TY - JOUR
AU - Török, Béla
AB - Abstract Due to declining hydrocarbon resources and strengthening environmental regulations, significant attention is directed toward sustainable and nontoxic supplies for the development of green technologies in a variety of industries. This account provides an overview on the sources and recent applications of such materials surveying the most common nontoxic and renewable resources that can be obtained from biological sources. Developing a broad array of technologies based on these materials would establish a truly sustainable green chemical industry. The study thematically discusses various compound groups, eg, carbohydrates, proteins, and triglycerides (oils). Since often the monomers or building blocks of these biopolymers are of significant importance and produced in large amounts, the applications of these compounds are also reviewed. sustainable raw materials, carbohydrates, glucose, starch, cellulose, oils, glycerol, amino acids, proteins Altough the application of petroleum resources dates back millennia; the large-scale use of crude mineral oil began in the mid19th century (Olah and Molnár, 2003). Petroleum-based precursors made the synthesis of fine chemicals easier and at the same time resulted in the unintentional release of toxic waste. Although the roots of Green Chemistry had been established after World War II, the movement celebrated its unofficial opening with a seminal book Green Chemistry: Theory and Practice, in which the basic foundations of green chemistry were outlined (Anastas and Warner, 1998). The mounting problems with hydrocarbon resources do not stop with their being a finite resource, they are stable materials that do not easily degrade in biological systems and are often highly toxic. Thus, the search for renewable, nontoxic and biodegradable industrial raw materials is a top priority. Many new technologies are surfacing and extensive efforts are made to find ways to use agricultural waste (Gallezot, 2012) and other natural resources, mostly biopolymers (Brigham, 2017) to supply renewable, nontoxic resources for industry. Herein, we review sources and applications of these materials and provide a critical survey of contemporary issues. CARBOHYDRATE-BASED MATERIALS Carbohydrate-based materials are one of the most common and widely available resources that conform to requirements of sustainability; they are renewable, nontoxic and biodegradable. Glucose is a nontoxic biodegradable monosaccharide, the most commonly applied natural resource for synthetic applications. Although it is traditionally generated from sucrose, it can also be obtained from starch, lignocellulose or sugarcane bagasse (Jiang et al., 2013). Although a simple hydrolysis of sucrose provides glucose, the process to obtain glucose from lignocellulose and starch requires additional steps (Presecki et al., 2013). The summary of sustainable sources of glucose is depicted in Figure 1. Figure 1. View largeDownload slide Schematic illustration of representative sustainable sources of glucose. Figure 1. View largeDownload slide Schematic illustration of representative sustainable sources of glucose. The major synthetic application of glucose is its use as reducing agent. It is also frequently applied as a starting material for the preparation of ethanol or hydrogen (Figure 2). Figure 2. View largeDownload slide Representative synthetic applications of glucose. Figure 2. View largeDownload slide Representative synthetic applications of glucose. Glucose is commonly used for the synthesis of several products, including nanocomposite materials, via reduction. Copper nanocrystals, crucial in microelectronics and catalysis, were synthesized in aqueous solution using glucose to reduce CuII to Cu0 (Jin et al., 2011). When used with hexadecylamine capping agent, Cu nanocrystals were obtained with controlled shape, high purity and uniformity. The synthesis of TiO2/reduced graphene oxide sheets was successfully performed with a 1-step hydrothermal method using glucose as the reducing agent (Shen et al., 2011a). The reaction utilized only glucose and water; the conditions are nontoxic, environmental friendly and scalable. A similar method was developed for the synthesis of magnetic, reduced graphene oxide sheets (Shen et al., 2011b). Glucose was an ideal substitute for the toxic and unstable hydrazines, typically used for graphene oxide reduction. This eco-friendly, productive, and simple process is an efficient way to synthesize magnetic nanocomposites that have wide range of applications in biomedical engineering and drug delivery. A glucose-modified siloxane surfactant was utilized for the synthesis of silver nanoparticles. Using glucose as the reducing agent the reaction was performed at ambient temperature in aqueous solution (Racles et al., 2010). Another work used glucose as reducing agent for the preparation of silver-chitosan nanocomposites (Susilowati et al., 2015). The synthesis was carried out at room temperature by reducing AgNO3 with glucose using chitosan as stabilizing agent and polymer matrix. The beneficial effect of glucose was demonstrated in the synthesis of gold nanoshells (Tharion et al., 2014), which are ideal candidates for biomedical imaging and therapeutics due to their tunable plasmonic optical resonance. Employing glucose as a reducing agent provided a controlled shell structure and high colloidal stability compared with typical methods that use the toxic formaldehyde. Nickel nanoparticles are widely used for their optical, magnetic, electronic, and catalytic properties. However, the toxicity of nanoscale Ni in humans and microorganisms is a major problem. A 1-step method was developed for the synthesis of biocompatible glucose-capped nickel nanoparticles using glucose as both reducing and capping agent (Vaseem et al., 2013). Not only does the use of this environmentally benign capping agent improve the hydrophilicity, and dispersion of the nanoparticles, it also conveys biocompatibility making these nanoparticles suitable for biological applications. Glucose can also be subjected to fermentation to afford ethanol or hydrogen. The fungi Fusarium verticillioides and Acremonium zeae were found to utilize glucose as a carbon source to produce ethanol (de Almeida et al., 2013). It was also demonstrated that the fungi allowed the production of ethanol directly from sugarcane bagasse with reasonable yields. The production of hydrogen via the fermentation of glucose was carried out by a culture of mixed anaerobic microflora in a stirred tank reactor (Mizuno et al., 2000). After 3 days of incubation under nitrogen atmosphere, the culture produced 1.43 mol of hydrogen per mol of glucose. Gasification of glucose in supercritical water is another method to produce hydrogen gas (Hao et al., 2003). Under optimized conditions glucose could be completely gasified and converted to a mixture of hydrogen and carbon dioxide. A biopolymer of glucose, starch is a biodegradable nontoxic raw material that can be isolated from plants by extraction and transformed to different products by chemical processes (Madson, 2012). Starch is currently obtained from potato (Leonel et al., 2016), yam (Zhang et al., 2014), quinoa (Li et al., 2016), corn (Cao et al., 1996), etc. The development of bio-based composite polymers using starch has attracted extensive attention due to its nontoxic, biodegradable and renewable nature. Although native starch is not thermoplastic, (Zia et al., 2015) in the presence of a plasticizer and heat, it undergoes destructurization and becomes thermoplastic starch (TPS). TPS has some limitations due to its thermal and water sensitivity; however, its properties can be improved by chemical and mechanical modifications. Blending it with synthetic hydrophobic polymers such as polyurethane improves water resistance and mechanical properties while maintaining biodegradability (Zia et al., 2015). A thermoplastic material based on starch and poly(caprolactone) was developed without plasticizer (Sun et al., 2016). The esterification of native starch with stearyl chloride improved the compatibility with the synthetic polymer matrix resulting in a composite with high water resistance. The reinforcement of starch-based biopolymers with other natural polymers is another alternative. The addition of agar (30%) to sugar palm starch-based thermoplastic via melt mixing and hot pressing, improved its thermal and tensile properties (Jumaidin et al., 2016). This eco-friendly nontoxic plastic found applications in packaging. Poly(lactic acid), when incorporated into a starch-based bilayer film, demonstrated improved physical, mechanical and thermal properties (Sanyang et al., 2016). The hydrophobicity of the poly(lactic acid) layer, reduced the water permeability and uptake, making the bilayer film suitable for food packaging. Microcrystalline cellulose, which is prepared by acidic hydrolysis of cellulose, has been used for filler and reinforcement of biopolymers as well. Starch-based biocomposites reinforced with microcrystalline cellulose and plasticized with glycerol or sorbitol can be prepared by melt processing (Rico et al., 2016) resulting in improved stiffness and resistance to water absorption and the material was suitable for short-life applications in food packaging. Chitosan is another biodegradable and natural material used to blend TPS. It derives from chitin, a nontoxic natural carbohydrate polymer and a constituent of the crustacean skeleton. The chitosan-starch composite offers application opportunities in agriculture, such as control-released fertilizers (Perez and Francois, 2016). The biodegradable composite modulates the frequency and the amount of fertilizer released to the soil, easing the exposure caused by intensive fertilization. Other composite materials, prepared from starch gel and tubular cellulose, were found to be useful in applications involving enzyme-catalyzed reactions. A starch gel, an aqueous solution of granular starch, was deposed into tubular cellulose to afford a porous material with nano size pores (Barouni et al., 2015). The high porosity allowed the entrapment and immobilization of enzymes. The enzyme rennin was successfully entrapped creating an active biocatalyst for milk coagulation with improved performance and stability compared with the free enzyme. In the preparation of aggregation-induced emission (AIE) luminescent starch-based bioprobes (Liu et al., 2016) AIE dyes were combined with carboxymethyl starch in a 1-pot synthesis. Amino phenylboronic acid served as a linkage between the dye and the starch to yield a water dispersible, noncytotoxic and highly fluorescent amphiphilic copolymer. This polymer is a good alternative to inorganic luminescent materials that are toxic and not suitable for biological imaging. Starch also serves as a starting material to produce glucose (vide supra). It is worth noting, however, that most sources of glucose and practically all sources of starch are staple foods throughout the world making their use to produce fuel or even chemical raw materials socially questionable. This controversy could be solved by using another polymeric carbohydrate, cellulose. It is a renewable, biodegradable and nontoxic material, the most abundant natural polymer on Earth. The major sources of cellulose are wood, seed fibers (cotton) and grasses (bagasse) (Nechyporchuk et al., 2016). Although some cellulose sources are used as animal feed, most are considered agricultural and industrial waste. The production of cellulose from plant extraction has been subject to extensive developments and is still under refinement (Ng et al., 2015; Thomas et al., 2013; Wang et al., 2012). The different approaches for the extraction of cellulose nanofibrils result in particles with varied crystallinity, surface chemistry and mechanical properties. However, it must be noted that while the plant cellulose is available in enormous quantities as agricultural waste, its isolation requires energy and the use of slightly toxic chemicals. The other pathway to produce cellulose is via biosynthesis. Bacterial cellulose is prepared in aqueous culture medium by microorganisms that utilize nitrogen, hydrogen, carbon, and oxygen sources (Machadoa et al., 2016). The structure of bacterial cellulose is the same as that of plant cellulose. The fact that it is completely free of lignin and hemicellulose is a great advantage in practical applications. The fermentation of cellulose by anaerobic bacteria produces ethanol, hydrogen, and organic acids. First, the cellulose is mainly broken down to cellobiose that can be further utilized by the organism to afford ethanol, acetic acid, lactic acid, hydrogen, and carbon dioxide (Ye et al., 2009). Thermophilic bacteria were found to have a great potential to utilize cellulose and produce hydrogen. The coculture of Clostridium thermocellum and Thermoanaerobacterium thermosacharrolyticum metabolized cellulose with a 2-fold increase in hydrogen production compared with the degradation of cellulose by C. thermocellum alone (Liu et al., 2008). Another coculture of a cellulolytic strain and a saccharolytic strain of Clostridium bacteria was effective on urban, agricultural and industrial cellulosic wastes to generate ethanol (Demain et al., 2005). Not only is the amount of ethanol higher than that produced from corn, the cellulose-to-ethanol route involves almost no contribution to the greenhouse effect and has a positive net energy balance. In addition, the process applies waste cellulose versus a food source such as starch. The chemical conversion of cellulose using metal catalysis allows the production of different compounds such as hexitols or ethylene glycol. The conversion of cellulose to polyols required the use of a metal catalyst supported on inorganic oxides to yield glucose and the subsequent hydrogenation of the sugar affords various polyols, eg, hexitols (sorbitol and mannitol) (Fukuoka and Dhepe, 2006). The water insoluble catalyst was easily separated from the hydrophilic products and recycled. Ru/ONbPO4 was also found to be a suitable catalyst for the transformation of cellulose to ethylene glycol and its monoether derivative (Xi et al., 2014). Converting cellulose to hydrocarbons by progressive removal of oxygen and convenient separation of the products was also described using Ru/C catalyst (Serrano-Ruiz et al., 2010). Cellulose has also been applied as a catalyst support, for immobilizing Mn(salen) (Mohammadinezhad et al., 2014) or Co(II)(phthalocyanine) (Shaabani et al., 2014) complexes for oxidative transformations. Cellulose nanocrystals (CNs) open new application opportunities of cellulose in many fields. CNs have attracted interest in the nanocomposites field due to their appealing and unique properties (high surface area, mechanical strength, low density, etc). They can be incorporated into polymer matrices such as polyethylene, polyurethanes, poly(vinyl alcohol), the most produced hydrophilic polymers in the world. These polymers are well suited for blending with the cellulose nanocrystals because of their high polarity that enables them to be dispersed in water. When reinforced with CNs, the stabilization of the polymer matrix under aqueous conditions was observed. This stabilization improves the behavior of the polar polymer under humid conditions and thus broadens their applicability (Roohani et al., 2008). However, it is challenging to reinforce hydrophobic polymer matrices with hydrophilic CNs. As a potential solution, the synthesis of poly(3-caprolactone)-grafted cellulose nanocrystals was developed (Habibi et al., 2008). The composite can be used in surgical and biomedical applications due to its biocompatibility and it is also finding its way to everyday applications such as packaging. Representative examples of applications of cellulose are summarized in Figure 3. Figure 3. View largeDownload slide Schematic representation of applications of cellulose. Figure 3. View largeDownload slide Schematic representation of applications of cellulose. VEGETABLE/PLANT OIL-BASED MATERIALS Glycerol (propane-1, 2, 3-triol) is one of the most common large scale industrial byproducts. It is a nontoxic, viscous, and colorless liquid, miscible in many substances due mainly to the presence of the 3 hydroxyls groups. With the extensive production of biodiesel the transesterification and saponification of triglycerides became the major source of glycerol. About 10%–20% of the total volume of products in biodiesel production is glycerol. Finding applications to utilize this nontoxic waste is therefore, a top priority for the biodiesel industry. However, the “crude glycerol” contains 70%–90% glycerol with impurities such as methanol or soap and requires refining via neutralization, stripping, filtration/centrifugation, and vacuum distillation to obtain the desired purity (Cravotto et al., 2011; Quispe et al., 2013). The use of glycerol as a solvent for organic synthesis has attracted considerable interest because glycerol is nontoxic, nonhazardous, nonvolatile, biodegradable, and recyclable. The application possibilities are broad (Scheme 1). Although glycerol can dissolve many organic and inorganic compounds, its high viscosity often requires the use of a fluidifying cosolvent. An ultrasound and microwave irradiation-based protocol was designed to overcome this problem. It enhanced mass transfer and was applied in various reactions such as transfer hydrogenation or Suzuki coupling (Cravotto et al., 2011). The immiscibility of glycerol with nonpolar organic solvents allowed the easy isolation of products and recycling of the medium. A recent study proposed a mixture of waste glycerol and choline chloride as a deep eutectic solvent prototype (Bewley et al., 2015). They have similar properties to ionic liquids, however, they are usually biodegradable and less expensive. Glycerol can also be easily transformed to 1,2,3-trimethoxypropane, which is an aprotic polar solvent with improved properties. It can be synthesized from glycerol in 1 step with a methylating agent and a phase transfer catalyst (Sutter et al., 2013). The product was evaluated as a solvent in transesterification, alkylations, organometallic and cross-coupling reactions and showed promising results. Glycerol has also been applied in synthetic processes as a starting material (Scheme 2). An approach using supercritical water was used to obtain syngas from glycerol in an energetically selfsufficient process. The syngas was then converted to methanol (Gutierrez Ortiz et al., 2013). 1,3-Propanediol, an essential starting material for the synthesis of polymers, especially poly(trimethylene-terephthalate), can also be obtained from glycerol. The bioconversion of sunflower oil biodiesel raw glycerol by Clostridium butyricum microorganism yielded 1,3-propanediol (Asad-ur-Rehman et al., 2008). The anaerobic fermentation of crude glycerol also leads to other alcohols such as butanol that is of particular interest as a petroleum fuel blending component due to its higher heating value and octane number, lower vapor pressure, and higher miscibility with petroleum fuel than ethanol. The bacteria Clostridium pasteurianum showed ability to metabolize glycerol and produce significant amount of butanol (Taconi et al., 2009). Various carboxylic acids can also be obtained from glycerol depending on the microorganism of choice. The yeast species Yarrowia lipolytica was investigated for producing citric acid from crude glycerol (Imandi et al., 2007). A strain from Escherichia coli was found to be the most suitable for the production of lactic acid (Hong et al., 2009). The catalytic conversion of glycerol with air on Pt catalysts leads to valuable chemicals such as dihydroxyacetone, an ingredient in tanning products and a building block of new biodegradable polymers (Garcia et al., 1995). A similar process yielded acrolein, a starting material for the synthesis of many chemicals such as acrylic acid and methionine. It is also directly applied as a herbicide, an algicide in irrigation canals, or a microbiocide in water treatment ponds or cooling water-towers (Yan et al., 2009). Glycerol has been used in heterogeneous catalytic approaches as well. Alumina and niobia supported CeO2 catalyzed the carboxylation of glycerol to glycerol carbonate (Dibenedetto et al., 2011) or the selective synthesis of propylene was achieved via hydrodeoxygenation of glycerol on Fe-Mo oxide catalysts (Zacharopoulou et al., 2015). The production of ethanol and hydrogen from glycerol was reported in many studies. Given its low price, the use of glycerol as a feedstock to produce ethanol has become an attractive biocompatible pathway. E. coli were able to catalyze the fermentation of glycerol and afford ethanol (Posada and Cardona, 2010). It appears that the production cost of ethanol from raw glycerol was comparable to its production cost from conventional materials such as sugarcane. Traditional hydrogen production processes are often energy intensive and have a damaging impact on the environment, showing the need for greener production methods (Press et al., 2009). Using glycerol as starting material, a screening of bacteria was carried out to establish the best hydrogen-producing method (Rossi et al., 2011). It was found that the bacteria from the genus Klebsiella and Pantoea had the capacity of producing hydrogen from raw glycerol. Another study proposed the use of surfactants and water to improve the hydrogen production from glycerol by decreasing its viscosity (Pachapur et al., 2016). The method demonstrated a significant improvement in the utilization of glycerol by the microorganisms, a coculture of Enterobacter aerogenes and Clostridium byturicum. The direct use of vegetable oils, mainly composed of triglycerides, has also attracted attention (Figure 4). The most produced vegetable oils worldwide are palm oil, soybean oil (SBO), rapeseed oil, and sunflower oil (Behr et al., 2008). The conventional method to extract vegetable oil is the Soxhlet extraction (Sulaiman et al., 2013). Ultrasound and microwave-assisted extractions are also efficient methods for the production of vegetable oils in short times, in improved yield and quality (Cravotto et al., 2008). Both methods disrupt the cell membranes releasing the oil into the solvent and afford the oil with considerably higher yield than the conventional method. In addition, the reaction time is reduced by an order of magnitude. Supercritical carbon dioxide extraction also has many advantages. It is a single step extraction that does not require additional toxic and flammable organic solvents. Not only does supercritical CO2 have low reactivity, it also has a high solvent power and selectivity and it can easily be removed from the product (Cvjetko et al., 2012). The cold press technology offers another green way to extract vegetable oils in absence of organic solvents (Khoddami et al., 2014). Figure 4. View largeDownload slide Application possibilities of vegetable oils. Figure 4. View largeDownload slide Application possibilities of vegetable oils. The main application of vegetable oils besides being a food source is the production of biodiesel. The biodiesel obtained is considered as environmentally friendly as it generates a positive energy balance (Rodriguez Portillo et al., 2014). The neat oils cannot be used as fuel, they must undergo transformations to reduce the viscosity and prevent engine deposits. Transesterification is the most common method to afford fatty acid methyl esters to be used as biodiesel. Methanol, ethanol, and butanol are the most effective alcohols for this purpose. Although the majority of applications are catalytic, it can be carried out without catalyst using supercritical methanol (Demirbas, 2002). Thermal decomposition which produces alkanes, alkenes, carboxylic acids, and aromatic compounds is another pathway to overcome the viscosity of vegetable oils to produce fuel. A recent study described a pyrolysis of SBO to obtain fuel (Xu et al., 2009). Triacylglycerols are excellent starting materials for polyurethane synthesis. The advantages are their availability, biodegradability, and potential to improve the properties of the product. Vegetable oils have to be converted by epoxidation followed by epoxide ring-opening. Flexible polyurethanes were synthesized from vegetable oil-based polyols using this method (Prociak et al., 2012). A similar study presents a 2-stage method for polyol preparation by epoxidation of natural oils and subsequent oxirane ring opening under microwave irradiation (Dworakowska et al., 2012). Two novel polyurethanes were obtained from canola oil-based polyols (Kong et al., 2012). Due to the negative impact of mineral oil-based lubricants on the environment, the biodegradable nontoxic vegetable oils have attracted extensive interest as an alternative to produce lubricants despite their poor oxidative and thermal stabilities. These issues can be addressed by the chemical modification of fatty acid chains of triglycerides to improve the performance as lubricants. The 1-pot synthesis of acyl derivatives of SBOs improved the stability of the raw oil (Sharma et al., 2008) (Scheme 3). Another study proposed using environmentally benign oil/water emulsions to prepare lubrication fluids (Doll and Sharma, 2011). A variety of oil emulsions (SBO and epoxidized SBO) utilizing different surfactant systems were explored. It was demonstrated that even 1% aqueous emulsion of the vegetable oils can reduce friction to nearly the same extent as the neat base oil. Vegetable oils were found to be good candidates to substitute mineral oils in grease formulation as well. Biodegradable and environmental friendly greases with improved oxidative stability and consistency are desirable for many applications where the grease is in contact with water, soil or the environment in general (Sharma et al., 2006). The possibility to use vegetable oils for the preparation of green detergents has also been investigated. Coconut and palm oils contain a high amount of lauric acid (C12), a fatty acid chain that is a suitable starting material to produce detergents (Behr et al., 2008). The fatty acid was transformed to alcohols by high-pressure hydrogenation and with an additional step; they can be converted to a variety of detergents. For instance, ethoxylated fatty alcohols constitute nonionic detergents and fatty alcohol sulfates correspond to anionic detergents. The encapsulation of vegetable oils is also important in the pharmaceutical and food industries. Several natural oils have inherent antibacterial, antifungal, or antiviral properties. In order to improve the stability, solubility and bioactivity, encapsulation has been proposed. A broad variety of encapsulation methods are available: formation of microparticles by spray-drying, polymer coating by solvent evaporation and supercritical fluid impregnation with encapsulating agents are among them (Sagiri et al., 2016). Mexican oregano essential oil demonstrated antibacterial and antioxidant activities when encapsulated with beta-cyclodextrin by spray drying method (Arana-Sanchez et al., 2010). The encapsulated essential oil was effective against 2 Gram-negative and 1 Gram-positive pathogenic food-related bacteria. Another study reported the inhibition of the growth of Salmonella enteric serovar Typhimurium LT2 and Listeria innocua bacteria that cause foodborne illnesses, by cinnamon bark extract containing trans-cinnamaldehyde and eugenol entrapped in beta-cyclodextrin (Hill et al., 2013). Cyclodextrin/soy bean oil beads were also used for drug delivery. For instance, the lipophilic drug progesterone was successfully dissolved in soy bean oil and encapsuled in cyclodextrin, providing an effective formulation of the drug that ensured sufficient oral bioavailability (Hamoudi et al., 2011). The antioxidant and antimicrobial properties of vegetable oils could also be exploited for other purposes such as food preservation. Bioactive films were developed to protect the food from bacterial invasion and from oxidation. When incorporated into starch films, Zataria multiflora Boiss essential oil was an effective barrier against E. coli and Staphylococcus aureus while also improving the mechanical properties of the film (Ghasemlou et al., 2013). PROTEIN-BASED MATERIALS Amino acids are common natural compounds, the basic structural units of proteins. They can either be obtained by isolation from natural sources or by chemical/biochemical synthesis. The sources of amino-acids in nature include plants, animals and the soil. Most amino acids are hydrophilic and therefore they are not easily extracted with conventional organic solvents. The extraction can be facilitated with the use of a macromolecule that forms a stable hydrophobic complex with the amino acid by hydrogen bonding protonated amino groups. A counter ion is often required to recover the amino acid. Ionic liquids have demonstrated the ability to extract amino acids without the use of a counter-ion even in the case of the most hydrophilic amino acids. For instance, 1-methyl-3-butylimidazolium hexafluorophosphate (bmim PF6)-crown-ether mixture performed the extraction of amino acids from aqueous fermentation broth with nearly quantitative yield (Smirnova et al., 2004). The crown-ether acts as a complexing agent and it is required to improve the yield. The free amino acids can be recovered by treatment with aqueous alkaline solution. The microwave- and ultrasound-assisted extractions are other rapid and low solvent-use, efficient and green techniques for obtaining free amino acids from plant or animal samples (Carrera et al., 2015; Kovacs et al., 1998). The bioavailable amino acids contained in soils are usually extracted using either cold demineralized water or ammonium acetate solution (Formanek et al., 2005). In addition, to the extraction methods, a broad range of unnatural amino acids can be prepared by chemical synthesis. Amino acids are building blocks for peptides synthesis (Guzman et al., 2007). They are also valuable raw materials for the preparation of surfactants due to their low toxicity and rapid biodegradation, properties that petrochemical-based surfactants do not possess (Figure 5). The hydrophilic amino acids can be combined with a broad range of nonpolar compounds allowing the design of surfactants. The amino acid moiety was linked to long aliphatic chains through the α-amino, α-COOH, or side chain groups to produce anionic, cationic, or amphoteric synthetic surfactants (Brito et al., 2011), that are biocompatible and possess enhanced interfacial properties compared with conventional examples. The hydrophobic nature of surfactant tails allows them to interact with and disrupt cytoplasmic membranes causing lysis and death of the microorganism cells. Thus they are useful as antimicrobial agents (Sanchez et al., 2007), demonstrating high activity while having low toxicity. Figure 5. View largeDownload slide Common applications of amino acids. Figure 5. View largeDownload slide Common applications of amino acids. Due to their biocompatibility and unique properties, amino acids are of great interest in medicinal applications. The antifungal activity of a series of synthesized β-amino-acids (Mittendorf et al., 2003) was due to a dual mode of action. First they accumulated in yeast cells by active transport and then inhibited the enzyme responsible for protein synthesis and cell growth. The application of single-wall nanotubes in biomedical applications attracted attention due to their cylindrical surface morphology that is stable under in vivo conditions. However, they suffer from low water solubility. With amino acids attached to the wall of the nanotubes, the hydrophilicity was greatly improved (Pulikkathara and Khabashesku, 2008). Amino acid-functionalized nanotubes that combine stability and biocompatibility have potential applications in drug delivery, tissue engineering and treatment of aging related problems (Figure 5). Production of peptides from natural sources includes their isolation from industrial wastes. A characteristic example is the valorization of bovine blood in slaughterhouses (Przybylski et al., 2016). After centrifugation, the blood is divided into 2 parts: plasma, the colorless fraction and cruor the red fraction. Plasma has a high content of proteins such as thrombin, fibrinogen, and bovine serum albumin while cruor mainly contains hemoglobin. All proteins can be hydrolyzed by enzymes to obtain peptides. Hemoglobin in particular is described as a rich source of bioactive peptides. It is also possible to extract peptides directly from animal tissues. Insulin is a protein directly obtained from the pancreas of animals. Peptides have various applications, in tissue regeneration, as antimicrobial or cancer drugs and in drug delivery due to their biocompatibility and tunable functionalities. Tissue engineering involves the use of a scaffold to assist the formation of new viable tissues. A peptide-based bioactive hydrogel, formed through molecular selfassembly, showed its potential to mimic natural extracellular matrix (ECM) (Zhou et al., 2009). A selfassembling peptide nanofiber scaffold that created a suitable environment for the regeneration of axons after neuronal damage with no toxicity to the central nervous system was also reported (Ellis-Behnke et al., 2006). Many peptides have antibacterial or antifungal properties, thus they can be developed to serve as antimicrobial agents (Kokel and Török, 2017). The main mode of action of antimicrobial peptides (AMPs) is the alteration of cytoplasmic membranes. This pathway is unlikely to induce drug resistance. In addition, the cytotoxicity of AMPs to mammalian cells is commonly low. Due to the different composition and surface charge of the membrane of mammalian cells and the membrane of bacterial cells, the interaction of AMPs with plasma membrane of mammalian cells is much weaker than that with bacteria. Recently, the 12-residue cationic AMP omiganan pentahydrochloride, a synthetic analog of indolicidin, demonstrated high activity against a wide variety of Gram-positive and Gram-negative bacteria as well as Candida (fungus) (Sader et al., 2004). Omiganan is currently undergoing clinical trials to treat bacterial or fungal infections focusing on catheter-related and cutaneous infections. Despite the attractive features of AMPs in drug design, clinical developments of AMPs are limited because of their in vivo instability. Oral bioavailability is also a problem; peptides can rarely be absorbed by the intestinal mucosa (Ötvös and Wade, 2014). Novel formulations of AMPs are being developed in nanotechnology to address these problems. The application of magnetic nanoparticles conjugated to AMPs was also investigated in overcoming infections (Lopez-Abarrategui et al., 2013). The encapsulation of AMPs with nanoparticles could offer a solution to overcome clinical obstaclesdue to the specific physicochemical properties of the nanoparticles. A variety of natural peptides possess anticancer properties with reduced side effects. It was observed that a peptide fraction isolated from pepsin hydrolysate of algae protein waste exhibited antiproliferation and antioxidant activities (Sheih et al., 2010). The study demonstrated the ability of the peptide to inhibit cell growth and promote the cell cycle arrest in human gastric cancer cells. Furthermore, it also appeared as a cancer preventive agent by scavenging free radicals that could attack essential biomolecules such as proteins or DNA. Snake venom is a known source of drugs; it contains toxins that have curative properties. However, its benefits are often covered by its high toxicity. The Caspian cobra venom, a mixture of proteins and smaller peptides, has recently been investigated for the treatment of cancer (Ebrahim et al., 2016). The results attested its potency as apoptosis inducer in cancer cells with minimum effects on healthy cells. AMPs conjugated with gold nanoparticles were found to be efficient carriers for gene delivery to stem cells (Peng et al., 2016). Even though their efficiency in vitro is high, they suffer from a low in vivo activity. Conjugation of functional peptides to gold nanoparticles appeared to enhance the targeting ability and the transfection efficiency of vectors. The peptides are essential to enhance the entry to the cell, and they promote the nanoparticle uptake. The peptide-conjugated gold nanoparticles also can inhibit the proliferation of bacteria. This ability, associated with the potential to deliver genes can treat infected wounds such as diabetic skin ulcer. The above listed applications are summarized in Figure 6. Figure 6. View largeDownload slide Application of peptides in various fields of medicine. Figure 6. View largeDownload slide Application of peptides in various fields of medicine. Scheme 1. View largeDownload slide Example reactions using glycerol as solvent. Scheme 1. View largeDownload slide Example reactions using glycerol as solvent. Scheme 2. View largeDownload slide Applications of glycerol as a synthetic starting material. Scheme 2. View largeDownload slide Applications of glycerol as a synthetic starting material. Scheme 3. View largeDownload slide Chemical modification of fatty acid chains of SBOs. Scheme 3. View largeDownload slide Chemical modification of fatty acid chains of SBOs. CONCLUSIONS AND OUTLOOK As illustrated earlier, significant efforts were devoted to finding renewable and nontoxic alternatives to the traditional petroleum-based raw materials for a range of industries, most prominently to the production of fine chemicals, pharmaceuticals and materials. Although the synthesis of sophisticated, value added compounds, such as drugs, certainly requires many synthetic steps it appears possible to base such industries on natural compounds/materials that are nontoxic and are available in large quantities in the form of either bio- (biomass, etc.) or food waste (eg, used oil, etc.). This way 2 major goals can be achieved; (1) the elimination of extensive amount of waste and (2) the steady stream of nontoxic industrial raw materials. This account gave an overview on the availability and application of the most common sources, carbohydrates, oils, and protein/peptide-based materials. Based on the large number of recent publications on this topic it is fair to predict that significant resources, both intellectual and financial, will be devoted to find sustainable alternatives that will provide starting materials for industries that work on maintaining and improving the living standards of the rapidly growing population while preserving and enhancing the health of our environment as well. ACKNOWLEDGMENTS The financial support provided by the University of Massachusetts Boston is gratefully acknowledged. REFERENCES Anastas P. T., Warner J. C. ( 1998) Green Chemistry: Theory and Pratice , Oxford University Press, New York. Arana-Sanchez A., Estarron-Espinosa M., Obledo-Vazquez E. N., Padilla-Camberos E., Silva-Vazquez R., Lugo-Cervantes E. ( 2010). Antimicrobial and antioxidant activities of Mexican oregano essential oils (Lippia graveolens H. B. K.) with different composition when microencapsulated in beta-cyclodextrin. Lett. Appl. Microbiol . 50, 585– 590. 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TI - Sustainable Production of Fine Chemicals and Materials Using Nontoxic Renewable Sources
JO - Toxicological Sciences
DO - 10.1093/toxsci/kfx214
DA - 2017-10-16
UR - https://www.deepdyve.com/lp/oxford-university-press/sustainable-production-of-fine-chemicals-and-materials-using-nontoxic-jr1UTSjXUT
SP - 214
EP - 224
VL - 161
IS - 2
DP - DeepDyve
ER -