[ACS Symposium Series] Green Polymer Chemistry: Biocatalysis and Materials II Volume 1144 || Green...

Chapter 1

Green Polymer Chemistry: A Brief Review

H. N. Cheng,*,1 Patrick B. Smith,2 and Richard A. Gross3

1Southern Regional Research Center, Agriculture Research Service,U.S. Department of Agriculture, 1100 Robert E. Lee Blvd.,

New Orleans, Louisiana 701242Michigan Molecular Institute, Midland, Michigan 48640

3Department of Chemistry and Chemical Biology,Rensselaer Polytechnic Institute, 110 8th Street,

Troy, New York 12180-3590*E-mail: [email protected]

This review briefly surveys the research done on green polymerchemistry in the past few years. For convenience, theseresearch activities can be grouped into 8 themes: 1) greenercatalysis, 2) diverse feedstock base, 3) degradable polymersand waste minimization, 4) recycling of polymer productsand catalysts, 5) energy generation or minimization duringuse, 6) optimal molecular design and activity, 7) benignsolvents, and 8) improved syntheses or processes in orderto achieve atom economy, reaction efficiency, and reducedtoxicity. All these areas have attracted worldwide attention,with contributions variously from academic, industrial, andgovernment laboratories. Many new promising technologiesare being developed. Whereas most aspects of green polymerchemistry are covered in this review, special attention has beenpaid to biocatalysis and biobased materials due to the specificresearch interests of the authors. Appropriate examples areprovided, taken particularly from the articles included in thissymposium volume.

© 2013 American Chemical Society

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In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Introduction

Green chemistry is the design of chemical products and processes thatreduce or eliminate the use or generation of hazardous substances (1, 2). Becauseof environmental concerns, energy demands, global warming, and interest insustainability, this concept has become very popular. Several books and reviewarticles have appeared in the past few years on this topic (1–6).

There is also increasing interest in green polymer chemistry. This can beseen in the number of books (7–9) and reviews (10, 11) on this topic. We havepreviously (12) categorized the developments in green polymer chemistry intoeight pathways (Table 1). These pathways also appear to be consistent with mostof themes discussed in recent articles and books on green chemistry (1–6).

Table 1. Major pathways for green polymer chemistry

Major Pathways Examples

Greener catalysts Biocatalysts, such as enzymes and whole cells

Diverse feedstock base Biobased building blocks and agricultural feedstock(sugars, peptides, triglycerides, lignin). Natural fillers incomposites. CO2 as monomer.

Degradable polymers andwaste minimization

Natural renewable materials. Some polyesters andamides.

Recycling of polymerproducts and catalysts

Many degradable polymers can potentially be recycled.Immobilized enzymes can be reused.

Energy generation orminimization of use

Biofuels. Reactive extrusion method. Microwave-assistedsynthesis.

Optimal molecular designand activity

Improved enzymes. Metabolic engineering. Proteinsynthesis.

Benign solvents Water, ionic liquids, or reactions without solvents

Improved syntheses andprocesses

atom economy, reaction efficiency, toxicity reduction.

The aim of this article is not to provide a comprehensive review of greenpolymer chemistry but to highlight major developments in this area, usingselective literature and emphasizing research reported in this symposium volume(13–39). A particular emphasis is placed on biocatalysis (e.g., (40–47)) andbiobased materials (e.g., (48–55)). Biocatalysis involves the use of enzymes,microbes, and higher organisms to facilitate chemical reactions. Because thereaction conditions are often mild, water-compatible, and environmentallyfriendly, they are good examples of green polymer chemistry. Likewise, manybiobased materials are biodegradable and recyclable, and their use represents anexemplar of green polymer chemistry.

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Green Polymer Chemistry: Eight PathwaysBiocatalysts

As noted earlier, biocatalysis is an accepted method for green polymerchemistry. Several reviews (40–43) and books (44–47) are available. There arealso ample examples of biocatalysis in this book. A total of 15 articles deal withbiocatalysis and biotransformations. Among them, 11 articles deal with enzymes(13–23) and 4 deal with whole cells and their biotransformations (24–27).

Campbell et al (13) provided a good overview of the perspectives andopportunities offered by enzyme-based technologies. As expected, lipases arethe most often used enzymes for synthesis. For example, Jiang (14) reviewedthe synthesis of high purity amino-bearing copolyesters via lipase catalysis.Hunley et al (15) described their comprehensive metrology approach to identifykey parameters to control enzymatic ring-opening polymerization of lactones.Barrera-Rivera and Martinez-Richa (16) used Yarrowia lipolytica lipase tosynthesize biodegradable polyesters via ring-opening polymerization of cyclicesters, including oligomeric diols, which could be subsequently convertedto biodegradable linear polyester urethanes. Mahapatro and Negron (17)reviewed the microwave-assisted polymerizations, particularly lipase-catalyzedpolymerization of caprolactone. Puskas et al (18) utilized lipase-catalyzedtransesterification to functionalize poly(ethylene glycol) (PEG). Poojari andClarson (19) reviewed a wide range of lipase-catalyzed reactions involvingpoly(dimethylsiloxane).

Kawai et al (20) constructed mutant cutinases using random and site-directedmutagenesis to improve activity and thermal stability and studied their hydrolyticmechanisms on polyesters. Gitsov and Simonyan (21) made polymer-modifiedlaccase complexes and produced copolymers of bisphenol A and diethyl stilbestrolwith them. Kadokawa (22) used phosphorylase-catalyzed α-glycosylationto make new polysaccharides, such as branched anionic polysaccharidesand amylose-grafted heteropolysaccharides. Renggli et al (23) reviewed thetechnique of biocatalytic atom transfer radical polymerization (ATRP), wheremetalloproteins (e.g., horseradish peroxidase and hemoglobin) were employed topolymerize vinyl monomers under ATRP conditions.

As for whole-cell approaches, Nduko at al (24) reviewed the microbialproduction of lactate-based polyesters, including the optimization ofculture conditions, metabolic engineering of bacteria, directed evolution oflactate-polymerizing enzyme, and copolymerization with lactate. Abdala etal (25) reported on the microbial synthesis of poly(R-3-hydroyoctanoate),its characterization, and its nanocomposite with thermally reducedgraphene. Tomizawa et al (26) provided a mini-review of their work onpoly(hydroxyalkanoate) production by marine bacteria, using sugars, plant oils,and three unsaturated fatty acids as sole carbon sources. Tada et al (27) coupledPEG to antibodies and oligonucleotides (through chemical means) to solubilizedthem in organic media. In addition, a genetic-encoding approach was devised forthe site-specific incorporation of PEG into t-RNA. The techniques of PEGylatedbiopolymers and the methodology for gene PEGylation seem to be promisingnew tools for the synthesis of designed (bio-)macromolecular structures

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Diverse Feedstock Base

There is growing interest in biobased materials, partly due to the uncertainlywith petroleum-based raw materials and partly due to the increasing appreciationof the limited resources of the world and the need for sustainability. Severalreviews (48–51) and books (52–55) are available on the use of natural renewablematerials as raw materials for synthesis and polymerization or as ingredients forcommercial products. In this book, 12 articles (28–39) are primarily involved withbiobased raw materials or products.

Several of these articles deal with polyesters. Thus, Ishii et al (28) carriedout polycondensation reaction on caffeic acid (a precursor in the biosynthesis oflignin) and measured the thermal properties. Tsui et al (29) made films and foamsof poly(3-hydroxybutyrate-co-3-hydroxyvalerate) blended with silk fibroin andstudied their properties. Zhang et al (30) monitored the polycondensation reactionof adipic acid and trimethylolpropane using 1H and 13CNMR as a function of time.Mahmood et al (31) carried out direct fluorination of polyhydroxyalkanoates atelevated pressure with elemental F2/N2 gas mixture and characterized the product.

Hablot et al (32) reviewed their work using all parts of soybean as rawmaterials for conversion to value-added products, including ozonation ofoil triglycerides to produce polyols, reactions of proteins to polyurethanes,dimer acids to polyurethanes, and silylation of triglycerides. Biswas et al (33)summarized their work involving common beans, particularly the extrusioncooking of whole beans as food, use of bean as fillers in polymeric composites,extraction of triglyceride oils and phenolic phytochemicals from beans, andconversion of bean starch to ethanol. Dowd and Hojilla-Evangelista (34) preparedprotein isolates from cottonseed meals and characterized the solubility and thefunctional properties of the protein isolates. Cheng et al (35) hydrogenatedtriglycerides using Ni, Pt and Pd catalysts and obtained oils with distinct amountsof mono- and di-enes, which could be derivatized to produce specific biobasedproducts.

Chung et al (36) developed new lignin-based graft copolymers via ATRPand click chemistry; these hybrid materials had a lignin center and poly(n-butylacrylate) or polystyrene grafts. Fundador et al (37) prepared xylan esterswith different alkyl chain lengths (C2-C12) and measured the mechanical andcrystallization properties of these esters. Wang and Shi (38) converted modifiedstarches into thermoplastic materials; new high-value products were then madefrom these materials using plasticizers or appropriate blends. Cheng et al(39) added cotton gin trash as filler in low-density polyethylene; the resultingcomposites are likely to be useful in applications where reduced cost is desirableand reductions in mechanical properties are acceptable.

Degradable Polymers and Waste Minimization

Because of ongoing interest in degradability, many degradable polymers havebeen reported. These can be categorized (56, 57) into three groups: a) syntheticpolymers, such as condensation polymers, water-soluble polymers, and additionpolymers with pro-oxidants or photosensitizers; b) biobased polymers, such as

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polysaccharides, proteins, lipids, and semi-natural polymers, c) polyblends, e.g.,blends of synthetic and biobased polymers, and biopolymer blends. Biobasedpolymers are beneficial in that many of them are biodegradable, often minimizewaste, and mitigate disposal problems. Biocatalysis is also helpful because theensuing products are potentially biodegradable, and the biocatalysts themselvesare usually biodegradable.

It may be noted that almost all the polymers described in this book (polyesters,polyamides, polypeptides, polysaccharides, proteins, triglycerides, lignin, PEG)are biodegradable or potentially biodegradable. Most of the enzymes used arehydrolases (e.g., lipases, cutinase) (13–19), and these can be employed forsynthesis or for polymer degradation and hydrolysis. Whereas polyethylene itselfis not degradable, the incorporation of a agri-based filler (33, 39) is a known tacticto improve the degradability of polyethylene.

Recycling of Polymer Products and Catalysts

Many of the degradable polymers can be potentially recycled. Certainlyagricultural raw materials and bio-based building blocks are amenable toenzymatic or microbial breakdown and (if economically justifiable) can becandidates for recycling. Currently even many plastics (e.g., polyesters,polyolefins, poly(vinyl chloride), polystyrene) are being recycled (58, 59).

Recycling is also important for biocatalysts in order to decrease process cost;this is one of the reasons for the use of immobilized enzymes. Several examples ofimmobilized enzymes appear in this book (14, 15, 17–19), particularly Novozym®435 lipase from Novozymes A/S, which is an immobilized lipase from Candidaantarctica.

Energy Generation and Minimization of Use

As global demand for energy continues to rise, it is desirable to decreaseenergy use in industrial processes. Biocatalysis is potentially beneficial in thisregard because their use often involves lower reaction temperatures and mildreaction conditions (13–27). Other examples of energy savings in this bookare microwave-assisted reactions (17), reactive extrusion technique (38) andextrusion cooking (33). An active area of current research is biofuels, and manyreview articles are available (60–63). An example of this technology in this bookis shown for the conversion of bean starch to ethanol (33).

Molecular Design and Activity

In biochemistry, a good example of molecular design is genetic engineering,which permits modification of protein structure in order to optimize a particularactivity. For example, Kawai et al (20) used random and site-specific mutagenesisto improve activity and thermostability of cutinase. In designing new lactatepolymers, Nduko et al (24) modified the bacteria via metabolic engineering.Tada, et al (27) utilized a genetic method to incorporate PEG into a peptide.

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In a different enzyme design, Gitsov and Simonyan (21) made supramolecularcomplexes of laccase, which facilitated one-pot copolymerization reactions.

In product development, structure-property and structure-activity correlationsare often employed as part of synthetic design, and several articles on syntheses inthis book implicitly incorporated this tactic (e.g., (25, 27, 29, 35, 37, 38)).

Benign Solvents

A highly desirable goal of green chemistry is to replace organic solvents inchemical reactions with water. Biocatalytic reactions are highly suited for this. Infact, several enzymatic reactions and whole-cell biotransformations in this bookwere done inwater (e.g., (22, 25, 26, 38)). An alternative is to carry out the reactionwithout any solvents, as exemplified by several articles in this book (17–19, 28,31, 35).

Improved Syntheses and Processes

Optimization of experimental parameters in synthesis and processimprovement during scale-up and commercialization are part of the work thatsynthetic scientists and polymer engineers do. The use of biocatalysis canpotentially improve processes because enzymatic reactions often involve fewerby-products and less (or no) toxic chemical reagents. An example is the useof biocatalysts instead of copper in ATRP (23). Hablot et al (32) illustrated anexample of process improvement in their effort to ozonize soybean oil to generatepolyols. Hunley et al (15) identified the key parameters to control enzymaticring-opening polymerization of lactone, which aided the design of better reactionconditions and next generation catalysts.

Polymer blends and composites are often produced as part of the strategytowards improved products and processes. In this book, examples of polyblendsinclude poly(hydroalkanoate)/silk fibroin (29), poly(vinyl alcohol)/bean (33),modified starch/polyester and modified starch/polyester/poly(vinyl alcohol) (38).Examples of polymeric composites include poly(hydroxyalkanoate)/graphene(25), polylactate/bean and polyethylene/bean (33), and polyethylene/cotton gintrash (39).

ConclusionFrom the foregoing discussion, it is clear that green polymer chemistry is very

much an active area of research and development. Both biocatalysis and biobasedmaterials hold much promise as platforms for innovative research and productdevelopments (64–66). These areas have attracted the attention of many R&Dpersonnel from academic, industrial, and government laboratories. An impressivearray of new structures and new methodologies have been developed. The key tocommercial viability is the cost versus benefit of the polymers in use relative toalternatives. For commodity applications like coatings, adhesives, packaging, andconstruction, cost is a major constraint, but for biomaterials, pharmaceuticals, and

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personal care there is more latitude. In view of the wide range of applications,as exemplified by the articles given in this symposium volume, we expect to seecontinued vigor and vitality in these fields in the future.

Acknowledgments

Thanks are due to the authors of various chapters of this symposium volumefor their contributions and for their cooperation during the peer review process.Mention of trade names or commercial products in this publication is solely forthe purpose of providing specific information and does not imply recommendationor endorsement by the U.S. Department of Agriculture. USDA is an equalopportunity provider and employer.

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15. Hunley, M. T.; Orski, S. V.; Beers, K. L. Metrology as a Tool to UnderstandImmobilized Enzyme Catalyzed Ring-Opening Polymerization. In GreenPolymer Chemistry: Biocatalysis and Materials II; Cheng, H. N., Gross, R.A., Smith, P. B., Eds.; ACS Symposium Series 1144; American ChemicalSociety: Washington, DC, 2013; Chapter 4.

16. Barrera-Rivera, K. A.; Martínez-Richa, A. Syntheses and Characterizationof Aliphatic Polyesters via Yarrowia lipolytica Lipase Biocatalysis. InGreenPolymer Chemistry: Biocatalysis and Materials II; Cheng, H. N., Gross, R.A., Smith, P. B., Eds.; ACS Symposium Series 1144; American ChemicalSociety: Washington, DC, 2013; Chapter 5.

17. Mahapatro, A.; Negrón,T. D. M. Microwave Assisted BiocatalyticPolymerizations. In Green Polymer Chemistry: Biocatalysis and MaterialsII; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACS Symposium Series1144; American Chemical Society: Washington, DC, 2013; Chapter 6.

18. Puskas, J. E.; Seo, K. S.; Castaño, M.; Casiano, M.; Wesdemiotis, C. GreenPolymer Chemistry: Enzymatic Functionalization of Poly(ethylene glycol)sUnder Solventless Conditions. In Green Polymer Chemistry: Biocatalysisand Materials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACSSymposium Series1144; American Chemical Society: Washington, DC,2013; Chapter 7.

19. Poojari, Y.; Clarson, S. J. Biocatalysis for the Preparation of SiliconeContaining Copolymers. In Green Polymer Chemistry: Biocatalysis andMaterials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACS SymposiumSeries 1144; American Chemical Society: Washington, DC, 2013; Chapter8.

20. Kawai, F.; Thumarat, U.; Kitadokoro, K.; Waku, T.; Tada, T.; Tanaka, N.;Kawabata, T. Comparison of Polyester-Degrading Cutinases from GenusThermobifida. In Green Polymer Chemistry: Biocatalysis and MaterialsII; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACS Symposium Series1144; American Chemical Society: Washington, DC, 2013; Chapter 9.

21. Gitsov, I.; Simonyan, A. “Green” Synthesis of Bisphenol Polymers andCopolymers, Mediated by Supramolecular Complexes of Laccase andLinear-Dendritic Block Copolymers. In Green Polymer Chemistry:Biocatalysis and Materials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.;ACS Symposium Series 1144; American Chemical Society: Washington,DC, 2013; Chapter 10

22. Kadokawa, J. Synthesis of New Polysaccharide Materials by Phosphorylase-catalyzed Enzymatic alpha-Glycosylations Using Polymeric GlycosylAcceptors. In Green Polymer Chemistry: Biocatalysis and Materials II;Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACS Symposium Series1144; American Chemical Society: Washington, DC, 2013; Chapter 11.

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23. Renggli, K.; Spulber, M.; Pollard, J.; Rother, M.; Bruns, N. BiocatalyticATRP: Controlled Radical Polymerizations Mediated by Enzymes. In GreenPolymer Chemistry: Biocatalysis and Materials II; Cheng, H. N., Gross, R.A., Smith, P. B., Eds.; ACS Symposium Series 1144; American ChemicalSociety: Washington, DC, 2013; Chapter 12.

24. Nduko, J. M.; Matsumoto, K.; Taguchi, S. Microbial Plastic Factory:Synthesis and Properties of the New Lactate-Based Biopolymers. In GreenPolymer Chemistry 2: Biocatalysis and Biobased Materials; Cheng, H. N.,Gross, R. A., Smith, P. B., Eds.; ACS Symposium Series 1144; AmericanChemical Society: Washington, DC, 2013; Chapter 13.

25. Abdala, A.; Barrett, J.; Srienc, F. Synthesis of Poly-(R)-3 Hydroxyoctanoate(PHO) and Its Graphene Nanocomposites. In Green Polymer Chemistry:Biocatalysis and Materials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.;ACS Symposium Series 1144; American Chemical Society: Washington,DC, 2013; Chapter 14.

26. Tomizawa, S.; Chuah, J.; Ohtani, M.; Demura, T.; Numata, K. Biosynthesisof Polyhydroxyalkanoate by a Marine Bacterium Vibrio sp. Strain UsingSugars, Plant Oil and Unsaturated Fatty Acids As Sole Carbon sources. InGreen Polymer Chemistry: Biocatalysis and Materials II; Cheng, H. N.,Gross, R. A., Smith, P. B., Eds.; ACS Symposium Series 1144; AmericanChemical Society: Washington, DC, 2013; Chapter 15.

27. Tada, S.; Abe, H.; Ito, Y. PEGylated Antibodies and DNA in Organic Mediaand Genetic PEGylation. In Green Polymer Chemistry: Biocatalysis andMaterials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACS SymposiumSeries 1144; American Chemical Society: Washington, DC, 2013; Chapter16.

28. Ishii, D.; Maeda, H.; Hayashi, H.; Mitani, T.; Shinohara, M.; Yoshioka,K.; Watanabe, T. Effect of Polycondensation Conditions on Structure andThermal Properties of Poly(caffeic acid). In Green Polymer Chemistry:Biocatalysis and Materials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.;ACS Symposium Series 1144; American Chemical Society: Washington,DC, 2013; Chapter 17.

29. Tsui, A.; Hu, X.; Kaplan, D. L.; Frank, C. W. Biodegradable Films andFoam of Poly(3-Hydroxybutyrate-co-3-hydroxyvalerate) Blended withSilk Fibroin. In Green Polymer Chemistry: Biocatalysis and Materials II;Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACS Symposium Series1144; American Chemical Society: Washington, DC, 2013; Chapter 18.

30. Zhang, T.; Howell, B. A.; Martin, P. K.; Martin, S. J.; Smith, P. B. TheSynthesis and NMR Characterization of Hyperbranched Polyesters fromTrimethylolpropane and Adipic Acid. In Green Polymer Chemistry:Biocatalysis and Materials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.;ACS Symposium Series 1144; American Chemical Society: Washington,DC, 2013; Chapter 19.

31. Mahmood, S. F.; Lund, B. R.; Yagneswaran, S.; Aghyarian, S.; Smith, Jr.,D.W.Direct Fluorination of Poly(3-hydroxybutyrate-co)-hydroxyhexanoate.In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H. N.,

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Gross, R. A., Smith, P. B., Eds.; ACS Symposium Series 1144; AmericanChemical Society: Washington, DC, 2013; Chapter 20.

32. Hablot, E.; Graiver, D.; Narayan, R. Biobased industrial products fromsoybean biorefinery. In Green Polymer Chemistry: Biocatalysis andMaterials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACS SymposiumSeries 1144; American Chemical Society: Washington, DC, 2013; Chapter21.

33. Biswas, A.; Lesch, W. C.; Cheng, H. N. Applications of Common Beans inFood and Biobased Materials. In Green Polymer Chemistry: Biocatalysisand Materials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACSSymposium Series 1144; American Chemical Society: Washington, DC,2013; Chapter 22.

34. Dowd, M. K.; Hojilla-Evangelista, M. Preparation and Characterization ofProtein Isolate from Glandless and Glanded Cottonseed. In Green PolymerChemistry: Biocatalysis and Materials II; Cheng, H. N., Gross, R. A., Smith,P. B., Eds.; ACS Symposium Series 1144; American Chemical Society:Washington, DC, 2013; Chapter 23.

35. Cheng, H. N.; Rau, M.; Dowd, M. K.; Easson, M. W.; Condon, B. D.Hydrogenated Cottonseed Oil as Raw Material for Biobased Materials. InGreen Polymer Chemistry: Biocatalysis and Materials II; Cheng, H. N.,Gross, R. A., Smith, P. B., Eds.; ACS Symposium Series 1144; AmericanChemical Society: Washington, DC, 2013; Chapter 24.

36. Chung, H.; Al-Khouja, A.; Washburn, N. R. Lignin-Based Graft Copolymersvia ATRP and Click Chemistry. In Green Polymer Chemistry: Biocatalysisand Materials II; Cheng, H. N., Gross, R. A., Smith, P. B., Eds.; ACSSymposium Series 1144; American Chemical Society: Washington, DC,2013; Chapter 25.

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[ACS Symposium Series] Green Polymer Chemistry: Biocatalysis and Materials II Volume 1144 || Green...

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