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*Corresponding Author: Pierfrancesco Morganti, Academy of History of Healthcare Art, 00186 Rome, Italy and China Medical University, 110001 Shenyang, China.
Citation: P Morganti, G Morganti, V E Yudin and H-D Chen. (2021) CHITIN AND LIGNIN: OLD POLYMERS AND NEW BIO-TISSUE- CARRIERS. Dermatology and Dermatitis. 6(3); Doi:10.31579/2578-8949/083
Copyright: ©2021 Pierfrancesco Morganti, This is an open-acscess 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.
Received: 16 August 2021 | Accepted: 28 August 2021 | Published: 06 October 2021
Keywords: chitin nanofibrils; lignin, polyhydroxyalkanoate; polylactic acid nanoparticles; beauty market; surgical maskl; waste; pollution; environment; covid-19
Worldwide consumers are nowadays much more focusing on their wealth and appearance, having increased their worry caused from the pollution, plastic wastes and the earth' disasters further increased for the COVID-19 pandemic. This trend has created an heightened demand for products which, formulated with natural and functional ingredients and carried by sustainable delivery systems, should be produced and packed with biodegradable compounds. The paper suggests to formulate innovative cosmetic and medical products based on the use of carriers made by biodegradable polysaccharide-tissues embedded by micro-nano particles of chitin nano fibril-nano lignin complexes, encapsulating different active ingredients. Thus, data on chitin, lignin and their complexes are reported and discussed, focusing the attention on their possible use to make innovative products, characterized for their effectiveness, safeness, and biodegradability.
The worldwide provisional increase of population to 9.15 billion with a contemporary increase of aging people projected to range 1.5 billion by 2050 [1], has created a major and different need for food, cosmetics, drugs and medical devices with a consequent production of a great quantity of plastic waste. Thus, the worldwide Beauty & Personal care market value was of USD 483 billion in 2020 with a prediction to exceed USD 784.6 billion by 2027 with an annual grow rate(CAGR) of 4.75% in the 2020-2027 forecast period (Figure 1) [2, 3],while the health and wellness food market is projected to grow to USD 235.94 million.
This growth, further increased from the COVID-19 pandemic, is due to the women and men 'research of an healthy and juvenile aspect, also because "looking old" or "ugly" is considered to have negative effects on self-esteem and social Interactions [4]. Unfortunately, the major consumption of these products has been also increased by the production of plastic waste which, invading lands and oceans, are provoking negative impacts on the Earth' ecosystems, causing environmental climatic disastersand serious human health problems [5, 6]. Just to remember the global cosmetic industry produces every year around 120 billion units of packaging much of which is not recycled [7]. Thus the necessity to change our way of living going versus a zero waste society. We have to leave the linear economy by which raw materials are collected and transformed into products to be used and discarded, for adopting the circular economy based on the 3R approach of reducing, reusing and recycling at zero waste [8] (figure 2).
Therefore, the urgent need to rethink the plastic production and consumption' systems reducing, substituting, recycling and disposing, the relative goods [8]. In the meantime, it should be necessary to take the opportunity for using all the actual waste bio-based materials to realize valuable and biodegradable bio-products, always remembering that bio- based materials are not necessarily compostable or biodegradable [9].
It is in fact, to underline that food waste, which accounts for nearly 60% of all the bio-waste produced, is rich of active ingredients as vitamins and minerals as well as of precious polymers, including biodegradable polysaccharides. It represents a precious raw material to make, for example, not only smart non-woven tissues and films for skin/body repairing [10, 11] and food and cosmetic packagings [12], but also smart carriers and innovative products [13, 14].
Among the polymers obtainable from waste, it is increasing a global interest for Chitin and Lignin with all their derived compounds [15, 16].
Thus, some activities of Chitin nanofibrils (CN) and Nano-Lignin(LG) will be reported, focusing the attention on the possibility to make different polymeric micro-nanoparticles (PL)which, embedded into biodegradable non-woven tissues and films, could be used as innovative carriersof Medical and Cosmetic use.
Chitin
Alpha-Chitin is a linear nitrogen-bearing biological polymer consisting of sugar molecules bonded together to form long polysaccharide chains. It consists of an sugar-like polymer of beta- [1, 4]-linked linear chains composed of more than 5,000 N-acetyl glucosamine units, representing the second most abundant natural polymer in Earth after cellulose[17]. In effect, chitin may be described as cellulose with one hydroxyl group on each monomer, replaced by an acetyl-amine group (fig.3).The polymer, as an unbranched chain of glucose, is recovered in many mineralized biological tissues combined with proteinaceus materials and organized in sheets of antiparallel polymeric chains (fig 4).These chains, held together by a large number of hydrogen bonds give to chitin an increased tensile strength. Its complex structure, in fact, provides the structural backbone of insect cuticles, crustacean exoskeletons, cephalopod shells, overing surfaces of many other living organisms and acting also as support of fungal, yeast and algae' cell walls
Therefore, the around 20 chains of Chitin, aggregated in the form of microfibrils, cross-linked with other components of the cell wall, are made by a complex hierarchical structure arranged in such a way to represent a structural biomaterial of high industrial interest for its particular mechanical properties. It, in fact, results useful to develop innovative natural composites when combined, for example, with its de-acetylated form chitosan or with other polymers, including polylactic acid (PLA) and polyhydroxyalkanoates (PHA) [18, 19]. However both Chitin and Chitosan have a great economic value because of their versatile biological and chemical activities, being alsobio- and eco-compatible, biodegradable, nontoxic nor allergizing agents [20, 21].Additionally the properties of these polymers, which depend from their selected origin and manufacturing process, are notably increased when they are used at micro-nano size dimension and pure stcrystallin form with a controlled grade of de-acetylation. At this purpose, our research group have produced pure Chitin nanofibrils (CN) and Chitosan obtained by a sustainable patented process at practically zero waste.
At this purpose, both CN and Chitosan were made from crustacean chitin of food grade, treating the polymeric powder by acid or alcaline solutions respectively, under continuous stirring at controlled temperature. The residue waste of nano-chitin and nano-chitosan at the last productive step, was practically zero. The remaining final exhausted powder, in fact, was used as plant fertilizer while the alkaline and acid solutions, mixed each to other, were used to produce a low quantity of sodium chloride. However, the 2% water suspension, obtained from the process with a pH interval between 2 and 4,contained around 300 trillions of chitin micro-nano crystals per milliliter with a mean dimension of 240x7x5 nano meters (fig 5),covered by positive charges [22,23].The presence of the positive charges on the chitin surface, has given the possibility to produce block co-polymeric micro/nano particles (PL) by its self-assembling (ionic gelation method) with electro negative polymers, including hyaluronic acid and Lignin (fig 6) [24].
Lignin
Weight of dry biomass on Earth is estimated to be 550 billion tons, 450 billionof which are represented by plants (Fig 7) [25].
It is however to remember that 75% of the plant biomass is composed of polysaccharides, 20% of which is represented by the biopolymer lignin.
Lignin, the structure of which is still unknown, is made up to 10-25% of a ligno-cellulosic biomass intimately bound like adhesive with cellulose and hemicellulose. It is represented by a complex phenolic three-dimensional and highly cross-linked polymeric molecules, composed of three substitute phenolic compounds such as,coumaryl, coniferyl and sinapsyl alcohols(fig 8) [26].
The polymer, as in cellulose or protein, lacks a regular and repetitive order of monomeric units, the composition of which varies according to the plant species. Thus lignin from herbaceous plants containsp-hydroxy phenyl, guaiacyl and syringyl units, whereas lignin from woody plants contains prevalently guaiacyl and syringyl ones [27].Unfortunately, this polymer available in large quantity as by-product from the industrial
processing of wood, energy crops, or agriculture residues, is until now commonly burned to obtain energy, while 2% only is used to produce low added value products, also if it represents an excellent source to produce valuable molecules and sustainable goods [28].However, lignin is considered an interesting antioxidant polymer to be used, for example, Slow down the ageing of both composites and biological systems [29]. Moreover, it has shown to possess an interesting UVA-UVB- absorbent ability attributable to the existence of abundance of chromophoric groups into its polymeric molecule [30]. Therefore, this specific activity may be of interest to develop transparent UV-absorbent film as well as UV-protective innovative non-woven cosmeceuticals-tissues and dressings [32, 41] Just as for chitin, effectiveness and safeness of lignin depends from its source, physicochemical characteristics, purity and size, so that, extracted from wheat straw, it has shown, for example, to have the greatest thermal stability and highest char-yield. For the reported reasons and its antibacterial activity, being an electro negative polymer, lignin has been selected from our research group in its nano-size to make micro-nano block polymeric particles with the electropositive CN [33, 34].At the nano-scale, in fact, size is one of the more important criteria that governs both physicochemical and biological behaviour of the final product. It has been shown, for example, that the ability of chitin to modulate the immune response depends on its size:its medium size (40-70 milli microns) activates TNF and IL-17 production having a pro-inflammatory activity, whereas the small-size(<40>)
Chitin-Lignin particles and biodegradable tissue-carriers
As shown by our previous studies[37, 38] this medical and cosmetic vehicle could represent an important part of any formulation, being fundamental for its effectiveness and safeness.
At this purpose for example, it is important for a formulation to predict how the vehicle' composition will affect the adsorption of the active ingredients into the skin controlling in advance the reactivity the product may have when applied on the different skin areas, or which might be the probable partition coefficient of the active ingredient, established between epidermis and the vehicle [39].Thus, the need to respect all the characteristics that a vehicle should have as reported on figure 9,considering also the active ingredients selected for the designed formulation.
As the right vehicle should be however, the primary purpose of the vehicle is to enable the cosmetic active ingredients to be conveniently released at level of the different skin layers, at the dose and time designed. It is to underline, in fact, that many parameters influence the final product composition, including physico chemical characteristics of both the active ingredients and the carrier selected as well as the formulation type and the final structure of the product with the manufacturing conditions used [39].
At this purpose we have proposed to utilize smart non-woven tissues and films as innovative carriers for medical and cosmetic use [40, 11]. These innovative carriers are made by natural polysaccharide-composites embedding micro-nano particles(NPs) of CN-LG [41] which in turn may encapsulate different active ingredients, necessary to characterize the tissues' activity. Thus, for example, nano-structured silver nano particles and glycyrrhetic acid have been realized to make advanced medications [16, 42] while micro-nano particles of nicotinamide, vitamins C and E have been used for making anti-aging cosmetic beauty masks (figure 10) [51, 42]. By the same technology, making pluri-strata tissues it should be possible to make biodegradable surgical masks [44-47], as well as it was possible to formulate gel and spray medications having an interesting skin repairing activity (figure 11) [16,48,49]. Regarding the surgical masks, the production and consumption of which have been increased for the COVID-19 pandemic, it is to remember not only the great waste caused from their use together with the other the non-biodegradable single-use plastic means [50], but also the irritative allergic contact dermatitis provoked on the face of medical doctors and patients [51].
As reported consumers, worried for the great waste and pollution invading our planet, are buying more cosmetics and food thinking this consumption useful for maintaining a nice look and an health y body [52]. Consequently, they are considering to purchase products skin- and environmeally-friendly, characterized for their effectiveness, safeness and for the ingredients used rather than for the price [53]. Moreover, consumers are oriented not only for products based on natural ingredients and made by sustainable technologies, but also packed by biodegradable containers, knowing that packagings constitute roughly 46% of the global plastic waste invading the oceans (54). Thus our propose to use these bio-based carriers in substitution of the usual emulsions go in this direction. In fact, both the non-woven tissues and films embedded by the reported micro- nanoparticles not only are made by natural and biodegradable polymers and ingredients, including chitin and lignin, but may be packed by biodegradable paper or aluminium foils.
Moreover, differently from the emulsions these innovative cosmeceutical- tissues are free of preservatives, emulsifiers, fragrances, colors and other chemicals often cause of allergic and sensitizing phenomena [10-16, 31-3337, 38, 40]. Least but not last, these innovative class of products are easily bio-degraded because the polymeric vehicles used to make the tissues as well as nano-chitin and nano-lignin utilized for the micro-Nano particles may be easily metabolized from the human enzymes, releasing molecule used as food and energy from the skin cells.
Idea of manuscript PM; writing original draft preparation PM, GM; writing-review and editing PM, GM, WEY, HDC; supervision PM, GM; All the authors have read and agreed to the publishing version of the manuscript.
None
The authors declared no conflict of interest
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