they are solid when applied but liquefy under pressure. Butters have become more and more important in personal care products, especially when the formulator desires materials that incorporate natural oils in a formulation requiring a solid form. Typically, butters are either natural or chemically altered oils or fats. The most common chemical alteration is a simple process called hydrogenation.

    Natural Butters
    Natural butters are materials that are produced from a natural source and are not chemically modified. Natural butters are extracted and refined by chemists; however, unlike hydrogenation, no chemical modification is made to the molecule. There are a number of naturally occurring butters including shea butter and cocoa butter. These materials are butters by virtue of their fatty compositions. Shea butter, a natural fat extracted from the nut of the African shea tree, is widely used in the cosmetic field as a moisturizer, salve or lotion. There are many natural oils that have a wide composition of materials and are liquids. These materials have a degree of unsaturation in the alkyl group of the triglyceride. Natural oils can be monosaturated or polysaturated, meaning they have one or many degrees of unsaturation. The steric hindrance of the double bond or bonds prevents the molecules from packing closely together and becoming solid.

    Hydrogenated Butters
    The most common way to solve the problem of natural “unrefined” oils is for a chemist to chemically alter the oil by hydrogenation. Hydrogenation changes the chemical structure of the materials in the oil and results in the conversion of liquid oil to a solid or semi-solid fat. The most common example of this margarine. Changing the fat’s degree of saturation alters some important physical properties such as the melting range, which is why liquid oils become semi-solid. The hydrogenation process was considered a mild reaction that adds two hydrogens and left the molecule “unchanged.” Karabulut et al. found that hydrogenation produced a large amount of trans fats. Trans fats are produced by chemical modification and have been found to be unhealthy in diets.

    Gelation Additives
    Another approach to making butters is to add gelation agents. These additives will provide structure to natural oils and make them into butters. The gelation agents are generally added at low concentrations (below 10%) and allow for alteration of the butter’s spread properties. These materials will be addressed in a subsequent “Comparatively Speaking” column.

    Butters in Formulation
    In the cosmetic field, formulation chemists have a tricky task ahead of them. The overall goal is to find a product that has the correct physical characteristics but is green. Natural oils like olive and soybean are used as solvents and natural additives in cosmetic products. The major advantage in using natural oils is that they are renewable and generally mild. Conversely, their rheological properties are typically weak, and the product has to be refined to improve its rheological properties. When these oils are added into a chemical formulation, they will weaken the structural integrity of the product. This is not a major problem when formulating a cream or liquid product, but it becomes a problem in lipstick, where the lack of structural integrity will lead to the product failing. There are a couple of ways to fix this problem. The first is to refine the hydrocarbons from the liquid oil. Refining or concentrating oils will produce a solid and does not chemically alter the chemical structure of the material. The second solution is to hydrogenate or chemically modify the chemical structure of the oil.

    References
    1.http://en.wikipedia.org/wiki/Shea_butter
    2. http://en.wikipedia.org/wiki/Hydrogenation
    3. I Karabulut, M Kayahan and S Yaprak, Determination of changes in some physical and chemical properties of soybean oil during hydrogenation, Food Chemistry, 81(3) 453–456 (2003)

    – See more at: http://www.cosmeticsandtoiletries.com/formulating/function/moisturizer/126610168.html#sthash.ur6xkrLE.dpuf

  3. http://www.mayoclinic.org/trans-fat/art-20046114

    Trans fat is double trouble for your heart health

    Trans fat raises your LDL (“bad”) cholesterol and lowers your HDL (“good”) (HDL) cholesterol. Find out more about trans fat and how to avoid it.
    By Mayo Clinic Staff

    Trans fat is considered by many doctors to be the worst type of fat you can eat. Unlike other dietary fats, trans fat — also called trans-fatty acids — both raises your LDL (“bad”) cholesterol and lowers your HDL (“good”) cholesterol.

    A high LDL cholesterol level in combination with a low HDL cholesterol level increases your risk of heart disease, the leading killer of men and women. Here’s some information about trans fat and how to avoid it.
    What is trans fat?

    Some meat and dairy products contain small amounts of naturally occurring trans fat. But most trans fat is formed through an industrial process that adds hydrogen to vegetable oil, which causes the oil to become solid at room temperature.

    This partially hydrogenated oil is less likely to spoil, so foods made with it have a longer shelf life. Some restaurants use partially hydrogenated vegetable oil in their deep fryers, because it doesn’t have to be changed as often as do other oils.
    Trans fat in your food

    The manufactured form of trans fat, known as partially hydrogenated oil, is found in a variety of food products, including:

    Baked goods. Most cakes, cookies, pie crusts and crackers contain shortening, which is usually made from partially hydrogenated vegetable oil. Ready-made frosting is another source of trans fat.
    Snacks. Potato, corn and tortilla chips often contain trans fat. And while popcorn can be a healthy snack, many types of packaged or microwave popcorn use trans fat to help cook or flavor the popcorn.
    Fried food. Foods that require deep frying — french fries, doughnuts and fried chicken — can contain trans fat from the oil used in the cooking process.
    Refrigerator dough. Products such as canned biscuits and cinnamon rolls often contain trans fat, as do frozen pizza crusts.
    Creamer and margarine. Nondairy coffee creamer and stick margarines also may contain partially hydrogenated vegetable oils.

    Reading food labels

    In the United States if a food has less than 0.5 grams of trans fat in a serving, the food label can read 0 grams trans fat. This hidden trans fat can add up quickly, especially if you eat several servings of multiple foods containing less than 0.5 grams a serving.

    When you check the food label for trans fat, also check the food’s ingredient list for partially hydrogenated vegetable oil — which indicates that the food contains some trans fat, even if the amount is below 0.5 grams.

  4. Trans-fats on skin are acted upon by skin bacteria using liapase and esterase to give free trans fatty acid which penetrates the skin.

    The Esterase and Lipase Activity of Aerobic Skin Bacteria

    Article in British Journal of Dermatology 85(1):18-23 ·

    — The production of esterase and lipase by aerobic bacteria from normal human skin surfaces was tested by simple plate tests against natural and artificial substrates. Almost all of 42 strains of Micrococcaceae representative of each of Baird-Parker’s subgroups produced strong esterases and lipases, as did most of the 82 strains of Sarcina spp., especially those most commonly present on healthy skin. Forty per cent of 50 aerobic skin diphtheroids and 20% of 58 aerobic nasal diphtheroids produced active lipases.

  5. Partially Hydrogenated Trans-fats

    http://www.drkaslow.com/html/trans_fats.html

    Your cells are defined by your membranes. They not only separate your cells from another, they also determine how your cells communicate with each other and govern their internal actions. Membranes are composed mostly of oils, with some protein and carbohydrate. The oils are continually renewed and replaced. Their composition is affected by the kinds of oils in your diet. Thus the very basic and crucial actions of cells and the proper functioning of your body are to a great extent dependent on the oils you consume every day.

    The oils you consume or apply to your body are chosen in part by what is available to you from the food and cosmetics industry. It is the story of what happens when capitalism has no rules and science is supported by industry. It is odd that our government has the power and the will to force the recall of strollers and scooters, etc. when deemed unsafe yet not the will or conscience to outlaw a poison in your food – trans fats. All partially hydrogenated vegetables oils contain trans fats.

    To be fair, trans fats include conjugated linoleic acid and vaccenic acid that originate in the rumen of beef, sheep, goats, and deer ending up in their meat and milk products (butter contains up to 4% trans fats). However these trans fats have different chemical configurations than the manufactured version found in processed foods.

    Health and nutrition information changes so often that you may be thinking that trans fats sound like one more in a long string of things that are not good for you. Perhaps you expect that like so many other foods, trans fats will be proven to be good for us or at least not as bad as once reported. No such possibility with trans fats. There has never been any scientific evidence of benefit from trans fats.

    One major reason that trans fats have been allowed to persist is that food additives in use before the FDA enacted the Food Additive Amendment in September 6, 1958 did not require FDA approval. In other words, trans fats were grandfathered in as acceptable because they were in use as of 1958.

    In the late 1970’s Mary Enig, Ph.D. at the University of Baltimore showed that addition of hydrogenated vegetable oil caused disruptive life patterns and lowered disease resistance. Initially ridiculed, Dr. Enig’s research began to be proven by others. In 1982 Kritchevsky published in Federation Proceedings about the effect of trans fat on the development of atherosclerosis. Many more publications in the top medical journals such as the New England Journal of Medicine, the Lancet, Annals of Internal Medicine, etc. on the risks of trans fats appeared before our government took action. On July 10, 2002, the government’s advisor on health policy, the Institute of Medicine at the National Academy of Sciences, reported that manufactured trans fatty acids is an ingredient that has no safe level for human consumption. In the words of the report, trans fats has an “upper intake level of zero.”

    Because trans fats accumulate, the poisoning is cumulative. Because there is no immediate visible effect of consuming trans fats the warning signs are missed until the damage is done years later. Here is what has been documented about trans fats thus far:

    Trans fats are absorbed in to your cell membrane where healthy essential fats should be integrated. The human lipase enzyme is ineffective with the trans configuration, so trans fat remains in the blood stream for a much longer period of time and is more prone to arterial deposition and subsequent plaque formation. Once in your cell membrane, trans fats can not be replaced.
    Trans fats irreversibly disrupt cell membrane function and communication with other cells.
    Trans fats raise LDL cholesterol and lower HDL cholesterol levels in your blood, which is the opposite of the ideal cardiovascular ratio. The Nurses Health Study I and II and the Health Professionals Follow-Up Study, Harvard School of Public Health, etc. provide consistent evidence that trans fats consumption increases the risk of coronary heart disease. Even the American Heart Association is in agreement – “Trans fats raise your bad (LDL) cholesterol levels and lower your good (HDL) cholesterol levels. Eating trans fats increases your risk of developing heart disease and stroke. It’s also associated with a higher risk of developing type 2 diabetes.” In 1994, Willett WC, Ascherio A was estimated that trans fats caused 30,000 deaths annually in the US from heart disease. (Am J Public Health 85 (3): 411–2).
    Trans fats alter arterial wall function leading to soft, weak, and stiff arteries which are susceptible to lesions, injury, and subsequent plaque formation.
    Esther Lopez-Garcia (The Journal of Nutrition 2005;135(3):562–6) studied over 700 nurses. Those consuming the most trans fat had blood levels of CRP that were 73% higher than those consuming the least trans fats. CRP is an indicator of inflammation and when elevated predicts cardiovascular disease.
    Trans fats pass from a pregnant woman’s placenta to her unborn child. The unborn child’s metabolism is adversely affected by trans fats in proportion to the amount consumed by its mother.
    Lactating mothers who consume substantial amounts of manufactured trans fats have less cream in their breast milk, since trans fats can lodge in the cellular spaces normally reserved for fatty acids. The cream is essential for maximum breast development of an infant.
    Diets high in manufactured trans fat correlate with the risk of type 2 diabetes as observed in The continuing Nurses’ Health Study I and II and the Health Professional Follow-up Study Conducted by the Harvard School of Public Health – a cohort of over 300,000 individuals.
    Trans fats inhibit the absorption of vitamin K into bones. Vitamin K is essential for healthy bone formation and strength.
    Chavarro Jorge, et al. (Proc. Amer. Assoc. Cancer Res 2006; 47) did a prospective study suggestive of a link between trans fat intake and prostate cancer.
    Research published by Anna Gosline in New Scientist (2006) indicates that trans fat may increase weight gain and abdominal fat, despite a similar caloric intake.
    M Mahfouz published a study (Acta biologica et medica germanica 1981;40(12):1699–1705) showing that trans fats are metabolized differently by the liver than other fats and interfere with delta 6 desaturase, which is an enzyme involved in converting essential fatty acids to arachidonic acid and prostaglandins both of which are important to the functioning of cells.
    In a retrospective study (Fertil Steril, 2007) involving 104 women reporting one or more pregnancies (participants in the Princeton School cardiovascular risk study) were followed for 25-30 years. Results indicate that increased dietary intake of trans fatty acids may be associated with an increased risk of fetal loss. The results also suggest that lower dietary intake of trans fat may be associated with a lower risk of fetal loss.
    You would think that given the obvious and incontrovertible evidence there would not be any trans fats allowed in our food supply. Denmark became the first country to introduce laws strictly regulating the sale of many foods containing trans fats in March 2003. Other countries and cities are following suit.

    However, the FDA still allows trans fats in our food supply due to the enormous influence of food and oil industries. Instead of mandating the elimination of trans fats from food as Denmark did, the FDA instituted a labeling requirement mandating that by 2006 all manufactured foods packaged foods indicate the presence of trans fats. They also gave the food processing industry a loophole. The FDA permits manufacturers to claim “zero grams trans fats” or “no trans fats” if it contains less than 0.5gm of trans fats per serving. Of course, anything can have “zero” using this method by reducing the size of the serving.

    The moral responsibility of the FDA has once again been usurped by corporate rather than public interests. As a result, you must be responsible for safe guarding yourself from trans fats by reading ingredients of every label:

    Any product that lists partially hydrogenated vegetable oil, whether it is derived from soy, coconut, canola, palm, cottonseed, corn, safflower, etc. There is no oil that is safe once it has been partially hydrogenated.
    Margarine, mono hydrogenated oils, vegetable shortening, shortening, hardened vegetable oil all contains trans fats and should be avoided no matter what the label claims. Furthermore, 0.5g of trans fats is like taking a 500mg capsule of trans fats. Benecol, for example contains 0.5gm of fat per 1 ½ teaspoonfuls. You are told to use it liberally, two to three times a day. That is a large amount of trans fats! As little as 2 grams daily of trans fats was associated with a 21% increase in coronary heart disease according to the findings of the Nurse’s Study of Harvard’s School of Public Health.
    Trans fats also occur in fast foods. It is estimated that an average meal from McDonald’s contains 3 grams of trans fat. Remember the Institute of Medicine warned there is no safe level for trans fats.
    Always question advertising on any box that says: low cholesterol, no cholesterol, trans free, TFA-free, or fat-free. The FDA leaves a lot of room for hiding trans fats. Look for products that state “no hydrogenated oils” or “hydrogenated oil free.”
    This list below is not all inclusive but presents some foods that you may not equate with trans fats but were loaded with them at the time of this publication:
    Oreos
    Carr’s crackers. Ritz
    Some ice creams
    Belgian chocolates.
    Snickers
    Wheat Thins.
    Triscuits.
    Pizza dough
    Krispy Kremes donuts
    Cheese Doritos
    Granolas
    Packaged cheeses
    Frozen snacks (pizza, pot pies, quiches, burritos, etc)
    Cupcake and cake icings
    Pepperidge Farms Gold fish
    Microwave popcorns
    Fried foods
    Soups
    Hot chocolate mixes
    Cool Whip
    Most potato chips
    Foods that should not contain manufactured trans fats are all on the Page Fundamental Food Plan:

    Fresh vegetables and fruits
    Proteins from grass-fed meat, poultry, fish, eggs, etc.
    Nuts, seeds, berries
    Butter, peanut oil, extra virgin olive oil, expeller-pressed coconut oil

  6. http://www.todayifoundout.com/index.php/2013/04/what-causes-acne/

    WHAT CAUSES ACNE

    Ah, acne! The facial blemish that powers many a pubescent date request rejection. Like millions of people worldwide, in my youth I waged a war with this aesthetic foe, with many a “Pizza-face” comment thrown my way. Medically known as Acne Vulgaris, this affliction is largely cosmetic and does not usually cause any debilitating problems, except maybe trouble getting a date in high school…

    The most common cause of acne is a class of bacteria called Propionibacterium (P- bacteria). They are named this due to their ability to manufacture propionic acid. According to the National Institute of Health, there are currently 90 known types of P-bacteria that cause acne.

    P-bacteria is an extremely common inhabitant of adult skin. They tend to reside in the sebaceous follicles (sweat glands) near your hair follicles. Most of the time they show no signs of being present and we go about our daily lives feeling like our face is clean. In actuality, your skin is rife with them and numerous other microbes. Shower anyone?

    These types of bacteria release an enzyme called lipase. The lipase produces fatty acids by digesting sebum (oil from your skin). When your body produces an excessive amount of sebum, these P- bacteria produce an excessive amount of fatty acids. Combined with the presence of bacterial antigens (proteins produced by the body’s natural immune response to fight off bacteria), they produce a local inflammation that bursts your hair follicles. A lesion might then form which can result in a pustule. This whitehead will then annoyingly mock you until you become frustrated and pop it like an over-sized balloon!
    While P-bacteria is the main culprit behind acne, there are a few other things that cause pimples such as excessive oil production, a clogged hair follicle, and any condition that causes your skin to inflame.
    If you’ve ever wondered why those pimples seem to only form on your face, neck, chest, and back, the answer is simple. These areas of the body contain the greatest number of sebaceous glands.

    The obvious question then becomes, why is acne most common in teenagers? When a person begins puberty, their body begins to produce a hormone known as androgen. Hair follicles contain large amounts of androgen receptors. When circulating androgens attach to these receptors, they can overstimulate your sebaceous glands causing abnormal levels of oil on your skin. The result is more oil for your P-bacteria to digest and create pimples. “Pizza-face” is the net result.
    Getting Rid of Acne
    Dermatologists will classify your acne based on your symptoms. Depending on the amount of non-inflamed, or inflamed comedones (the bumps from your white or blackhead), the amount of breakout activity, amount of inflammation, and the areas of the body affected, you will be diagnosed in one of 4 separate grades, grade 1 being the mildest form and grade 4 being the most severe.
    Knowing the cause, the general treatment for acne is mostly common sense- reduce oil production, fight bacterial infection, reduce inflammation, and speed up skin cell turnover, or any combination of the four. In mild cases, over the counter facial cleansers and lotions can work. They contain ingredients like benzoyl peroxide, sulfur, and salicylic acid. These ingredients cause oily skin to dry up, kill bacteria, and help remove dead skin cells.
    Should you have a more moderate case of acne, you might require prescription strength topical treatments, from Vitamin A based lotions that help in preventing the plugging of your hair follicle, to any number of topical antibiotics that help kill excess bacteria.
    If you have a more severe case of acne, your doctor can try several other types of treatment that are a bit more invasive. They can prescribe oral antibiotics or a stronger drug known as Isotretinoin. In women, oral contraceptives have been shown to help. Should your doctor want to go the extra mile, there is always light and laser therapy. Several different types of chemical peels and microdermabrasion can also be helpful.
    In the end, acne will tend to clear up by age 25 and only about 20% of people over 25 will continue to show signs of these facial blemishes. Unfortunately for the ladies out there, you are much more susceptible than men to acne after the age of 25. One study found that 50% of women between age 20 and 29 have acne and 25% of women between 40-49 show signs. With periods, child birth, bras, make-up, maintaining elaborate hair styles, more pressure about body weight, and now significantly increased chance of adult acne- I’ve said it before, and I’ll continue to say it, “I’m glad I was born a man.”

  7. Anti-Dandruff Shampoo Ingredients
    By ShawnTe Pierce
    eHow Contributor
    http://www.ehow.com/about_5460777_basic-antidandruff-shampoo-ingredients.html

    Itchy, flaky scalps are a common symptom of dandruff and seborrheic dermatitis. Fortunately, there are many products available over the counter (OTC) to reduce and sometimes eliminate dandruff. Shampoos specifically designed to treat dandruff are one of the most widely used anti-dandruff treatments. Learn about the basic and active ingredients found in most OTC anti-dandruff shampoos.

    Causes of Dandruff
    A common misconception about dandruff is that dry skin is the root cause of this condition. Dry skin rarely produces flakes that are visible to the naked eye. Dandruff can be the result of an excessively oily scalp or a yeast infection of the scalp. An oily scalp can be freed from dandruff with regular shampooing by massaging the shampoo into the scalp for five minutes and thoroughly rinsing the shampoo out. The scalp massage loosens the dead skin cells while the shampoo removes excess oil. Both the shampoo and dead skin are washed away when the hair is rinsed. However, for dandruff caused by yeast or seborrheic dermatitis, anti-dandruff shampoos are needed to fight the fungal infection and dissolve the dead skin. Before treating any scalp condition, consult a doctor to rule out any underlying health causes for your dandruff.

    Basic Shampoo Ingredients
    Most OTC shampoos contain water, a detergent (cleaning agent), surfactant (lather making agent), salt, fragrance (natural and artificial), preservative and food coloring. With the exception of water and salt (sodium chloride), different chemical compounds are used depending on the desired result of the shampoo. For example, when it comes to choosing a surfactant, one shampoo may use sodium laureth sulfate while another may use potassium or ammonium laureth sulfate–it depends on the manufacturer’s formula. Many shampoos also contain vitamins and moisturizing alcohols to prevent too much of the hair and scalp’s natural oils from being stripped away during cleansing. In the case of anti-dandruff shampoos, another ingredient, which may be listed on the product as the active ingredient, is used to help control dandruff.

    Coal Tar
    Coal tar is the active ingredient in Neutrogena’s T-Gel Shampoo. This ingredient is used to treat many scalp conditions that involve dandruff and other thick crust conditions such as eczema and psoriasis. The Mayo Clinic recommends massaging a shampoo with coal tar into the scalp and leaving it there for five minutes. It is advised to rinse the hair and scalp thoroughly after use. Limit your sun exposure after using a shampoo containing this ingredient because the treated area will be sensitive to direct sunlight or sunlamps and it can increase your risk of getting skin cancer.

    




    Salicylic Acid and Sulfur
    Salicylic acid and sulfur are used in combination to treat many skin disorders including dandruff. Sebex uses this combination in its anti-dandruff shampoo. The two ingredients work together to provide temporary control of scaling and itching as a result of psoriasis, dandruff and seborrheic dermatitis. Salicylic acid works to break down the dead skin cells to reveal the new skin underneath. It also aids in the penetration of antifungal agents. Salicylic acid also is a mild antiseptic that may heal any irritation to the scalp from scratching. Sulfur is an antifungal ingredient that gets rid of the yeast (fungus) that causes dandruff in some people.

    Ketoconazole
    This ingredient is found in Nizoral shampoo. Ketoconazole is a fungicide and is used in shampoos to treat dandruff that develops because of a yeast infection of the scalp. Shampoos containing this ingredient are most often prescribed for serious fungal infections. A shampoo containing 2 percent ketoconazole can help control moderate dandruff. The shampoo must be massaged into the scalp and left on for at least five minutes so the ketoconazole can work at removing the infection. Consult a doctor before using a shampoo containing ketoconazole as the ingredient may cause liver damage.

    Selenium Sulfide
    The Selsun Blue line of dandruff shampoos uses selenium
    sulfide as its active ingredient. OTC shampoos contain 1
    percent selenium sulfide while 2 1/2 percent is available by prescription only. Selenium sulfide works to get rid of the yeast that causes dandruff. The Mayo Clinic recommends only using this ingredient twice a week by applying one or two teaspoons of the shampoo on the scalp, massaging it in and leaving on for no more than three minutes. If your hair has been chemically treated or if you have light-colored hair, the product may discolor the hair if not rinsed out completely.

    Zinc Pyrithione
    Head & Shoulders is a popular OTC shampoo that uses zinc pyrithione as its active ingredient. Zinc pyrithione is an antifungal ingredient that also works to break down the dead skin cells and treat any fungus that may be the underlying cause of the dandruff. Unlike many of the other anti-dandruff ingredients, zinc pyrithione is gentle enough for everyday use. For the ingredient to remain effective, it is recommended that it be used at least twice a week. Shampoos containing this ingredient are massaged into the scalp and left on for several minutes before rinsing. Once the dandruff is under control, treatment can be downgraded to once a week.

  8. Is Hydrogenated Oil In Skin Care Products Bad
    By Chelsea

    While hydrogenated oil is increasingly included in skin care products, there is no conclusion about its effects on human skin. My knowledge about hydrogenated oil applied to skin is also limited, but I hope that the following analysis is helpful for you to decide whether you would like to put hydrogenated oil on your skin.
    People try to avoid hydrogenated oil primarily because partial hydrogenation generates trans fats, and trans fats have a series of negative health implications. In fact, the hydrogenated oil we encounter is almost always partially hydrogenated, so pretty much all hydrogenated oils have trans fats. Even products marketed as “zero grams trans fats per serving” can have trans fats as long as the trans fat content is up to 7% by weight. And that is already after the hydrogenated oil is mixed with other types of fat. Therefore, unless the hydrogenated oil is labeled as “completely hydrogenated”, which makes all fats saturated, it has trans fats. But when trans fats are applied to skin, it is different from when it is ingested. Then could it possibly cause some undesired effects?
    Unfortunately, it takes a long time to demonstrate the long-term effects of an ingredient. We cannot draw a conclusion yet. Theoretically, trans fats affect lipids. And lipids in the skin are essential to skin health. So the possibility of interactions cannot be denied. For example, the skin has a cascade of desaturation processes, namely, converting saturated fats to unsaturated, and converting unsaturated fats to highly unsaturated. If we apply unsaturated oils, such as safflower oil and sunflower oil, we constrain the process of converting saturated fat to unsaturated. This makes sense in a way that we have supplemented the unsaturated oil to our skin. But if we put on trans fats, the process of converting unsaturated fat to highly unsaturated fat will be inhibited. This can be a concern because it alters the process without supplementing the substance that is expected as the result of this process. This is much more irregular compared with that of natural fats although we do not know whether this causes problems.
    The connection between trans fats and cancer risks is still in debate. Some European studies, however, have demonstrated positive associations between trans fats and breast cancer. With more fat tissue to deposit undesired substances, breasts are subject to cancer. As I have pointed out, skin also has fat, so there is a possibility that trans fats can increase skin cancer risks. We are waiting for such tests.
    Another consideration of using hydrogenated oil in skin care products is that common production of hydrogenated oil requires metal catalysts. There can be metal residues in hydrogenated oil. Of course, skin care products containing other industrially produced ingredients can also have tons of bad residues. But hydrogenated oil is commonly used in natural and high-end skin care products. So if you are using natural skin care products, you may not be far away from bad residues if the product contains hydrogenated oil.
    After all, no product is pristine. The decision is ultimately yours. I would say that hydrogenated oil risks are comparable to parabens. Whether you are going to use skin care products with hydrogenated oil depends on how much you want to shun away from unnatural and risky ingredients.
    References
    Selective effects of isomeric cis and trans fatty acids on fatty acyl delta 9 and delta 6 desaturation by human skin fibroblasts.
    Adipose tissue trans fatty acids and breast cancer in the European Community Multicenter Study on Antioxidants, Myocardial Infarction, and Breast Cancer.
    Association between serum trans-monounsaturated fatty acids and breast cancer risk in the E3N-EPIC Study.

  9. Shea Butter: An Opposite Replacement for Trans Fat in Margarine
    By Malachi Oluwaseyi Israel*
    Biochemistry Department, Afe Babalola University, Ado-Ekiti, Nigeria
    Corresponding Author : Malachi Oluwaseyi Israel

    Biochemistry DepartmentAfe Babalola University
    Ado-Ekiti, NigeriaTel: 2348068846518
    E-mail: malachiseyi@gmail.com
    Received: May 06, 2015 Accepted: June 11, 2015 Published:June 15, 2015
    Citation:Israel MO (2015) Shea Butter: An Opposite Replacement for Trans Fat in Margarine. J Nutr Food Sci S11: S11-001. doi: 10.4172/2155-9600.1000S11-001
    Copyright: ©2015 Israel MO, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

    Abstract
    Shea butter is the edible fat extracted from the nut of African Shea tree (Vitellaria paradoxa). Consequence of having half of its fatty acids saturated, Shea butter melts at a very high temperature and will be a suitable raw material for margarine production. Margarine is a butter mimicry that is produced from vegetable oils and water. The production of margarine requires a solid fat. Hence hydrogenation is employed to “harden” the vegetable oil. However, hydrogenation generates trans unsaturated fatty acids which are more detrimental to cardiovascular health than the highly denunciated saturated fatty acids. Since Shea butter is a stable solid at room temperature and has its saturated fatty acid fraction predominated by stearic acid, the use of Shea butter as a raw material for margarine will not only eliminate trans unsaturated fatty acids from the product but also make use of the least deleterious saturated fatty acid because stearic acid has been reported as the healthiest saturated fatty acid as regards cardiovascular health. Also, the unsaponifiables of Shea butter have been credited for their anti-hypercholesterolemic effects in experimental animals. This increases the healthfulness of dietary Shea butter, and of course, the margarine end product.

    Keywords
    Margarine; Shea butter; Cardiovascular disease; Saturated fatty acid; Stearic acid

    Introduction
    Shea butter is an off-white or ivory-colored fat extracted from the nut of Shea tree (Vitellaria paradoxa formerly Butryspermum paradoxum, B. parkii and B. paradoxa) [1]. Shea tree is native to the dry savanna belt of West Africa, where it grows wild across a 5000 km wide belt of savanna [2,3]; inhabiting West African countries of Senegal, Burkina Faso, Côte d’Ivoire, Mali, Ghana, Togo, Benin, Nigeria, Cameroon, Niger, and further east into Sudan, Uganda and Ethiopia [4,5]. The West African trees are classified as the subspecies “paradoxa” and the East African one as “nilotica” [6-8].

    Shea butter is solid at room temperature with a good buttery consistency. It is edible and is used in food preparation in Africa [9,10] and as a substitute for cocoa butter in chocolate industry [3], although the taste is noticeably different [11]. Shea butter is also renowned for its use as a component of cosmetic formulations [9,12]. There are no reports of allergic reaction owing to consumption of Shea butter or its produce [13,14].

    Margarine is a butter mimicry used for spreading, baking and cooking [15]. While butter is made from butterfat of milk, margarine is made principally from vegetable oil and water, and may also contain milk. Like butter, margarine, consists of a water-in-fat emulsion, with tiny droplets of water dispersed uniformly throughout a fat phase which is in a stable crystalline form [16]. Margarine has a minimum fat content of 80%, the same as butter, but unlike butter, reduced-fat varieties of margarine can also be labeled as margarine.

    Margarine was formulated in the 19th century as a replacement for butter because of inability of the low class to afford dairy butter [17]. Although the raw material for the original margarine formulation was beef fat, shortages in beef fat supply combined with advances in the hydrogenation of plant materials led to its replacement with hydrogenated vegetable oils [18].

    In recent decades, the composition of margarine has changed significantly in efforts to increase its healthfulness; notably in relation to cardiovascular disease. Hydrogenation of vegetable oils has consequently been severely discouraged as it leads to the generation of trans-unsaturated fatty acids which increase levels of LDL, lower levels of HDL and therefore increases the risk of coronary heart disease [19], the leading cause of death [20]. The use of tropical vegetable oils including palm oil, palm kernel oil and coconut oil, which are rich in saturated fatty acid, is progressively reducing hydrogenation in margarine production. Shea butter is a stable solid at room temperature, even in the warm tropics unlike other tropical oils, and will therefore require no hydrogenation for production of margarine. This work therefore presents Shea butter as a more suitable raw material for margarine production than other tropical oils.

    Dietary Lipid and Cardiovascular Health
    Cardiovascular diseases are the leading cause of global death [20], and are projected to remain the single leading cause of death till 2030 [21]. Cardiovascular diseases are multi-factorial and several risk factors have been identified. These risk factors include: gender, age, physical inactivity, unhealthy diet, family history of cardiovascular disease, tobacco use, excessive alcohol consumption, obesity, raised blood pressure (hypertension), raised blood cholesterol (hyperlipidemia), raised blood sugar (diabetes mellitus), psychosocial factors, poverty and low educational status and air pollution [22-25]. While some of these risk factors such as age, gender or family history are immutable; many important cardiovascular risk factors are modifiable by social change, lifestyle change, drug treatment and prevention of hyperlipidemia, hypertension, and diabetes.

    Of the risk factors that can be modified to improve cardiovascular health is healthy dietary lipid [26]. It has become clear that it is the composition and not the total amount of fat intake that affects cardiovascular health [27,28]. While it is evident that the dynamics of cholesterol homeostasis and development of cardiovascular disease are extremely complex and multifactorial [29], researchers maintain that cholesterol intake increases the risks of cardiovascular diseases [29-31]. Also, dietary saturated fatty as well as trans-unsaturated fatty acids increases the risks of cardiovascular diseases as they both raise levels of LDL cholesterol and lower levels of HDL cholesterol [26,27,32-34].

    It is also clear that different type of saturated fatty acids contribute differently to cardiovascular disease [35]. An isotope labeling study in humans [36] concluded that the fraction of dietary stearic acid (18:0) that oxidatively desaturates to oleic acid (18:1) is 2.4 times higher than the fraction of palmitic acid (16:0) analogously converted to palmitoleic acid (16:1). This demonstrates that dietary palmitic acid (16:0) contributes to progression of cardiovascular disease than stearic acid (18:0). Also, in a systemic review of clinical and epidemiological studies [37], dietary Stearic acid (18:0) was found to be associated with lower LDL and directionally lower total cholesterol/HDL cholesterol ratio compared to any other saturated fatty acid. Substitution of Stearic acid (18:0) for trans-unsaturated fatty acid also decreased LDL cholesterol, increased HDL cholesterol and decreased the total cholesterol/HDL cholesterol ratio. However, when compared with unsaturated fatty acids, Stearic acid raised LDL cholesterol, lowered HDL cholesterol, and increased the total cholesterol/HDL cholesterol ratio. It was thus concluded that Stearic acid (18:0) is a reasonable substitute for trans-unsaturated fatty acids and cholesterol-raising saturated fatty acids for solid fat applications.

    Composition and Properties of Shea Butter
    In addition to a stearic and oleic acids rich saponifiable fraction, Shea butter contains an unsaponifiable fraction composed of bioactive substances that are responsible for its medicinal properties [38]. These bioactive compounds are majorly triterpene alcohols, with some hydrocarbons, sterols, and other minor components such as vitamin E [39-42]. The saponifiable triglyceride fraction of Shea butter constitutes about 90% by mass of the butter [39-43] and is composed primarily of stearic and oleic acids with lesser amounts of palmitic, linoleic and arachidic acids [44]. While Shea butter has about 50% of its fatty acid saturated, about 83% of the saturated fatty acid is made up of stearic acid [44], the least deleterious of the saturated fatty acids [37] (Table 1).

    Shea butter has a relatively high melting point compared to other vegetable oils. When contrasted with highly unsaturated vegetable oils like grape seed oil, olive oil, canola oil and soybean oil that have saturated fatty acid fraction less than 20% [47-50], the elevated melting point of Shea butter can be attributed to its high saturation [51]. However, Shea butter melts between 51°C and 56°C; a temperature much higher than the melting points of highly saturated tropical vegetable oils like palm oil (35°C), palm kernel oil (24°C) and Coconut oil (24°C). This is because the saturated fatty acid fraction of Shea butter is majorly constituted by stearic acid while that of palm kernel oil, palm oil and coconut oil is majorly constituted by lauric, palmitic and lauric acids respectively [49]. Lauric and palmitic acids are of shorter carbon chains, hence have lower melting points, than stearic acid [52,53].

    The high melting point of Shea butter can also be in part due to its high content of unsaponifiables which make up 8-10% of Shea butter [38]. These unsaponifiables are majorly triterpene alcohols and sterols [39-42], which have high melting points [54].

    Margarine and its Ingredients
    Margarine is basically a water-in-fat emulsion [16] made from vegetable oil or animal fat, mixed with skim milk, salt, and emulsifiers like lecithin [55,56]. The vegetable oils are hydrogenated by passing hydrogen through the oil in the presence of a nickel or palladium catalyst, under controlled conditions [57]. The hydrogenation process increases the melting point of (“Harden”) the oil by reducing the unsaturated bonds (alkenic double C=C bonds) to saturated C-C bonds [58]. While the Soft vegetable fat spreads and Margarines in bottle can circumvent hydrogenation by making use of tropical oils like palm oil, coconut oil and palm kernel oil that are naturally rich in saturated fatty acids and are semi-solid at room temperature, hard margarines, used for cooking and baking, unavoidably requires hardening to increase its melting point [59].

    Shea Butter versus Other Tropical Oils as Raw Material for Margarine
    While the manufacture of margarine requires a vegetable fat that is solid at room temperature, most vegetable oils are liquid at room temperature. Increasing the melting point of such oils through partial hydrogenation leads to the generation of trans unsaturated fatty acids which increases the risk of cardiovascular diseases [19]. To reduce hydrogenation in margarine production, tropical oils like palm oil and palm kernel oil, with high melting points are increasingly gaining application in margarine production [60]. However, while this tropical oils which are semi solid at room temperature, are saturated enough to eliminate the need for hydrogenation in the production of softer tub margarines, the production of solid block margarines that are required for cooking and baking, requires further saturation [59]. Hence hydrogenation is unavoidable even with the use of such oils.

    Shea butter, by contrast, is a stable solid at room temperature and will remain a solid even at a temperature as high as 50°C [61]. The use for Shea butter for the production of margarine will therefore require no further hardening. Hence no generation of trans unsaturated fatty acids. This will consequently eliminate the risk of cardiovascular disease associated with the consumption of trans unsaturated fatty acids in margarine. Albeit, the mechanisms through which trans unsaturated fatty acids contribute to cardiovascular disease are still poorly understood, research has shown that trans unsaturated fatty acids are more deleterious to cardiovascular health than the highly denounced saturated fatty acids [37,62,63].

    Also, stearic acid, which constitutes the saturated fraction of Shea butter [49], is considered the least deleterious of the saturated fatty acids [36,37]. Therefore, the use of Shea butter for the manufacture of margarine will not only eliminate trans unsaturated fatty acids from the product but will also make use of the healthiest saturated fatty acid as a source of “hardening” in the product. Another edge Shea butter has over other tropical vegetable oil with regards to cardiovascular health is that it is exceptionally high in unsaponifiables and these unsaponifiables have been credited for anti-hypercholesterolemic activities in experimental animals [64,65].

    Finally, looking from the manufacturers’ point of view, Shea butter as a raw material for margarine production will reduce cost of production as it does not require hardening. The cost of hydrogenation will thus be eliminated (Table 2).

    Conclusion
    Due to its high stearic acid concentration and high melting point, Shea butter as a raw material for margarine production is healthier, as regards to cardiovascular health, than other vegetable oils because it eradicate the presence of the much criticized trans unsaturated fatty acids from the product while it making use of the least deleterious saturated fatty acid. The unsaponifiable fraction of Shea butter also contributes to cardiovascular health. The exclusion of hydrogenation process, which is otherwise used for “hardening” vegetable oils, will reduce the cost of production of margarine from Shea butter.

    Acknowledgement
    A huge thank you goes to Pastor David Adebayo his encouragement and kindness. The guidance of Professor OB. Ajayi is highly appreciated.

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  10. Fatty Acids Penetration Into Human Skin Biology Essay
    Published: 23, March 2015
    https://www.ukessays.com/essays/biology/fatty-acids-penetration-into-human-skin-biology-essay.php

    Abstract: Fatty acids are recognised as lipophilic chemical penetration enhancers (CPEs) which might cause the fluidization and perturbation of stratum corneum (SC) lipid matrix. The prerequisite for fatty acid enhancing effect on drug permeation is its penetration into skin and following disruption of skin lipids arrangement. The aim of this study was to demonstrate the penetration of oleic, linoleic, lauric and capric acids into human skin layers by time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging after 12 hours of in vitro experiment and relate these data to enhancing effect of fatty acids on penetration of lipophilic model drug tolnaftate into human epidermis and dermis ex vivo. Visualization as well as spatial localization of fatty acids penetrating into human skin layers were performed using ToF-SIMS, operated with primary Bi3+ cluster ions. Statistical analysis revealed that only oleic acid significantly (P < 0.05) enhanced tolnaftate penetration into epidermis comparing to the control solution and the enhancing ratio was equal to 1.867. Treatment of human skin in vitro for 12 h with donor solutions resulted in significant penetration of oleic and lauric acid into human skin as compared to the control and was confirmed by ion images. Linoleic and capric acids were not significantly penetrating into the skin nor significantly enhancing tolnaftate penetration. In conclusion, ToF-SIMS imaging of oleic and lauric acids in the skin confirmed their penetration and possible interaction with lipid molecules in SC, but only oleic acid had significant enhancing effect on model drug penetration. Fatty acids vary in their physicochemical properties and thus in mechanisms of interaction with components of extracellular matrix of SC. Significant penetration of lauric acid into skin did not result in enhancement of lipophilic model drug penetration in vitro. Vice versa, negligible penetration of oleic acid causes significant enhancing effect on tolnaftate penetration into skin. INTRODUCTION Stratum corneum (SC), composed of corneocytes and extracellular lipid matrix, is recognized as the main barrier layer for passive diffusion of drug molecules into and through the skin. The composition of extracellular lipids is already known, but SC lipid structural organization, which is mainly responsible for the barrier properties and which is described by several theoretical models, is still being under thorough elucidation. Knowledge about SC lipid organization allow for better understanding and interpretation of low permeability of drugs through SC and the modes of temporal and reversible action of chemical penetration enhancers (CPE). Lipophilic CPEs are supposed to alter structural organization of lipids in extracellular matrix and in this way increase the permeation of active drugs through the skin. SC multilamellar lipid matrix is mainly composed of neutral lipids: ceramides (CER), cholesterol (CHOL) and long-chain saturated free fatty acids (FFA) (1-5) in an approximate molar ratio of 3:2:1 (6). Freeze-fracture (7-8) and ruthenium tetroxide post-fixation (9) electron microscopy studies revealed that lipids are arranged into bilayers (10-12). CER are formed of long-chain (mainly C20-C36) fatty acid (non-hydroxylated, α-hyroxylated or linoleic acid linked ω-hydroxylated) bound to the amino group of hydrophilic sphingoid base (sphingosine, phytosphingosine, and 6-hydroxy-sphingosine) (1-2, 13-15). Amide-linked fatty acid chains in CER are nonbranched and saturated. FFAs predominantly have saturated and straight chains of 22 (docosanoic acid), 24 (lignocerin acid) and 26 (hexacosanoic acid) carbon atoms (2-3, 5, 16). Oleic and linoleic acids are the only unsaturated fatty acids detected in SC (17). Lipid chains tend to pack in tight lateral highly ordered packing (according to packing density: liquid < hexagonal (gel) < orthorhombic (crystalline) phases), which influences the barrier properties of SC and which has been studied using atomic force microscopy (18), Fourier transformed infrared spectroscopy (19), wide-angle X-ray diffraction (20-21) and electron diffraction (10). All three phases coexist, but it is believed that conformationally ordered orthorhombic packing of lipids is mainly responsible for the resistance to transdermal delivery of molecules (22). Small-angle X-ray diffraction (23-25) as well as electron microscopy (26-27) studies demonstrated that two lamellar structures, namely long and short periodicity phases (LPP and SPP, respectively), are characteristic to lamellar ordering of lipid bilayers (10, 16, 28). The lipid lamella is oriented in parallel to corneocyte surface and its LPP has a repeat distance of 13 nm and SPP - of 6 nm (16, 29). LPP is organized in trilamellar repeat units of broad-narrow-broad electron lucent bands (6, 30) and is considered to highly impact the barrier properties of SC. Several theoretical SC lipid model systems were proposed in order to describe the ordering of lipids in lamella. These models, such as the stacked monolayer model (proposed by Swartzendruber et al. (27)), the domain mosaic model (by Forslind (31)), the sandwich model (by Bouwstra et al. (25)) and single gel phase model (by Norlen (32)) comprise the architecture of lipid molecules arrangement and the phase behaviour of lipid matrix (1, 4). Lamellar but not lateral lipid organization is dependent on pH (13), thus pH of human SC is also maintaining skin barrier capacity and is in the range of 4.0-5.5 (3, 5). Well-defined SC lipid composition, organization and phase behaviour of extracellular matrix allow for better interpretation of CPE interactions with lipid molecules. In order to relate the penetration of oleic, linoleic, lauric and capric fatty acids and their enhancing effect on lipophilic model drug penetration into human skin layers ex vivo, two techniques were applied: in vitro skin penetration studies and mass spectrometry imaging (MSI). In vitro skin penetration studies were carried out using Bronaugh-type flow-through diffusion cells mounted with full-thickness human skin. Donor solutions of polyethylene glycol 400 (PEG 400) having a hydrophobic model drug and CPE dissolved were applied on the skin surface. The amount of model drug penetrating into 1 cm2 of epidermis and dermis was quantified using a validated HPLC-UV method and then the enhancing ratio (ER) of fatty acid on model drug's penetration was calculated. In order to demonstrate the penetration of CPEs into human skin layers, MSI was applied after in vitro skin penetration studies. MSI is becoming a more and more widely used method for chemical mapping of organic and inorganic compounds from various surfaces, especially tissue sections. Among the various techniques aiming to map the surface of the sample, MSI is the only analytical method capable of providing in a single run the spatial distribution of a wide range of molecules over the surface of a biological sample (33). Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a technique of choice for MSI. This technology consists of the bombardment of the sample by a beam of mono- or polyatomic ions, which induces desorption/ionization of secondary ions from the sample surface (34-38). It also offers the possibility to localize various molecules, mainly lipids and metabolites, with a mass-to-charge ratio up to m/z 1000-1500 and a lateral resolution from 400 nm to 1-2 µm, which makes the technology particularly efficient for the analysis of tissue sections. The field of research of ToF-SIMS imaging is then rapidly expanding and more widely used in many applications, mainly in biological sciences and medicine (39-42). In the present work, we have used ToF-SIMS imaging in order to visualize and evaluate the penetration and location of externally applied fatty acids into human skin layers. A thiocarbamate antifungal drug tolnaftate was chosen as a model compound for in vitro skin penetration experiments. High hydrophobicity (XLogP = 5.5), low molecular weight (307.4 Da), weak basic properties and melting point of 109-112°C (Eur. Pharm. 6.0; 01/2008:1158) are physicochemical properties which ensure tolnaftate's capability of passive diffusion through SC via lipoidal intercellular route and accumulation in superficial layers of skin. Hydrophilic skin layers (viable epidermis and dermis) form a barrier for tolnaftate deeper penetration.

  11. Microbiome Article –

    Barrier function and microbiotic dysbiosis in atopic dermatitis

    Authors Seite S, Bieber T

    Received 1 July 2015

    Accepted for publication 6 August 2015

    Published 15 September 2015 Volume 2015:8 Pages 479—483

    DOI https://doi.org/10.2147/CCID.S91521

    Sophie Seite,1 Thomas Bieber2

    1La Roche-Posay Dermatological Laboratories, Asnières, France; 2Department of Dermatology and Allergy, Friedrich-Wilhelms-University, Bonn, German

    Abstract: Atopic dermatitis (AD) or atopic eczema is the common inflammatory skin disorder, the prevalence of which has considerably increased during the last 30 years. It affects 15%–30% of children and 2%–10% of adults. AD characteristically alternates between periods of exacerbation or flares and periods of remission, which may be therapeutically induced or spontaneous. Current knowledge about AD includes abnormalities of the skin barrier (physical and chemical), the immune barrier, and more recently, the microbial barrier or microbiota. There is growing evidence for a tight relationship between them. To obtain satisfactory control of this condition, the clinical strategy to manage AD involves prescribing both anti-inflammatory medications and dermocosmetic products. The role of the physician is therefore to advise the patient with regard to hygiene measures aimed to help to improve these three barriers or to prevent any further deterioration.

  12. Transesterification of Oil

    Vegetable oils and products synthesized from natural raw materials (either of vegetable or animal origin) are having a strong comeback in recent decades. One of the major
    reasons for the increased utilization of fatty chemicals for industrial use has been the ability to tailor the products to specific needs. Major areas of applications are in
    foods, soaps and detergents, cosmetics, pharmaceuticals, textiles and papers, oil field chemicals, fat-based emulsifiers, synthetic lubricants, metal working fluids, and last but not least, introduction into the transportation fuel sector as biodiesel.

    History:

    The concept of using vegetable oil as an engine fuel likely dates to when Rudolf Diesel (1858-1913) developed the first engine to run on peanut oil, as he demonstrated at the World Exhibition in Paris in 1900.
    Rudolf Diesel firmly believed the utilization of a biomass fuel to be the real future of his engine. He wanted to provide farmers the opportunity to produce their own fuel. In 1911, he said, “The diesel engine can be fed with vegetable oils and would help considerably in the development of agriculture of the countries which use it.”
    “The use of vegetable oils for engine fuels may seem insignificant today. But such oils may become, in the course of time, as important as the petroleum and coal tar products of the present time.”
    Rudolf Diesel, 1912
    Unfortunately, Rudolf Diesel died in 1913 before his vision of a vegetable oil powered engine was fully realized. At the time of Diesel’s death, the petroleum industry was rapidly developing and producing a cheap by-product called “diesel fuel” that would power a modified “diesel engine”. Thus, clean vegetable oil was forgotten as a renewable source of power. Modern diesels are now designed to run on a less viscous (easier flowing) fuel than straight vegetable oil, but, in times of fuel shortages, cars and trucks were successfully run on preheated peanut oil and animal fat.
    In the mid 1970’s, fuel shortages spurred interest in diversifying fuel resources, and thus biodiesel as fatty esters was developed as an alternative to petroleum diesel. Later, in the 1990’s, interest was rising due to the large pollution reduction benefits coming from the use of biodiesel. Today’s diesel engines require a clean-burning, stable fuel that will operate under a variety of conditions. The resurgence of biodiesel has been affected by legislation and regulations in all countries. Many of the regulation and mandates center around promoting a country’s agricultural economy, national security, and reducing climate pollution/change.
    What is Biodiesel?
    Biodiesel is simply a liquid fuel derived from vegetable oils and fats, which has similar combustion properties to regular petroleum diesel fuel. Biodiesel can be produced from straight vegetable oil, animal oil/fats, tallow and waste cooking oil. Biodiesel is biodegradable, nontoxic, and has significantly fewer emissions than petroleum-based diesel when burned.

    Biodiesel is an alternative fuel similar to conventional or “fossil/petroleum” diesel. The process used to convert these oils to biodiesel is called transesterification. This process is described in more detail below. The largest possible source of suitable oil comes from oil crops such as soybean, rapeseed, corn, and sunflower.

    At present, oil straight from the agricultural industry represents the greatest potential source, but it is not being used for commercial production of biodiesel simply because the raw oil is too expensive. After the cost of converting it to biodiesel has been added, the price is too high to compete with petroleum diesel. Waste vegetable oil can often be obtained for free or already treated for a small price. One disadvantage of using waste oil is it must be treated to remove impurities like free fatty acids (FFA) before conversion to biodiesel is possible. In conclusion, biodiesel produced from waste vegetable/animals oil and fats can compete with the prices of petroleum diesel without national subsidies.

    Making Biodiesel: Transesterification

    Transesterification of natural glycerides with methanol to methylesters is a technically
    important reaction that has been used extensively in the soap and detergent manufacturing industry worldwide for many years. Almost all biodiesel is produced in a similar chemical process using base catalyzed transesterification as it is the most economical process, requiring only low temperatures and pressures while producing a 98% conversion yield. The transesterification process is the reaction of a triglyceride (fat/oil) with an alcohol to form esters and glycerol. A triglyceride has a glycerine molecule as its base with three long chain fatty acids attached. The characteristics of the fat are determined by the nature of the fatty acids attached to the glycerine. The nature of the fatty acids can, in turn, affect the characteristics of the biodiesel.

    During the esterification process, the triglyceride is reacted with alcohol in the presence of a catalyst, usually a strong alkaline like sodium hydroxide. The alcohol reacts with the fatty acids to form the mono-alkyl ester, or biodiesel, and crude glycerol. In most production, methanol or ethanol is the alcohol used (methanol produces methyl esters, ethanol produces ethyl esters) and is base catalyzed by either potassium or sodium hydroxide. Potassium hydroxide has been found more suitable for the ethyl ester biodiesel production, but either base can be used for methyl ester production.

    The figure below shows the chemical process for methyl ester biodiesel. The reaction between the fat or oil and the alcohol is a reversible reaction, so the alcohol must be added in excess to drive the reaction towards the right and ensure complete conversion.

    Source: http://www.esru.strath.ac.uk/EandE/Web_sites/02-03/biofuels/what_biodiesel.htm
    The products of the reaction are the biodiesel itself and glycerol.

    A successful transesterification reaction is signified by the separation of the methyl ester (biodiesel) and glycerol layers after the reaction time. The heavier co-product, glycerol, settles out and may be sold as is or purified for use in other industries, e.g. pharmaceutical, cosmetics, and detergents.

    After the transesterification reaction and the separation of the crude heavy glycerin phase, the producer is left with a crude light biodiesel phase.   This crude biodiesel requires some purification prior to use.

    Biodiesel has a viscosity similar to petroleum diesel and can be used as an additive in formulations of diesel to increase the lubricity. Biodiesel can be used in pure form (B100) or may be blended with petroleum diesel at any concentration in most modern diesel engines. Biodiesel will degrade natural rubber gaskets and hoses in vehicles (mostly found in vehicles manufactured before 1992), although these tend to wear out naturally and most likely will have already been replaced with Viton type seals and hoses which are nonreactive to biodiesel. Biodiesel’s higher lubricity index compared to petroleum diesel is an advantage and can contribute to longer fuel injector life.

    Biodiesel is a better solvent than petroleum diesel and has been known to break down deposits of residue in the fuel lines of vehicles that have previously been run on petroleum diesel. Fuel filters may become clogged with particulates if a quick transition to pure biodiesel is made, as biodiesel “cleans” the engine in the process. It is, therefore, recommended to change the fuel filter within 600-800 miles after first switching to a biodiesel blend.

    Biodiesel’s commercial fuel quality is measured by the ASTM standard designated D 6751. The standards ensure that biodiesel is pure and the following important factors in the fuel production process are satisfied:
    Complete reaction
    Removal of glycerin
    Removal of catalyst
    Removal of alcohol
    Absence of free fatty acids
    Low sulfur content

    Biodiesel is, at present, the most attractive market alternative among the non-food applications of vegetable oils for transportation fuels. The different stages in the production of plant/seed oil methyl ester generate by-products which offer further outlets. Oil cake, the protein rich fraction obtained after the oil has been extracted from the seed, is used for animal feed. Glycerol, the other important by-product, has numerous applications in the oil and chemical industries such as the cosmetic, pharmaceutical, food, and painting industries.

    Benefits/Advantages of Biodiesel:

    Biodiesel is biorenewable. Feedstocks can be renewed one or more times in a generation.

    Biodiesel is carbon neutral. Plants use the same amount of CO2 to make the oil that is released when the fuel is burned.

    Biodiesel is rapidly biodegradable and completely nontoxic, meaning spillages represent far less risk than petroleum diesel spillages.

    Biodiesel has a higher flash point than petroleum diesel, making it safer in the event of a crash.

    Blends of 20% biodiesel with 80% petroleum diesel can be used in unmodified diesel engines. Biodiesel can be used in its pure form but may require certain engine modifications to avoid maintenance and performance problems.
    Biodiesel can be made from recycled vegetable and animal oils or fats.
    Biodiesel is nontoxic and biodegradable. It reduces the emission of harmful pollutants, mainly particulates, from diesel engines (80% less CO2 emissions, 100% less sulfur dioxide). But emissions of nitrogen oxide, the precursor of ozone, are increased.
    Biodiesel has a high cetane number of above 100, compared to only 40 for petroleum diesel fuel. The cetane number is a measure of a fuel’s ignition quality. The high cetane numbers of biodiesel contribute to easy cold starting and low idle noise.
    The use of biodiesel can extend the life of diesel engines because it is more lubricating and, furthermore, power output is relatively unaffected by biodiesel.
    Biodiesel replaces the exhaust odor of petroleum diesel with a more pleasant smell of popcorn or French fries.

    Educational Standards
    Each teacher is responsible for determining the state and/or national standards this activity satisfies with their district. A comprehensive set of national and state science and math standards related to this entire curriculum can be found at the website. The standards can be downloaded as a Microsoft® Word document to make it easier to transfer the standards to this and other documents.

    Resources:
    http://www.arborbiofuelscompany.com/transesterification_101.html
    http://www.cyberlipid.org/glycer/biodiesel.htm
    http://www.esru.strath.ac.uk/EandE/Web_sites/02-03/biofuels/what_biodiesel.htm
    http://www.anl.gov/PCS/acsfuel/preprint%20archive/Files/Volumes/Vol40-4.pdf

  13. HEAT INDUCED CIS/TRANS ISOMERIZATION IN VEGETABLE OILS AND OLEIC ACID

    Author(s): John-Harwood Scott, Sarah E. G. Porter
    Filed under Chemistry, Research, Volume 4

    Abstract

    With the FDA mandating that all foodstuff labels list the amount of trans fats within their product, it becomes necessary to have a rapid and reproducible method for quantifying trans content within foods. Research has led to the advent of an analytical method that utilizes attenuated total reflectance with a Fourier transform infrared spectrometer to quantitatively measure trans fat in foodstuffs. The method is possible because of an infrared absorbance band at 966 cm­-1 that is unique to nutritional trans fats. This research used the aforementioned method to quantify trans fat content in common cooking vegetable oils. Before analysis, the oil samples were heated to different temperatures that were less than or equal their respective smoke point. Results from all heated oil samples provided data that was below the calibration range (0.5 – 40% trans fat).

    Introduction

    In order to improve taste, shelf-life, and cooking quality at a low cost, the food industry has long been in the practice of converting vegetable oils into margarines and shortenings, via a hydrogenation process, that are to be used primarily in most packaged foodstuffs.1 Fatty acids, the main constituents of vegetable oils, are a carboxylic group attached to a long hydrocarbon tail of varying length.1 Saturated fatty acids have no double bonds in the tail while mono- and polyunsaturated fatty acids have one or many respectively.1 A saturated and a polyunsaturated fat are shown in Figure 1a-b. The linear geometry of saturated fats allows them to compact and be in a solid state at room temperature. The bent geometry of unsaturated fats inhibits compaction and makes them liquid state at room temperature.1

    During hydrogenation, the double bonds present in the polyunsaturated and monounsaturated fatty acids are converted to saturated fatty acids.1,2 It is a simple process that consists of mixing heated vegetable oil with hydrogen gas in the presence of a catalyst.1 Flavor stability and longevity is achieved with hydrogenation because, in reducing the amount of double bonds, the process limits possible sites for oxidation.1 Complete hydrogenation requires ample energy input through catalyst concentration and pressure and does not always provide the desired functional characteristics in the oil product.3

    In order to elicit the desired characteristics from hydrogenated oil, the food industry implements a selective hydrogenation process.1,2,4 The process is selective in that the catalyst used hydrogenates fats with the highest degree of unsaturation first (poly-) before hydrogenating di- or monounsaturated fats.1 This allows more control over the level of hydrogenation within the oil product.1 The vegetable oils are modulated by temperature, pressure, agitation, and catalyst concentration during hydrogenation to keep desired quantities of unsaturated fats in the final product. The remaining unsaturated fats give the hydrogenated oil a better liquid to solid fat ratio and therein, better functionality.1

    During hydrogenation, the natural cis-geometry carbon-carbon double bonds of the unsaturated fatty acids in vegetable oils are broken.5 The freed electron density goes toward adding hydrogen to both the carbons that had previously been double bonded.3 This process, like any other reaction, is expedited with heat and is rapidly facilitated by a two-step nickel catalyst.2,3 However, in partial hydrogenation, where there are unsaturated fats that remain throughout hydrogenation, the double bond can break from the heat or an incomplete interaction with the catalyst and subsequently reform.3 When reformation occurs, the trans geometry of the double bond is strongly favored over the natural cis for both thermodynamic and steric reasons.3 The resulting fatty acid by-product is then termed a trans fat.1,2,3 Since trans fats are linear in geometry, like a saturated fat, they increase the solid ratio of the hydrogenated oil. A comparison of a cis and trans fat is shown in Figure 2 a-b. Margarine and shortening stocks produced commercially from vegetable oils can have trans fat concentration as high as 40%.2

    The formation of trans fatty acids during the production of partially hydrogenated oils in the food industry is a negative consequence due to the adverse health effects that have been attributed to dietary trans fats.2,5,6,7 In particular, initial research showed that increases of dietary trans fats gave rise to significantly higher risks of coronary heart disease (CHD) in humans. 2,5,6,7 More clinical research and trials followed to investigate why trans fats contribute to CHD, and subsequently atherosclerosis.2

    Human digestive enzymes that specialize in the uptake, transport, and degradation of fatty acids are shape-specific to the natural, cis double bond formation.5 Without uptake or degradation, an ingested trans fat will not have the metabolic or structural potential of the original fatty acid.5 Furthermore, trans fats mimic the shape of a saturated fat.5 Body cells can attempt to incorporate trans fats into structures, like membrane phospholipids, resulting in a deficiency of said structure to perform its desired task.5

    With respect to CHD, trans fats show their most adverse effect on the levels of blood lipid carrier molecules: low-density lipoprotein (LDL) cholesterol and high-density lipoprotein (HDL) cholesterol.5,6,7,8 Both molecules are measured by the ratio of their respective concentration in the blood.5 A high percentage of LDL (the unhealthy lipid cholesterol) in comparison to HDL (the healthy lipid cholesterol) has long been the standard indicator for both CHD and an elevated risk for atherosclerosis.5 Saturated fats, which are also considered unhealthy, raise LDL levels but leave HDL levels constant.5 Trans fats however, not only increase the amount of LDL but decrease the amount of HDL in the blood, leaving a cholesterol ratio that is far worse than what saturated fats produce.5,8 Such malevolent health effects found in epidemiological and cellular studies brought trans fat to the attention of the public, food suppliers, and government regulation agencies.4

    The United States’ Food and Drug Administration (FDA) has the responsibility to guarantee that products intended for human ingestion are safe for consumption.4 The jurisdiction of the FDA is outlined primarily in the Fair Packaging and Labeling Act and Federal Food, Drug, and Cosmetic Act (FFDCA); both of which provide the federal laws necessary to inspect and regulate the safety of almost all U.S. foodstuffs.4 In 1990, the Nutrition Labeling and Education Act sought to expand the required nutritional elements, previously listed in the FFDCA, that are required to be present on the labels of all foods and supplements. However, when the FDA implemented its final rule in 1993 and turned the act into law, trans fats were not included in the amended list of required nutrients for labeling purposes.4 At the time, the FDA considered research on the health implications of trans fats to be incomplete, making it premature to require the amount of trans present to be listed on a label.4

    In light of more and more research that corroborated the findings outlined above concerning the negative health effects of trans fats, the FDA was forced to revisit the issue of trans fat labeling.4 Expert panels were convinced by the scientific evidence and were strongly suggesting that the American consumption of trans fats should be limited.4 Their recommendation, in parallel with old recommendations concerning saturated fats, was that consumers should purchase foods that had low, if any, trans fat content.4 The FDA conceded to both the experts and a growing public outcry in 1999. In 2003, a final rule passed which mandated that the trans fat content of all foods and supplements be listed, starting in 2006.9 As dictated in the final rule, companies are obligated to list the exact trans fat content, unless it is less than 0.5 g / serving size in which case trans content can be labeled as zero .9

    With the labeling of trans fat content mandatory, it became necessary for regulators and manufacturers to have a simple, rapid, and reproducible method for assessing trans content in foodstuffs.2,10-13 As food manufacturers attempt to reduce and limit the amount of trans fat in their product, the analytical method employed must also be particularly sensitive to quantify lower concentrations (e.x % trans < 5% trans fat) in order to ensure label accuracy.4,10-14

    A capillary gas chromatography (GC) method was initially used to quantify trans fat in food samples.4,10-14 An official GC method was approved and released by the Association of Official Analytical Chemists (AOAC).4 Accurate and reproducible determination of trans fat content and identification of each specific trans fatty acid present are both very possible with the GC method.4,10-13 However, GC has limitations in its use for regulatory purposes.

    The use of a long (100 m) capillary column coated with a highly polar stationary phase is required to achieve the needed separation of every fatty acid.4 Sufficient separations can take as long as 1.5 hours for a single analysis.4,10,11 Therefore, despite its reliable accuracy and detailed information on fat content, the time involved with sample preparation and analysis makes the GC method inefficient for the quick and repetitive determination of trans fats needed for labeling and regulatory oversight.4,10,11

    Another technique has been tested and implemented for rapid determination of trans fats: infrared spectroscopy (IR).4,10-14 The IR method relies on the spectroscopic properties of trans fatty acids, particularly a CH out-of-plane deformation band seen at 966 cm-1 that represents an isolated trans double bond absorption.4 This is particularly useful because the band is unique to the specific trans double bond that the FDA uses to define a nutritional trans fat: an unsaturated fatty acid that has one or more non-conjugated, trans double bonds.4,9 Fatty acids that posses conjugated trans bonds have been shown in research to not have the adverse health effects of isolated trans bonds.15 In fact, some actually exert positive health benefits.15,16

    Conjugated double bonds that are found naturally in unsaturated fatty acids and other molecules have absorption bands that are shifted to 985 – 990 cm-1 and to 940 – 950 cm-1.12 Therefore, if a food sample contained heavily conjugated molecules, such as lycopene shown in Figure 3a, or a conjugated fatty acid, like conjugated linoleic acid shown in Figure 3b, absorption from the conjugated trans bonds would not interfere with the trans absorbance at 966 cm-1. This spectrometric characteristic makes the 966 cm-1 band exclusive to nutritional trans fatty acids.4,10-14

    Quantification is achieved by standards and a calibration curve constructed from the area under the 966 cm-1 band. Integration is used, as opposed to the individual absorbance value at 966 cm-1, in order to fully encompass the infrared absorption intensity.4,12,13 Unfortunately, the absorption at 966 cm-1 occurs over an elevated and sloping baseline, as seen in Figure 4, which gives rise to inaccuracies in quantification via integration, particularly as trans concentration gets smaller.4,10-14

    In order to achieve better accuracy and resolution, internal reflection methods are used for infrared absorption analysis.4,10-14 In particular, attenuated total reflection (ATR) has been commonly implemented because of its ability to analyze a sample that has not been specially prepared or a total lipid extract sample.4 During ATR analysis, infrared radiation barely penetrates (only a few µm) the fat or oil sample that rests above an internal reflection crystal.4,10 As IR light oscillates, undergoing internal reflections, within the crystal, small amounts of radiation penetrates the sample.4,10 The radiation intensity quickly decays, thus changing the wave’s frequency which can be used to measure the depth the wave penetrated.4,10 Using radiation angles, penetration depth, and Fourier transform, the attenuation of IR within the sample can be calculated and used to form a spectrum that has greater accuracy and better resolution than conventional IR spectroscopy.4,10 An ATR diagram is shown in Figure 5.

    Spectra from a trans free reference oil, ideally of similar fatty acid structure, are used as a background to compare with a trans present sample.4,10 The official AOAC method for analyzing trans fats using IR methods recommends ATR with Fourier transform infrared spectroscopy (ATR-FTIR).4,10-14,14

    The addition of ATR and Fourier transform in the official method did eliminate the baseline offset and slope, yet its accuracy at lower concentrations ( less than 5%) was only slightly improved.4,10 The remaining inaccuracy was attributed to the inability to find a reference fat that is absolutely trans free and has a composition that closely matches every test sample.4,11,12,13 Also, saturated fatty acids were concluded to be causing absorbance interference in the spectra of samples with low trans content.4,12,13

    Nevertheless, further research on the ATR-FTIR method has led to improvements that have increased its accuracy and sensitivity.4, 12,13 In specific, a negative second derivative method (-2D) has been implemented successfully and is now nearing the end of a validation process by the AOAC.4,12,13 The second derivative has commonly been used to enhance spectral resolution, particularly with Fourier spectra.4,12,13 The negative in the method’s name simply means the spectra are multiplied by -1 to have the second derivative absorption peak face up for convenience. Even when trans fat standards were analyzed relative to air, as opposed to a reference oil, the -2D method eliminated the sloping baseline, and clearly resolved bands from interfering fats away from the 966 cm-1 band.4,12,13An absorbance spectrum compared to a second derivative absorbance spectrum is shown in Figure 6a-b. As shown in Figure 6b, the starting and finishing points of the 966 cm-1 band is clearly defined. The precision of the -2D method is considered to be 0.5% trans fat as a percentage of total fat.2,15

    As indicated by the FDA mandating that trans fat content be listed on the label of all foods and supplements, there is considerable public concern relating to trans-fats.17 Consumers are increasingly more likely to buy products that contain natural polyunsaturated fats, which have been correlated to a lesser risk of coronary heart disease.17,18 An example of this shift is seen in the purchasing of oiled cooking products.17 People are now more inclined to cook with a vegetable oil medium, to avoid the saturated fats of butter or margarine and to have the health benefits from the oil’s polyunsaturated fats.17 However, the health benefits of the vegetable oil would perhaps be reduced if the heat and duration of cooking induces cis-unsaturated fats to isomerize to trans, much like it does in hydrogenation and vegetable oil deodorization processes.1,19

    This research investigated the effects of heating common cooking oils on their trans fat content. Furthermore, oleic acid, which is the greatest monounsaturated fat constituent in canola oil, was also studied in this manner. The hypothesis was that the isomerization of cis oleic acid to trans oleic acid could be easily analyzed and could conceptually represent what was occurring in the cooking oils. Each oil was heated to a series of designated temperatures below, equal to, or slightly above its respective smoke point. The smoke point is the temperature at which the fatty oil starts produce smoke from internal hydrolysis and oxidation.1 This temperature is a common indicator of when a fatty oil begins to degrade and lose culinary functionality (like taste).1 At each temperature, aliquots of each oil were removed at designated times for ATR-FTIR testing. The -2D method was employed to achieve the greatest accuracy in quantifying total trans fat concentration in the oils. For the purposes of comparing methods, a fatty acid rich cooking medium was analyzed qualitatively via GC-MS. The results from which greatly emphasized the advantages of ATR-FTIR.

    Experimental

    ATR-FTIR Method

    In accordance with past research that quantified trans fat content, standards were prepared using trielaidin (2,3-bis[[(E)-octadec-9-enoyl]oxy]propyl (E)-octadec-9-enoate) as a pure trans fatty acid and triolein (2,3-Bis[[(Z)-octadec-9-enoyl]oxy]propyl (Z)-octadec-9-enoate) as a pure cis fatty acid standard.11,12 Specifically, Nu-Chek Prep trielaidin and MP Biomedicals triolein were used. These fatty acids are identical, except for the geometry of their carbon-carbon double bond. Structures for trielaidin and triolein are shown in Figures 7a and 7b respectively. Standard concentrations ranged from 0.5 – 40% trans/cis fat w/w.

    The specific oils used in this experiment were Fisher® reagent grade pure oleic acid, Great Value® (GV) pure corn oil, GV pure canola oil, GV pure olive oil, and Filippo Berio® olive oil. Except for oleic acid, all oils were purchased at Wal-Mart® which sells Great Value® products as the generic brand. Therefore, the GV pure olive oil was considered the generic brand and Filippo Berio® olive oil the name, or premium brand.

    For each heated sample, moderately sized aliquots of the cooking oils were put in a beaker and heated with a Corning PC-420D hot plate. A stir bar was added to each sample to ensure temperature uniformity throughout the oil. Fisher® thermometers, held on a clamp, were used to monitor temperature.

    The smoke point of all oils tested is listed in Table 1. For all oils, except canola oil, samples were brought to the smoke point, 50 °C below the smoke point, and 100 °C below the smoke point. Canola oil samples were heated to temperatures starting at 100 °C and going to 240 °C (the smoke point) by 20 °C increments. An additional measurement for canola oil and generic olive oil was taken where an oil sample was heated to 10 °C above the smoke point. The exact temperatures used for each oil is outlined in Table 1.

    In order to assess production of trans fats at a given temperature over the course of time, small aliquots were removed at different time intervals from each heated sample. Initially, said intervals were 1, 3, 5, 10, and 15 minutes. However, the intervals were modified to 1, 5, and 12 minutes, to save time and materials.

    All standards and samples were analyzed using a Thermo Nicolet Avatar 360 FT-IR with Smart MIRacle. The ATR apparatus had a zinc selenide crystal. In accordance to past research, 256 scans were taken per analysis with a resolution of 4 cm-1.4,10-14

    Absorbance spectra were taken from the FTIR and uploaded into the data analysis program, MatLab® 7.9.0 (R2009b). Matlab did not have pre-written functions to take a second derivative or area under a spectrum curve. A function was written to take both the negative second derivative of all spectra and the area under the 966 cm-1. Peak area was estimated using the trapezoid rule, shown in Figure 8 where ‘S(X)’ represents the spectral output at any given wavenumber (X), and X0 and Xn represent the starting and final wavenumbers for integration.

    The area for the 966 cm-1 band was taken from wavenumbers 955 – 974 cm-1. This range is smaller than what was used in past research.4,12,13 However, the range used encompassed the entire trans band of even 40% trans standards and still provided a sufficient number of data points for integration via trapezoid rule.

    Gas Chromatography-Mass Spectrometry (GC-MS) Method

    The cooking medium to be assessed qualitatively was Crisco® All-Vegetable Shortening because it closely matched the shortening used in past research with GC-MS.21 In order to be compatible for chromatography, the shortening had to be prepped with a lipid extraction and a transesterfication to convert the fatty acids to methyl esters for volatility.4,21 In accordance with previous research, a 100 mg sample of shortening was dissolved in 25 ml of hexane.21 Roughly 5 ml of the mixture solution was added to 250 µl of 0.5 M sodium methoxide/methanol solution and vortexed. A 5 ml aliquot of saturated NaCl solution was added. The container was shaken vigorously and allowed to settle before transferring 3 ml of the hexane layer to another vial to be mixed with sodium sulfate to remove any residual water before GC analysis.

    A Varian 3900 GC oven and Varian 2000 GC-MS were used for analysis. A FactorFourTM VF-1ms capillary column (30 m x 0.25 mm, 0.25 μm film thickness) was used out of convenience because it was already connected within the oven. Again, in accordance with past research using GC-MS, the injection volume was 1 µl, injection temperature was 250 ºC, and the injection split ratio was 100.21 The best fatty acid methyl ester separation seen in previous research utilized the following temperature programming: initial temperature 150 ºC, hold 10 minutes, ramp at 2.7 ºC/min, final temperature 210 ºC, hold for 3 minutes.21

    Results and Discussion

    ATR-FTIR Results

    Calibration Curve

    Spectra from the trans standards were successfully analyzed in Matlab using the -2D method. As shown in Figure 9, the trans peak of -2D spectra maintained a consistent shape with all standards and increased in height as the percent trans increased. However, as seen in Figure 9, some of the -2D absorbance data points in the integration range (955 – 974 cm-1) were negative. In order to avoid using negative data points for integration, the spectra over the integration range was offset so that the lowest point became zero. For consistency, all subsequent spectra from oil samples were offset in the same way.

    The area of the 966 cm-1 band for each standard is listed in Table 2. A calibration curve was composed from this data, as shown in Figure 10. In accordance with the literature, a positive linear correlation was seen between area and % trans fat that had a correlation coefficient of 0.9499. 4,10-13

    Vegetable Oil Samples

    Canola Oil

    The complete area values for all canola samples are listed in Table 3. Regardless of temperature or duration, all areas of the 966 cm-1 band were below the calibration range, meaning their band area was below 0.034. Therefore, the trans concentration is below 0.5%. As seen in Table 3, there was no correlation between area of the trans band with duration of heating for a given temperature. For convenience, all area values for a given temperature were averaged together and are listed in Table 4 in comparison to the trans band area of “neat,” or unheated, canola oil.

    Interesting to note, the neat canola oil had a larger trans band area than samples heated at 100 °C and 120 °C. This is misleading, considering how the shape of the trans band, particularly its width, changed with temperature, as seen in Figure 11. The change in trans band shape can be attributed to interference from other fatty acids, particularly saturated fatty acids.13 This is in accordance with past research which noted that noted that trans levels below 0.5% were subject to shifting because the trans absorbance at those concentrations is too feeble to outcompete interference from saturated fats.4,13 Yet, as seen in Figure 12 and 13, the trans band started to have a more consistent shape and got more prominent with increasing temperature. Differences in area, however, were minimal. As seen in Figure 14, there was no correlation between temperature and the 966 cm-1 band area within the experiments time range.

    Corn Oil, Generic and Premium Olive Oil

    The areas of the 966 cm-1 band for all corn oil, generic olive oil, and premium olive oil were under the calibration range. Thus the trans concentration was below 0.5%. As with canola oil, band areas fluctuated slightly within a given temperature and no correlation was seen between area and increasing time. The areas for all samples within a given temperature were averaged together and are listed in Tables 5-7 in comparison to the trans band area of the neat oil. Once again, the areas of the neat oils were higher than some of the heated sample averages. This is still explained by the change of shape the spectra experienced with heating.
    Unlike canola oil, spectra of unheated neat samples from the remaining vegetable oils showed no initial trans band, shown in Figures 15-17. Spectra shape shifted with increasing temperature in the same way as canola oil for the remaining oils. Nevertheless, temperatures near the smoke point produced spectra that had an easily identifiable trans band, also shown in Figures 15-17.

    Oleic Acid

    Spectra from oleic acid samples, seen in Figure 18, showed a trans band that was clearly defined and easily distinguishable, much like spectra from the calibration standards. This is due to the fact that there were no saturated fatty acids in the samples to interfere with trans absorption.

    Nevertheless, band areas fluctuated slightly within a given temperature and no correlation was seen between area and increasing time. Once again, the areas for all samples within a given temperature were averaged together and are listed below in Tables 8 in comparison to the trans band area of the neat oleic acid. Area of the trans band in 100°C and 150°C samples were less than the area of neat oleic acid, while the area of the 200°C was slightly larger than neat oleic acid. However, this is indicative of very little, considering how identical the spectra of neat oleic acid and the 200°C sample are, as seen in Figure 18. Differences in area can thus be attributed to minor fluctuations in band shape that occur inherently within analyzing multiple samples.

    GC-MS Results

    The GC-MS method used here did not elicit the desired chromatogram.4,10,14,19 Instead of a clearly isolated peak for every individual fatty acid, the peaks overlapped and had long tails as they eluted, as seen in Figure 19. The sample that was injected was perhaps too concentrated and the peak splitting observed in Figure 19 could then be attributed to column overload. Furthermore, the all purpose VF-1ms column used was not prepped before analysis. The first two feet of the column were not cut off to prevent contamination and, because of this omitted caution, such possible contamination could have also contributed to the poor chromatogram results.

    All peaks in the chromatogram were identified by the mass spectrum to be fatty acid methyl esters. The first large peak, starting at around 24 minutes, was flagged and the identification data from the MS is shown in Figure 20.

    Nevertheless, the results from the GC-MS further emphasize the advantages of ATR-FTIR over GC when it comes to analyzing trans fat content. The ATR-FTIR, without any special modification, was able to assess trans content from standards and oil samples, that required no preparation, in about 5 minutes per analysis. With the GC-MS, each sample took between 30 and 35 min to pass through the column. Every sample for analysis had to be extracted and converted to methyl esters before it could be used in the GC. Furthermore, for a desirable spectrum to be obtained, the proper column would have to be purchased and properly installed in the GC oven. The above limitations of the GC-MS alone, without further complications from analyzing quantitatively, would have made it a very cumbersome, time consuming, and expensive method use in order to analyze the trans fat content in the vegetable oil samples of this experiment.

    Conclusion

    The negative second derivative method successfully resolved the infrared trans absorption band at 966 cm-1 for all trans standards. A functional calibration curve was constructed using the area of the -2D trans band from each trans standard. However, the area of the trans bands for all samples of heated vegetable oil and heated oleic acid were below the calibration range (0.5 – 40% trans fat). Furthermore, the trans peak from heated oil samples was not strong enough to overcome interferences created by saturated fat absorptions. This led to fluctuating baselines and inconsistent shapes for the trans band. Despite the above, a qualitative analysis using GC-MS emphasized the GC method’s limitations and ATR-FTIR method’s advantages for multiple and rapid determination of trans fat content.

    The results indicate that heating canola, corn, and premium and generic olive oil to their smoke point for at least 15 minutes does not quantifiably increase their respective concentration of trans fatty acids. Those who are inclined to cook with a vegetable oil medium, to avoid the saturated fats of butter or margarine and to have the health benefits from the oil’s polyunsaturated fats, now have further justification for their choice of cooking medium.

    Results could have been improved by using a data analysis program that was equipped with a pre-existing and more accurate integration function. The trapezoid rule, while reliable, is nonetheless an approximation method for integration. Future work could also include heating oil samples to higher temperatures and for longer durations to assess when significant quantities of heat induced cis/trans isomerization does occur. Results from this would perhaps not be as relevant to human health or cooking but would provide interesting data.

    Acknowledgements

    I would like to acknowledge those who have made it possible for me to conduct this research project. I would especially like to thank Dr. Sara Porter for her guidance and oversight. I would also like to thank Dr. Porter for her significant investment in this research and her expectation that I never settle and that I always push further. Also, I would like to thank the Longwood University Department of Chemistry and Physics for funding, research space, and professors who are more than happy to satisfy my curiosity. Furthermore, I would like to thank the Cormier Honors College for their financial support and enabling me to present at the 240th American Chemical Society National Meeting held in Anaheim in March 2011. Finally, I would like to thank my father and brother, Porter and Thomas Scott, for their wisdom, guidance, and encouragement to fully develop my potential.

    References

    1. O’Brian, R.K.; 2009 Fats and oils: formulating and processing for applications. CRC Press, Boca Raton, FL.

    2. Eller, F.J., List, G.R., Teel, J.A., Steidley, K.R., Adlof, R.O.; Preparation of Spread Oils Meeting U.S. Food and Drug Administration Labeling Requirements for Trans Fatty Acids via Pressure-Controlled Hydrogenation. J. Agric. Food Chem. 2005, 53, 5982-5984

    3. Hsu, N., Diosady, L.L., Rubin, L. J.; Catalytic behavior of palladium in the hydrogenation of edible oils II. Geometrical and positional isomerization characteristics. JOAC., 1998, 66 (2), 232-236.

    4. Mossoba, M.M., Moss, J., Kramer, J.K. Trans fat labeling and levels in U.S. foods: assessment of gas chromatographic and infrared spectroscopic techniques for regulatory compliance. Journal Of AOAC International 2009, 92, pp. 1284-1300.

    5. Ascherio, A., Willett, W.C.; Health effects of trans fatty acids. Am J Clin Nutr. 1997, 66, 1006S-lOS.

    6. Booker, C., Mann J. Trans fatty acids and cardiovascular health: translation of the evidence base. Nutrition, Metabolism, And Cardiovascular Diseases: NMCD 2008, 18, pp.448-456.

    7. Hunter, J.E.; Dietary levels of trans-fatty acids: basis for health concerns and industry effort to limit use. Nutrition Research. 2005, 25, 499-513.

    8. Mozaffarian, D.,Clarke, R.; Quantitative effects on cardiovascular risk factors and coronary heart disease risk of replacing partially hydrogenated vegetable oils with other fats and oils. European Journal of Clinical Nutrition 2009, 63, S22–S33.

    9. Food and Drug Admistration, HHS; Food labeling: trans fatty acids in nutrition labeling, nutrient content claims, and health claims. Final rule. Federal Register 2003; 68, pp. 41433-41506.

    10. Mossoba, M.M., Kramer, J.K.G., Delmonte, P., Yurawecz, M.P., Rader, J.I.; 2005 In: Kodali, D.R, List, G.R., (eds) Trans Fat Alternatives. AOCS Press, Champaig, IL, 47-70.

    11. Mossoba, M. M., Milosevic, V., Milosevic, M., Kramer J. K. G., Azizian H. Determination of total trans fats and oils by infrared spectroscopy for regulatory compliance. Analytical And Bioanalytical Chemistry 2007, 389, 87-92.

    12. Mossoba, M. M., Milosevic, V., Milosevic, M., Kramer J. K. G., Azizian H. Determining low levels of trans fatty acids in foods using improved ATR-FTIR procedure. Lipid Technology 2004, 16, 252-254.

    13. Mossoba, M. M., Milosevic, V., Milosevic, M., Kramer J. K. G.; Interference of Saturated Fats in the Determination of Low Levels of trans Fats (below 0.5%) by Infrared Spectroscopy. J. Amer. Oil Chem. Soc. 2007, 84, 339-342.

    14. AOAC Official Method 2000.10 Editor, Howitz, W., Eds. Official Methods of Analysis; 18th Edition; AOAC International, 2010.

    15. Salminen, I., Mutanen, M., Jauhiainen, M., Aro, A.; Dietary trans fatty acids increase conjugated linoleic acid levels in human serum, The Journal of Nutritional Biochemistry. 1998, 9(2), 93-98,

    16. Nicolosi, R.J., Rogers, E.J., Kritchevsky, D., Scimeca, J.A., Huth, P.J.; Dietary conjugated linoleic acid reduces plasma lipoproteins and early aortic atherosclerosis in hypercholesterolemic hamsters. Artery. 1997, 22(5), 266-77.

    17. Greenblatt, A.; Obesity Epidemic. Congressional Quarterly. 2003, 13(4), 73-104.
    18. Oh, K., Hu, F. B., Manson, J. E., Stampfer, M. J., Willett, W. C. Dietary fat intake and risk of coronary heart disease in women: 20 years of follow-up of the nurses’ health study. American Journal Of Epidemiology 2005, 161, pp. 672-679.

    19. Ceriani, Roberta., Meirelles, A.J.A., Formation of trans PUFA during deodorization of canola oil: A study through computational simulation. Chemical Engineering and Processing 2007, 46, pp. 375-385.
    20. Detwiler, S. B., Markley, K. S.; Smoke, flash, and fire points of soybean and other vegetable oils. J. Amer. Oil Chem. Soc. 1940, 17, 39-40.

    21. Huang, Z., Wang, B., Crenshaw, A.A.; A simple method for the analysis of trans fatty acid with GC-MS and ATTM-Silar-90 capillary column. Food Chemistry 2006, 98, 593-598.

  14. SCC News
    Trans-fats in Skin Care Workshop Is Dec. 9
    November 2, 2015
    – See more at: http://www.happi.com/issues/2015-11-01/view_scc-news/trans-fats-in-skin-care-workshop-is-dec-9/#sthash.TDZT4G9w.dpuf

    In conjunction with AOCS, SCC has planned a special current events briefing for Dec. 9 in New York City covering the study of trans-fats in skin care. The course, “Is non-edible non-applicable? The study of Trans-fats in Skin Care Applications-Biochemistry, Biology and Physics” will be held from 1-5:30pm. The FDA is stating on its website that it took a “step to remove artificial trans-fat from the food supply. This step is expected to reduce coronary heart disease and prevent thousands of fatal heart attacks every year.” In addition, deficiency in essential nutritional fatty acids may be of equal magnitude for cause of disease. It is often mistakenly thought that if compounds are edible they are also necessarily safe to be applied to skin and that digested beneficial nutrients are as valuable topically. However the skin presents a very different environment when compared to the digestive system and functions as a semi-autonomic organ; therefore, exposure to skin should be viewed in relation to its characteristics and means of application. When this dogma is presented from a different angle; pointing toward non-healthy food being potentially harmful to skin or healthy nutrients digestion contributing to skin health; is it valid? This question will be discussed in this newly formed workshop focusing on trans-fats in skin care applications and role of essential fatty acids in skin health. Trans-fats are hydrogenated fatty acid that lost their double bond to become solidified and more stable to oxidation. Essential fatty acids are omega 3 and 6. The workshop will further delve into compounds properties; skin interaction, health aspects, bioavailability and biochemistry paths. – See more at: http://www.happi.com/issues/2015-11-01/view_scc-news/trans-fats-in-skin-care-workshop-is-dec-9/#sthash.TDZT4G9w.dpuf

  15. Let’s Talk Oleic Acid and Vegetable Oils
    FEBRUARY 14, 2014
    tags: beauty, chemistry, cosmetic chemistry, Oleic Acid, skin care, vegetable oils
    by RealizeBeautyEd

    It was during a conversation a week ago that I became aware of a potential…. let’s say ‘situation’ can occur with Oleic Acid. Oleic acid is commonly found in vegetable oils and is a major component in each of the following oils where it may account for up to 80% of the fatty acids present:

    Sunflower
    Olive
    Pecan
    Canola
    Macadamia
    Soybean
    The situation is that Oleic Acid is a known penetration enhancer and as such has been widely studies by the Pharmaceutical industry as a potential vehicle for delivering actives through the skin. This research showed that Oleic acid works in two key ways, firstly by helping to solubilise the active – a better solubilised active will penetrate better and secondly by damaging the skin barrier – a weak skin barrier is easier to penetrate so watch out eczema prone-folk! The second mode of action rang alarm bells with me and many others in the cosmetics industry as damaging the skin barrier is NOT something we want to achieve and while Oleic Acid has been classified as irritant rather than down right mutant it is still worth keeping an eye on.

    So, does that mean that the oils listed above that are high in Oleic Acid are damaging to the skin?

    Well. I initially thought so but then I stopped and though on……

    When we say ‘oleic acid’ are we talking about the same beast?

    A little bit of digging and a dash of experience shows me that the Oleic Acid ‘fatty acid’ in a fat is part of a triglyceride. This means that the oleic acid is attached at one end to a molecule of glycerine – a glycerine molecule that also has two other fatty acids in its grip.

    A Triglyceride looks like this:

    triglyceride with oleic acid

    The process of breaking triglycerides up is called Hydrolysis (hydro= water, lysis = splitting or something Latin) (found on this website)

    Hydrolysis of fatty acids

    So, once I realised this I took a step back and worked out that the knowledge gap is a little clearer now….

    I know that Oleic Acid is a penetration enhancer because I have seen plenty of evidence of that and it has a long history of use in the pharmaceutical arena.
    I know that Oleic acid is present in some vegetable oils BUT not usually as the free acid, as part of a triglyceride.
    I know that triglycerides can be broken down relatively easily.
    My questions then became:

    Does Oleic Acid in a triglyceride have the same skin penetration properties as FREE oleic acid?
    Does Oleic Acid in a triglyceride have the same irritation potential as FREE oleic acid?
    How much FREE oleic acid is usually floating around in a vegetable oil?
    Does the amount of FREE oleic acid in a vegetable oil change over time in any way?
    The flighty part of my thinking process decided that rather than go through my own questions in order I should just check out point three first. After all this might be something that oil manufacturers measure and it makes sense to start off by comparing apples with apples (and here the apple is FREE OLEIC ACID).

    It didn’t take long to find out that Virgin Olive Oil has a provision for free Oleic Acid – it has to be kept to below 0.8% (at least here in Australia it does) of the oil to pass. Standard Olive Oil can have up to 2% Oleic Acid before it is failed. This was both interesting and encouraging as such a small level probably means that I don’t have to worry too much about Olive Oil damaging my skin barrier……

    Apparently too much free Oleic Acid can alter the taste of the oil. It’s presence is also a sign of poor fruit handling or frost damage which is also interesting.

    I found a level of 0.05% Free Oleic Acid in a specification for Sunflower Seed Oil (high Oleic Acid grade) and values ranging from 0.5-3.7% in Canola oil depending on how it had been processed and its age.

    From doing this I confirmed my suspicions that Oleic Acid content does rise over time – it is part of the ‘going rancid’ process, that it can vary depending on how the oil is distilled and that it changes from season to season. Free Oleic Acid can be formed in any oil that has an oleic acid based triglyceride and its presence can be hastened by the usual suspects – heat, UV light, oxygen, water but also before that from a poorly managed crop or distillation process.

    So that’s questions 3 and 4 answered but what about 1 and 2?

    To answer the question (in my head) about skin penetration potential of the Free Fatty Acid vs the Triglyceride I have to think both about the Free oleic acid chemistry and about the barrier damaging potential. I feel that we can get the barrier damaging potential out-of-the-way quickly – a vegetable oil is complex and oily and as such is quite likely to sit on the top of the skin and hydrate it by preventing moisture loss. This SHOULD help to maintain barrier function. In addition most vegetable oils contain skin-friendly antioxidants, soothing agents and Omega fats which also aid in building a better barrier. So, I would not expect the oleic acid rich oil to be as damaging as the free oleic acid….

    Oleic Acid stick model from Wikipedia
    Oleic Acid stick model from Wikipedia

    When I see this I start to see why the triglyceride Oleic Acid is most likely no problem at all in terms of skin irritation. The functional group of this chemical is the O and the H. This is the acid part. The double bond on the kink in the middle is also important but less so than the head. In a triglyceride this functional head group is clinging on to glycerine so unless it drops that the fat is going to be nothing more than fatty and can’t really disrupt any barrier.

    But would it still encourage skin penetration?

    This is where it gets a little more difficult and where I have to stop for today. While I have managed to get a bit more insight into some of my questions this one now has me perplexed. I have read much about the skin penetration improvements seen with things like vegetable and animal oils vs mineral oils but have never managed to work out the what’s and why’s exactly. After all skin penetration can be enhanced in many ways (we have looked at two of them today).

    So I think that the best thing to do is to come back to this later once I have had time to do a bit more reading.

    But in the meantime it looks like we can use high Oleic vegetable oils with confidence just as long as the FREE oleic acid content is relatively low – we should be able to find that information our from our oil suppliers and can help things along by storing our oils correctly and using whilst fresh!

    I love science, don’t you?

    Amanda x

  16. Monolaurin Health Benefits
    by DARLA FERRARA

    Monolaurin, or glycerin monolaurate or GML, is a substance formed from a mixture combining glycerol and lauric acid from coconut oil. Lauric acid is a component in human breast milk and known to help protect infants from infection. According to a study in the October 2007 issue of “Journal of Drugs in Dermatology,” coconut oil has fatty acids made from lauric acid. Monolaurin is an antimicrobial agent that has some promising health benefits, especially in the arena of combating infection.
    Immune System Health

    The human body will naturally convert coconut oil to monolaurin. Beth Beisel, a registered dietitian, claims in an article for NourishedMagazine.com that ingesting coconut oil daily helps to build up the immune system and fight infection from attacking agents, such as swine flu. In the magazine piece, Dr. Mary Enig adds that 2 to 3 tablespoons of the oil provides enough lauric acid to help fight virulent infections. The magazine encourages using coconut oil for cooking or as part of a recipe for salad dressing.

  17. Franz Cell Testing that considered microbiome

    Are there any suggestions on modifications of Franz Cell testing for skin penetration that take into consideration the presence of microbiome and the related enzymes? I am specifically interested in the effect of esterases and lipases.

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