Author: james.runkle@drummondst.com

Here’s a hot flash you may not have heard before.  You’re not aging.  You’re rusting. As we get older, we start to face a complexion that looks duller, dingy, cloudier, less luminous. And more unevenly discolored.  The reason?  Iron is the most abundant transition metal in human body and the best-known driving force behind oxygen free radical formation through Fenton and Haber-Weiss reactions (Pierre and Fontecave 1999). Yes, the irony of iron is that iron is the element essential for building strong structures and machines but can also be the cause of their deterioration through rust. Oxidative damage a.k.a. – rusting is due to two distinct but surprisingly related functions: the build-up of iron in the skin as we get older coupled with a slowing of the skin’s natural exfoliation process. These result in iron staying in the skin for 56 days instead of 28 days as skin turnover time (Weintraub et al. 1965).

Here’s another conundrum.  In pre-menopause, excess iron in the body and skin is eliminated two ways: through monthly menstruation and through exfoliation. When menstruation ceases, iron levels can surge. Excess iron in the body is common with the onset of menopause.  In fact, iron can accumulate in the skin and is clinically shown to increase by as much as +42% pre through post menopause (Pelle et al. 2013). This excess iron is normally eliminated through menstruation as well as natural exfoliation.  The cessation of menstruation coupled with the deceleration of exfoliation limits the capacity to remove excess iron from the skin.

When body iron storage increases, skin too is exposed to higher levels of iron, which in turn can cause oxidative damage as the excess iron reacts with UVA. The result: skin aging and photoaging is accelerated. For example, ferritin is the iron storage protein for excess iron with a capacity of binding up to 4,500 atoms of iron per ferritin. It consists of heavy (H) and light (L) chain subunits. It was shown that ferritin can be immediately degraded by UVA doses of 100 and 250 kJ/m², releasing large amounts of iron for Fenton and Haber-Weiss reactions, producing oxygen free radicals (Pourzand et al. 1999). In a cell culture model mimicking menopausal conditions, increased iron and UVA were found to significantly increase an enzyme called collagenase-1 (Jian et al. 2011). Increased activity of collagenase-1 increases collagen degradation, causing wrinkles initially and skin thinning when we get older.

Like rust on metal, higher levels of iron when exposed to UV radiation, blue light, air pollutants and irritants from other sources results in increased oxidative damage in skin.  If you’ve ever seen a rusty bicycle, you know the corrosive damage the environment has on metal.  Oxidative stress begets skin-aging yellowing, dullness, dark spots and discolorations as well as wrinkles, loss of elasticity and other signs of aging.

Until now, antioxidants have been the only defense to attempt to neutralize oxidants after they are formed. Chelation can be used to sequester “free” iron, but it cannot compete to take away from iron in ferritin. The antioxidant and chelation approaches are retroactive and often too late (Table 1). They can only battle the symptoms, but they do not treat the underlying cause.

Table 1. Mode of actions of antioxidants, chelation, and de-ironizing inducer (DII) *

*: The skin is subject to a constant onslaught of free radicals catalyzed by iron-mediated Fenton and Haber-Weiss reactions.

A novel class of actives termed De-ironizing Inducers Technology (DII®) can do what no free-radical neutralizing antioxidant or chelation can do. It reduces iron in ferritin before it is converted to skin-damaging free radicals.  The patented DII® features 3-o-ethyl-ascorbic acid and pearl powder in the right ratios to effectively reduce iron in skin (US Patent 10792240). Research shows that when either alone or when too much of one exists without the other, iron reduction cannot be accomplished.  Ascorbic acid, also known as vitamin C helps release iron deposits from ferritin. Pearl Powder, a soft form of calcium carbonate, absorbs the released iron ions by exchanging them with calcium ions and, thus, removes skin-rusting iron deposits (Figure 1). These two previously incompatible ingredients work in unison to help prevent oxidative stress from forming in the first place, rather than attempting to neutralize free radicals after they appear as most antioxidants do. Without the need to fight free radicals, skin-rejuvenating Hyaluronic Acid plus Tetrapeptide-11 repair previous damage done and the goes one step further to help rebuild collagen, clarity, elasticity and tone / skin’s health and appearance.

Your skin glows with good health. And rust is history!

It is important to note that, while this discovery is made using menopausal model, the DII® is applicable to all ages. Estrogen peaks at age 25 and iron starts to increase from the same age. While estrogen sharply decreases during the menopausal transition period, iron dramatically increases during the same period. DII® may be more age defying in young women but more disrupting with higher success rate in older women. Man starts to accumulate iron from the 20s to the 30s and skin pigmentation is higher in man than in woman (Rahrovan et al. 2018). As a result, DII® is also applicable to man.

References:

Jian J, Pelle E, Yang Q, Pernodet N, Maes D, Huang X. (2011). Iron sensitizes keratinocytes and fibroblasts to uva-mediated matrix metalloproteinase-1 through tnf-alpha and erk activation. Exp Dermatol 20:249-254. https://www.ncbi.nlm.nih.gov/pubmed/20701626

Pelle E, Jian J, Zhang Q, Muizzuddin N, Yang Q, Dai J, et al. (2013). Menopause increases the iron storage protein ferritin in skin. J Cosmet Sci 64:175-179. https://www.ncbi.nlm.nih.gov/pubmed/23752032

Pierre JL, Fontecave M. (1999). Iron and activated oxygen species in biology: The basic chemistry. Biometals 12:195-199. https://www.ncbi.nlm.nih.gov/pubmed/10581682

Pourzand C, Watkin RD, Brown JE, Tyrrell RM. (1999). Ultraviolet a radiation induces immediate release of iron in human primary skin fibroblasts: The role of ferritin. Proc Natl Acad Sci U S A 96:6751-6756. https://www.ncbi.nlm.nih.gov/pubmed/10359784

Rahrovan S, Fanian F, Mehryan P, Humbert P, Firooz A. (2018). Male versus female skin: What dermatologists and cosmeticians should know. Int J Womens Dermatol 4:122-130. https://www.ncbi.nlm.nih.gov/pubmed/30175213

About the Author

Biography: Xi Huang has investigated iron’s role in diseases for more than three decades and is credited in more than 90 peer-reviewed publications, many of which demonstrate that excess iron is an important risk factor in women’s health. Dr. Huang was a faculty member at New York UniversitySchool of Medicine and his research laboratory has shown that iron accumulation due to the cessation of menstruation in postmenopausal women contributes to osteoporosis and skin aging. Dr. Huang is the founder and president of FE:I Beauty Tech, the parent company of i-On Skincare (www.ionskincare.com). Dr. Huang received his Ph.D. and M.S. in Toxicology and Applied Pharmacology from the Université Denis Diderot – Paris VII and received his undergraduate degree from China Agricultural University.

Coloring agents are essential components of certain cosmetic products, especially color cosmetic formulations. Most cosmetic colorants are synthetic and are regulated globally.  In the US, they are regulated by FDA with monographs for each and all located in Title 21 of the Code of Federal regulations, Parts 73 and 74. In the EU, allowed cosmetic colorants are listed in Annex IV, Regulation 1223/2009/EC on Cosmetic Products, as corrected by Corrigendum to Commission Regulation (EU) 2021/850, 17 June 2021. Many colorants on that list are also used in food and have corresponding E (Europe) numbers such as E-171 for TiO₂ and E-172 for iron oxides. In such cases, the specifications for food colorants are used for cosmetic application.  Therefore, it is common to see a note in technical datasheet for a cosmetic colorant stating it complies with the 21CFR and E number (like E-172 for iron oxides) specifications.

Although many of us formulate with colorants frequently, we seem to need help on gaining complete clarity on certain aspects of them. In this blog, we will go over some fundamentals and a few common confusions about certain pigments.  Let’s first start with some terms that we often hear.

Dye:  It is a material that imparts a color and is soluble in the vehicle or substrate in which it is dispersed.

Pigment:  It is a material that is insoluble in the vehicle or substrate in which it is dispersed. True pigments are colorants completely insoluble based on their chemical structure and constituent groups. They typically do not contain the normal substitution groups that promote water solubility, such as sulfonates (-SO₃), carboxylic acid (-COOH) or hydroxyl groups (-OH). Hence, there is no bleeding in hydrous systems. There are only two examples of true pigments used in cosmetics:  D&C Red No. 30 and D&C Red No. 36.

For leave-on cosmetic applications, pigments instead of dyes are often used because dyes are hard to remove after use, thus, stain the skin. Dyes are more commonly used in rinse-off products such as shampoo and mouth rinse. Now let’s go a little further:

Toner:  It is a pigment that is produced by precipitating a water-soluble dye as a metal salt. Typical metals used for this precipitation are sodium, calcium, barium and strontium. e.g., D&C Red 7 Ca Salt. (be aware that it is not a lake)

Lake:  It is a pigment produced by absorbing a water-soluble dye or a primary toner onto an insoluble substrate. All the lakes are pigments.

F, D and C codes in the names of a colorant stands for its approved use in Food, Drug and Cosmetics. A colorant must meet its purities requirements to ensure its safety. FDA separates color additives into two categories:

1. Colorant subject to certification: they are derived primarily from petroleum and are known as coal-tar Most synthetic, organic colorants fall in this category. They must be batch certified by the FDA. They are further divided into two categories:
2. Certifiable Primary Colors: They are pure color which contain no extenders or diluents. They have color names and numbers assigned such as FD&C Yellow 5, D&C Red 6 and Ext. D&C Violet 2.
3. Certifiable Color Lakes: Lakes follow the same restrictions as the primary colors with the additional rule that they must have the name of the precipitating metal and the word “lake”. An example would be FD&C Yellow 5 Al Lake.
4. Colorant exempt from certification: These are natural organic colorants and synthetic inorganics obtained largely from mineral, plant, or animal sources. Although batch certification is not required, purity must be tested by the manufacturer to meet FDA specifications. Examples are Titanium dioxide and Iron oxides.

Now that we have gone over the general terms and regulatory aspects of colorants, let’s look at common ambiguities about a few specific pigments:

1. Rutile and anatase

First, they both are TiO₂, but refer to two crystalline structures. It is like using Coke or Pepsi to represent carbonated soft drinks. Anatase is slightly softer and less abrasive than rutile. This makes little difference to the skin feel but can make a big difference in TiO₂ production process.  Rutile is so abrasive that it can wear out the equipment that processes hundred to thousands of tons per campaign. Consequently, rutile is often surface treated with alumina to extend the useful life of the equipment in addition to provide other benefits.

Rutile has a slightly higher refractive index than anatase, and thus, it can scatter light more effectively. So, does it mean that Rutile is more opaque? Not quite. Opacity is the result of scattering which depends as much on the size and size distribution of the pigment particles as on its refractive index. In reality, it is rare to find a rutile and an anatase that have the same particle size, let alone size distribution. Therefore, being rutile or anatase does not necessarily indicate a higher or lower opacity.

Commercial anatase is usually made to have a small primary particle size, in a range of about 140 – 170 nm. That of rutile is often bigger, roughly 170 – 250 nm.  Due to its smaller size, anatase scatters blue light slightly more, and thus, imparts a blueish undertone.  This is the reason that anatase is often said to be bluer than rutile.

Lastly, the production processes, chloride and sulphate, are often brought into discussion about TiO₂.  In Chloride process, TiCl₄ is vaporized and burnt into rutile.  In sulphate process, Ti(SO₄)₂ is neutralized with base to generate anatase. If aluminum salt is used as the inducer, rutile TiO₂ can also be made via the sulphate process. TiO₂ made from a Chloride process often has a lower level of contaminants, which translates into high purity and clean color. This had been indeed the case in the past, but not so much anymore since the sulphate process technology has been greatly improved over the years.

1. Carbon black

 Carbon black can be made via several processes. In the US, carbon black as a cosmetic color additive is called D&C Black No. 2, a high-purity carbon black prepared by the oil furnace process.¹ It is manufactured by the combustion of aromatic petroleum oil feedstock and consists essentially of pure carbon, formed as aggregated fine particles with a surface area range of 200 to 260 m²/g.

JSCI monograph requires Carbon black to be obtained by incomplete combustion of natural gas or liquid hydrocarbon. Such carbon black is often called channel black and is not approved by the FDA.  This, unfortunately, adds unnecessary complexity to formulating for the global market.

2. Chromium oxide and Chromium hydroxide green

Hexavalent Chromium (Cr⁶⁺) is known to be carcinogenic, thus, it should not be present or at a very low level in cosmetics products. However, its presence is unavoidable due to the chemistry and manufacturing process. For both pigments, the FDA set a limit of 2% NaOH extract, not more than 0.1% as Cr₂O₃ (based on sample weight). ² This limit is equivalent to 684 or 513 ppm maximum Hexavalent Chromium, respectively. The actual level of Cr⁶⁺ in a commercial grade needs to be tested for calculating the final level in a finished formulation.

3. Mica and Pearlescent pigments

A common restriction people often talk about is the size limit of 150 mm. Mica is an approved colorant for drug use, and the FDA has imposed a size limit on it.  Mica can also be used as a colorant for cosmetic applications for which the FDA does not list any size limit in the monograph. Moreover, mica can be used in cosmetics as filler, a category that the FDA does not regulate with specific requirements.

Efforts have been made to list Mica-based pearlescent pigments as approved colorants for cosmetic purposes, but this has not happened yet. as of now, such pigments have been approved as colorants only for drug use, and the corresponding specifications require that the mica meets the colorant specifications for drug use.  This is likely the reason that we hear the 150-mm size limit in our industry.  As mentioned above, mica-based pigments are not approved colorants for cosmetic use. Consequently, the composition has to be expressed as a mixture of individual components such as, for instance, mica and titanium dioxide. Each of these ingredients needs to meet the corresponding FDA specification if applicable.  The size limit on mica for drug use may not be observed.

4. Zinc oxide

Zinc oxide is a long approved cosmetic colorant, though its use as opacificer in cosmetics is limited. That main reason is that its opacity is much lower than TiO₂ due to its lower refractive index (2 vs. 2.7).  Roughly 3 times more ZnO is needed to achieve the same degree of opacity of TiO₂. Moreover, ZnO is slightly soluble in water, resulting in the pH of formulations containing ZnO to be above 7.5.

As of August 7, 2022, the use of TiO₂ as food colorant has been banned in the EU, directly affecting its use in lip and oral products. Respirable TiO₂ is considered carcinogenic, according to Proposition 65 of the state of California, affecting the use of TiO₂ in some powder and spray formulations. TiO₂ is difficult to replace because of its unique performance and inertness. In light of the regulatory restriction, ZnO with the right size and high opacity has gained attention recently, especially for anhydrous formulations.

5. Red 6 lake and red 7 lake in Japan

Most FDA approved colorants can be used in Japan. Red 6 lake, widely used in lip products, is a notable exception. The reason is that Red 6 lake is Red 6 Barium salt laked on barium sulfate, but Red 6 Barium salt is not an approved colorant in Japan. On the other hand, Red 7 lake is Red 6 Calcium salt laked on barium sulfate but Red 6 Calcium salt is approved in Japan.  In the case that the shade cannot be achieved without Red 6, Red 6 sodium salt can be used. However, it must be noted that red 6 sodium salt is water soluble, which is opposite to Red 6 lake.

Currently, the FDA has approved 64 color additives for cosmetic use, each of which has its merits and drawbacks due to their unique chemistry and production process.³ The knowledge is important not only for formulating the right color shade, but also for troubleshooting instability and especially, regulatory compliance. The author hopes that this blog will contribute to your learning of cosmetic colorants.

References:

1. https://www.ecfr.gov/current/title-21/chapter-I/subchapter-A/part-74/subpart-C/section-74.2052
2. https://www.ecfr.gov/current/title-21/chapter-I/subchapter-A/part-73/subpart-C/section-73.2327
3. https://www.fda.gov/industry/color-additive-inventories/summary-color-additives-use-united-states-foods-drugs-cosmetics-and-medical-devices#table3A

Introduction

For years, hair care products have been focused on addressing damage by providing solutions to repair, prevent and maintain hair health. With increased awareness, consumers now recognize that healthy scalp is also a fundamental foundation for healthy hair. Holistic care means to restore the hair at its core while maintaining a healthy scalp. With personalization and self-care at the forefront, consumers are looking for solutions that are inspired from skin care with an emphasis on natural and clean ingredients. In this article, we will discuss factors that affect scalp and hair health and provide an overview of the innovative technologies including specialized product treatments that help restore hair and scalp equilibrium.

Stressors that impact hair and scalp equilibrium

Hair and scalp are affected by several factors such as UV exposure, pollution, humidity, mechanical, chemical, physical stressors, and occlusion such as hats and head protectors (like wigs, protective styles etc.) [1]. Sebum on the scalp diffuses along the hair shaft and can attract product build-up and dust from air which can affect the scalp’s overall health. Additionally, the bacterial and yeast proliferation on the scalp is commonly associated with enhanced desquamation, itching, scratching and redness [1]. Some hair products may leave deposits on the scalp, while others can strip hair’s natural oils to the point that it begins to over-produce sebum [2].

Oxidative stress, i.e., free radicals from sources like UV and pollution, can weaken scalp skin health and cause aging [3]. Sensitive scalp syndrome has been reported to arise from increasing levels of air pollution. Symptoms of sensitive scalp include itching, prickling in the scalp, dandruff, oily scalp, and pain in the hair roots. Pollutants also can migrate into the dermis and through the hair follicle (HF), leading to oxidative stress and hair fall [3]. Hormonal changes, medical conditions, heredity, and aging are cited as common causes of hair fall, but there has been a lot of searches for hair loss associated after COVID-19 (+250%) and how to stop hair fall post COVID increased by a whopping 1,250% [4].

The skin surface and follicular openings are recognized sites of rich microbial colonization and intense immune citation, with crosstalk across the skin barrier [5]. A disrupted microbiome may cause infections and inflammation to the scalp [6]. This disruption may aggravate scalp disorders that can lead to acne, eczema, alopecia, scalp psoriasis, seborrheic dermatitis/dandruff, etc. The aforementioned diseases of the skin and the hair follicles [HFs] are all due to the dysfunction of dysbiosis – the imbalance of the skin microbiome [5]. Scalp conditions also impact the quality of hair causing the resultant cuticular cells to be less flexible than normal, which may impair both anchorage and subsequent fiber surface integrity due to an oxidative stress environment [7]. Hair fibers become more brittle and chip off. This results in a rougher cuticle that is also less functionally effective [7].

Cleansing of hair and scalp is also vital. How often you should cleanse your hair is determined based on your overall scalp health and can be attributed to hair texture. Some cleansers can be harsh and overly stripping, removing all natural oils, which disturbs the bacterial environment and can lead to irritation, redness, and flaking [8], while others may have a high oil load that can have a detrimental effect on oily scalp.

As scalp and hair go hand-in-hand, there is also tremendous focus on the damage hair sustains from the environment, washing, bleaching, coloring, and the use of different styling regiments. Hair damage affects all types of cross-linking bonds, including disulfide bonds, and can negatively affect the overall structure and ordering of hair lipids and CMC lipids [9]. Bleaching and coloring leads to dry, brittle-feeling hair and fiber breakage. Repeated washing results in lifted cuticles, while heat damage from drying, straightening, or curling leads to a loss of moisture, frizzy hair, and split ends [10].

Market drivers and trends

Over the past five years, scalp-focused searches have increased by 270% which is tied to the fact that one in two people suffer from a scalp issue [11]. Reportlinker projects the global hair and scalp care market will reach $121.4 billion by 2027 and will grow at an estimated 6.5% CAGR over the next five years [12]. Based on the latest data, Spate recommends that brands offer hair and scalp solutions that support skin barrier repair, moisturization and conditioning of damaged locks [12]. There has also been a rise in complex hair and scalp routines among millennials [4]. Need for different scalp products has increased globally, which aligns with consumers’ desire for benefits that address their individual scalp and hair needs. Consumers are also demanding transparency from brands and want to learn more about the ingredients used in their products and their mechanism of action. They also place a growing emphasis on the use of natural, organic, and clean alternative ingredients.

Advances in technology targeting hair and scalp concerns.

There have been many advancements in technology that provide holistic solutions to help protect, prevent, and restore hair and scalp equilibrium.

Sebum Control:

An ingredient that leverages a novel encapsulation technology*, ensures targeted delivery and controlled release of actives onto the scalp and hair to deliver instant sebum reduction [12]. This ingredient allows consumers to leave more time between washes, leading to water conservation [12]. A naturally occurring amino acid (INCI: Glycerin (and) Water (and) Sarcosine) effectively aids in the reduction of an oily scalp. It helps to reduce flakes on the scalp and assists in rebalancing the microbiome. Additionally, this ingredient also helps fight against stress, pollution, and product build-up [2]. Another ingredient, based on lamellar body-inspired delivery system (INCI: Aqua, Lecithin, Niacinamide, Lysolecithin, Phenethyl Alcohol, Caprylhydroxamic Acid, Tocopheryl Acetate, Caprylyl Glycol, Phytic Acid), has been designed to target hair follicles where it delivers actives to regulate sebum and the microbiome [6].

Oxidative Stress:

Antioxidants are very well known and can be added to any kind of hair product due to their water-based molecular structure. They help to prevent the formation of oxidative stress and provide a wide range of benefits to both hair and scalp. A blend of three natural and powerful antioxidants, an extract of a medicinal plant forms a non-occlusive shield against urban pollution and protects hair and scalp against environmental stress [13]. A fermented extract of organically grown yerba mate leaves (INCI: water (aqua) (and) glycerin (and) Ilex paraguariensis leaf extract) is designed to help protect hair from oxidative stress-induced damage and help maintain healthy hair roots for optimal growth after only one shampoo treatment [12]. Brands like Keep It Anchored (P&G owned) are developing formulas that are powered by a combination of antioxidant salts that relieve oxidative stress, a zinc compound to improve scalp condition and B vitamins known for skin barrier health [8].

* INCI: Aqua (and) Cetyl Palmitate (and) Cucurbita pepo seed extract (and) Disodium EDTA (and) Ethylhexylglycerin (and) Helianthus annuus seed oil (and) Lauryl Glucoside (and) Melaleuca alternifolia leaf oil (and) Phenoxyethanol (and) Rosmarinus officinalis leaf extract (and) Sorbitan Stearate (and) Tocopheryl Acetate

Dandruff:

With zinc pyrithiones (ZPT’s) ban in Europe in cosmetic applications, formulators are now scouting for new active ingredients. A biomarine ingredient derived via biotechnology (INCI: Water (aqua) (and) Pseudoalteromonas Ferment Extract (and) Sodium Salicylate) has been shown to reduce sebum, itchiness, and flakes on the scalp, while also preventing their recurrence in both rinse-off and leave-on applications [4]. An algae oil (INCI: Triolein), containing more than 90% of the beneficial omega-9 helps hydrate, rejuvenate, and repair the scalp. It also nourishes hair follicles and protects against hair fiber lipid degradation upon UV exposure [4]. In addition, another ingredient positioned as an emollient with antimicrobial properties (INCI: decylene glycol), helps protect the skin from scalp to toe. Among other functions, this ingredient supports dandruff control concepts. It also provides a China-compliant alternative to the antidandruff active zinc pyrithione [12].

Hair Loss:

Broccoli and pumpkin seed seem like unexpected choices for formulators developing anti-hair loss products. Sulforaphane, which is an isothiocyanate isolated from broccoli, increased the expression of an enzyme in the liver that accelerated DHT degradation and consequently inhibited hair loss, as shown in an animal model [14]. Clinical efficacy of pumpkin seed oil (PSO) versus 5% minoxidil foam in subjects with female pattern hair loss (FPHL)after three months of treatment showed the pumpkin oil significantly decreased hair shaft diversity and the number of vellus hairs with results comparable to the minoxidil foam [14]. Another ingredient, a protein and peptide combination (INCI: Keratin (and) Hydrolyzed Keratin (and) Oxidized Keratin (and) Water) stimulates skin cells to proliferate by up to 160% faster than a placebo while simultaneously stimulating human keratinocyte migration and the expression of collagens IV and VII, thus improving the anchoring of follicles. The ingredient’s anti-inflammatory agent reduced the PGE2 response in cells undergoing inflammatory stress by up to 70%, reducing scalp inflammation, itching and premature hair follicle death [15].

Balancing the Biome:

Inhibition of the growth of harmful bacteria can lead to a better balance in oil secretion; this can be achieved using a unique probiotic fermentation technology rich in amino acids, polysaccharides, protein, and other biologically active substances [16]. A natural prebiotic (INCI: Inulin) can also help rebalance the skin’s microbiota and offer skin hydration that outperforms hyaluronic acid. The prebiotic is based on inulin extracted from chicory root and agave and works by selectively supporting protective organisms to help restore the microbiota layer [6]. Since 2020, We have witnessed a burgeoning of scalp products with Cannabidiol (CBD) boasting microbiome benefits [5] and recently we also have seen use of Cannabigerol (CBG) that helps to rebalance the scalp microbiome and promotes hair growth. Lastly, an ingredient (INCI: Lactobacillus Ferment Lysate) that utilizes the properties of prebiotic oligosaccharides as an approach to postbiotic bacteriocin procurement can deliver scalp moisturization and redness reduction [4].

Protecting hair, beyond the scalp,

Hair, after it rises from the scalp surface, also goes through damage from consumers’ grooming practices and external stimuli. Cleansing, conditioning, and strengthening solutions have been extensively discussed in the past. Currently, the use of bond builders is trending and growing in hair care. They are promoted as being able to penetrate into the hair to improve or restore the internal structure, giving rise to an improvement in mechanical properties [9]. According to this definition, bond builders include a broad range of actives, including organic acids, proteins, and lipids [9]. Brands are employing patented peptide technologies and amino acid complexes in multiple product formats that can help prevent and protect hair from the inside-out against all forms of damage.

What’s new and what’s next.

Ingestible hair care products, such as Nutrafol are gaining popularity for promoting hair and scalp health which has helped fuel further ingredient innovation. The introduction of Keranat in food supplements for hair (soft gels, capsules, beauty drinks/shots and cosmetics is said to offer a natural, vegan solution to effectively fight against hair loss while restoring beauty and brightness [12]. The design of neurocosmetic ingredients that modulate neuronal response to improve scalp care and hair quality could be a promising approach for the development of new hair and scalp care routines [17].

Finally, brands like L’Oréal are fostering partnerships with health tech companies to better understand the biological, clinical, and environmental factors that contribute to skin and hair health over time. This comprehensive understanding contributes to the development of a more precise and inclusive skincare approach that cater to the diverse needs of individuals worldwide [18].

Conclusion

The beauty and personal care industry has made great advancements in understanding the role of microbiome that impacts scalp and hair health. New research and findings help steer brands and ingredient suppliers to develop natural, organic, and sustainable solutions that will be a key focus area for future innovation. Furthermore, ingredients inspired by skin care, traditional ingredients, and biotech will continue to drive the growth of the hair and scalp care category.  It is imperative that brands continue their efforts in developing inclusive and personalized solutions to address consumers specific scalp and hair care needs. Finally, educating consumers on choosing the right products and regime that address their specific needs is crucial, in addition to providing guidance on how to use the products effectively to achieve the desired benefit.

References

1. Luigi Rigano, Ph.D., Rigano Laboratories S.r.l., Milan, Italy, “Hair and Scalp Care Go Hand-in-Hand,” Global Cosmetic Industry, 2016
2. BASF Corporation, “Rebalance the scalp microbiome with Scalposine,” Cosmetics & Toiletries (March 2020)
3. D. Roddick-Lanzilotta, Ph.D., R.J. Kelly, Ph.D., and P.R. Sapsford, “Keratin Blend Anchors Follicles and Prevents Pollution-induced Hair Fall,” Cosmetics & Toiletries (September 2019)
4. Ashlee Cannady, Aprinnova Juliana Gomiero, Stephanie Neplaz, Raphaelle Tron, “Hair and Scalp Cleansing and Care Skinification, ZPT Ban, Fermentation and Damage Repair Self-care,” Cosmetics & Toiletries (June 2022)
5. Sharleen Surin-Lord, Dermatologist, “The ‘Skinification’ of Hair Care” Happi (June 2021)
6. Laura Lam-Phaure, “Formulating on Trend: Skinification of Hair,” Cosmetics & Toiletries (June 2022)
7. “Effect of Scalp Health on Hair Growth,” MedEsthetics (December,2021)
8. Christine Esposito, “Natural Ingredients in Shampoos & Conditioners Benefit Scalp & Hair” Happi (December ,2021)
9. Paul Cornwell, Ph.D., TRI Princeton, Princeton, NJ; and Jennifer Marsh, Ph.D., Procter & Gamble, “How Bond Builders ‘Repair’ Hair,” Cosmetics & Toiletries (February 2023)
10. Rachel Grabenhofer, “Patent Pick: Binding Agreement for Hair Repair,” Global Cosmetic Industry (October 2019)
11. Julia Wray, “Why applicators are the secret ingredients for scalp care,” Cosmetic Business (April 2023)
12. Lisa Doyle, “Hair & Scalp Care: Targeted and Premiumized,” Global Cosmetic Industry (September 2022)
13. Rahn Ag, “Radicare®-Eco: The Urban Antidote for Hair and Scalp,” Cosmetics & Toiletries (April 2022)
14. Mohamed l. Elsaie, Lee Reuveni, Stephanie Neplaz, Sebastien Massard, “Restoring and Reviving Hair: Scalp Health, Laser Treatments, Natural/Sustainable and Deep Repair,” Cosmetics & Toiletries (February 2022)
15. Michele Behrens, “FK Scalp from Keraplast Prevents Hair and Scalp Health Pollution,” Cosmetics & Toiletries (February 2020)
16. Peter Smedley, “Bloomage Highlights Hair Shield, Scalp Care and Fermented Anti-aging at SCC76”, Cosmetics & Toiletries (December 2022)
17. Maria Jose Lopez-Gonzalez, Nuria García and Isabel Devesa, AntalGenics S.L., Elche, Spain, “Neuro-cosmetic Targets for Scalp and Hair Care,” Cosmetics & Toiletries (June 2022)
18. Julia Wray, “L’Oréal embarks on world’s ‘largest and most diverse’ skin and hair study”, Cosmetic Business (July 2023)

The Use of Natural Oils to Treat the Skin

Roger L. McMullen

Fairleigh Dickinson University and Ashland Inc.

The term natural oil refers to a fixed (nonvolatile) oil of animal or plant origin. These types of oils—in contrast to essential (volatile) oils, which are obtained by steam distillation methods of plant matter—are typically obtained from plant seeds and nuts by a mechanical pressing technique or solvent extraction. Natural oils have been used to treat the skin for millennia. For example, evidence suggests that the ancient Egyptians used almond (Prunus amygdalus), balanos (Balanos aegyptiaca), castor (Ricinus communis), moringa (Moringa oleifera), olive (Olea europea), and sesame oil (Sesamum indicum) in cosmetic preparations (1). The natural movement in cosmetics of the twenty first century has led to renewed interest in formulating skin care products with botanical ingredients. In this article, I highlight the use of natural oils in skin care and their benefits for skin health.

Benefits of Natural Oil Treatment

Natural oils nourish, smoothen, sooth, and clean the skin. Skin nourishment is provided by biologically active ingredients in natural oils such as antioxidants and essential fatty acids (2). As an example, the antioxidant activity and health benefits of grape seed oil (Vitis vinifera) mostly stems from the presence of tocopherol, linolenic acid, resveratrol, quercetin, procyanidins, carotenoids, and phytosterols in the oil (3). Essential fatty acids, obtained through the diet or applied topically, are important for maintaining skin health (essential fatty acid deficiently leads to dermatitis) and preventing trans-epidermal water loss (4, 5).

Dry skin is typically rough due to ineffective desquamation. Plant oils can smoothen the surface of skin by providing a lubrication effect and by helping the skin maintain a healthy level of hydration through fortification of the skin barrier. Natural oils can also have a soothing effect on the skin. Anti-inflammatory compounds in the oils can help to reduce skin redness and irritation. Studies have shown that olive, sunflower seed (Helianthus annuus), coconut (Cocos nucifera), safflower seed (Carthamus tinctorius), argan (Argania spinosa), soybean (Glycine max), sesame, jojoba (Simmondsia chinensis), and oat (Avena sativa) oil provide an anti-inflammatory effect in skin (6).

Natural oil-based cleaners are used to remove sebum and makeup from the skin. While conventional surfactants can be very efficacious at cleaning the skin, they can also disrupt the barrier function of skin and remove lipid components important for barrier integrity. A good example of a natural oil-based cleaner was provided by researchers at Mae Fah Luang University in Thailand who demonstrated the effectiveness of tea seed oil (Camellia sinensis) at removing foundation and eyeliner (7).

Composition of Natural Oils

The chief components of natural oils are triglycerides. They usually represent greater than 95% of the composition of natural oils. Triglycerides are formed by the esterification of free fatty acids to glycerol resulting in a molecule with a polar headgroup and three hydrophobic tails (see Figure 1). Triglycerides are synthesized by animals and plants as energy reserves and contain various proportions of saturated, polyunsaturated, and monounsaturated fatty acids. In animals, the fatty acid constituents of triglycerides have greater levels of saturated fats (relative to polyunsaturated and monounsaturated fats), whereas in plants there are greater amounts of polyunsaturated and monounsaturated fats. For this reason, most plant oils are in the liquid state at room temperature.

Figure 1: Molecular structure of a triglyceride. In this example, that fatty acid moieties of the triglyceride contain three distinct entities. The three fatty acid chains in triglycerides can be the same or they can be a mixture. Starting from top to bottom, this triglyceride is composed of palmitic acid (16:0), oleic acid (18:1), and alpha-linolenic acid (18:3).

The fatty acid components of triglycerides can vary in chain length—they can be short (≤ 6 carbons), medium (≤ 12 carbons), or long (12 – 22 carbons)—which effects their physicochemical behavior. In some cases, triglycerides may contain omega-3, omega-6, and omega-9 essential fatty acids. The overall composition of the triglycerides (the types of fatty acids, their length, and the degree of saturation/unsaturation) is unique for each natural oil. For example, coconut oil has higher levels of saturated fats than most plant oils, which is why it exists in the solid state at room temperature.

Natural Oils in Wound Healing

Wound healing consists of the regeneration and tissue repair processes after the development of a chronic (pathological condition) or acute (trauma) lesion in the skin. There are three principal stages in wound healing, which include the inflammatory, proliferative, and remodeling stage. Essentially, these stages are characterized by a series of biochemical and cellular events that involve cytokines, growth factors, and other important bioactive molecules that eventually lead to fibroblast proliferation, collagen synthesis, and epithelialization.

In recent years, it has been established that bioactive fatty acids play an important role in the inflammatory stage of wound healing (8, 9). Essential polyunsaturated fatty acids and their metabolic products are believed to play an integral role in modulating wound healing. Omega-3 (e.g., alpha-linolenic acid) and omega-6 (e.g., linoleic acid) fatty acids metabolize to a number of different molecules including leukotrienes, lipoxins, prostaglandins, and thromboxanes—twenty-carbon chain length bioactive compounds known as eicosanoids (10). In addition to alpha-linolenic acid and linoleic acid, omega-9 fatty acids (oleic acid and erucic acid) were also reported to provide positive anti-inflammatory effects during wound healing (11). In summary, anti-inflammatory and wound healing properties have been demonstrated for various botanical oils including olive oil, grape seed oil, coconut oil, argan oil, jojoba oil, and numerous other oils (6, 12-15).

Natural Oils and Diseases of the Skin

A brief survey of the scientific literature reveals a number of studies investigating the effects of oils on various diseases encountered in dermatology (16). In addition to fatty acids and other lipids in the oils, there are numerous biologically important molecules such as monoterpenes, sesquiterpenes, diterpines (e.g., cannabinoids, tocopherols), triterpenoids (e.g., squalene, sterols), carotenoids, and polyphenols (17). These phytochemicals have been shown to efficaciously alleviate the symptoms of inflammatory skin diseases, such as contact dermatitis, atopic dermatitis, and psoriasis. In addition, dietary supplementation with essential fatty acids has shown beneficial effects in the treatment of acne, atopic dermatitis, pruritis, psoriasis, and skin ulcers (18-20).  Furthermore, supplementation with an omega-3 fatty acid was shown to reduce the risk of skin cancer in organ transplant recipients (patients who undergo transplant procedures have a very high risk of developing skin cancer) (21). There has also been considerable interest in utilizing natural oils produced by the plant Cannabis sativa for the treatment of skin inflammatory diseases. Hemp seed and cannabidiol (CBD) oil have been found to be the most efficacious oils from Cannabis sativa for treating skin inflammatory conditions (22).

Therapeutic Benefits of Natural Oils

One of the principal benefits of treating skin with natural oils is to alleviate dry skin by enhancing its barrier function. Due to compositional differences, each natural oil interacts uniquely with the skin. Some of the most commonly used oils for skin therapy are almond, argan, coconut, evening primrose (Oenothera biennis), jojoba, oat, and olive oil (23, 24). It is noteworthy that while olive oil has a number of reported benefits for skin—mostly for treatment of skin aging, pruritis, and xerosis—there are concerns that it negatively affects skin barrier function (25). Regardless, natural oils help form a physical barrier on the skin surface and function as a source of lipids to fortify the skin’s barrier. Future research could help identify specific oils that should be used for a particular skin treatment modality (26).

Aroma massage therapy consists of the use of essential oils in conjunction with massage techniques. Natural oils are used as carrier oils for the essential oils. In addition to diluting the essential oil, the carrier oil lubricates the skin surface facilitating the massage procedure. Some common carrier oils are almond, coconut, grapeseed, jojoba, and sunflower oil. In general, carrier oils should have a pleasant scent and be aesthetically pleasing when applied to the skin. When choosing a carrier oil, it is best to find an oil that is absorbed well by the skin that does not result in an oleaginous (greasy) sensation.

Neonatal Skin Care

Newborn infants are especially prone to developing dry skin conditions as their skin adapts to life outside of the uterus. From a physiological perspective, infant skin is quite different from adult skin. In infant skin the stratum corneum and epidermis are thinner and there is significant risk of trans-epidermal water loss due to less barrier lipids and natural moisturizing factor. In addition, there is an accelerated breakdown of corneodesmosomes due to the higher surface pH (which affects desquamation) (27). Several studies highlight the possible benefits of treating neonatal skin with botanical oils, such as sunflower, coconut, almond, olive, palm (Elaeis guineensis), and mustard oil (Brassica juncea); however, there seems to be a consensus that further study is warranted to determine efficacy and any proposed mechanisms (28-30). For example, researchers at the University of Sheffield in the UK found that treatment of neonatal skin with olive oil compromised skin barrier integrity and induced mild erythema in patients (31). Furthermore, researchers at Columbia University in New York City reported that olive oil can exacerbate atopic dermatitis and xerosis in pediatric subjects (32).

The Paradoxical Behavior of Natural Oils in Relation to Epidermal Barrier Function

The stratum corneum of skin contains corneocyte cells embedded in a matrix of endogenous lipids consisting of long-chain ceramides, cholesterol, and free fatty acids, organized into multilamellar structures. Sebum is found on the surface of the skin and contains a mixture of triglycerides, wax esters, free fatty acids, squalene, and cholesterol esters. One would expect that treatment of skin with natural oils could help maintain the moisture levels of skin by enhancing its epidermal barrier function via the formation of an occlusive lipid layer on the surface thereby preventing trans-epidermal water loss. However, in recent years it has been discovered that some natural oils may disrupt the skin’s structural lipids thereby compromising stratum corneum barrier function.

Treatment with some oils can fluidize stratum corneum lipids and compromise epidermal barrier function. In fact, natural oils have been used as penetration enhancers in the transdermal delivery of active pharmaceutical ingredients (33, 34). More than likely, the triglycerides in oils that are applied to the skin will be hydrolyzed by resident lipases resulting in the formation of free fatty acids, which can disrupt the ordered structure of lipid lamellae in the stratum corneum (35). In general, the paradoxical effect produced by some oils is thought to be more prevalent in patients suffering from atopic dermatitis and other skin conditions.

Concluding Remarks

Natural lipids are employed in several applications in skin care. In this article, we introduce some of the traditional treatment modalities and highlight some of the most recent studies published in the scientific literature which find health benefits to the skin. The available data suggest an important role for natural oils in treating skin inflammatory disorders, wound healing, skin therapy, and neonatal skin care. Despite the widespread use of natural oils in cosmetic formulations, there is considerable need to conduct further research in this area to better elucidate the mechanisms responsible for the efficacious nature of the oils. Looking ahead to the future, such action will require us to proactively investigate the bioactivity of the components of a broad range of natural oils in a systematic manner. In addition, a better understanding of the detrimental effects of certain oils to epidermal barrier function in specific types of skin needs to be elucidated in future studies.

Acknowledgements

The author expresses his sincere gratitude to Drs. Gopinathan Menon and David J. Moore for revising the text and offering useful suggestions.

References

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The topic of “biodegradability” has become extremely important over recent years, but still may not be fully understood. The following is a basic overview for formulators and anyone wishing to know more about this critical issue. (Note that regulations, definitions, and practical guidelines on biodegradability are continually changing, and the comments in this blog are intended to offer general insights, not legal definitions or advice.)

Simply put, biodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi[1], and once broken down, the byproducts are carbon dioxide and water vapor. “Bio” is the key prefix here; the difference between “degradable” and “biodegradable” is that while “degradable” products can be broken down by chemical or biological processes, “biodegradable” materials can only be broken down by biological processes.

The concern for biodegradable products began with the issue of microplastics, first detected in the 1970s in the ocean as plastic residue, but not termed “microplastics” until the mid-2000s. (A good and comprehensive article on this by Napper and Thompson was published online in 2020[2].) Many multinational companies have stopped using microplastics (microbeads) in their formulations and other brands are following, but let’s clearly define what are, and are NOT, microplastics! To qualify as a microplastic, four criteria must be met:

1. It must be a polymer
2. It must be solid (at RT)
3. It must be in particulate form
4. It must be under 5mm in size

All four criteria must be met – if even a single one of these four is not present, the substance is NOT considered a microplastic. And to complicate matters further, there are many exclusions even if these four criteria are met, including the following:

1. The material is natural
2. The material is degradable
3. Its solubility is > 2 g/liter
4. No carbon atoms in its chemical structure
5. Its release to the environment is prevented when used
6. Its physical properties are permanently modified during end use
7. It is permanently incorporated into a solid matrix during end use
8. And likely more…

Just because your products may be “natural” does not mean they are “biodegradable” – measurement is key! As mentioned by Dr. Martin Perry, Advanced Development Safety Laboratories, at SCS Formulate in 2021: “Although natural content is good to know, and there is a perception that natural ingredients are more biodegradable than synthetic ones, knowing the biodegradability is important. The natural content of your product or your organic content is not going to be sufficient for you to substantiate anything on biodegradability.”[3]

To be precise, most companies adhere to the standard of “readily biodegradable”, defined as the ability of a product to biodegrade quickly and completely (≥ 60% by OECD 301A-F/ASTM D7373 testing) within 28 days. You might also hear the term “inherently biodegradable,” defined as between 20% and 60% biodegradability as measured by OECD 301A-F testing, but “readily biodegradable” is stricter and preferable.

From the OECD iLibrary: “The OECD Guidelines for the Testing of Chemicals is a collection of about 150 of the most relevant internationally agreed testing methods used by government, industry and independent laboratories to identify and characterize potential hazards of chemicals. They are a set of tools for professionals, used primarily in regulatory safety testing and subsequent chemical and chemical product notification, chemical registration and in chemical evaluation. They can also be used for the selection and ranking of candidate chemicals during the development of new chemicals and products and in toxicology research. This group of tests covers environmental fate and behaviour. In 2017, the section 3 “Degradation and Accumulation” was renamed to “Environmental fate and behaviour” to take into account Test Guidelines measuring endpoints such as dispersion, aggregation.”[4]

As a final note, microplastics and biodegradability concerns are part of a larger issue of minimizing environmental pollution. Some may equate this trend with the apparent discovery of reef damage caused by certain organic sun filters, specifically octinoxate and oxybenzone. There are bans in place on octinoxate and oxybenzone in many countries, including the US (Hawaii, Florida, US Virgin Islands), Aruba, Bonaire (off the coast of Venezuela), Palau and parts of Mexico. However, this is not a biodegradability issue as much as it is a toxicity issue, and the science is still unclear as to the actual effect of residual organic sunscreens on coral reefs.

[1] Focht DD. “Biodegradation”. AccessScience. doi:10.1036/1097-8542.422025.

[2] Napper & Thompson, “Plastic Debris in the Marine Environment: History and Future Challenges”. Global Challenges. doi: 10.1002/gch2.201900081.

[3] https://www.cosmeticsdesign.com/Article/2021/11/18/Biodegradable-beauty-focus-needed-in-natural-and-organics-before-regulatory-change-says-expert#

[4] https://www.oecd-ilibrary.org/environment/test-no-301-ready-biodegradability_9789264070349-en

Ben Blinder is the Executive Director, Business Operations at Gattefossé USA, with P/L responsibility for the personal care and pharmaceutical business units in the US and Mexico. He is also a founding member of the Advisory Committee on Diversity & Inclusion for Gattefossé in North America. Ben holds a BS in chemical engineering from Lehigh University.