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Sample records for polyhydroxyalkanoate copolymers production

  1. Microbial production of polyhydroxyalkanoate block copolymer by recombinant Pseudomonas putida.

    Science.gov (United States)

    Li, Shi Yan; Dong, Cui Ling; Wang, Shen Yu; Ye, Hai Mu; Chen, Guo-Qiang

    2011-04-01

    Polyhydroxyalkanoate (PHA) synthesis genes phaPCJ(Ac) cloned from Aeromonas caviae were transformed into Pseudomonas putida KTOY06ΔC, a mutant of P. putida KT2442, resulting in the ability of the recombinant P. putida KTOY06ΔC (phaPCJ(A.c)) to produce a short-chain-length and medium-chain-length PHA block copolymer consisting of poly-3-hydroxybutyrate (PHB) as one block and random copolymer of 3-hydroxyvalerate (3HV) and 3-hydroxyheptanoate (3HHp) as another block. The novel block polymer was studied by differential scanning calorimetry (DSC), nuclear magnetic resonance, and rheology measurements. DSC studies showed the polymer to possess two glass transition temperatures (T(g)), one melting temperature (T(m)) and one cool crystallization temperature (T(c)). Rheology studies clearly indicated a polymer chain re-arrangement in the copolymer; these studies confirmed the polymer to be a block copolymer, with over 70 mol% homopolymer (PHB) of 3-hydroxybutyrate (3HB) as one block and around 30 mol% random copolymers of 3HV and 3HHp as the second block. The block copolymer was shown to have the highest tensile strength and Young's modulus compared with a random copolymer with similar ratio and a blend of homopolymers PHB and PHVHHp with similar ratio. Compared with other commercially available PHA including PHB, PHBV, PHBHHx, and P3HB4HB, the short-chain- and medium-chain-length block copolymer PHB-b-PHVHHp showed differences in terms of mechanical properties and should draw more attentions from the PHA research community. © Springer-Verlag 2010

  2. Metabolic modelling of polyhydroxyalkanoate copolymers production by mixed microbial cultures

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    Reis Maria AM

    2008-07-01

    Full Text Available Abstract Background This paper presents a metabolic model describing the production of polyhydroxyalkanoate (PHA copolymers in mixed microbial cultures, using mixtures of acetic and propionic acid as carbon source material. Material and energetic balances were established on the basis of previously elucidated metabolic pathways. Equations were derived for the theoretical yields for cell growth and PHA production on mixtures of acetic and propionic acid as functions of the oxidative phosphorylation efficiency, P/O ratio. The oxidative phosphorylation efficiency was estimated from rate measurements, which in turn allowed the estimation of the theoretical yield coefficients. Results The model was validated with experimental data collected in a sequencing batch reactor (SBR operated under varying feeding conditions: feeding of acetic and propionic acid separately (control experiments, and the feeding of acetic and propionic acid simultaneously. Two different feast and famine culture enrichment strategies were studied: (i either with acetate or (ii with propionate as carbon source material. Metabolic flux analysis (MFA was performed for the different feeding conditions and culture enrichment strategies. Flux balance analysis (FBA was used to calculate optimal feeding scenarios for high quality PHA polymers production, where it was found that a suitable polymer would be obtained when acetate is fed in excess and the feeding rate of propionate is limited to ~0.17 C-mol/(C-mol.h. The results were compared with published pure culture metabolic studies. Conclusion Acetate was more conducive toward the enrichment of a microbial culture with higher PHA storage fluxes and yields as compared to propionate. The P/O ratio was not only influenced by the selected microbial culture, but also by the carbon substrate fed to each culture, where higher P/O ratio values were consistently observed for acetate than propionate. MFA studies suggest that when mixtures of

  3. Production of co-polymers of polyhydroxyalkanoates by regulating the hydrolysis of biowastes.

    Science.gov (United States)

    Kumar, Prasun; Ray, Subhasree; Kalia, Vipin C

    2016-01-01

    Production of polyhydroxyalkanoate (PHA) co-polymers by Bacillus spp. was studied by feeding defined volatile fatty acids (VFAs) obtained through controlled hydrolysis of various wastes. Eleven mixed hydrolytic cultures (MHCs) each containing 6 strains could generate VFA from slurries of (2% total solids): pea-shells (PS), potato peels (PP), apple pomace (AP) and onion peels (OP). PS hydrolysates (obtained with MHC2 and MHC5) inoculated with Bacillus cereus EGU43 and Bacillus thuringiensis EGU45 produced co-polymers of PHA at the rate of 15-60mg/L with a 3HV content of 1%w/w. An enhancement in PHA yield of 3.66-fold, i.e. 205-550mg/L with 3HV content up to 7.5%(w/w) was observed upon addition of OP hydrolysate and 1% glucose (w/v) to PS hydrolysates. This is the first demonstration, where PHA co-polymer composition, under non-axenic conditions, could be controlled by customizing VFA profile of the hydrolysate by the addition of different biowastes. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Microbial production of polyhydroxyalkanoates (PHAs) and its copolymers: A review of recent advancements.

    Science.gov (United States)

    Anjum, Anbreen; Zuber, Mohammad; Zia, Khalid Mahmood; Noreen, Aqdas; Anjum, Muhammad Naveed; Tabasum, Shazia

    2016-08-01

    Traditional mineral oil based plastics are important commodity to enhance the comfort and quality of life but the accumulation of these plastics in the environment has become a major universal problem due to their low biodegradation. Solution to the plastic waste management includes incineration, recycling and landfill disposal methods. These processes are very time consuming and expensive. Biopolymers are important alternatives to the petroleum-based plastics due to environment friendly manufacturing processes, biodegradability and biocompatibility. Therefore use of novel biopolymers, such as polylactide, polysaccharides, aliphatic polyesters and polyhydroxyalkanoates is of interest. PHAs are biodegradable polyesters of hydroxyalkanoates (HA) produced from renewable resources by using microorganisms as intracellular carbon and energy storage compounds. Even though PHAs are promising candidate for biodegradable polymers, however, the production cost limit their application on an industrial scale. This article provides an overview of various substrates, microorganisms for the economical production of PHAs and its copolymers. Recent advances in PHAs to reduce the cost and to improve the performance of PHAs have also been discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Characterisation of polyhydroxyalkanoate copolymers with controllable four-monomer composition.

    Science.gov (United States)

    Dai, Yu; Lambert, Lynette; Yuan, Zhiguo; Keller, Jurg

    2008-03-20

    Polyhydroxyalkanoate (PHA) copolymers comprising the four monomers 3-hydroxybutyrate (3HB), 3-hydroxyvalerate (3HV), 3-hydroxy-2-methylvalerate (3HMV) and 3-hydroxy-2-methylbutyrate (3HMB) were generated using the recently discovered Defluviicoccus vanus-related glycogen accumulating organisms (DvGAOs) under anaerobic conditions without applying any nutrient limitations. The composition could be manipulated in a defined range by modifying the ratio of propionate and acetate provided in the feed stream. The PHAs produced were characterised as random copolymers (from propionate alone) or a mixture of random copolymers (from mixture of propionate and acetate) through microstructure analysis using 13C NMR spectroscopy. The sequence distribution of all eight comonomer pairs in the carbonyl region of 3HB and 3HV was identified and assigned with confidence utilising two-dimensional heteronuclear multiple bond coherence (HMBC) spectroscopy. Weight average molecular weights were in the range 390-560 kg/mol. Differential scanning calorimetry (DSC) traces showed that the melting temperature (Tm) varied between 70 and 161 degrees C and glass transition temperature (Tg) ranged from -8 to 0 degrees C. The incorporation of considerable amounts of 3HMV and 3HMB monomer units introduced additional "defects" into the PHBV copolymer structure and hence greatly lowered the crystallinity. The data indicate the potential of these four-monomer PHAs to be employed for practical applications, considering their favourable properties and the cost-effective production process using a mixed culture and simple carbon sources.

  6. Novel polyhydroxyalkanoate copolymers produced in Pseudomonas putida by metagenomic polyhydroxyalkanoate synthases.

    Science.gov (United States)

    Cheng, Jiujun; Charles, Trevor C

    2016-09-01

    Bacterially produced biodegradable polyhydroxyalkanoates (PHAs) with versatile properties can be achieved using different PHA synthases (PhaCs). This work aims to expand the diversity of known PhaCs via functional metagenomics and demonstrates the use of these novel enzymes in PHA production. Complementation of a PHA synthesis-deficient Pseudomonas putida strain with a soil metagenomic cosmid library retrieved 27 clones expressing either class I, class II, or unclassified PHA synthases, and many did not have close sequence matches to known PhaCs. The composition of PHA produced by these clones was dependent on both the supplied growth substrates and the nature of the PHA synthase, with various combinations of short-chain-length (SCL) and medium-chain-length (MCL) PHA. These data demonstrate the ability to isolate diverse genes for PHA synthesis by functional metagenomics and their use for the production of a variety of PHA polymer and copolymer mixtures.

  7. Agro-industrial residues and starch for growth and co-production of polyhydroxyalkanoate copolymer and α-amylase by Bacillus sp. CFR-67

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    T. R. Shamala

    2012-09-01

    Full Text Available Polyhydroxyalkanoates (PHA and α-amylase (α-1,4 glucan-4-glucanohydrolase, E.C. 3.2.1.1 were co-produced by Bacillus sp. CFR-67 using unhydrolysed corn starch as a substrate. Bacterial growth and polymer production were enhanced with the supplementation of hydrolysates of wheat bran (WBH or rice bran (RBH individually or in combination (5-20 g L-1, based on weight of soluble substrates-SS. In batch cultivation, a mixture of WBH and RBH (1:1, 10 g L-1 of SS along with ammonium acetate (1.75 g L-1 and corn starch (30 g L-1 produced maximum quantity of biomass (10 g L-1 and PHA (5.9 g L-1. The polymer thus produced was a copolymer of polyhydroxybutyrate-co-hydroxyvalerate of 95:5 to 90:10 mol%. Presence of WBH and corn starch (10-50 g L-1 in the medium enhanced fermentative yield of α-amylase (2-40 U mL-1 min-1. The enzyme was active in a wide range of pH (4-9 and temperature (40-60ºC. This is the first report on simultaneous production of copolymer of bacterial PHA and α-amylase from unhydrolysed corn starch and agro-industrial residues as substrates.

  8. Polyhydroxyalkanoate (PHA) production from waste.

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    Rhu, D H; Lee, W H; Kim, J Y; Choi, E

    2003-01-01

    PHA (polyhydroxyalkanoate) production was attempted with SBRs from food waste. Seed microbes were collected from a sewage treatment plant with a biological nutrient removal process, and acclimated with synthetic substrate prior to the application of the fermented food waste. Laboratory SBRs were used to produce PHA with limited oxygen and nutrients. The maximum content of 51% PHA was obtained with an anaerobic/aerobic cycle with P limitation, and the yield was estimated to be about 0.05 gPHA(produced)/gCOD(applied) or 25 kg PHA/dry ton of food waste, assuming more than 40% of the PHA contents were recoverable. PHB/PHA ratios were 0.74 to 0.77 due to the higher acetate concentrations. Economical analysis seemed to suggest the PHA produced from the food waste could be an alternative material to produce the biodegradable plastic to be used for the collection bags for solid waste.

  9. Advances in cyanobacterial polyhydroxyalkanoates production.

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    Singh, Akhilesh Kumar; Mallick, Nirupama

    2017-11-01

    Polyhydroxyalkanoates (PHAs) have received much attention in the current scenario due to their attractive material properties, namely biodegradability, biocompatibility, thermoplasticity, hydrophobicity, piezoelectricity and stereospecificity. All these properties make them highly competitive for various industrial applications similar to non-degradable conventional plastics. In PHA biosynthesis, PHA synthase acts as a natural catalyst for PHA polymerization process using the (R)-hydroxyacyl-CoA as substrate. Cyanobacteria can accumulate PHAs under photoautotrophic and/or mixotrophic growth conditions with organic substrates such as acetate, glucose, propionate, valerate, and so on. The natural incidence of PHA accumulation by the cyanobacteria is known since 1966. Nevertheless, PHA accumulation in cyanobacteria based on the cell biomass and volumetric productivity is critically lower than the heterotrophic bacteria. Consequently, cyanobacteria are nowadays not considered for commercial production of PHAs. Thus, strain improvements by genetic modification, new cultivation and harvesting techniques, advanced photobioreactor development, efficient and sustainable downstream processes, alternate economical carbon sources and usage of various metabolic inhibitors are suggested for enhancing cyanobacterial PHA accumulation. In addition, identification of transcriptional regulators like RNA polymerase sigma factor (SigE) and a response regulator (Rre37) together with the recent major scientific breakthrough on the existence of complete Krebs cycle in cyanobacteria would be helpful in taking PHA production from cyanobacteria to a new-fangled height in near future. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  10. Synthesis of Medium-Chain-Length Polyhydroxyalkanoate Homopolymers, Random Copolymers, and Block Copolymers by an Engineered Strain of Pseudomonas entomophila.

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    Wang, Ying; Chung, Ahleum; Chen, Guo-Qiang

    2017-04-01

    Medium-chain-length polyhydroxyalkanoates (mcl-PHAs), widely used in medical area, are commonly synthesized by Pseudomonas spp. This study tries to use β-oxidation pathways engineered P. entomophila to achieve single source of a series of mcl-monomers for microbial production of PHA homopolymers. The effort is proven successful for the first time to obtain a wide range of mcl-PHA homopolymers from engineered P. entomophila LAC23 grown on various fatty acids, respectively, ranging from poly(3-hydroxyheptanoate) to poly(3-hydroxytetradecanoate). Effects of a PHA monomer chain length on thermal and crystallization properties including the changes of T m , T g , and T d5% are investigated. Additionally, strain LAC23 is used to synthesize random copolymers of 3-hydroxyoctanoate (3HO) and 3-hydroxydodecanoate (3HDD) or 3-hydroxytetradecanoates, their compositions could be controlled by adjusting the ratios of two related fatty acids. Meanwhile, block copolymer P(3HO)-b-P(3HDD) is synthesized by the same strain. It is found for the first time that even- and odd number mcl-PHA homopolymers have different physical properties. When the gene of the PHA synthase in the engineered P. entomophila is replaced by phaC from Aeromonas hydrophila 4AK4, poly(3-hydroxybutyrate-co-30 mol%-3-hydroxyhexanoate) is synthesized. Therefore, P. entomophila can be used to synthesize the whole range of PHA (C7-C14) homopolymers, random- and block copolymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Cybernetic structured modeling of the production of polyhydroxyalkanoates by Alcaligenes Eutrophus

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    L. FERRAZ

    1999-06-01

    Full Text Available This paper presents a cybernetic structured mathematical model developed for the fermentation step of the process of production of the copolymer of polyhydroxyalkanoates by the bacteria Alcaligenes eutrophus. This process is performed in two different fermentation stages. The first emphasizes the growth of the microorganism in a batch operation without substrates limitations, while in the second, the focus is on copolymer production by a fed-batch operation in the absence of the nitrogen source. This paper presents the results of the treatment of experimental data and of preliminary parameter estimation. The fitting of the proposed model to the experimental data of a standard experiment showed a good agreement.

  12. Recent Advances and Challenges towards Sustainable Polyhydroxyalkanoate (PHA) Production

    DEFF Research Database (Denmark)

    Kourmentza, Constantina; Plácido, Jersson; Venetsaneas, Nikolaos

    2017-01-01

    Sustainable biofuels, biomaterials, and fine chemicals production is a critical matter that research teams around the globe are focusing on nowadays. Polyhydroxyalkanoates represent one of the biomaterials of the future due to their physicochemical properties, biodegradability, and biocompatibility...

  13. Bacterial production of the biodegradable plastics polyhydroxyalkanoates.

    Science.gov (United States)

    Urtuvia, Viviana; Villegas, Pamela; González, Myriam; Seeger, Michael

    2014-09-01

    Petroleum-based plastics constitute a major environmental problem due to their low biodegradability and accumulation in various environments. Therefore, searching for novel biodegradable plastics is of increasing interest. Microbial polyesters known as polyhydroxyalkanoates (PHAs) are biodegradable plastics. Life cycle assessment indicates that PHB is more beneficial than petroleum-based plastics. In this report, bacterial production of PHAs and their industrial applications are reviewed and the synthesis of PHAs in Burkholderia xenovorans LB400 is described. PHAs are synthesized by a large number of microorganisms during unbalanced nutritional conditions. These polymers are accumulated as carbon and energy reserve in discrete granules in the bacterial cytoplasm. 3-hydroxybutyrate and 3-hydroxyvalerate are two main PHA units among 150 monomers that have been reported. B. xenovorans LB400 is a model bacterium for the degradation of polychlorobiphenyls and a wide range of aromatic compounds. A bioinformatic analysis of LB400 genome indicated the presence of pha genes encoding enzymes of pathways for PHA synthesis. This study showed that B. xenovorans LB400 synthesize PHAs under nutrient limitation. Staining with Sudan Black B indicated the production of PHAs by B. xenovorans LB400 colonies. The PHAs produced were characterized by GC-MS. Diverse substrates for the production of PHAs in strain LB400 were analyzed. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Recent Advances and Challenges towards Sustainable Polyhydroxyalkanoate (PHA) Production.

    Science.gov (United States)

    Kourmentza, Constantina; Plácido, Jersson; Venetsaneas, Nikolaos; Burniol-Figols, Anna; Varrone, Cristiano; Gavala, Hariklia N; Reis, Maria A M

    2017-06-11

    Sustainable biofuels, biomaterials, and fine chemicals production is a critical matter that research teams around the globe are focusing on nowadays. Polyhydroxyalkanoates represent one of the biomaterials of the future due to their physicochemical properties, biodegradability, and biocompatibility. Designing efficient and economic bioprocesses, combined with the respective social and environmental benefits, has brought together scientists from different backgrounds highlighting the multidisciplinary character of such a venture. In the current review, challenges and opportunities regarding polyhydroxyalkanoate production are presented and discussed, covering key steps of their overall production process by applying pure and mixed culture biotechnology, from raw bioprocess development to downstream processing.

  15. Polyhydroxyalkanoate-based natural-synthetic hybrid copolymer films: A small-angle neutron scattering study

    International Nuclear Information System (INIS)

    Foster, L. John R.; Knott, Robert; Sanguanchaipaiwong, Vorapat; Holden, Peter J.

    2006-01-01

    Polyhydroxyalkanoates have attracted attention as biodegradable alternatives to conventional thermoplastics and as biomaterials. Through modification of their biosynthesis using Pseudomonas oleovorans, we have manipulated the material properties of these biopolyesters and produced a natural-synthetic hybrid copolymer of polyhydroxyoctanoate-block-diethylene glycol (PHO-b-DEG). A mixture of PHO and PHO-DEG were solvent cast from analytical grade chloroform and analysed using small-angle neutron scattering. A scattering pattern, easily distinguished above the background, was displayed by the films with a diffraction ring at q∼0.12 A -1 . This narrow ring of intensity is suggestive of a highly ordered system. Analysis of the diffraction pattern supported this concept and showed a d-spacing of approximately 50 A. In addition, conformation of the hybrid polymer chains can be manipulated to support their self-assembly into ordered microporous films

  16. Production of polyhydroxyalkanoates (PHAs) in transgenic potato

    NARCIS (Netherlands)

    Romano, A.

    2002-01-01

    Polyhydroxyalkanoates (PHAs) represent a large class of microbial polyesters which are widely distributed in prokaryotes. Because of the current environmental concerns related to the use of mineral-oil-based plastics, PHAs gained a considerable interest for

  17. Metabolic modeling of mixed substrate uptake for polyhydroxyalkanoate (PHA) production

    NARCIS (Netherlands)

    Jiang, Y.; Hebly, M.; Kleerebezem, R.; Muyzer, G.; van Loosdrecht, M.C.M.

    2011-01-01

    Polyhydroxyalkanoate (PHA) production by mixed microbial communities can be established in a two-stage process, consisting of a microbial enrichment step and a PHA accumulation step. In this study, a mathematical model was constructed for evaluating the influence of the carbon substrate composition

  18. Accumulation of a poly(hydroxyalkanoate) copolymer containing primarily 3-hydroxyvalerate from simple carbohydrate substrates by Rhodococcus sp. NCIMB 40126.

    Science.gov (United States)

    Haywood, G W; Anderson, A J; Williams, D R; Dawes, E A; Ewing, D F

    1991-04-01

    A number of taxonomically-related bacteria have been identified which accumulate poly(hydroxyalkanoate) (PHA) copolymers containing primarily 3-hydroxyvalerate (3HV) monomer units from a range of unrelated single carbon sources. One of these, Rhodococcus sp. NCIMB 40126, was further investigated and shown to produce a copolymer containing 75 mol% 3HV and 25 mol% 3-hydroxybutyrate (3HB) from glucose as sole carbon source. Polyesters containing both 3HV and 3HB monomer units, together with 4-hydroxybutyrate (4HB), 5-hydroxyvalerate (5HV) or 3-hydroxyhexanoate (3HHx), were also produced by this organism from certain accumulation substrates. With valeric acid as substrate, almost pure (99 mol% 3HV) poly(3-hydroxyvalerate) was produced. N.m.r. analysis confirmed the composition of these polyesters. The thermal properties and molecular weight of the copolymer produced from glucose were comparable to those of PHB produced by Alcaligenes eutrophus.

  19. Process optimization for polyhydroxyalkanoate (PHA) production from waste via microbial enrichment cultures

    NARCIS (Netherlands)

    Korkakaki, E.

    2017-01-01

    Polyhydroxyalkanoates (PHA) are compounds naturally produced by microorganisms, with many industrial applications, either as bioplastics or as precursors for production of chemicals. Until now, industrial PHA production was conducted with pure strains of bacteria fed with well-defined feedstocks,

  20. Potential of Diverse Prokaryotic Organisms for Glycerol-based Polyhydroxyalkanoate Production

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    Martin Koller

    2015-06-01

    Full Text Available The potential and performance of various Gram-negative, Gram-positive and archaeal wild type microorganisms, and bacterial mixed cultures, as well as the application of genetically engineered strains as whole-cell biocatalysts for glycerol-based polyhydroxyalkanoate production are analyzed and assessed. This encompasses the comparison of growth and polyhydroxyalkanoate accumulation kinetics, thermo-mechanical properties of isolated glycerol-based polyhydroxyalkanoate of different composition on the monomeric level, and the presentation of mathematical models developed to describe glycerol-based polyhydroxyalkanoate production processes. For all these aspects, the article provides a detailed compilation of the contemporary state of knowledge, and gives an outlook to expected future developments.

  1. Potential and Prospects of Continuous Polyhydroxyalkanoate (PHA Production

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    Martin Koller

    2015-05-01

    Full Text Available Together with other so-called “bio-plastics”, Polyhydroxyalkanoates (PHAs are expected to soon replace established polymers on the plastic market. As a prerequisite, optimized process design is needed to make PHAs attractive in terms of costs and quality. Nowadays, large-scale PHA production relies on discontinuous fed-batch cultivation in huge bioreactors. Such processes presuppose numerous shortcomings such as nonproductive time for reactor revamping, irregular product quality, limited possibility for supply of certain carbon substrates, and, most of all, insufficient productivity. Therefore, single- and multistage continuous PHA biosynthesis is increasingly investigated for production of different types of microbial PHAs; this goes for rather crystalline, thermoplastic PHA homopolyesters as well as for highly flexible PHA copolyesters, and even blocky-structured PHAs consisting of alternating soft and hard segments. Apart from enhanced productivity and constant product quality, chemostat processes can be used to elucidate kinetics of cell growth and PHA formation under constant process conditions. Furthermore, continuous enrichment processes constitute a tool to isolate novel powerful PHA-producing microbial strains adapted to special environmental conditions. The article discusses challenges, potential and case studies for continuous PHA production, and shows up new strategies to further enhance such processes economically by developing unsterile open continuous processes combined with the application of inexpensive carbon feedstocks.

  2. Synthetic routes to degradable copolymers deriving from the biosynthesized polyhydroxyalkanoates: A mini review

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    Y. Ke

    2016-01-01

    Full Text Available Polyhydroxyalkanoates are a family of natural polyesters being produced as intracellular carbon and energy reserves by a wide variety of microorganisms. They have developed rapidly in both research and development efforts globally in the last 15 years. Till now, over 100 different types of PHAs have been successfully biosynthesized using both genetic engineering and fermentation techniques. Their unique biodegradable, biocompatible and thermoplastic characteristics make PHAs promising candidates for the commodity and biomedical applications. This review focused on the chemical synthesis of the derivatives of the biosynthesized PHAs.

  3. Production of functionalized polyhydroxyalkanoates by genetically modified Methylobacterium extorquens strains

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    Miguez Carlos B

    2010-09-01

    Full Text Available Abstract Background Methylotrophic (methanol-utilizing bacteria offer great potential as cell factories in the production of numerous products from biomass-derived methanol. Bio-methanol is essentially a non-food substrate, an advantage over sugar-utilizing cell factories. Low-value products as well as fine chemicals and advanced materials are envisageable from methanol. For example, several methylotrophic bacteria, including Methylobacterium extorquens, can produce large quantities of the biodegradable polyester polyhydroxybutyric acid (PHB, the best known polyhydroxyalkanoate (PHA. With the purpose of producing second-generation PHAs with increased value, we have explored the feasibility of using M. extorquens for producing functionalized PHAs containing C-C double bonds, thus, making them amenable to future chemical/biochemical modifications for high value applications. Results Our proprietary M. extorquens ATCC 55366 was found unable to yield functionalized PHAs when fed methanol and selected unsaturated carboxylic acids as secondary substrates. However, cloning of either the phaC1 or the phaC2 gene from P. fluorescens GK13, using an inducible and regulated expression system based on cumate as inducer (the cumate switch, yielded recombinant M. extorquens strains capable of incorporating modest quantities of C-C double bonds into PHA, starting from either C6= and/or C8=. The two recombinant strains gave poor results with C11=. The strain containing the phaC2 gene was better at using C8= and at incorporating C-C double bonds into PHA. Solvent fractioning indicated that the produced polymers were PHA blends that consequently originated from independent actions of the native and the recombinant PHA synthases. Conclusions This work constitutes an example of metabolic engineering applied to the construction of a methanol-utilizing bacterium capable of producing functionalized PHAs containing C-C double bonds. In this regard, the PhaC2 synthase

  4. Effect of process variables on the production of Polyhydroxyalkanoates by activated sludge

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    Mokhtarani Nader

    2012-09-01

    Full Text Available Abstract Polyhydroxyalkanoates are known to be temporarily stored by microorganisms in activated sludge, especially in anaerobic-aerobic processes. Due to the problems resulted from the disposals of plastic wastes and excess sludge of wastewater treatment plants, the production of polyhydroxyalkanoates by treating activated sludge and determining the effect of process variables were the main issues of this paper. In this research, an anaerobic-aerobic sequencing batch reactor was used to make microorganism adapted and a batch aerobic reactor was used for enriching them. The variables affecting polyhydroxyalkanoates production including aeration time, sludge retention time, and volatile fatty acids concentration of the influent in sequencing batch reactor, and also carbon to nitrogen ratio and cultivation time in polymer production reactor, were investigated using Taguchi statistical approach to determine optimum conditions. The maximum polymer production of 29% was achieved at sludge retention time of 5–10 days, aeration time of 2 hours, supplementation of 40% of volatile fatty acids in the influent and increasing of carbon to nitrogen ratio of polymer production reactor to above 25 g/g. Based on the results, in optimum conditions, the volatile fatty acids concentration which increased the production of polyhydroxyalkanoates up to 49% was the most effective variable. Carbon to nitrogen ratio, sludge retention time and aeration time were ranked as the next affecting parameters. Although the polyhydroxyalkanoates content achieved in present study is much lower than that by pure culture, but the proposed method may still serve well as an environmental friendly means to convert waste into valuable product.

  5. Effect of Process Variables on the Production of Polyhydroxyalkanoates by Activated Sludge

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    Nader Mokhtarani

    2012-09-01

    Full Text Available Polyhydroxyalkanoates are known to be temporarily stored by microorganisms in activated sludge, especially in anaerobic-aerobic processes. Due to the problems resulted from the disposals of plastic wastes and excess sludge of wastewater treatment plants, the production of polyhydroxyalkanoates by treating activated sludge anddetermining the effect of process variables were the main issues of this paper. In this research, an anaerobic-aerobic sequencing batch reactor was used to make microorganism adapted and a batch aerobic reactor was used for enriching them. The variables affecting polyhydroxyalkanoates production including aeration time, sludge retention time, and volatile fatty acids concentration of the influent in sequencing batch reactor, and also carbon to nitrogenratio and cultivation time in polymer production reactor, were investigated using Taguchi statistical approach to determine optimum conditions. The maximum polymer production of 29% was achieved at sludge retention time of 5–10 days, aeration time of 2 hours, supplementation of 40% of volatile fatty acids in the influent and increasing of carbon to nitrogen ratio of polymer production reactor to above 25 g/g. Based on the results, in optimum conditions, the volatile fatty acids concentration which increased the production of polyhydroxyalkanoates up to 49% was the most effective variable. Carbon to nitrogen ratio, sludge retention time and aeration time were ranked as the next affecting parameters. Although the polyhydroxyalkanoates content achieved in present study is muchlower than that by pure culture, but the proposed method may still serve well as an environmental friendly means to convert waste into valuable product.

  6. Synthetic Biology of Polyhydroxyalkanoates (PHA).

    Science.gov (United States)

    Meng, De-Chuan; Chen, Guo-Qiang

    Microbial polyhydroxyalkanoates (PHA) are a family of biodegradable and biocompatible polyesters which have been extensively studied using synthetic biology and metabolic engineering methods for improving production and for widening its diversity. Synthetic biology has allowed PHA to become composition controllable random copolymers, homopolymers, and block copolymers. Recent developments showed that it is possible to establish a microbial platform for producing not only random copolymers with controllable monomers and their ratios but also structurally defined homopolymers and block copolymers. This was achieved by engineering the genome of Pseudomonas putida or Pseudomonas entomophiles to weaken the β-oxidation and in situ fatty acid synthesis pathways, so that a fatty acid fed to the bacteria maintains its original chain length and structures when incorporated into the PHA chains. The engineered bacterium allows functional groups in a fatty acid to be introduced into PHA, forming functional PHA, which, upon grafting, generates endless PHA variety. Recombinant Escherichia coli also succeeded in producing efficiently poly(3-hydroxypropionate) or P3HP, the strongest member of PHA. Synthesis pathways of P3HP and its copolymer P3HB3HP of 3-hydroxybutyrate and 3-hydroxypropionate were assembled respectively to allow their synthesis from glucose. CRISPRi was also successfully used to manipulate simultaneously multiple genes and control metabolic flux in E. coli to obtain a series of copolymer P3HB4HB of 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB). The bacterial shapes were successfully engineered for enhanced PHA accumulation.

  7. Antibiotics-free stable polyhydroxyalkanoate (PHA) production from carbon dioxide by recombinant cyanobacteria.

    Science.gov (United States)

    Akiyama, Hideo; Okuhata, Hiroshi; Onizuka, Takuo; Kanai, Shozo; Hirano, Masahiko; Tanaka, Satoshi; Sasaki, Ken; Miyasaka, Hitoshi

    2011-12-01

    A practical antibiotics-free plasmid expression system in cyanobacteria was developed by using the complementation of cyanobacterial recA null mutation with the EscherichiacolirecA gene on the plasmid. This system was applied to the production of polyhydroxyalkanoate (PHA), a biodegradable plastic, and the transgenic cyanobacteria stably maintained the pha genes for PHA production in the antibiotics-free medium, and accumulated up to 52% cell dry weight of PHA. Copyright © 2011 Elsevier Ltd. All rights reserved.

  8. Differential sensitivity of polyhydroxyalkanoate producing bacteria to fermentation inhibitors and comparison of polyhydroxybutyrate production from Burkholderia cepacia and Pseudomonas pseudoflava

    OpenAIRE

    Dietrich, Diane; Illman, Barbara; Crooks, Casey

    2013-01-01

    Background The aim of this study is determine the relative sensitivity of a panel of seven polyhydroxyalkanoate producing bacteria to a panel of seven lignocellulosic-derived fermentation inhibitors representing aliphatic acids, furans and phenolics. A further aim was to measure the polyhydroxybutyrate production of select organisms on lignocellulosic-derived monosaccharides arabinose, xylose, glucose and mannose. Findings We examined the sensitivity of seven polyhydroxyalkanoate producing ba...

  9. Production of Polyhydroxyalkanoates from Sludge Palm Oil Using Pseudomonas putida S12.

    Science.gov (United States)

    Kang, Du-Kyeong; Lee, Cho-Ryong; Lee, Sun Hee; Bae, Jung-Hoon; Park, Young-Kwon; Rhee, Young Ha; Sung, Bong Hyun; Sohn, Jung-Hoon

    2017-05-28

    Polyhydroxyalkanoates (PHAs) are biodegradable plastics produced by bacteria, but their use in diverse applications is prohibited by high production costs. To reduce these costs, the conversion by Pseudomonas strains of P HAs from crude s ludge p alm oil ( SPO) a s an inexpensive renewable raw material was tested. Pseudomonas putida S12 was found to produce the highest yield (~41%) of elastomeric medium-chain-length (MCL)-PHAs from SPO. The MCL-PHA characteristics were analyzed by gas-chromatography/mass spectrometry, gel permeation chromatography, and differential scanning calorimetry. These findings may contribute to more widespread use of PHAs by reducing PHA production costs.

  10. Statistical media design for efficient polyhydroxyalkanoate production in Pseudomonas sp. MNNG-S.

    Science.gov (United States)

    Saranya, V; Rajeswari, V; Abirami, P; Poornimakkani, K; Suguna, P; Shenbagarathai, R

    2016-07-03

    Polyhydroxyalkanoate (PHA) is a promising polymer for various biomedical applications. There is a high need to improve the production rate to achieve end use. When a cost-effective production was carried out with cheaper agricultural residues like molasses, traces of toxins were incorporated into the polymer, which makes it unfit for biomedical applications. On the other hand, there is an increase in the popularity of using chemically defined media for the production of compounds with biomedical applications. However, these media do not exhibit favorable characteristics such as efficient utilization at large scale compared to complex media. This article aims to determine the specific nutritional requirement of Pseudomonas sp. MNNG-S for efficient production of polyhydroxyalkanoate. Response surface methodology (RSM) was used in this study to statistically design for PHA production based on the interactive effect of five significant variables (sucrose; potassium dihydrogen phosphate; ammonium sulfate; magnesium sulfate; trace elements). The interactive effects of sucrose with ammonium sulfate, ammonium sulfate with combined potassium phosphate, and trace element with magnesium sulfate were found to be significant (p production more than fourfold (from 0.85 g L(-1) to 4.56 g L(-1)).

  11. Perspectives on the production of polyhydroxyalkanoates in biorefineries associated with the production of sugar and ethanol.

    Science.gov (United States)

    Silva, Luiziana Ferreira; Taciro, Marilda Keico; Raicher, Gil; Piccoli, Rosane Aparecida Moniz; Mendonça, Thatiane Teixeira; Lopes, Mateus Schreiner Garcez; Gomez, José Gregório Cabrera

    2014-11-01

    Polyhydroxyalkanoates (PHA) are biodegradable and biocompatible bacterial thermoplastic polymers that can be obtained from renewable resources. The high impact of the carbon source in the final cost of this polymer has been one of the major limiting factors for PHA production and agricultural residues, mainly lignocellulosic materials, have gained attention to overcome this problem. In Brazil, production of 2nd generation ethanol from the glucose fraction, derived from sugarcane bagasse hydrolysate has been studied. The huge amounts of remaining xylose will create an opportunity for the development of other bioprocesses, generating new products to be introduced into a biorefinery model. Although PHA production from sucrose integrated to a 1G ethanol and sugar mill has been proposed in the past, the integration of the process of 2G ethanol in the context of a biorefinery will provide enormous amounts of xylose, which could be applied to produce PHA, establishing a second-generation of PHA production process. Those aspects and perspectives are presented in this article. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Novel approach for productivity enhancement of polyhydroxyalkanoates (PHA) production by Cupriavidus necator DSM 545.

    Science.gov (United States)

    Berezina, Nathalie

    2013-01-25

    In the global context of increased concerns for our environment, the use of bioplastics as a replacement for existing petroleum-based polymers is an important challenge. Indeed, bioplastics hardly meet economical and technical constraints. One, of the most promising among currently studied bioplastics, is the polyhydroxyalkanoate (PHA). To circumvent the economical issue for this particular biopolymer one solution can be the enhancement of the overall productivity by the improvement of the nutritional medium of the microorganism producing the biopolymer. Thus, several nutrition media, supplemented or not with sodium glutamate, were tested for the growth and the PHA production by Cupriavidus necator DSM 545 strain. The most efficient for the biomass and the PHA production improvement were found to be the Luria broth (LB) and the Bonnarme's media, both supplemented with 10 g/L sodium glutamate. Hence the overall productivity was 33 times enhanced comparing to traditional cultivation methods. These results open a new route for the PHA production by C. necator which appears to be more suitable on a rich, or enriched, medium with no limiting factors. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Differential sensitivity of polyhydroxyalkanoate producing bacteria to fermentation inhibitors and comparison of polyhydroxybutyrate production from Burkholderia cepacia and Pseudomonas pseudoflava

    Science.gov (United States)

    Diane Dietrich; Barbara Illman; Casey Crooks

    2013-01-01

    The aim of this study is determine the relative sensitivity of a panel of seven polyhydroxyalkanoate producing bacteria to a panel of seven lignocellulosic-derived fermentation inhibitors representing aliphatic acids, furans and phenolics. A further aim was to measure the polyhydroxybutyrate production of select organisms on lignocellulosic-derived monosaccharides...

  14. Biofilm lifestyle enhances diesel bioremediation and biosurfactant production in the Antarctic polyhydroxyalkanoate producer Pseudomonas extremaustralis.

    Science.gov (United States)

    Tribelli, Paula M; Di Martino, Carla; López, Nancy I; Raiger Iustman, Laura J

    2012-09-01

    Diesel is a widely distributed pollutant. Bioremediation of this kind of compounds requires the use of microorganisms able to survive and adapt to contaminated environments. Pseudomonas extremaustralis is an Antarctic bacterium with a remarkable survival capability associated to polyhydroxyalkanoates (PHAs) production. This strain was used to investigate the effect of cell growth conditions--in biofilm versus shaken flask cultures--as well as the inocula characteristics associated with PHAs accumulation, on diesel degradation. Biofilms showed increased cell growth, biosurfactant production and diesel degradation compared with that obtained in shaken flask cultures. PHA accumulation decreased biofilm cell attachment and enhanced biosurfactant production. Degradation of long-chain and branched alkanes was observed in biofilms, while in shaken flasks only medium-chain length alkanes were degraded. This work shows that the PHA accumulating bacterium P. extremaustralis can be a good candidate to be used as hydrocarbon bioremediation agent, especially in extreme environments.

  15. Enhancing the Production of Polyhydroxyalkanoate Biopolymer by Azohydromonas Australica Using a Simple Empty and Fill Bioreactor Cultivation Strategy

    OpenAIRE

    G. Gahlawat; A. K. Srivastava

    2018-01-01

    Polyhydroxyalkanoates (PHAs) are biodegradable polymers which are considered as an effective alternative for conventional plastics due to their mechanical properties similar to the latter. However, widespread use of these polymers is still hampered due to their high cost of production. This shortcoming could partly be resolved by obtaining high yields and productivity. In the present study, a drain-and-fill strategy of repeated-batch cultivation was adopted for the enhanced production of p...

  16. A techno-economic analysis of polyhydroxyalkanoate and hydrogen production from syngas fermentation of gasified biomass.

    Science.gov (United States)

    Choi, DongWon; Chipman, David C; Bents, Scott C; Brown, Robert C

    2010-02-01

    A techno-economic analysis was conducted to investigate the feasibility of a gasification-based hybrid biorefinery producing both hydrogen gas and polyhydroxyalkanoates (PHA), biodegradable polymer materials that can be an attractive substitute for conventional petrochemical plastics. The biorefinery considered used switchgrass as a feedstock and converted that raw material through thermochemical methods into syngas, a gaseous mixture composed mainly of hydrogen and carbon monoxide. The syngas was then fermented using Rhodospirillum rubrum, a purple non-sulfur bacterium, to produce PHA and to enrich hydrogen in the syngas. Total daily production of the biorefinery was assumed to be 12 Mg of PHA and 50 Mg of hydrogen gas. Grassroots capital for the biorefinery was estimated to be $55 million, with annual operating costs at $6.7 million. With a market value of $2.00/kg assumed for the hydrogen, the cost of producing PHA was determined to be $1.65/kg.

  17. Recycling of Waste Streams of the Biotechnological Poly(hydroxyalkanoate Production by Haloferax mediterranei on Whey

    Directory of Open Access Journals (Sweden)

    Martin Koller

    2015-01-01

    Full Text Available For manufacturing “bioplastics” such as poly(hydroxyalkanoates (PHA, the combination of utilization of inexpensive carbon sources with the application of robust microbial production strains is considered a decisive step to make this process more cost-efficient and sustainable. PHA production based on surplus whey from dairy industry was accomplished by the extremely halophile archaeon Haloferax mediterranei. After fermentative production of PHA-rich biomass and the subsequent cell harvest and downstream processing for PHA recovery, environmentally hazardous, highly saline residues, namely spent fermentation broth and cell debris, remain as residues. These waste streams were used for recycling experiments to assess their recyclability in subsequent production processes. It was demonstrated that spent fermentation broth can be used to replace a considerable part of fresh saline fermentation medium in subsequent production processes. In addition, 29% of the expensive yeast extract, needed as nitrogen and phosphate source for efficient cultivation of the microorganism, can be replaced by cell debris from prior cultivations. The presented study provides strategies to combine the reduction of costs for biomediated PHA production with minimizing ecological risks by recycling precarious waste streams. Overall, the presented work shall contribute to the quick economic success of these promising biomaterials.

  18. Pseudomonas pseudoalcaligenes CECT5344, a cyanide-degrading bacterium with by-product (polyhydroxyalkanoates) formation capacity.

    Science.gov (United States)

    Manso Cobos, Isabel; Ibáñez García, María Isabel; de la Peña Moreno, Fernando; Sáez Melero, Lara Paloma; Luque-Almagro, Víctor Manuel; Castillo Rodríguez, Francisco; Roldán Ruiz, María Dolores; Prieto Jiménez, María Auxiliadora; Moreno Vivián, Conrado

    2015-06-10

    Cyanide is one of the most toxic chemicals produced by anthropogenic activities like mining and jewelry industries, which generate wastewater residues with high concentrations of this compound. Pseudomonas pseudoalcaligenes CECT5344 is a model microorganism to be used in detoxification of industrial wastewaters containing not only free cyanide (CN(-)) but also cyano-derivatives, such as cyanate, nitriles and metal-cyanide complexes. Previous in silico analyses suggested the existence of genes putatively involved in metabolism of short chain length (scl-) and medium chain length (mcl-) polyhydroxyalkanoates (PHAs) located in three different clusters in the genome of this bacterium. PHAs are polyesters considered as an alternative of petroleum-based plastics. Strategies to optimize the bioremediation process in terms of reducing the cost of the production medium are required. In this work, a biological treatment of the jewelry industry cyanide-rich wastewater coupled to PHAs production as by-product has been considered. The functionality of the pha genes from P. pseudoalcaligenes CECT5344 has been demonstrated. Mutant strains defective in each proposed PHA synthases coding genes (Mpha(-), deleted in putative mcl-PHA synthases; Spha(-), deleted in the putative scl-PHA synthase) were generated. The accumulation and monomer composition of scl- or mcl-PHAs in wild type and mutant strains were confirmed by gas chromatography-mass spectrometry (GC-MS). The production of PHAs as by-product while degrading cyanide from the jewelry industry wastewater was analyzed in batch reactor in each strain. The wild type and the mutant strains grew at similar rates when using octanoate as the carbon source and cyanide as the sole nitrogen source. When cyanide was depleted from the medium, both scl-PHAs and mcl-PHAs were detected in the wild-type strain, whereas scl-PHAs or mcl-PHAs were accumulated in Mpha(-) and Spha(-), respectively. The scl-PHAs were identified as homopolymers of 3

  19. Syngas obtained by microwave pyrolysis of household wastes as feedstock for polyhydroxyalkanoate production in Rhodospirillum rubrum.

    Science.gov (United States)

    Revelles, Olga; Beneroso, Daniel; Menéndez, J Angel; Arenillas, Ana; García, J Luis; Prieto, M Auxiliadora

    2017-11-01

    The massive production of urban and agricultural wastes has promoted a clear need for alternative processes of disposal and waste management. The potential use of municipal solid wastes (MSW) as feedstock for the production of polyhydroxyalkanoates (PHA) by a process known as syngas fermentation is considered herein as an attractive bio-economic strategy to reduce these wastes. In this work, we have evaluated the potential of Rhodospirillum rubrum as microbial cell factory for the synthesis of PHA from syngas produced by microwave pyrolysis of the MSW organic fraction from a European city (Seville). Growth rate, uptake rate, biomass yield and PHA production from syngas in R. rubrum have been analysed. The results revealed the strong robustness of this syngas fermentation where the purity of the syngas is not a critical constraint for PHA production. Microwave-induced pyrolysis is a tangible alternative to standard pyrolysis, because it can reduce cost in terms of energy and time as well as increase syngas production, providing a satisfactory PHA yield. © 2016 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

  20. Polyhydroxyalkanoates production with Ralstonia eutropha from low quality waste animal fats.

    Science.gov (United States)

    Riedel, Sebastian L; Jahns, Stefan; Koenig, Steven; Bock, Martina C E; Brigham, Christopher J; Bader, Johannes; Stahl, Ulf

    2015-11-20

    Polyhydroxyalkanoates (PHAs) are biodegradable and biocompatible polyesters considered as alternatives to petroleum-based plastics. Ralstonia eutropha is a model organism for PHA production. Utilizing industrially rendered waste animal fats as inexpensive carbon feedstocks for PHA production is demonstrated here. An emulsification strategy, without any mechanical or chemical pre-treatment, was developed to increase the bioavailability of solid, poorly-consumable fats. Wild type R. eutropha strain H16 produced 79-82% (w/w) polyhydroxybutyrate (PHB) per cell dry weight (CDW) when cultivated on various fats. A productivity of 0.3g PHB/(L × h) with a total PHB production of 24 g/L was achieved using tallow as carbon source. Using a recombinant strain of R. eutropha that produces poly(hydroxybutyrate-co-hydroxyhexanoate) [P(HB-co-HHx)], 49-72% (w/w) of PHA per CDW with a HHx content of 16-27 mol% were produced in shaking flask experiments. The recombinant strain was grown on waste animal fat of the lowest quality available at lab fermenter scale, resulting in 45 g/L CDW with 60% (w/w) PHA per CDW and a productivity of 0.4 g PHA/(L × h). The final HHx content of the polymer was 19 mol%. The use of low quality waste animal fats as an inexpensive carbon feedstock exhibits a high potential to accelerate the commercialization of PHAs. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Differential sensitivity of polyhydroxyalkanoate producing bacteria to fermentation inhibitors and comparison of polyhydroxybutyrate production from Burkholderia cepacia and Pseudomonas pseudoflava.

    Science.gov (United States)

    Dietrich, Diane; Illman, Barbara; Crooks, Casey

    2013-06-04

    The aim of this study is determine the relative sensitivity of a panel of seven polyhydroxyalkanoate producing bacteria to a panel of seven lignocellulosic-derived fermentation inhibitors representing aliphatic acids, furans and phenolics. A further aim was to measure the polyhydroxybutyrate production of select organisms on lignocellulosic-derived monosaccharides arabinose, xylose, glucose and mannose. We examined the sensitivity of seven polyhydroxyalkanoate producing bacteria: Azohydromonas lata, Bacillus megaterium, Bacillus cereus, Burkholderia cepacia, Pseudomonas olevorans, Pseudomonas pseudoflava and Ralstonia eutropha, against seven fermentation inhibitors produced by the saccharification of lignocellulose: acetic acid, levulinic acid, coumaric acid, ferulic acid, syringaldehyde, furfural, and hyroxymethyfurfural. There was significant variation in the sensitivity of these microbes to representative phenolics ranging from 0.25-1.5 g/L coumaric and ferulic acid and between 0.5-6.0 g/L syringaldehyde. Inhibition ranged from 0.37-4 g/L and 0.75-6 g/L with acetic acid and levulinic acid, respectively. B. cepacia and P. pseudoflava were selected for further analysis of polyhydroxyalkanoate production. We find significant differences in sensitivity to the fermentation inhibitors tested and find these variations to be over a relevant concentration range given the concentrations of inhibitors typically found in lignocellulosic hydrolysates. Of the seven bacteria tested, B. cepacia demonstrated the greatest inhibitor tolerance. Similarly, of two organisms examined for polyhydroxybutyrate production, B. cepacia was notably more efficient when fermenting pentose substrates.

  2. Production and optimization of polyhydroxyalkanoates from non-edible Calophyllum inophyllum oil using Cupriavidus necator.

    Science.gov (United States)

    Arumugam, A; Senthamizhan, S G; Ponnusami, V; Sudalai, S

    2018-06-01

    Polyhydroxyalkanoates (PHA) are biodegradable polymers found in the cellular masses of a wide range of bacterial species and the demand for PHA is steadily growing. In this work we have produced PHA from a low-cost substrate, Calophyllum inophyllum oil, using Cupriavidus necator. Effects of various process parameters such as Oil concentration, Nitrogen source and inoculum size on the production of PHA were studied using Response Surface Methodology. A quadratic equation was used in the model to fit the experimental data. It was found that the model could satisfactorily predict the PHA yield (R 2 =99.17%). Linear, quadratic and interaction terms used in the model were found to be statistically significant. Maximum PHA yield of 10.6gL -1 was obtained under the optimized conditions of oil concentration - 17.5%, inoculum concentration - 50mL/L and nitrogen content - 1.125gL -1 , respectively. The product obtained was characterized using FTIR and NMR to confirm that it was PHA. The results demonstrate that C. inophyllum oil, a non-edible oil, can be potentially used as a low-cost substrate for the production of PHA. Copyright © 2018 Elsevier B.V. All rights reserved.

  3. Genome-engineered Sinorhizobium meliloti for the production of poly(lactic-co-3-hydroxybutyric) acid copolymer.

    Science.gov (United States)

    Tran, Tam T; Charles, Trevor C

    2016-02-01

    Economically competitive commercial production of biodegradable bioplastics with desirable properties is an important goal. In this study, we demonstrate the use of chromosome engineering of an alternative bacterial host, Sinorhizobium meliloti, for production of the copolymer, poly(lactate-co-3-hydroxybutyrate). Codon-optimized genes for 2 previously engineered enzymes, Clostridium propionicum propionate CoA transferase (Pct532Cp) and Pseudomonas sp. strain MBEL 6-19 polyhydroxyalkanoate (PHA) synthase 1 (PhaC1400Ps6-19), were introduced into S. meliloti Rm1021 by chromosome integration, replacing the native phbC gene. On the basis of phenotypic analysis and detection of polymer product by gas chromatography analysis, synthesis and accumulation of the copolymer was confirmed. The chromosome integrant strain, with the introduced genes under the control of the native phbC promoter, is able to produce over 15% cell dry mass of poly(lactate-co-3-hydroxybutyrate), containing 30 mol% lactate, from growth on mannitol. We were also able to purify the polymer from the culture and confirm the structure by NMR and GC-MS. To our knowledge, this is the first demonstration of production of this copolymer in the Alphaproteobacteria. Further optimization of this system may eventually yield strains that are able to produce economically viable commercial product.

  4. Perspectives on the production, structural characteristics and potential applications of bioplastics derived from polyhydroxyalkanoates.

    Science.gov (United States)

    Albuquerque, Priscilla B S; Malafaia, Carolina B

    2018-02-01

    Since the last two decades, the use of synthetic materials has increased and become more frequent in this capitalist system. Polymers used as raw materials are usually disposed very rapidly and considered serious damages when they return to the environment. Because of this behaviour, there was an increasing in the global awareness by minimizing the waste generated, in addition to the scientific community concern for technological alternatives to solve this problem. Alternatively, biodegradable polymers are attracting special interest due to their inherent properties, which are similar to the ones of the conventional plastics. Bioplastics covers plastics made from renewable resources, including plastics that biodegrade under controlled conditions at the end of their use phase. Polyhydroxyalkanoates (PHAs) are polyesters composed of hydroxy acids, synthesized by a variety of microorganisms as intracellular carbon and energy storage. These environmentally friendly biopolymers have excellent potential in domestic, agricultural, industrial and medical field, however their production on a large scale is still limited. This review considered the most recent scientific publications on the production of bioplastics based on PHAs, their structural characteristics and the exploitation of different renewable sources of raw materials. In addition, there were also considered the main biotechnological applications of these biopolymers. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Polyhydroxyalkanoate production by a novel bacterium Massilia sp. UMI-21 isolated from seaweed, and molecular cloning of its polyhydroxyalkanoate synthase gene.

    Science.gov (United States)

    Han, Xuerong; Satoh, Yasuharu; Kuriki, Yumi; Seino, Teruyuki; Fujita, Shinji; Suda, Takanori; Kobayashi, Takanori; Tajima, Kenji

    2014-11-01

    We successfully isolated one microorganism (UMI-21) from Ulva, a green algae that contains starch. The strain UMI-21 can produce polyhydroxyalkanoate (PHA) from starch, maltotriose, or maltose as a sole carbon source. Taxonomic studies and 16S rDNA sequence analysis revealed that strain UMI-21 was phylogenetically related to species of the genus Massilia. The PHA content under the cultivation condition using a 10-L jar fermentor was 45.5% (w/w). This value was higher than that obtained after cultivation in a flask, suggesting the possibility of large-scale PHA production by UMI-21 from starch. A major issue for the industrial production of microbial PHAs is the very high production cost. Starch is a relatively inexpensive substrate that is also found in abundant seaweeds such as Ulva. Therefore, the strain isolated in this study may be very useful for producing PHA from seaweeds containing polysaccharides such as starch. In addition, a 3.7-kbp DNA fragment containing the whole PHA synthase gene (phaC) was obtained from the strain UMI-21. The results of open reading frame (ORF) analysis suggested that the DNA fragment contained two ORFs, which were composed of 1740 (phaC) and 564 bp (phaR). The deduced amino acid sequence of PhaC from strain UMI-21 shared high similarity with PhaC from Ralstonia eutropha, which is a representative PHA-producing bacterium with a class I PHA synthase. This is the first report for the cloning of the PHA synthase gene from Massilia species. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  6. Variation analysis of bacterial polyhydroxyalkanoates production using saturated and unsaturated hydrocarbons

    Directory of Open Access Journals (Sweden)

    Saiqa Tufail

    Full Text Available ABSTRACT Polyhydroxyalkanoates (PHA are efficient, renewable and environment friendly polymeric esters. These polymers are synthesized by a variety of microbes under stress conditions. This study was carried out to check the suitability of waste frying oil in comparison to other oils for economical bioplastic production. Six bacterial strains were isolated and identified as Bacillus cereus (KF270349, Klebsiella pneumoniae (KF270350, Bacillus subtilis (KF270351, Brevibacterium halotolerance (KF270352, Pseudomonas aeruginosa (KF270353, and Stenotrophomonas rhizoposid (KF270354 by ribotyping. All strains were PHA producers so were selected for PHA synthesis using four different carbon sources, i.e., waste frying oil, canola oil, diesel and glucose. Extraction of PHA was carried out using sodium hypochlorite method and maximum amount was detected after 72 h in all cases. P. aeruginosa led to maximum PHA production after 72 h at 37 °C and 100 rpm using waste frying oil that was 53.2% PHA in comparison with glucose 37.8% and cooking oil 34.4%. B. cereus produced 40% PHA using glucose as carbon source which was high when compared against other strains. A significantly lesser amount of PHA was recorded with diesel as a carbon source for all strains. Sharp Infrared peaks around 1740-1750 cm-1 were present in Fourier Transform Infrared spectra that correspond to exact position for PHA. The use of waste oils and production of poly-3hydroxybutyrate-co-3hydroxyvalerate (3HB-co-3HV by strains used in this study is a good aspect to consider for future prospects as this type of polymer has better properties as compared to PHBs.

  7. Evaluation of Factors Affecting Polyhydroxyalkanoates Production by Comamonas sp. EB172 Using Central Composite Design

    Directory of Open Access Journals (Sweden)

    Noor Azman Mohd Johar

    2012-09-01

    Full Text Available Aims: Statistical approach, central composite design (CCD was used to investigate the complex interaction among temperature (25-37 °C, initial medium pH (5-9, inoculum size (4-10 % (v/v, concentration of (NH42SO4 (0-1 g/L and concentration of mixed organic acids (5-10 g/L in the production of polyhydroxyalkanoates by Comamonas sp. EB172.Methodology and Results: Mixed organic acids derived from anaerobically treated palm oil mill effluent (POME containing acetic:propionic:butyric (ratio of 3:1:1 were used as carbon source in the batch culture of Comamonas sp. EB172 to produce polyhydoxyalkanoates (PHAs. The analysis of variance (ANOVA showed that all five factors were significantly important in the batch fermentation by shake flask with a P value of less than 0.001. The optimal temperature, initial medium pH, inoculum size, concentration of (NH42SO4 and concentration of mixed organic acids were 30 °C, 7.04, 4.0 % (v/v, 0.01 g/L and 5.05 g/L respectively.Conclusion, significance and impact of study: Optimization of the production medium containing mixed organic acids has improved the PHA production for more than 2 folds. Under optimal condition in the shake flask fermentation, the predicted growth is 2.98 g/L of dry cell weight (DCW with 47.07 wt % of PHA content. The highest yield of PHA was 0.28 g of PHA per g mixed organic acids.

  8. Commercialization of bacterial cell factories for the sustainable production of polyhydroxyalkanoate thermoplastics: progress and prospects.

    Science.gov (United States)

    Kumar, Abhishek; Srivastava, Janmejai K; Mallick, Nirupama; Singh, Akhilesh K

    2015-01-01

    Ubiquitous conventional plastics, generally manufactured from finite, nonsustainable fossil fuels are non-biodegradable wonder entities but their ill effect on Mother Nature has subsequently raised major environmental concerns like their safe disposal, solid waste management and several potential hazards. Such concerns have fuelled initiatives for research globally towards development of sustainable and eco-friendly bioplastics. The new generation of plastics called 'bioplastics' are polymers of long chain of repeating monomer units that are classified as photodegradable, semi-biodegradable, chemically synthesized and polyhydroxyalkanoates (PHAs). The commonly emerged novel bioplastics are polyesters of hydroxyalkanoates (HAs) called PHAs, which are lipoidic storage materials found in the cytosol of vast and diverse forms of bacteria. Among 150 different PHAs known so far, poly- 3-hydroxybutyrate is the most common and comprehensively characterized PHA. Interestingly, PHAs are only completely biodegradable plastics with material properties comparable to conventional plastics that can be achieved by regulating the co-monomers incorporation into PHAs backbone. PHA bioplastics are exploited in the form of user-friendly goods viz. films, absorbable sutures, bone plates, drug carriers, etc. Besides advantages, such useful entity(s) has major shortcomings as well like high production cost compared to conventional plastics. Precisely, in PHAs production, about fifty percent of the overall price is due to the carbon substrates. Consequently, exploring novel cost-effective substrates is a major compulsion for successful commercialization of this bioplastic, which is anticipated to reduce the cost of production as a result of advancing and intensifying research work. This review presents an insight and patent developments in the field of PHAs bioplastics.

  9. Utilization of cellulosic waste from tequila bagasse and production of polyhydroxyalkanoate (PHA) bioplastics by Saccharophagus degradans.

    Science.gov (United States)

    Alva Munoz, Luis Esteban; Riley, Mark R

    2008-08-01

    Utilization of wastes from agriculture is becoming increasingly important due to concerns of environmental impact. The goals of this work were to evaluate the ability of an unusual organism, Saccharophagus degradans (ATCC 43961), to degrade the major components of plant cell walls and to evaluate the ability of S. degradans to produce polyhydroxyalkanoates (PHAs, also known as bioplastics). S. degradans can readily attach to cellulosic fibers, degrade the cellulose, and utilize this as the primary carbon source. The growth of S. degradans was assessed in minimal media (MM) containing glucose, cellobiose, avicel, and bagasse with all able to support growth. Cells were able to attach to avicel and bagasse fibers; however, growth on these insoluble fibers was much slower and led to a lower maximal biomass production than observed with simple sugars. Lignin in MM alone did not support growth, but did support growth upon addition of glucose, although with an increased adaptation phase. When culture conditions were switched to a nitrogen depleted status, PHA production commences and extends for at least 48 h. At early stationary phase, stained inclusion bodies were visible and two chronologically increasing infrared light absorbance peaks at 1,725 and 1,741 cm(-1) confirmed the presence of PHAs. This work demonstrates for what we believe to be the first time, that a single organism can degrade insoluble cellulose and under similar conditions can produce and accumulate PHA. Additional work is necessary to more fully characterize these capabilities and to optimize the PHA production and purification. (c) 2008 Wiley Periodicals, Inc.

  10. Production and Characterization of Polyhydroxyalkanoates and Native Microorganisms Synthesized from Fatty Waste

    Directory of Open Access Journals (Sweden)

    Javier Ricardo Gómez Cardozo

    2016-01-01

    Full Text Available Polyhydroxyalkanoates (PHAs are biodegradable and biocompatible plastics. They are synthesized by a wide variety of microorganisms (i.e., fungi and bacteria and some organisms such as plants, which share characteristics with petrochemical-based plastics. The most recent studies focus on finding inexpensive substrates and extraction strategies that allow reducing product costs, thus moving into a widespread market, the market for petroleum-based plastics. In this study, the production of polyhydroxybutyrate (PHB was evaluated using the native strains, Bacillus megaterium, Bacillus sp., and Lactococcus lactis, and glycerol reagent grade (GRG, residual glycerol (RGSB byproduct of biodiesel from palm oil, Jatropha oil, castor oil, waste frying oils, and whey as substrates. Different bacteria-substrate systems were evaluated thrice on a laboratory scale under different conditions of temperature, pH, and substrate concentration, employing 50 mL of broth in 250 mL. The bacterial growth was tested in all systems; however, the B. megaterium GRG system generated the highest accumulation of PHA. The previous approach was allowed to propose a statistical design optimization with RGSB (i.e., RGSB, 15 g/L, pH 7.0, and 25°C. This system reached 2.80 g/L of PHB yield and was the optimal condition tested; however, the optimal biomass 5.42 g/L occurs at pH 9.0 and 25°C, with a substrate concentration of 22 g/L.

  11. Bacterial polyhydroxyalkanoates: Still fabulous?

    Science.gov (United States)

    Możejko-Ciesielska, Justyna; Kiewisz, Robert

    2016-11-01

    Bacterial polyhydroxyalkanoates (PHA) are polyesters accumulated as carbon and energy storage materials under limited growth conditions in the presence of excess carbon sources. They have been developed as biomaterials with unique properties for the past many years being considered as a potential substitute for conventional non-degradable plastics. Due to the increasing concern towards global climate change, depleting petroleum resource and problems with an utilization of a growing number of synthetic plastics, PHAs have gained much more attention from industry and research. These environmentally friendly microbial polymers have great potential in biomedical, agricultural, and industrial applications. However, their production on a large scale is still limited. This paper describes the backgrounds of PHAs and discussed the current state of knowledge on the polyhydroxyalkanoates. Ability of bacteria to convert different carbon sources to PHAs, the opportunities and challenges of their introduction to global market as valuable renewable products have been also discussed. Copyright © 2016 Elsevier GmbH. All rights reserved.

  12. Impact of nitrogen feeding regulation on polyhydroxyalkanoates production by mixed microbial cultures.

    Science.gov (United States)

    Silva, Fernando; Campanari, Sabrina; Matteo, Stefania; Valentino, Francesco; Majone, Mauro; Villano, Marianna

    2017-07-25

    A sequencing batch reactor (SBR) is typically used for selecting mixed microbial cultures (MMC) for polyhydroxyalkanoate (PHA) production. Since many waste streams suitable as process feedstock for PHA production are nitrogen-deficient, a nutrient supply in the SBR is typically required to allow for efficient microbial growth. The scope of this study was to devise a nitrogen feeding strategy which allows controlling the nitrogen levels during the feast and famine regime of a lab-scale SBR, thereby selecting for PHA-storing microorganisms. At the beginning of the cycle the reactor was fed with a synthetic mixture of acetic and propionic acids at an overall organic load rate of 8.5gCODL -1 d -1 (i.e. 260CmmolL -1 d -1 ), whereas nitrogen (in the form of ammonium sulphate) was added either simultaneously to the carbon feed (coupled feeding strategy) or after the end of the feast phase (uncoupled feeding strategy). As a main result, PHA production was more than doubled (up to about 1300±64mgCODL -1 ) when carbon and nitrogen were separately fed and the higher PHA production also corresponded to an 82% increase in the polymer HV content (up to 20±1%, wtwt -1 ). Three SBR runs were performed with the uncoupled carbon and nitrogen feeding at different carbon to nitrogen (C/N) ratios (of 14.3, 17.9, and 22.3CmolNmol -1 , respectively) which were varied by progressively reducing the concentration of the nitrogen feeding. In spite of a comparable PHA storage yield at 14.3 and 17.9CmolNmol -1 (0.41±0.05 gCOD PHA gCOD VFA -1 and 0.38±0.05 gCOD PHA gCOD VFA -1 , respectively), the storage response of the selected MMC significantly decreased when the C/N ratio was set at the highest investigated value. Notably, an increase in this parameter also resulted in a change in the HV content in the polymer regardless the composition of the organic acids solution. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Production of polyhydroxyalkanoates from methanol by a new methylotrophic bacterium Methylobacterium sp. GW2.

    Science.gov (United States)

    Yezza, A; Fournier, D; Halasz, A; Hawari, J

    2006-11-01

    A new bacterial strain, isolated from groundwater contaminated with explosives, was characterized as a pink-pigmented facultative methylotroph, affiliated to the genus Methylobacterium. The bacterial isolate designated as strain GW2 was found capable of producing the homopolymer poly-3-hydroxybutyrate (PHB) from various carbon sources such as methanol, ethanol, and succinate. Methanol acted as the best substrate for the production of PHB reaching 40 % w/w dry biomass. PHB accumulation was observed to be a growth-associated process, so that there was no need for two-step fermentation. Optimal growth occurred at 0.5 % (v/v) methanol concentration, and growth was strongly inhibited at alpha concentration above 2 % (v/v). Methylobacterium sp. strain GW2 was also able to accumulate the copolyester poly-3-hydroxybutyrate-poly-3-hydroxyvalerate (PHB/HV) when valeric acid was supplied as an auxiliary carbon source to methanol. After 66 h, a copolymer content of 30 % (w/w) was achieved with a PHB to PHV ratio of 1:2. Biopolymers produced by strain GW2 had an average molecular weight ranging from 229,350 to 233,050 Da for homopolymer PHB and from 362,430 to 411,300 Da for the copolymer PHB/HV.

  14. Evaluation of medium-chain-length polyhydroxyalkanoate production by Pseudomonas putida LS46 using biodiesel by-product streams.

    Science.gov (United States)

    Fu, Jilagamazhi; Sharma, Umesh; Sparling, Richard; Cicek, Nazim; Levin, David B

    2014-07-01

    Medium-chain-length polyhydroxyalkanoate (mcl-PHA) production by Pseudomonas putida LS46 was analyzed in shake-flask-based batch reactions, using pure chemical-grade glycerol (PG), biodiesel-derived "waste" glycerol (WG), and biodiesel-derived "waste" free fatty acids (WFA). Cell growth, substrate consumption, mcl-PHA accumulation within the cells, and the monomer composition of the synthesized biopolymers were monitored. The patterns of mcl-PHA synthesis in P. putida LS46 cells grown on PG and WG were similar but differed from that of cells grown with WFA. Polymer accumulation in glycerol-based cultures was stimulated by nitrogen limitation and plateaued after 48 h in both PG and WG cultures, with a total accumulation of 17.9% cell dry mass and 16.3% cell dry mass, respectively. In contrast, mcl-PHA synthesis was independent of nitrogen concentration in P. putida LS46 cells cultured with WFA, which accumulated to 29% cell dry mass. In all cases, the mcl-PHAs synthesized consisted primarily of 3-hydroxyoctanoate (C(8)) and 3-hydroxydecanoate (C(10)). WG and WFA supported similar or greater cell growth and mcl-PHA accumulation than PG under the experimental conditions used. These results suggest that biodiesel by-product streams could be used as low-cost carbon sources for sustainable mcl-PHA production.

  15. Polyhydroxyalkanoate production by a novel bacterium Massilia sp UMI-21 isolated from seaweed, and molecular cloning of its polyhydroxyalkanoate synthase gene

    OpenAIRE

    Han, Xuerong; Satoh, Yasuharu; Kuriki, Yumi; Seino, Teruyuki; Fujita, Shinji; Suda, Takanori; Kobayashi, Takanori; Tajima, Kenji

    2014-01-01

    We successfully isolated one microorganism (UMI-21) from Ulva, a green algae that contains starch. The strain UMI-21 can produce polyhydroxyalkanoate (PHA) from starch, maltotriose, or maltose as a sole carbon source. Taxonomic studies and 16S rDNA sequence analysis revealed that strain UMI-21 was phylogenetically related to species of the genus Massilia. The PHA content under the cultivation condition using a 10-L jar fermentor was 45.5% (w/w). This value was higher than that obtained after ...

  16. Production of Medium Chain Length Polyhydroxyalkanoates From Oleic Acid Using Pseudomonas putida PGA1 by Fed Batch Culture

    Directory of Open Access Journals (Sweden)

    Sidik Marsudi

    2010-10-01

    Full Text Available Bacterial polyhydroxyalkanoates (PHAs are a class of p0lymers currently receiving much attention because of their potential as renewable and biodegradable plastics. A wide variety of bacteria has been reported to produce PHAs including Pseudomonas strains. These strains are known as versatile medium chain length PHAs (PHAs-mcl producers using fatty acids as carbon source. Oleic acid was used to produce PHAs-mcl using Pseudomonas putida PGA 1 by continuous feeding of both nitrogen and carbon source, in a fed batch culture. During cell growth, PHAs also accumulated, indicating that PHA production in this organism is growth associated. Residual cell increased until the nitrogen source was depleted. At the end of fermentation, final cell concentration, PHA content, and roductivity were 30.2 g/L, 44.8 % of cell dry weight, and 0.188 g/l/h, respectively.

  17. Enhancing the Production of Polyhydroxyalkanoate Biopolymer by Azohydromonas Australica Using a Simple Empty and Fill Bioreactor Cultivation Strategy

    Directory of Open Access Journals (Sweden)

    G. Gahlawat

    2018-01-01

    Full Text Available Polyhydroxyalkanoates (PHAs are biodegradable polymers which are considered as an effective alternative for conventional plastics due to their mechanical properties similar to the latter. However, widespread use of these polymers is still hampered due to their high cost of production. This shortcoming could partly be resolved by obtaining high yields and productivity. In the present study, a drain-and-fill strategy of repeated-batch cultivation was adopted for the enhanced production of polyhydroxybutyrate PHB using Azohydromonas australica. In this strategy, 20 % (v/v of the culture broth was removed from the reactor and supplemented with an equal volume of fresh medium. This strategy demonstrated a 3.3 fold and 1.8 fold increase in PHB concentration and productivity, respectively, as compared to batch cultivation. Repeated cultivation had also the benefit of avoiding non-productive time required for cleaning, refilling and sterilization of bioreactor during batch, thereby increasing the overall volumetric productivity and industrial importance of the process.

  18. Analysis and optimization of process parameters for production of polyhydroxyalkanoates along with wastewater treatment by Serratia sp. ISTVKR1.

    Science.gov (United States)

    Gupta, Asmita; Kumar, Madan; Thakur, Indu Shekhar

    2017-10-01

    A previously reported biodegrading bacterial strain Serratia sp. ISTVKR1 was studied for polyhydroxyalkanoate (PHA) production along with wastewater contaminant removal. Nile red fluorescence, GC-MS, FT-IR, NMR and TEM confirmed the accumulation of homopolymer poly-3-hydroxyvalerate (PHV) within the bacterial cells. Analysis of culture after 72h of bacterial treatment showed maximum COD removal (8.4-fold), non-detection of organic contaminants such as 1H-Cyclopropa [a] naphthalene (R.T.=10.12) using GC-MS and increased proportion of elements like Cr, Mn, Fe, Ni, Cu, Cd and Pb in the bacterial cell pellets by SEM-EDX analysis. Optimization of process parameters for enhanced PHA production along with wastewater treatment done using Response Surface Methodology (RSM) showed 5% and 0.74% increase in the PHA production (0.3368±0.13gL -1 ) and % COD reduction (88.93±2.41) of wastewater, respectively. The study, thus established the production of PHA along with wastewater contaminant removal by Serratia sp. ISTVKR1. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Production of polyhydroxyalkanoates (PHA) by bacterial consortium from excess sludge fermentation liquid at laboratory and pilot scales.

    Science.gov (United States)

    Jia, Qianqian; Xiong, Huilei; Wang, Hui; Shi, Hanchang; Sheng, Xinying; Sun, Run; Chen, Guoqiang

    2014-11-01

    The generation of polyhydroxyalkanoates (PHA) from excess sludge fermentation liquid (SFL) was studied at lab and pilot scale. A PHA-accumulated bacterial consortium (S-150) was isolated from activated sludge using simulated SFL (S-SFL) contained high concentration volatile fatty acids (VFA) and nitrogen. The maximal PHA content accounted for 59.18% in S-SFL and dropped to 23.47% in actual SFL (L-SFL) of the dry cell weight (DCW) at lab scale. The pilot-scale integrated system comprised an anaerobic fermentation reactor (AFR), a ceramic membrane system (CMS) and a PHA production bio-reactor (PHAR). The PHA content from pilot-scale SFL (P-SFL) finally reached to 59.47% DCW with the maximal PHA yield coefficient (YP/S) of 0.17 g PHA/g COD. The results indicated that VFA-containing SFL was suitable for PHA production. The adverse impact of excess nitrogen and non-VFAs in SFL might be eliminated by pilot-scale domestication, which might resulted in community structure optimization and substrate selective ability improvement of S-150. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Production of medium-chain-length polyhydroxyalkanoate by Pseudomonas oleovorans grown in sugary cassava extract supplemented with andiroba oil

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    Diego Aires da Silva

    2014-12-01

    Full Text Available Pseudomonas oleovorans were grown on sugary cassava extracts supplemented with andiroba oil for the synthesis of a mediumchain- length polyhydroxyalkanoate (PHA MCL. The concentration of total sugars in the extract was approximately: 40 g/L in culture 1, 15 g/L in cultures 2 and 3, and 10 g/L in culture 4. Supplementation with 1% andiroba oil and 0.2 g/L of (NH42HPO4 was performed 6.5 hours after growth in culture 3, and supplementation with the same amount of andiroba oil and 2.4 g/L of (NH42HPO4 was performed at the beginning of growth in culture 4. The synthesis resulted mainly in 3-hydroxy-decanoate and 3-hydroxy-dodecanoate units; 3-hydroxy-butyrate, 3-hydroxy-hexanoate; and 3-hydroxy-octanoate monomers were also produced but in smaller proportions. P. oleovorans significantly accumulated PHA MCL in the deceleration phase of growth with an oxygen limitation but with sufficient nitrogen concentration to maintain cell growth. The sugary cassava extract supplemented with andiroba oil proved to be a potential substrate for PHA MCL production.

  1. Mixed culture polyhydroxyalkanoates production from sugar molasses: the use of a 2-stage CSTR system for culture selection.

    Science.gov (United States)

    Albuquerque, M G E; Concas, S; Bengtsson, S; Reis, M A M

    2010-09-01

    Polyhydroxyalkanoates (PHAs) are promising biodegradable polymers. The use of mixed microbial cultures (MMC) and low cost feedstocks have a positive impact on the cost-effectiveness of the process. It has typically been carried out in Sequencing Batch Reactors (SBR). In this study, a 2-stage CSTR system (under Feast and Famine conditions) was used to effectively select for PHA-storing organisms using fermented molasses as feedstock. The effect of influent substrate concentration (60-120 Cmmol VFA/L) and HRT ratio between the reactors (0.2-0.5h/h) on the system's selection efficiency was assessed. It was shown that Feast reactor residual substrate concentration impacted on the selective pressure for PHA storage (due to substrate-dependent kinetic limitation). Moreover, a residual substrate concentration coming from the Feast to the Famine reactor did not jeopardize the physiological adaptation required for enhanced PHA storage. The culture reached a maximum PHA content of 61%. This success opens new perspectives to the use of wastewater treatment infrastructure for PHA production, thus valorizing either excess sludge or wastewaters. Copyright 2010 Elsevier Ltd. All rights reserved.

  2. Community proteomics provides functional insight into polyhydroxyalkanoate production by a mixed microbial culture cultivated on fermented dairy manure.

    Science.gov (United States)

    Hanson, Andrea J; Guho, Nicholas M; Paszczynski, Andrzej J; Coats, Erik R

    2016-09-01

    Polyhydroxyalkanoates (PHAs) are bio-based, biodegradable polyesters that can be produced from organic-rich waste streams using mixed microbial cultures (MMCs). To maximize PHA production, MMCs are enriched for bacteria with a high polymer storage capacity through the application of aerobic dynamic feeding (ADF) in a sequencing batch reactor (SBR), which consequently induces a feast-famine metabolic response. Though the feast-famine response is generally understood empirically at a macro-level, the molecular level is less refined. The objective of this study was to investigate the microbial community composition and proteome profile of an enriched MMC cultivated on fermented dairy manure. The enriched MMC exhibited a feast-famine response and was capable of producing up to 40 % (wt. basis) PHA in a fed-batch reactor. High-throughput 16S rRNA gene sequencing revealed a microbial community dominated by Meganema, a known PHA-producing genus not often observed in high abundance in enrichment SBRs. The application of the proteomic methods two-dimensional electrophoresis and LC-MS/MS revealed PHA synthesis, energy generation, and protein synthesis prominently occurring during the feast phase, corroborating bulk solution variable observations and theoretical expectations. During the famine phase, nutrient transport, acyl-CoA metabolism, additional energy generation, and housekeeping functions were more pronounced, informing previously under-determined MMC functionality under famine conditions. During fed-batch PHA production, acetyl-CoA acetyltransferase and PHA granule-bound phasin proteins were in increased abundance relative to the SBR, supporting the higher PHA content observed. Collectively, the results provide unique microbial community structural and functional insight into feast-famine PHA production from waste feedstocks using MMCs.

  3. How Does Poly(hydroxyalkanoate) Affect Methane Production from the Anaerobic Digestion of Waste-Activated Sludge?

    Science.gov (United States)

    Wang, Dongbo; Zhao, Jianwei; Zeng, Guangming; Chen, Yinguang; Bond, Philip L; Li, Xiaoming

    2015-10-20

    Recent studies demonstrate that, besides being used for production of biodegradable plastics, poly(hydroxyalkanoate) (PHA) that is accumulated in heterotrophic microorganisms during wastewater treatment has another novel application direction, i.e., being utilized for enhancing methane yield during the anaerobic digestion of waste-activated sludge (WAS). To date, however, the underlying mechanism of how PHA affects methane production remains largely unknown, and this limits optimization and application of the strategy. This study therefore aims to fill this knowledge gap. Experimental results showed that with the increase of sludge PHA levels from 21 to 184 mg/g of volatile suspended solids (VSS) the methane yield linearly increased from 168.0 to 246.1 mL/g of VSS (R(2) = 0.9834). Compared with protein and carbohydrate (the main components of a cell), PHA exhibited a higher biochemical methane potential on a unit VSS basis. It was also found that the increased PHA not only enhanced cell disruption of PHA cells but also benefited the soluble protein conversion of both PHA- and non-PHA cells. Moreover, the reactor fed with higher PHA sludge showed greater sludge hydrolysis and acidification than those fed with the lower PHA sludges. Further investigations using fluorescence in situ hybridization and enzyme analysis revealed that the increased PHA enhanced the abundance of methanogenic Archaea and increased the activities of protease, acetate kinase, and coenzyme F420, which were consistent with the observed methane yield. This work provides insights into PHA-involved WAS digestion systems and may have important implications for future operation of wastewater treatment plants.

  4. High polyhydroxybutyrate production in Pseudomonas extremaustralis is associated with differential expression of horizontally acquired and core genome polyhydroxyalkanoate synthase genes.

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    Mariela V Catone

    Full Text Available Pseudomonas extremaustralis produces mainly polyhydroxybutyrate (PHB, a short chain length polyhydroxyalkanoate (sclPHA infrequently found in Pseudomonas species. Previous studies with this strain demonstrated that PHB genes are located in a genomic island. In this work, the analysis of the genome of P. extremaustralis revealed the presence of another PHB cluster phbFPX, with high similarity to genes belonging to Burkholderiales, and also a cluster, phaC1ZC2D, coding for medium chain length PHA production (mclPHA. All mclPHA genes showed high similarity to genes from Pseudomonas species and interestingly, this cluster also showed a natural insertion of seven ORFs not related to mclPHA metabolism. Besides PHB, P. extremaustralis is able to produce mclPHA although in minor amounts. Complementation analysis demonstrated that both mclPHA synthases, PhaC1 and PhaC2, were functional. RT-qPCR analysis showed different levels of expression for the PHB synthase, phbC, and the mclPHA synthases. The expression level of phbC, was significantly higher than the obtained for phaC1 and phaC2, in late exponential phase cultures. The analysis of the proteins bound to the PHA granules showed the presence of PhbC and PhaC1, whilst PhaC2 could not be detected. In addition, two phasin like proteins (PhbP and PhaI associated with the production of scl and mcl PHAs, respectively, were detected. The results of this work show the high efficiency of a foreign gene (phbC in comparison with the mclPHA core genome genes (phaC1 and phaC2 indicating that the ability of P. extremaustralis to produce high amounts of PHB could be explained by the different expression levels of the genes encoding the scl and mcl PHA synthases.

  5. Enhanced production of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymer and antimicrobial yellow pigmentation from Cupriavidus sp. USMAHM13 with antibiofilm capability.

    Science.gov (United States)

    Ismail, Iszatty; Gurusamy, Tana Poorani; Ramachandran, Hema; Al-Ashraf Amirul, Abdullah

    2017-04-21

    Antibiofilm polymers have the ability to inhibit bacterial biofilm formation, which is known to occur ubiquitously in the environment and pose risks of infection. In this study, production of P(3HB-co-4HB) copolymer and antimicrobial yellow pigment from Cupriavidus sp. USMAHM13 are enhanced through medium optimization. Before the improvement of yellow pigment production, screening for the best additional supplement was performed resulting in high-yield yellow pigmentation using yeast extract with optimum concentration of 2 g/L. Effects of different concentrations of 1,4-butanediol, ammonium acetate, and yeast extract were studied using central composite design. Under optimal conditions, 53 wt% of polyhydroxyalkanoate (PHA) content, 0.35 g/L of pigment concentration, and 5.87 g/L of residual biomass were achieved at 0.56 wt% C of 1,4-butanediol, 1.14 g/L of ammonium acetate, and 2 g/L of yeast extract. Antibiofilm tests revealed that the yellow pigment coated on P(3HB-co-4HB) copolymer had significant effect on the inhibition of bacteria proliferation and colonization from 6 hr onward reaching 100% inhibition by 12 hr, hence effectively inhibiting the biofilm formation.

  6. Comparative life cycle assessment and financial analysis of mixed culture polyhydroxyalkanoate production.

    Science.gov (United States)

    Gurieff, Nicholas; Lant, Paul

    2007-12-01

    A life cycle assessment and financial analysis of mixed culture PHA (PHA(MC)) and biogas production was undertaken based on treating an industrial wastewater. Internal rate of return (IRR) and non-renewable CO(2)eq emissions were used to quantify financial viability and environmental impact. PHA(MC) was preferable to biogas production for treating the specified industrial effluent. PHA(MC) was also financially attractive in comparison to pure culture PHA production. Both PHA production processes had similar environmental impacts that were significantly lower than HDPE production. A large potential for optimisation exists for the PHA(MC) process as financial and environmental costs were primarily due to energy use for downstream processing. Under the conditions used in this work PHA(MC) was shown to be a viable biopolymer production process and an effective industrial wastewater treatment technology. This is the first study of its kind and provides valuable insight into the PHA(MC) process.

  7. Characterization and optimization of antibiotic resistant bacterial strains for polyhydroxyalkanoates (phas) production

    International Nuclear Information System (INIS)

    Rehman, S. U.; Jamil, N.; Hussain, S.

    2005-01-01

    In this investigation, sugarcane soil, sewage water and soil containing long chain hydrocarbons was screened to obtain bacterial strains that were able to synthesize poly-beta-hydroxyalkanoates (PHA). The potential to synthesize PHA was tested qualitatively by Sudan Black staining of colonies growing in glucose and sucrose. Sixteen bacterial strains were isolated, purified and characterized for Gram reaction, biochemical analysis and PHA production. Isolates showed a wide range of tolerance to different commonly used antibiotics. PHA extraction was done by solvent extraction and hypochlorite digestion method. PHA production was optimized for different nitrogen concentrations. (author)

  8. Mesorhizobium bacterial strains isolated from the legume Lotus corniculatus are an alternative source for the production of polyhydroxyalkanoates (PHAs) to obtain bioplastics.

    Science.gov (United States)

    Marcos-García, Marta; García-Fraile, Paula; Filipová, Alena; Menéndez, Esther; Mateos, Pedro F; Velázquez, Encarna; Cajthaml, Tomáš; Rivas, Raúl

    2017-07-01

    Polyhydroxyalkanoic acids (PHAs) are natural polyesters that can be used to produce bioplastics which are biodegradable. Numerous microorganisms accumulate PHAs as energy reserves. Combinations of different PHAs monomers lead to the production of bioplastics with very different properties. In the present work, we show the capability of strains belonging to various phylogenetic lineages within the genus Mesorhizobium, isolated from Lotus corniculatus nodules, to produce different PHA monomers. Among our strains, we found the production of 3-hydroxybutyrate, 3-hydroxyvalerate, 3-hydroxydodecanoate, and 3-hydroxyhexadecanoate. Most of the PHA-positive strains were phylogenetically related to the species M. jarvisii. However, our findings suggest that the ability to produce different monomers forming PHAs is strain-dependent.

  9. Occurrence, metabolism, metabolic role, and industrial uses of bacterial polyhydroxyalkanoates.

    OpenAIRE

    Anderson, A J; Dawes, E A

    1990-01-01

    Polyhydroxyalkanoates (PHAs), of which polyhydroxybutyrate (PHB) is the most abundant, are bacterial carbon and energy reserve materials of widespread occurrence. They are composed of 3-hydroxyacid monomer units and exist as a small number of cytoplasmic granules per cell. The properties of the C4 homopolymer PHB as a biodegradable thermoplastic first attracted industrial attention more than 20 years ago. Copolymers of C4 (3-hydroxybutyrate [3HB]) and C5 (3-hydroxyvalerate [3HV]) monomer unit...

  10. Biosynthesis and composition of bacterial poly(hydroxyalkanoates).

    Science.gov (United States)

    Anderson, A J; Haywood, G W; Dawes, E A

    1990-04-01

    It is well established that Alcaligenes eutrophus can accumulate a copolymer containing 3-hydroxybutyrate and 3-hydroxyvalerate, but longer 3-hydroxyacid monomers have not been reported to occur in this organism. The properties of the enzymes of poly(hydroxyalkanoate) (PHA) biosynthesis are discussed and it is proposed that the substrate specificity of the polymerizing enzyme restricts the range of monomer units incorporated into PHA. Various other bacteria produce similar copolymers from propionic acid and/or valeric acid. A number of Pseudomonas species accumulate PHAs containing longer-chain monomer units from linear alkanoic acids, alkanes and alcohols.

  11. Valorization of waste glycerol for the production of poly (3-hydroxybutyrate) and poly (3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer by Cupriavidus necator and extraction in a sustainable manner.

    Science.gov (United States)

    Gahlawat, Geeta; Soni, Sanjeev Kumar

    2017-11-01

    Glycerol is a by-product of many industrial processes and huge amounts of it are generated in the form of waste, thereby necessitating a search for the method of its disposal. An interesting solution is the valorization of crude glycerol into value added product such as polyhydroxyalkanoates (PHAs). The feasibility of producing PHAs by Cupriavidus necator was evaluated using crude glycerol (WG). Various cultivation strategies were designed for the production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer by adding different organic acids as precursors at different concentrations levels. Batch cultivation of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) production showed accumulation of 6.76g/L biomass containing 4.84g/L copolymer on WG with a maximum 3-hydroxyvalerate content of 24.6mol%. PHAs extraction using a non-toxic and recyclable solvent, 1,2 propylene carbonate, showed the highest recovery yield (90%) and purity (93%) at 120°C temperature and 30min incubation. This is the first report on jatropha based glycerol valorization for poly(3-hydroxybutyrate-co-3-hydroxyvalerate) production coupled with extraction using non-toxic solvent. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Bio-plastic (poly-hydroxy-alkanoate) production from municipal sewage sludge in the Netherlands: a technology push or a demand driven process?

    Science.gov (United States)

    Bluemink, E D; van Nieuwenhuijzen, A F; Wypkema, E; Uijterlinde, C A

    Valorisation of components from municipal 'waste' water and sewage sludge gets more and more attention in order to come to a circular economy by developing an efficient 'waste' to value concept. On behalf of the transition team 'Grondstoffenfabriek' ('Resource factory') a preliminary research was performed for all the Dutch water boards to assess the technical and economical feasibility of poly-hydroxy-alkanoate (PHA)-production from sewage sludge, a valuable product to produce bio-plastics. This study reveals that the production of bio-plastics from sewage sludge is feasible based on technical aspects, but not yet economically interesting, even though the selling price is relatively close to the actual PHA market price. (Selling price is in this particular case the indicative cost effective selling price. The cost effective selling price covers only the total production costs of the product.) Future process optimization (maximizing the volatile fatty acids production, PHA storage capacity, etc.) and market developments are needed and will result in cost reductions of the various sub-processes. PHA-production from sewage sludge at this stage is just a technology; every further research is needed to incorporate the backward integration approach, taking into account the market demand including associated product quality aspects.

  13. A reduction in growth rate of Pseudomonas putida KT2442 counteracts productivity advances in medium-chain-length polyhydroxyalkanoate production from gluconate

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    Zinn Manfred

    2011-04-01

    Full Text Available Abstract Background The substitution of plastics based on fossil raw material by biodegradable plastics produced from renewable resources is of crucial importance in a context of oil scarcity and overflowing plastic landfills. One of the most promising organisms for the manufacturing of medium-chain-length polyhydroxyalkanoates (mcl-PHA is Pseudomonas putida KT2440 which can accumulate large amounts of polymer from cheap substrates such as glucose. Current research focuses on enhancing the strain production capacity and synthesizing polymers with novel material properties. Many of the corresponding protocols for strain engineering rely on the rifampicin-resistant variant, P. putida KT2442. However, it remains unclear whether these two strains can be treated as equivalent in terms of mcl-PHA production, as the underlying antibiotic resistance mechanism involves a modification in the RNA polymerase and thus has ample potential for interfering with global transcription. Results To assess PHA production in P. putida KT2440 and KT2442, we characterized the growth and PHA accumulation on three categories of substrate: PHA-related (octanoate, PHA-unrelated (gluconate and poor PHA substrate (citrate. The strains showed clear differences of growth rate on gluconate and citrate (reduction for KT2442 > 3-fold and > 1.5-fold, respectively but not on octanoate. In addition, P. putida KT2442 PHA-free biomass significantly decreased after nitrogen depletion on gluconate. In an attempt to narrow down the range of possible reasons for this different behavior, the uptake of gluconate and extracellular release of the oxidized product 2-ketogluconate were measured. The results suggested that the reason has to be an inefficient transport or metabolization of 2-ketogluconate while an alteration of gluconate uptake and conversion to 2-ketogluconate could be excluded. Conclusions The study illustrates that the recruitment of a pleiotropic mutation, whose effects might

  14. Enhanced Agarose and Xylan Degradation for Production of Polyhydroxyalkanoates by Co-Culture of Marine Bacterium, Saccharophagus degradans and Its Contaminant, Bacillus cereus

    Directory of Open Access Journals (Sweden)

    Shailesh S. Sawant

    2017-02-01

    Full Text Available Over reliance on energy or petroleum products has raised concerns both in regards to the depletion of their associated natural resources as well as their increasing costs. Bioplastics derived from microbes are emerging as promising alternatives to fossil fuel derived petroleum plastics. The development of a simple and eco-friendly strategy for bioplastic production with high productivity and yield, which is produced in a cost effective manner utilising abundantly available renewable carbon sources, would have the potential to result in an inexhaustible global energy source. Here we report the biosynthesis of bioplastic polyhydroxyalkanoates (PHAs in pure cultures of marine bacterium, Saccharophagus degradans 2-40 (Sde 2-40, its contaminant, Bacillus cereus, and a co-culture of these bacteria (Sde 2-40 and B. cereus degrading plant and algae derived complex polysaccharides. Sde 2-40 degraded the complex polysaccharides agarose and xylan as sole carbon sources for biosynthesis of PHAs. The ability of Sde 2-40 to degrade agarose increased after co-culturing with B. cereus. The association of Sde 2-40 with B. cereus resulted in increased cell growth and higher PHA production (34.5% of dry cell weight from xylan as a carbon source in comparison to Sde 2-40 alone (22.7% of dry cell weight. The present study offers an innovative prototype for production of PHA through consolidated bioprocessing of complex carbon sources by pure and co-culture of microorganisms.

  15. Production and characterization of a biodegradable poly (hydroxybutyrate-co-hydroxyvalerate) (PHB-co-PHV) copolymer by moderately haloalkalitolerant Halomonas campisalis MCM B-1027 isolated from Lonar Lake, India.

    Science.gov (United States)

    Kulkarni, S O; Kanekar, P P; Nilegaonkar, S S; Sarnaik, S S; Jog, J P

    2010-12-01

    Several microorganisms produce polyhydroxyalkanoates (PHA). They are accumulated intracellularly as energy storage compounds. The PHAs are of interest because of their potential in biomedical applications. Halophilic bacteria and archaea are known to produce polyhydroxybutyrate (PHB). This paper describes production of a biodegradable copolymer, PHB-co-PHV by a moderately haloalkalitolerant Halomonas campisalis, isolated from Lonar Lake, India. The production of PHA was in the range of 45-81% on dry cell weight basis when the organism was grown in a production medium containing 1% (w/v) maltose and 0.1% (w/v) yeast extract, at pH ranging from 6 to 9 with an inoculum density of 10(5)-10(7) cells/ml of medium, for incubation period of 15-30 h and at 37 degrees C. The polymer produced by the organism is a hydroxyester with molecular weight of 1.3014 x 10(6). Its melting temperature was 171 degrees C. The (1)H NMR analysis revealed that the polymer was a copolymer of PHB-co-PHV. This could be achieved by providing simple carbon source viz. maltose. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  16. Polyhydroxyalkanoates (PHA) production from fermented crude glycerol: Study on the conversion of 1,3-propanediol to PHA in mixed microbial consortia

    DEFF Research Database (Denmark)

    Burniol Figols, Anna; Varrone, Cristiano; Daugaard, Anders Egede

    2018-01-01

    Crude glycerol, a by-product from the biodiesel industry, can be converted by mixed microbial consortia into 1,3-propanediol (1,3-PDO) and volatile fatty acids. In this study, further conversion of these main products into polyhydroxyalkanoates (PHA) was investigated with the focus on 1,3-PDO. Two...... different approaches for the enrichment of PHA accumulating microbial consortia using an aerobic dynamic feeding strategy were applied. With the first approach, where nitrogen was present during the whole cycle, no net production of PHA from 1,3-PDO was observed in the fermented effluent, not even...... the storage response. Nitrogen was still supplied during the famine phase. With the latter strategy, a net production of PHA from 1,3-PDO was observed at a yield of 0.24 Cmol PHA/Cmol 1,3-PDO. The overall yield from the fermented effluent was 0.42 Cmol PHA/Cmol substrate. Overall, the PHA yield from 1,3-PDO...

  17. Selecting optimal feast-to-famine ratio for a new polyhydroxyalkanoate (PHA) production system fed by valerate-dominant sludge hydrolysate.

    Science.gov (United States)

    Hao, Jiuxiao; Wang, Hui; Wang, Xiujin

    2018-04-01

    The feast-to-famine ratio (F/F) represents the extent of selective pressure during polyhydroxyalkanoate (PHA) culture selection. This study evaluated the effects of F/F on a new PHA production system by an enriched culture with valerate-dominant sludge hydrolysate and selected the optimal F/F. After the original F/F 1/3 was modified to 1/1, 1/2, 1/4, and 1/5, F/F did not affect their lengths of feast phase, but affected their biomass growth behaviors during the famine phase and PHA-producing abilities. The optimal F/F was 1/2, and compared with 1/3, it increased the maximal PHA content and the fraction of 3-hydroxyvalerate (3HV) and 3-hydroxy-2-methylvalerate (3H2MV) monomers, with higher productivity and better polymer properties. Although F/F 1/2 impaired the advantage of the dominant genus Delftia, it improved the PHA production rate while decreased biomass growth rate, meanwhile enhancing the utilization and conversion of valerate. These findings indicate that in contrast to previous studies using acetate-dominant substrate for PHA production, the new system fed by valerate-dominant substrate can adopt a higher F/F.

  18. The Molecular Level Characterization of Biodegradable Polymers Originated from Polyethylene Using Non-Oxygenated Polyethylene Wax as a Carbon Source for Polyhydroxyalkanoate Production.

    Science.gov (United States)

    Johnston, Brian; Jiang, Guozhan; Hill, David; Adamus, Grazyna; Kwiecień, Iwona; Zięba, Magdalena; Sikorska, Wanda; Green, Matthew; Kowalczuk, Marek; Radecka, Iza

    2017-08-28

    There is an increasing demand for bio-based polymers that are developed from recycled materials. The production of biodegradable polymers can include bio-technological (utilizing microorganisms or enzymes) or chemical synthesis procedures. This report demonstrates the corroboration of the molecular structure of polyhydroxyalkanoates (PHAs) obtained by the conversion of waste polyethylene (PE) via non-oxygenated PE wax (N-PEW) as an additional carbon source for a bacterial species. The N-PEW, obtained from a PE pyrolysis reaction, has been found to be a beneficial carbon source for PHA production with Cupriavidus necator H16. The production of the N-PEW is an alternative to oxidized polyethylene wax (O-PEW) (that has been used as a carbon source previously) as it is less time consuming to manufacture and offers fewer industrial applications. A range of molecular structural analytical techniques were performed on the PHAs obtained; which included nuclear magnetic resonance (NMR) and electrospray ionisation tandem mass spectrometry (ESI-MS/MS). Our study showed that the PHA formed from N-PEW contained 3-hydroxybutyrate (HB) with 11 mol% of 3-hydroxyvalerate (HV) units.

  19. The Crc protein inhibits the production of polyhydroxyalkanoates in Pseudomonas putida under balanced carbon/nitrogen growth conditions.

    Science.gov (United States)

    La Rosa, Ruggero; de la Peña, Fernando; Prieto, María Axiliadora; Rojo, Fernando

    2014-01-01

    Pseudomonas putida synthesizes polyhydroxyalkanoates (PHAs) as storage compounds. PHA synthesis is more active when the carbon source is in excess and the nitrogen source is limiting, but can also occur at a lower rate under balanced carbon/nitrogen ratios. This work shows that PHA synthesis is controlled by the Crc global regulator, a protein that optimizes carbon metabolism by inhibiting the expression of genes involved in the use of non-preferred carbon sources. Crc acts post-transcriptionally. The mRNAs of target genes contain characteristic catabolite activity (CA) motifs near the ribosome binding site. Sequences resembling CA motifs can be predicted for the phaC1 gene, which codes for a PHA polymerase, and for phaI and phaF, which encode proteins associated to PHA granules. Our results show that Crc inhibits the translation of phaC1 mRNA, but not that of phaI or phaF, reducing the amount of PHA accumulated in the cell. Crc inhibited PHA synthesis during exponential growth in media containing a balanced carbon/nitrogen ratio. No inhibition was seen when the carbon/nitrogen ratio was imbalanced. This extends the role of Crc beyond that of controlling the hierarchical utilization of carbon sources and provides a link between PHA synthesis and the global regulatory networks controlling carbon flow. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

  20. The influence of substrate source on the growth of Ralstonia eutropha, aiming at the production of polyhydroxyalkanoate

    Directory of Open Access Journals (Sweden)

    Marangoni C.

    2001-01-01

    Full Text Available With the aim of producing polyhydroxyalkanoates, a study of the influence of culture conditions (nitrogen and carbon sources and temperature on the growth of Ralstonia eutropha in stirred flasks was carried out and the use of some low-cost sources (hydrolyzed lactose, inverted sugar and corn steep liquor as evaluated. The best specific growth rate was obtained when inverted sugar was utilized as the substrate (mumax = 0.26 h-1. Two different phases in the assimilation of the carbon source were observed when hydrolyzed lactose was present, suggesting the assimilation first of glucose and then of galactose. To confirm the growth of Ralstonia eutropha using galactose as the only carbon source, experiments were carried out and the results showed that this bacterium is able to grow in the presence of this sugar at a growth rate of 0.13 h-1. The use of galactose by Ralstonia eutropha for its growth has not been reported in the literature until now. Corn steep liquor was found to be a viable alternative nitrogen source to ammonium sulfate. The results of experiments carried out at 30°C and 34°C were similar.

  1. Polyhydroxyalkanoate Production on Waste Water Treatment Plants: Process Scheme, Operating Conditions and Potential Analysis for German and European Municipal Waste Water Treatment Plants

    Directory of Open Access Journals (Sweden)

    Timo Pittmann

    2017-06-01

    Full Text Available This work describes the production of polyhydroxyalkanoates (PHA as a side stream process on a municipal waste water treatment plant (WWTP and a subsequent analysis of the production potential in Germany and the European Union (EU. Therefore, tests with different types of sludge from a WWTP were investigated regarding their volatile fatty acids (VFA production-potential. Afterwards, primary sludge was used as substrate to test a series of operating conditions (temperature, pH, retention time (RT and withdrawal (WD in order to find suitable settings for a high and stable VFA production. In a second step, various tests regarding a high PHA production and stable PHA composition to determine the influence of substrate concentration, temperature, pH and cycle time of an installed feast/famine-regime were conducted. Experiments with a semi-continuous reactor operation showed that a short RT of 4 days and a small WD of 25% at pH = 6 and around 30 °C is preferable for a high VFA production rate (PR of 1913 mgVFA/(L×d and a stable VFA composition. A high PHA production up to 28.4% of cell dry weight (CDW was reached at lower substrate concentration, 20 °C, neutral pH-value and a 24 h cycle time. A final step a potential analysis, based on the results and detailed data from German waste water treatment plants, showed that the theoretically possible production of biopolymers in Germany amounts to more than 19% of the 2016 worldwide biopolymer production. In addition, a profound estimation regarding the EU showed that in theory about 120% of the worldwide biopolymer production (in 2016 could be produced on European waste water treatment plants.

  2. Photoautotrophic production of polyhydroxyalkanoates in a synthetic mixed culture of Synechococcus elongatus cscB and Pseudomonas putida cscAB.

    Science.gov (United States)

    Löwe, Hannes; Hobmeier, Karina; Moos, Manuel; Kremling, Andreas; Pflüger-Grau, Katharina

    2017-01-01

    One of the major challenges for the present and future generations is to find suitable substitutes for the fossil resources we rely on today. Cyanobacterial carbohydrates have been discussed as an emerging renewable feedstock in industrial biotechnology for the production of fuels and chemicals, showing promising production rates when compared to crop-based feedstock. However, intrinsic capacities of cyanobacteria to produce biotechnological compounds are limited and yields are low. Here, we present an approach to circumvent these problems by employing a synthetic bacterial co-culture for the carbon-neutral production of polyhydroxyalkanoates (PHAs) from CO 2 . The co-culture consists of two bio - modules : Bio - module I , in which the cyanobacterial strain Synechococcus elongatus cscB fixes CO 2 , converts it to sucrose, and exports it into the culture supernatant; and bio - module II , where this sugar serves as C-source for Pseudomonas putida cscAB and is converted to PHAs that are accumulated in the cytoplasm. By applying a nitrogen-limited process, we achieved a maximal PHA production rate of 23.8 mg/(L day) and a maximal titer of 156 mg/L. We will discuss the present shortcomings of the process and show the potential for future improvement. These results demonstrate the feasibility of mixed cultures of S. elongatus cscB and P. putida cscAB for PHA production, making room for the cornucopia of possible products that are described for P. putida . The construction of more efficient sucrose-utilizing P. putida phenotypes and the optimization of process conditions will increase yields and productivities and eventually close the gap in the contemporary process. In the long term, the co-culture may serve as a platform process, in which P. putida is used as a chassis for the implementation of synthetic metabolic pathways for biotechnological production of value-added products.

  3. [Synthesis of reserve polyhydroxyalkanoates by luminescent bacteria].

    Science.gov (United States)

    Boiandin, A N; Kalacheva, G S; Rodicheva, E K; Volova, T G

    2008-01-01

    The ability of marine luminescent bacteria to synthesize polyesters of hydroxycarboxylic acids (polyhydroxyalkanoates, PHA) as reserve macromolecules was studied. Twenty strains from the collection of the luminescent bacteria CCIBSO (WDSM839) of the Institute of Biophysics, Siberian Branch, Russian Academy of Sciences, assigned to different taxa (Photobacterium leiognathi, Ph. phosphoreum, Vibrio harveyi, and V. fischeri) were analyzed. The most productive strains were identified, and the conditions ensuring high polymer yields in batch culture (40-70% of the cell dry mass weight) were determined. The capacity of synthesizing two- and three-component polymers containing hydroxybutyric acid as the main monomer and hydroxyvaleric and hydroxyhexanoic acids was revealed in Ph. leiognathi and V. harveyi strains. The results allow luminescent microorganisms to be regarded as new producers of multicomponent polyhydroxyalkanoates.

  4. Production of medium-chain-length polyhydroxyalkanoates by sequential feeding of xylose and octanoic acid in engineered Pseudomonas putida KT2440

    Directory of Open Access Journals (Sweden)

    Le Meur Sylvaine

    2012-08-01

    Full Text Available Abstract Background Pseudomonas putida KT2440 is able to synthesize large amounts of medium-chain-length polyhydroxyalkanoates (mcl-PHAs. To reduce the substrate cost, which represents nearly 50% of the total PHA production cost, xylose, a hemicellulose derivate, was tested as the growth carbon source in an engineered P. putida KT2440 strain. Results The genes encoding xylose isomerase (XylA and xylulokinase (XylB from Escherichia coli W3110 were introduced into P. putida KT2440. The recombinant KT2440 exhibited a XylA activity of 1.47 U and a XylB activity of 0.97 U when grown on a defined medium supplemented with xylose. The cells reached a maximum specific growth rate of 0.24 h-1 and a final cell dry weight (CDW of 2.5 g L-1 with a maximal yield of 0.5 g CDW g-1 xylose. Since no mcl-PHA was accumulated from xylose, mcl-PHA production can be controlled by the addition of fatty acids leading to tailor-made PHA compositions. Sequential feeding strategy was applied using xylose as the growth substrate and octanoic acid as the precursor for mcl-PHA production. In this way, up to 20% w w-1 of mcl-PHA was obtained. A yield of 0.37 g mcl-PHA per g octanoic acid was achieved under the employed conditions. Conclusions Sequential feeding of relatively cheap carbohydrates and expensive fatty acids is a practical way to achieve more cost-effective mcl-PHA production. This study is the first reported attempt to produce mcl-PHA by using xylose as the growth substrate. Further process optimizations to achieve higher cell density and higher productivity of mcl-PHA should be investigated. These scientific exercises will undoubtedly contribute to the economic feasibility of mcl-PHA production from renewable feedstock.

  5. Biosynthesis and Lipase-Catalysed Hydrolysis of 4-Hydroxybutyrate-Containing Polyhydroxyalkanoates from Delftia acidovorans

    Directory of Open Access Journals (Sweden)

    Diana Hooi-Ean Ch’ng

    2012-09-01

    Full Text Available Aims: Polyhydroxyalkanoates (PHA having various molar fractions of 4-hydroxybutyrate has been successfully synthesized by Delftia acidovorans.Methodology and results: The monomer compositions of the PHA were varied by cultivating the bacterium in a mixture of 1,4-butanediol and sodium valerate, γ-butyrolactone and sodium valerate as well as 4-hydroxybutyric acid and sodium valerate, which resulted in the production of PHA terpolymers. Although the highest terpolymer content achieved was only 57 wt% of the dry cell weight, the 4HB molar fractions can be regulated from 2-50 mol% when culture conditions such as initial pH, inoculum concentration and aeration were varied. The in vitro degradation of [P(3HB-co-50 % 4HB] synthesized by D. acidovorans were also studied by monitoring the erosion rate of the copolymer in aqueous solutions of lipases (Lipase A ‘Amano’ 12 and Newlase F. Results have shown that the types of lipases, concentration of lipase solution and pH of the buffer solution influenced the degradation rate of the PHA copolymer.Conclusion, significance and impact of the study: The overall results have shown that D. acidovorans is a very promising strain for the production of 4HB containing PHAs with specific compositions which are very suitable to be tailor made into biodegradable and biocompatible materials for medical applications.

  6. Process of irradiating an ethylene-vinyl acetate copolymer to produce low melt index copolymers, and products of said process

    International Nuclear Information System (INIS)

    Potts, J.E.

    1976-01-01

    Application of ionizing radiation in a dose between 0.5 and 1.5 megareps to copolymers of ethylene and vinyl acetate lowers the melt index and increases the toughness and flexibility of the copolymers without substantially decreasing solubility or thermoplasticity. The increased toughness and flexibility carries over into blends with wax or polyethylene. (author)

  7. Synthetic biology of microbes synthesizing polyhydroxyalkanoates (PHA

    Directory of Open Access Journals (Sweden)

    Guo-Qiang Chen

    2016-12-01

    Full Text Available Microbial polyhydroxyalkanoates (PHA have been produced as bioplastics for various purposes. Under the support of China National Basic Research 973 Project, we developed synthetic biology methods to diversify the PHA structures into homo-, random, block polymers with improved properties to better meet various application requirements. At the same time, various pathways were assembled to produce various PHA from glucose as a simple carbon source. At the end, Halomonas bacteria were reconstructed to produce PHA in changing morphology for low cost production under unsterile and continuous conditions. The synthetic biology will advance the PHA into a bio- and material industry.

  8. Genome-scale reconstruction and in silico analysis of the Ralstonia eutropha H16 for polyhydroxyalkanoate synthesis, lithoautotrophic growth, and 2-methyl citric acid production

    Directory of Open Access Journals (Sweden)

    Kim Tae

    2011-06-01

    Full Text Available Abstract Background Ralstonia eutropha H16, found in both soil and water, is a Gram-negative lithoautotrophic bacterium that can utillize CO2 and H2 as its sources of carbon and energy in the absence of organic substrates. R. eutropha H16 can reach high cell densities either under lithoautotrophic or heterotrophic conditions, which makes it suitable for a number of biotechnological applications. It is the best known and most promising producer of polyhydroxyalkanoates (PHAs from various carbon substrates and is an environmentally important bacterium that can degrade aromatic compounds. In order to make R. eutropha H16 a more efficient and robust biofactory, system-wide metabolic engineering to improve its metabolic performance is essential. Thus, it is necessary to analyze its metabolic characteristics systematically and optimize the entire metabolic network at systems level. Results We present the lithoautotrophic genome-scale metabolic model of R. eutropha H16 based on the annotated genome with biochemical and physiological information. The stoichiometic model, RehMBEL1391, is composed of 1391 reactions including 229 transport reactions and 1171 metabolites. Constraints-based flux analyses were performed to refine and validate the genome-scale metabolic model under environmental and genetic perturbations. First, the lithoautotrophic growth characteristics of R. eutropha H16 were investigated under varying feeding ratios of gas mixture. Second, the genome-scale metabolic model was used to design the strategies for the production of poly[R-(--3hydroxybutyrate] (PHB under different pH values and carbon/nitrogen source uptake ratios. It was also used to analyze the metabolic characteristics of R. eutropha when the phosphofructokinase gene was expressed. Finally, in silico gene knockout simulations were performed to identify targets for metabolic engineering essential for the production of 2-methylcitric acid in R. eutropha H16. Conclusion The

  9. Microbial community-based polyhydroxyalkanoates (PHAs) production from wastewater : Techno-economic analysis and ex-ante environmental assessment

    NARCIS (Netherlands)

    Fernandez Dacosta, Cora; Posada, John A.; Kleerebezem, Robbert; Cuellar, Maria C.; Ramirez, Andrea

    2015-01-01

    This work investigates the potential for polyhydroxybutyrate (PHB) production from wastewater, from a techno-economic and an environmental perspective, examining scale-up opportunities and bottlenecks prior to commercialisation. Conceptual process design, economic, environmental impacts and

  10. Isolation of Bacillus sp Producing Polyhydroxyalkanoate (PHA from Isfahan Refinery Wastewater and Qualification of Production in Submerged Fermentation

    Directory of Open Access Journals (Sweden)

    Mahsa Keshavarz Azam

    2015-12-01

    Full Text Available Introduction: The aim of present study was isolation of polyhydroxybutyrate producing Bacillus species from oil refinery waste water, Isfahan, Iran and primarily optimization of production condition. Petroleum wastes are rich of carbon sources and have low amounts of nitrogen and phosphorus sources. AS the most important factor in production of intracellular inclusions is increasing the C/N ratio, it seemed that polyhydroxybutyrate producing microorganisms will be found in these wastes. Materials and methods: Bacillus species were isolated and purified from oil refinery wastewater. The polymer was verified using different staining procedures. Polymer was extracted by digestion method and the optimum production conditions were investigated in minimal salt medium with the organic carbon source by submerged fermentation. Production of polyhydroxybutyrate was studied using dry weight and optical density measurement. Results: Between various isolated Bacillus strains, two of them (B1 and B2 were polyhydroxybutyrate producers. Maximum PHA production based on dry weight and concentration were obtained for strain B1 after 72 hours incubation, at 31°C, in the presence of glucose as carbon source and yeast extract as nitrogen source, pH=7, and aeration in 120 rpm; and for strain B2 in the same condition, except optimal temperature which was 32°C. The most production amounts were 367 mg.ml-1 for B1 and 473 mg.ml-1 for B2 isolates. Also the most polymer percentage was 52/16 and 58.43 for B1 and B2 isolates respectively. Discussion and conclusion: The results showed that the production of polyhydroxybutyrate was increased by optimization of the conditions in both isolates. Using petroleum wastes as well as production of biodegradable plastics, leads to decontamination of theses wastes.

  11. Isolation and recovery of microbial polyhydroxyalkanoates

    Directory of Open Access Journals (Sweden)

    2011-07-01

    Full Text Available The deleterious environmental impacts caused by plastic wastes have attracted worldwide concern. The biobased and biodegradable polyhydroxyalkanoate (PHA appears to be one of the potential candidates to replace some conventional plastics. However, high production cost of PHAs has limited their market penetration. The major cost absorbing factors are the upstream fermentation processes and the downstream PHA recovery technologies. The latter significantly affects the overall process economics. Various recovery technologies have been proposed and studied in small scales in the laboratory as well as in industrial scales. These include solvent extraction, chemical digestion, enzymatic treatment and mechanical disruption, supercritical fluid disruption, flotation techniques, use of gamma irradiation and aqueous two-phase system. This paper reviews all the recovery methods known to date and compares their efficiency and the quality of the resulting PHA. Some of the large-scale production of PHA and the strategies employed to reduce the production cost are also discussed.

  12. Bacillus subtilis as potential producer for polyhydroxyalkanoates

    Directory of Open Access Journals (Sweden)

    Patel Sanjay KS

    2009-07-01

    Full Text Available Abstract Polyhydroxyalkanoates (PHAs are biodegradable polymers produced by microbes to overcome environmental stress. Commercial production of PHAs is limited by the high cost of production compared to conventional plastics. Another hindrance is the brittle nature and low strength of polyhydroxybutyrate (PHB, the most widely studied PHA. The needs are to produce PHAs, which have better elastomeric properties suitable for biomedical applications, preferably from inexpensive renewable sources to reduce cost. Certain unique properties of Bacillus subtilis such as lack of the toxic lipo-polysaccharides, expression of self-lysing genes on completion of PHA biosynthetic process – for easy and timely recovery, usage of biowastes as feed enable it to compete as potential candidate for commercial production of PHA.

  13. Bacillus subtilis as potential producer for polyhydroxyalkanoates.

    Science.gov (United States)

    Singh, Mamtesh; Patel, Sanjay Ks; Kalia, Vipin C

    2009-07-20

    Polyhydroxyalkanoates (PHAs) are biodegradable polymers produced by microbes to overcome environmental stress. Commercial production of PHAs is limited by the high cost of production compared to conventional plastics. Another hindrance is the brittle nature and low strength of polyhydroxybutyrate (PHB), the most widely studied PHA. The needs are to produce PHAs, which have better elastomeric properties suitable for biomedical applications, preferably from inexpensive renewable sources to reduce cost. Certain unique properties of Bacillus subtilis such as lack of the toxic lipo-polysaccharides, expression of self-lysing genes on completion of PHA biosynthetic process - for easy and timely recovery, usage of biowastes as feed enable it to compete as potential candidate for commercial production of PHA.

  14. Polyhydroxyalkanoates: bioplastics with a green agenda.

    Science.gov (United States)

    Keshavarz, Tajalli; Roy, Ipsita

    2010-06-01

    Production of polyhydroxyalkanoates (PHAs) has been investigated for more than eighty years but recently a number of factors including increase in the price of crude oil and public awareness of the environmental issues have become a notable driving force for extended research on biopolymers. The versatility of PHAs has made them good candidates for the study of their potential in a variety of areas from biomedical/medical fields to food, packaging, textile and household material. While production costs are still a drawback to wider usage of these biopolymers, their application as low volume high cost items is becoming a reality. The future trend is to focus on the development of more efficient and economical processes for PHA production, isolation, purification and improvement of PHA material properties. Copyright 2010 Elsevier Ltd. All rights reserved.

  15. Current trends in biodegradable polyhydroxyalkanoates.

    Science.gov (United States)

    Chanprateep, Suchada

    2010-12-01

    The microbial polyesters known as polyhydroxyalkanoates (PHAs) positively impact global climate change scenarios by reducing the amount of non-degradable plastic used. A wide variety of different monomer compositions of PHAs has been described, as well as their future prospects for applications where high biodegradability or biocompatibility is required. PHAs can be produced from renewable raw materials and are degraded naturally by microorganisms that enable carbon dioxide and organic compound recycling in the ecosystem, providing a buffer to climate change. This review summarizes recent research on PHAs and addresses the opportunities as well as challenges for their place in the global market. Copyright © 2010 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  16. Occurrence, metabolism, metabolic role, and industrial uses of bacterial polyhydroxyalkanoates.

    Science.gov (United States)

    Anderson, A J; Dawes, E A

    1990-12-01

    Polyhydroxyalkanoates (PHAs), of which polyhydroxybutyrate (PHB) is the most abundant, are bacterial carbon and energy reserve materials of widespread occurrence. They are composed of 3-hydroxyacid monomer units and exist as a small number of cytoplasmic granules per cell. The properties of the C4 homopolymer PHB as a biodegradable thermoplastic first attracted industrial attention more than 20 years ago. Copolymers of C4 (3-hydroxybutyrate [3HB]) and C5 (3-hydroxyvalerate [3HV]) monomer units have modified physical properties; e.g., the plastic is less brittle than PHB, whereas PHAs containing C8 to C12 monomers behave as elastomers. This family of materials is the centre of considerable commercial interest, and 3HB-co-3HV copolymers have been marketed by ICI plc as Biopol. The known polymers exist as 2(1) helices with the fiber repeat decreasing from 0.596 nm for PHB to about 0.45 nm for C8 to C10 polymers. Novel copolymers with a backbone of 3HB and 4HB have been obtained. The native granules contain noncrystalline polymer, and water may possibly act as a plasticizer. Although the biosynthesis and regulation of PHB are generally well understood, the corresponding information for the synthesis of long-side-chain PHAs from alkanes, alcohols, and organic acids is still incomplete. The precise mechanisms of action of the polymerizing and depolymerizing enzymes also remain to be established. The structural genes for the three key enzymes of PHB synthesis from acetyl coenzyme A in Alcaligenes eutrophus have been cloned, sequenced, and expressed in Escherichia coli. Polymer molecular weights appear to be species specific. The factors influencing the commercial choice of organism, substrate, and isolation process are discussed. The physiological functions of PHB as a reserve material and in symbiotic nitrogen fixation and its presence in bacterial plasma membranes and putative role in transformability and calcium signaling are also considered.

  17. Polyhydroxyalkanoates (PHA) Bioplastic Packaging Materials

    Science.gov (United States)

    2010-05-01

    the non-isothermal melt-crystallization kinetics of the subject PHB copolymers. In this test, the specimen (cut from a disc compression molded at...of PHB was determined to be about 1.10 g/cm3 at 160 °C; this value was used in all the calculations. Specifically, the specimen disc was placed

  18. Engineering bacteria for enhanced polyhydroxyalkanoates (PHA biosynthesis

    Directory of Open Access Journals (Sweden)

    Guo-Qiang Chen

    2017-09-01

    Full Text Available Polyhydroxyalkanoates (PHA have been produced by some bacteria as bioplastics for many years. Yet their commercialization is still on the way. A few issues are related to the difficulty of PHA commercialization: namely, high cost and instabilities on molecular weights (Mw and structures, thus instability on thermo-mechanical properties. The high cost is the result of complicated bioprocessing associated with sterilization, low conversion of carbon substrates to PHA products, and slow growth of microorganisms as well as difficulty of downstream separation. Future engineering on PHA producing microorganisms should be focused on contamination resistant bacteria especially extremophiles, developments of engineering approaches for the extremophiles, increase on carbon substrates to PHA conversion and controlling Mw of PHA. The concept proof studies could still be conducted on E. coli or Pseudomonas spp. that are easily used for molecular manipulations. In this review, we will use E. coli and halophiles as examples to show how to engineer bacteria for enhanced PHA biosynthesis and for increasing PHA competitiveness.

  19. Mechanical Properties of Polyhydroxyalkanoate Bioceramic Nanocomposites

    Institute of Scientific and Technical Information of China (English)

    江涛; 胡平; 柳林; 李亚栋

    2002-01-01

    New composites prepared containing nanoscale hydroxyapatite or monetite uniformly distributed in a polyhydroxyalkanoate (polyhydroxybutyrate or polyhydroxybutyrate-hydroxyvalerate) matrix with mass fractions of 1%5% were then injected into dumb-like specimens. The results show that the tensile strength and the tensile modulus of the composites are improved. The microstructures of the composites were observed using transmission electron microscopy (TEM).

  20. Funding initiates production of tunable nano-porous block copolymer membranes

    KAUST Repository

    Peinemann, Klaus-Viktor

    2013-01-01

    - on top of a non-ordered sponge-like layer. It is fabricated in a fast, one-step process by combining the self-assembly of an amphiphilic block copolymer (PS- b-P4VP) with non-solvent-induced phase separation. The university's "Seed Fund" has helped

  1. Chicken feather hydrolysate as an inexpensive complex nitrogen source for PHA production by Cupriavidus necator on waste frying oils.

    Science.gov (United States)

    Benesova, P; Kucera, D; Marova, I; Obruca, S

    2017-08-01

    The chicken feather hydrolysate (FH) has been tested as a potential complex nitrogen source for the production of polyhydroxyalkanoates by Cupriavidus necator H16 when waste frying oil was used as a carbon source. The addition of FH into the mineral salt media with decreased inorganic nitrogen source concentration improved the yields of biomass and polyhydrohyalkanoates. The highest yields were achieved when 10 vol.% of FH prepared by microwave-assisted alkaline hydrolysis of 60 g l -1 feather was added. In this case, the poly(3-hydroxybutyrate) (PHB) yields were improved by more than about 50% as compared with control cultivation. A positive impact of FH was also observed for accumulation of copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) when sodium propionate was used as a precursor. The copolymer has superior processing and mechanical properties in comparison with PHB homopolymer. The application of FH eliminated the inhibitory effect of propionate and resulted in altered content of 3-hydroxyvalerate (3HV) in copolymer. Therefore, the hydrolysed feather can serve as an excellent complex source of nitrogen for the polyhydroxyalkanoates (PHA) production. Moreover, by the combination of two inexpensive types of waste, such as waste frying oil and feather hydrolysate, it is possible to produce PHA with substantially improved efficiency and sustainability. Millions of tons of feathers, important waste product of poultry-processing industry, are disposed off annually without any further benefits. Thus, there is an inevitable need for new technologies that enable ecologically and economically sensible processing of this waste. Herein, we report that alkali-hydrolysed feathers can be used as a complex nitrogen source considerably improving polyhydroxyalkanoates production on waste frying oil employing Cupriavidus necator. © 2017 The Society for Applied Microbiology.

  2. A microbial polyhydroxyalkanoates (PHA) based bio- and materials industry.

    Science.gov (United States)

    Chen, Guo-Qiang

    2009-08-01

    Biopolyesters polyhydroxyalkanoates (PHA) produced by many bacteria have been investigated by microbiologists, molecular biologists, biochemists, chemical engineers, chemists, polymer experts and medical researchers. PHA applications as bioplastics, fine chemicals, implant biomaterials, medicines and biofuels have been developed and are covered in this critical review. Companies have been established or involved in PHA related R&D as well as large scale production. Recently, bacterial PHA synthesis has been found to be useful for improving robustness of industrial microorganisms and regulating bacterial metabolism, leading to yield improvement on some fermentation products. In addition, amphiphilic proteins related to PHA synthesis including PhaP, PhaZ or PhaC have been found to be useful for achieving protein purification and even specific drug targeting. It has become clear that PHA and its related technologies are forming an industrial value chain ranging from fermentation, materials, energy to medical fields (142 references).

  3. Recovery of polyhydroxyalkanoates from municipal secondary wastewater sludge.

    Science.gov (United States)

    Kumar, Manish; Ghosh, Pooja; Khosla, Khushboo; Thakur, Indu Shekhar

    2018-05-01

    In the current study, the feasibility of utilizing municipal secondary wastewater sludge for Polyhydroxyalkanoate (PHA) extraction was improved by optimization of various parameters (temperature, duration and concentration of sludge solids). Optimized process parameters resulted in PHA recovery of 0.605 g, significantly higher than un-optimized conditions. The characterization of PHA was carried out by GC-MS, FT-IR and NMR ( 1 H and 13 C) spectroscopy. The PHA profile was found to be dominated by mcl PHA (58%) along with other diverse PHA. The results of the present study show rich diversity of PHA extracted from a raw material which is readily available at minimal cost. In conclusion, exploring the potential of wastes for production of bioplastics not only reduces the cost of bioplastic production, but also provides a sustainable means for waste management. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Whole-Genome Microarray and Gene Deletion Studies Reveal Regulation of the Polyhydroxyalkanoate Production Cycle by the Stringent Response in Ralstonia eutropha H16

    Energy Technology Data Exchange (ETDEWEB)

    Brigham, CJ; Speth, DR; Rha, C; Sinskey, AJ

    2012-10-22

    Poly(3-hydroxybutyrate) (PHB) production and mobilization in Ralstonia eutropha are well studied, but in only a few instances has PHB production been explored in relation to other cellular processes. We examined the global gene expression of wild-type R. eutropha throughout the PHB cycle: growth on fructose, PHB production using fructose following ammonium depletion, and PHB utilization in the absence of exogenous carbon after ammonium was resupplied. Our results confirm or lend support to previously reported results regarding the expression of PHB-related genes and enzymes. Additionally, genes for many different cellular processes, such as DNA replication, cell division, and translation, are selectively repressed during PHB production. In contrast, the expression levels of genes under the control of the alternative sigma factor sigma(54) increase sharply during PHB production and are repressed again during PHB utilization. Global gene regulation during PHB production is strongly reminiscent of the gene expression pattern observed during the stringent response in other species. Furthermore, a ppGpp synthase deletion mutant did not show an accumulation of PHB, and the chemical induction of the stringent response with DL-norvaline caused an increased accumulation of PHB in the presence of ammonium. These results indicate that the stringent response is required for PHB accumulation in R. eutropha, helping to elucidate a thus-far-unknown physiological basis for this process.

  5. Improved detergent-based recovery of polyhydroxyalkanoates (PHAs).

    Science.gov (United States)

    Yang, Yung-Hun; Brigham, Christopher; Willis, Laura; Rha, ChoKyun; Sinskey, Anthony

    2011-05-01

    Extracting polyhydroxyalkanoate (PHA) polymer from bacterial cells often involves harsh conditions, including use of environmentally harmful solvents. We evaluated different detergents under various conditions to extract PHA from Ralstonia eutropha and Escherichia coli cells. Most detergents tested recovered highly pure PHA polymer from cells in amounts that depended on the percentage of polymer present in the cell. Detergents such as linear alkylbenzene sulfonic acid (LAS-99) produced a high yield of high purity polymer, and less detergent was needed compared to the amount of SDS to produce comparable yields. LAS-99 also has the advantage of being biodegradable and environmentally safe. Chemical extraction of PHA with detergents could potentially minimize or eliminate the need to use harsh organic solvents, thus making industrial PHA production a cleaner technology process. © Springer Science+Business Media B.V. 2011

  6. Processes for producing polyhydroxybutyrate and related polyhydroxyalkanoates in the plastids of higher plants

    Science.gov (United States)

    Somerville, C.R.; Nawrath, C.; Poirier, Y.

    1997-03-11

    The present invention relates to a process for producing poly-D-(-)-3-hydroxybutyric acid (PHB) and related polyhydroxyalkanoates (PHA) in the plastids of plants. The production of PHB is accomplished by genetically transforming plants with modified genes from microorganisms. The genes encode the enzymes required to synthesize PHB from acetyl-CoA or related metabolites and are fused with additional plant sequences for targeting the enzymes to the plastid. 37 figs.

  7. Characterization of a polyhydroxyalkanoate obtained from pineapple peel waste using Ralsthonia eutropha.

    Science.gov (United States)

    Vega-Castro, Oscar; Contreras-Calderon, Jose; León, Emilson; Segura, Almir; Arias, Mario; Pérez, León; Sobral, Paulo J A

    2016-08-10

    Agro-industrial waste can be the production source of biopolymers such as polyhydroxyalkanoates. The aim of this study was to produce and characterize Polyhydroxyalkanoates produced from pineapple peel waste fermentation processes. The methodology includes different pineapple peel waste fermentation conditions. The produced biopolymer was characterized using FTIR, GC-MS and NMR. The best fermentation condition for biopolymer production was obtained using pH 9, Carbon/Nitrogen 11, carbon/phosphorus 6 and fermentation time of 60h. FTIR analyzes showed PHB group characteristics, such as OH, CH and CO. In addition, GC-MS showed two monomers with 4 and 8 carbons, referred to PHB and PHBHV. H(1) NMR analysis showed 0.88-0.97 and 5.27ppm signals, corresponding to CH3 and CH, respectively. In conclusion, polyhydroxyalkanoate production from pineapple peels waste is an alternative for the treatment of waste generated in Colombia's fruit industry. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Funding initiates production of tunable nano-porous block copolymer membranes

    KAUST Repository

    Peinemann, Klaus-Viktor

    2013-06-01

    Researchers in Saudi Arabia at King Abdullah University of Science & Technology have created a membrane comprising a thin layer of densely packed, highly ordered cylindrical channels with uniform pore sizes - oriented perpendicular to its surface - on top of a non-ordered sponge-like layer. It is fabricated in a fast, one-step process by combining the self-assembly of an amphiphilic block copolymer (PS- b-P4VP) with non-solvent-induced phase separation. The university\\'s "Seed Fund" has helped the researchers to start manufacturing this membrane, which is particularly suited to size-selective and charge-based separation of bio-molecules. © 2013 Elsevier Ltd.

  9. Carbon Sources for Polyhydroxyalkanoates and an Integrated Biorefinery

    Directory of Open Access Journals (Sweden)

    Guozhan Jiang

    2016-07-01

    Full Text Available Polyhydroxyalkanoates (PHAs are a group of bioplastics that have a wide range of applications. Extensive progress has been made in our understanding of PHAs’ biosynthesis, and currently, it is possible to engineer bacterial strains to produce PHAs with desired properties. The substrates for the fermentative production of PHAs are primarily derived from food-based carbon sources, raising concerns over the sustainability of their production in terms of their impact on food prices. This paper gives an overview of the current carbon sources used for PHA production and the methods used to transform these sources into fermentable forms. This allows us to identify the opportunities and restraints linked to future sustainable PHA production. Hemicellulose hydrolysates and crude glycerol are identified as two promising carbon sources for a sustainable production of PHAs. Hemicellulose hydrolysates and crude glycerol can be produced on a large scale during various second generation biofuels’ production. An integration of PHA production within a modern biorefinery is therefore proposed to produce biofuels and bioplastics simultaneously. This will create the potential to offset the production cost of biofuels and reduce the overall production cost of PHAs.

  10. Carbon Sources for Polyhydroxyalkanoates and an Integrated Biorefinery.

    Science.gov (United States)

    Jiang, Guozhan; Hill, David J; Kowalczuk, Marek; Johnston, Brian; Adamus, Grazyna; Irorere, Victor; Radecka, Iza

    2016-07-19

    Polyhydroxyalkanoates (PHAs) are a group of bioplastics that have a wide range of applications. Extensive progress has been made in our understanding of PHAs' biosynthesis, and currently, it is possible to engineer bacterial strains to produce PHAs with desired properties. The substrates for the fermentative production of PHAs are primarily derived from food-based carbon sources, raising concerns over the sustainability of their production in terms of their impact on food prices. This paper gives an overview of the current carbon sources used for PHA production and the methods used to transform these sources into fermentable forms. This allows us to identify the opportunities and restraints linked to future sustainable PHA production. Hemicellulose hydrolysates and crude glycerol are identified as two promising carbon sources for a sustainable production of PHAs. Hemicellulose hydrolysates and crude glycerol can be produced on a large scale during various second generation biofuels' production. An integration of PHA production within a modern biorefinery is therefore proposed to produce biofuels and bioplastics simultaneously. This will create the potential to offset the production cost of biofuels and reduce the overall production cost of PHAs.

  11. Characterization of Polyhydroxyalkanoates Produced by ...

    African Journals Online (AJOL)

    Contaminated Soil Bacteria using Wastewater and Glucose as Carbon ... compare the use of wastewater as a carbon source for PHA production. .... The microorganisms were identified using ... the polymer production with respect to substrate.

  12. Production of Polyhydroxyalkanoates, a bacterial biodegradable ...

    African Journals Online (AJOL)

    African Journal of Biotechnology. Journal Home · ABOUT THIS JOURNAL · Advanced Search · Current Issue · Archives · Journal Home > Vol 3, No 1 (2004) >. Log in or Register to get access to full text downloads.

  13. Polyhydroxyalkanoate production from unexplored sugar substrates

    Directory of Open Access Journals (Sweden)

    Alejandro Salazar

    2014-01-01

    Full Text Available La producción de biopolímeros a escala industrial es restringida por los elevados costos de producción, en comparación con aquellos asociados a polímeros sintéticos (no biodegradables y no biocompatibles. En este estudio evaluamos por primera vez dos sustratos de carbono de bajo costo (i.e. pulpa de algarrobo y jugo de fique para la producción a escala de laboratorio de polyhydroxyalcanoato (PHA con Bacillus megaterium. La detección e identificación de PHA se hizo mediante cromatografía de gases con detector selectivo de masas operado en el modo de Monitoreo de Ion Selectivo (GC-MS/SIM. Los resultados sugieren que la producción de PHA a partir de pulpa de algarrobo (de Hymenaea courbaril puede ser tan alta como con melaza de caña. Más aún, puede servir para la síntesis del tipo de PHA más comercializado (i.e. polihidroxibutirato; PHB y/o de otras variedades (e.g. polihidroxi-butirato-co-valerato; PHBV con diferentes propiedades y posibles aplicaciones.

  14. Synthesis of polyhydroxyalkanoate from palm oil and some new applications.

    Science.gov (United States)

    Sudesh, Kumar; Bhubalan, Kesaven; Chuah, Jo-Ann; Kek, Yik-Kang; Kamilah, Hanisah; Sridewi, Nanthini; Lee, Yan-Fen

    2011-03-01

    Polyhydroxyalkanoate (PHA) is a potential substitute for some petrochemical-based plastics. This biodegradable plastic is derived from microbial fermentation using various carbon substrates. Since carbon source has been identified as one of the major cost-absorbing factors in PHA production, cheap and renewable substrates are currently being investigated as substitutes for existing sugar-based feedstock. Plant oils have been found to result in high-yield PHA production. Malaysia, being the world's second largest producer of palm oil, is able to ensure continuous supply of palm oil products for sustainable PHA production. The biosynthesis and characterization of various types of PHA using palm oil products have been described in detail in this review. Besides, by-products and waste stream from palm oil industry have also demonstrated promising results as carbon sources for PHA biosynthesis. Some new applications in cosmetic and wastewater treatment show the diversity of PHA usage. With proper management practices and efficient milling processes, it may be possible to supply enough palm oil-based raw materials for human consumption and other biotechnological applications such as production of PHA in a sustainable manner.

  15. Recycling of plastic wastes with poly (ethylene-co-methacrylic acid) copolymer as compatibilizer and their conversion into high-end product.

    Science.gov (United States)

    Rajasekaran, Divya; Maji, Pradip K

    2018-04-01

    This paper deals with the utilization of plastic wastes to a useful product. The major plastic pollutants that are considered to be in maximum use i.e. PET bottle and PE bags have been taken for consideration for recycling. As these two plastic wastes are not compatible, poly (ethylene-co-methacrylic acid) copolymer has been used as compatibilizer to process these two plastic wastes. Effect of dose of poly (ethylene-co-methacrylic acid) copolymer as compatibilizer has been studied here. It has been shown that only 3 wt% of poly (ethylene-co-methacrylic acid) copolymer is sufficient to make 3:1 mass ratio of PET bottle and polyethylene bags compatible. Compatibility has been examined through mechanical testing, thermal and morphological analysis. After analysing the property of recyclates, better mechanical and thermal property has been observed. Almost 500% of tensile property has been improved by addition of 3 wt% of poly (ethylene-co-methacrylic acid) copolymer in 3:1 mass ratio blend of PET bottle and PE bags than that of pristine blend. Morphological analysis by FESEM and AFM has also confirmed the compatibility of the blend. Experimental data showed better performance than available recycling process. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. Exploration of Global Trend on Biomedical Application of Polyhydroxyalkanoate (PHA): A Patent Survey.

    Science.gov (United States)

    Ponnaiah, Paulraj; Vnoothenei, Nagiah; Chandramohan, Muruganandham; Thevarkattil, Mohamed Javad Pazhayakath

    2018-01-30

    Polyhydroxyalkanoates are bio-based, biodegradable naturally occurring polymers produced by a wide range of organisms, from bacteria to higher mammals. The properties and biocompatibility of PHA make it possible for a wide spectrum of applications. In this context, we analyze the potential applications of PHA in biomedical science by exploring the global trend through the patent survey. The survey suggests that PHA is an attractive candidate in such a way that their applications are widely distributed in the medical industry, drug delivery system, dental material, tissue engineering, packaging material as well as other useful products. In our present study, we explored patents associated with various biomedical applications of polyhydroxyalkanoates. Patent databases of European Patent Office, United States Patent and Trademark Office and World Intellectual Property Organization were mined. We developed an intensive exploration approach to eliminate overlapping patents and sort out significant patents. We demarcated the keywords and search criterions and established search patterns for the database request. We retrieved documents within the recent 6 years, 2010 to 2016 and sort out the collected data stepwise to gather the most appropriate documents in patent families for further scrutiny. By this approach, we retrieved 23,368 patent documents from all the three databases and the patent titles were further analyzed for the relevance of polyhydroxyalkanoates in biomedical applications. This ensued in the documentation of approximately 226 significant patents associated with biomedical applications of polyhydroxyalkanoates and the information was classified into six major groups. Polyhydroxyalkanoates has been patented in such a way that their applications are widely distributed in the medical industry, drug delivery system, dental material, tissue engineering, packaging material as well as other useful products. There are many avenues through which PHA & PHB could be

  17. Conversion of industrial food wastes by Alcaligenes latus into polyhydroxyalkanoates.

    Science.gov (United States)

    Yu, P H; Chua, H; Huang, A L; Ho, K P

    1999-01-01

    Broader usage of biodegradable plastics in packaging and disposable products as a solution to environmental problems would heavily depend on further reduction of costs and the discovery of novel biodegradable plastics with improved properties. As the first step in our pursuit of eventual usage of industrial food wastewater as nutrients for microorganisms to synthesise environmental-friendly bioplastics, we investigated the usage of soya wastes from a soya milk dairy, and malt wastes from a beer brewery plant as the carbon sources for the production of polyhydroxyalkanoates (PHA) by selected strain of microorganism. Bench experiments showed that Alcaligenes latus DSM 1124 used the nutrients from malt and soya wastes to biosynthesise PHAs. The final dried cell mass and specific polymer production of A. latus DSM 1124 were 32g/L and 70% polymer/cells (g/g), 18.42 g/L and 32.57% polymer/cell (g/g), and 28 g/L and 36% polymer/cells (g/g), from malt waste, soya waste, and from sucrose, respectively. These results suggest that many types of food wastes might be used as the carbon source for the production of PHA.

  18. A novel route for the production of chitosan/poly(lactide-co-glycolide) graft copolymers for electrospinning

    International Nuclear Information System (INIS)

    Xie Deming; Huang Huamei; Blackwood, Keith; MacNeil, Sheila

    2010-01-01

    Both chitosan and polylactide/polyglycolide have good biocompatibility and can be used to produce tissue engineering scaffolds for cultured cells. However the synthetic scaffolds lack groups that would facilitate their modification, whereas chitosan has extensive active amide and hydroxyl groups which would allow it to be subsequently modified for the attachment of peptides, proteins and drugs. Also chitosan is very hydrophilic, whereas PLGA is relatively hydrophobic. Accordingly there are many situations where it would be ideal to have a copolymer of both, especially one that could be electrospun to provide a versatile range of scaffolds for tissue engineering. Our aim was to develop a novel route of chitosan-g-PLGA preparation and evaluate the copolymers in terms of their chemical characterization, their performance on electrospinning and their ability to support the culture of fibroblasts as an initial biological evaluation of these scaffolds. Chitosan was first modified with trimethylsilyl chloride, and catalyzed by dimethylamino pyridine. PLGA-grafted chitosan copolymers were prepared by reaction with end-carboxyl PLGA (PLGA-COOH). FT-IR and 1 H-NMR characterized the copolymer molecular structure as being substantially different to that of the chitosan or PLGA on their own. Elemental analysis showed an average 18 pyranose unit intervals when PLGA-COOH was grafted into the chitosan molecular chain. Differential scanning calorimetry results showed that the copolymers had different thermal properties from PLGA and chitosan respectively. Contact angle measurements demonstrated that copolymers became more hydrophilic than PLGA. The chitosan-g-PLGA copolymers were electrospun to produce either nano- or microfibers as desired. A 3D fibrous scaffold of the copolymers gave good fibroblast adhesion and proliferation which did not differ significantly from the performance of the cells on the chitosan or PLGA electrospun scaffolds. In summary this work presents a

  19. A novel route for the production of chitosan/poly(lactide-co-glycolide) graft copolymers for electrospinning

    Energy Technology Data Exchange (ETDEWEB)

    Xie Deming [Tissue Engineering Laboratory, Department of Biomedical Engineering, Jinan University, Guangzhou, 510630 (China); Huang Huamei [Morphological Experiments Center of Medical College, Jinan University, Guangzhou, 510630 (China); Blackwood, Keith; MacNeil, Sheila [Tissue Engineering Group, Department of Engineering Materials and Division of Biomedical Sciences and Medicine, Kroto Research Institute, University of Sheffield North Campus, Broad Lane, Sheffield S3 7HQ (United Kingdom)

    2010-12-15

    Both chitosan and polylactide/polyglycolide have good biocompatibility and can be used to produce tissue engineering scaffolds for cultured cells. However the synthetic scaffolds lack groups that would facilitate their modification, whereas chitosan has extensive active amide and hydroxyl groups which would allow it to be subsequently modified for the attachment of peptides, proteins and drugs. Also chitosan is very hydrophilic, whereas PLGA is relatively hydrophobic. Accordingly there are many situations where it would be ideal to have a copolymer of both, especially one that could be electrospun to provide a versatile range of scaffolds for tissue engineering. Our aim was to develop a novel route of chitosan-g-PLGA preparation and evaluate the copolymers in terms of their chemical characterization, their performance on electrospinning and their ability to support the culture of fibroblasts as an initial biological evaluation of these scaffolds. Chitosan was first modified with trimethylsilyl chloride, and catalyzed by dimethylamino pyridine. PLGA-grafted chitosan copolymers were prepared by reaction with end-carboxyl PLGA (PLGA-COOH). FT-IR and{sup 1}H-NMR characterized the copolymer molecular structure as being substantially different to that of the chitosan or PLGA on their own. Elemental analysis showed an average 18 pyranose unit intervals when PLGA-COOH was grafted into the chitosan molecular chain. Differential scanning calorimetry results showed that the copolymers had different thermal properties from PLGA and chitosan respectively. Contact angle measurements demonstrated that copolymers became more hydrophilic than PLGA. The chitosan-g-PLGA copolymers were electrospun to produce either nano- or microfibers as desired. A 3D fibrous scaffold of the copolymers gave good fibroblast adhesion and proliferation which did not differ significantly from the performance of the cells on the chitosan or PLGA electrospun scaffolds. In summary this work presents a

  20. Biodegradability of Poly(hydroxyalkanoate Materials

    Directory of Open Access Journals (Sweden)

    Keiji Numata

    2009-08-01

    Full Text Available Poly(hydroxyalkanoate (PHA, which is produced from renewable carbon resources by many microorganisms, is an environmentally compatible polymeric material and can be processed into films and fibers. Biodegradation of PHA material occurs due to the action of extracellular PHA depolymerase secreted from microorganisms in various natural environments. A key step in determining the overall enzymatic or environmental degradation rate of PHA material is the degradation of PHA lamellar crystals in materials; hence, the degradation mechanism of PHA lamellar crystals has been studied in detail over the last two decades. In this review, the relationship between crystal structure and enzymatic degradation behavior, in particular degradation rates, of films and fibers for PHA is described.

  1. Studium biodegradace polyhydroxyalkanoátů.

    OpenAIRE

    Wurstová, Agáta

    2014-01-01

    Diplomová práce je zaměřena na studium biodegradace polyhydroxyalkanoátů, konkrétně polymeru polyhydroxybutyrátu. První část práce se zabývá studiem biodegradace polyhydroxybutyrátu ve formě PHB prášku a PHB fólie pomocí vybraných druhů mikroorganismů z řad bakterií, kvasinek a plísní. Jako zástupce bakterií byl vybrán mikroorganismus Delftia acidovorans, z řad kvasinek Aureobasidium pullulans a ze zástupců plísní Aspergillus fumigatus. Aktivita extracelulární PHB depolymerázy byla analyzován...

  2. Microbial bio-based plastics from olive-mill wastewater: Generation and properties of polyhydroxyalkanoates from mixed cultures in a two-stage pilot scale system.

    Science.gov (United States)

    Ntaikou, I; Valencia Peroni, C; Kourmentza, C; Ilieva, V I; Morelli, A; Chiellini, E; Lyberatos, G

    2014-10-20

    The operational efficiency of a two stage pilot scale system for polyhydroxyalkanoates (PHAs) production from three phase olive oil mill wastewater (OMW) was investigated in this study. A mixed anaerobic, acidogenic culture derived from a municipal wastewater treatment plant, was used in the first stage, aiming to the acidification of OMW. The effluent of the first bioreactor that was operated in continuous mode, was collected in a sedimentation tank in which partial removal of the suspended solids was taking place, and was then forwarded to an aerobic reactor, operated in sequential batch mode under nutrient limitation. In the second stage an enriched culture of Pseudomonas sp. was used as initial inoculum for the production of PHAs from the acidified waste. Clarification of the acidified waste, using aluminium sulphate which causes flocculation and precipitation of solids, was also performed, and its effect on the composition of the acidified waste as well as on the yields and properties of PHAs was investigated. It was shown that clarification had no significant qualitative or quantitative effect on the primary carbon sources, i.e. short chain fatty acids and residual sugars, but only on the values of total suspended solids and total chemical oxygen demand of the acidified waste. The type and thermal characteristics of the produced PHAs were also similar for both types of feed. However the clarification of the waste seemed to have a positive impact on final PHAs yield, measured as gPHAs/100g of VSS, which reached up to 25%. Analysis of the final products via nuclear magnetic resonance spectroscopy revealed the existence of 3-hydroxybutyrate (3HB) and 3-hydroxyoctanoate (HO) units, leading to the conclusion that the polymer could be either a blend of P3HB and P3HO homopolymers or/and the 3HB-co-3HO co-polymer, an unusual polymer occurring in nature with advanced properties. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Perspectives of medium chain length poly(hydroxyalkanoates), a versatile set of bacterial bioplastics

    Science.gov (United States)

    Witholt; Kessler

    1999-06-01

    Medium chain length (mcl) poly(hydroxyalkanoic acids) (PHAs) are polyesters accumulated by fluorescent Pseudomonads and other bacteria. Work on the genetics of mcl-PHA formation has led to polymer synthesis in recombinant bacteria and plants. Several high and medium cost applications are now emerging. With optimized bacterial mcl-PHA synthesis on inexpensive agro-substrates and the development of plant-based mcl-PHAs in the next decade, the production economics of these bioplastics will ultimately permit their sustainable production for bulk applications.

  4. Conversion of post consumer polyethylene to the biodegradable polymer polyhydroxyalkanoate.

    Science.gov (United States)

    Guzik, Maciej W; Kenny, Shane T; Duane, Gearoid F; Casey, Eoin; Woods, Trevor; Babu, Ramesh P; Nikodinovic-Runic, Jasmina; Murray, Michael; O'Connor, Kevin E

    2014-05-01

    A process for the conversion of post consumer (agricultural) polyethylene (PE) waste to the biodegradable polymer medium chain length polyhydroxyalkanoate (mcl-PHA) is reported here. The thermal treatment of PE in the absence of air (pyrolysis) generated a complex mixture of low molecular weight paraffins with carbon chain lengths from C8 to C32 (PE pyrolysis wax). Several bacterial strains were able to grow and produce PHA from this PE pyrolysis wax. The addition of biosurfactant (rhamnolipids) allowed for greater bacterial growth and PHA accumulation of the tested strains. Some strains were only capable of growth and PHA accumulation in the presence of the biosurfactant. Pseudomonas aeruginosa PAO-1 accumulated the highest level of PHA with almost 25 % of the cell dry weight as PHA when supplied with the PE pyrolysis wax in the presence of rhamnolipids. The change of nitrogen source from ammonium chloride to ammonium nitrate resulted in faster bacterial growth and the earlier onset of PHA accumulation. To our knowledge, this is the first report where PE is used as a starting material for production of a biodegradable polymer.

  5. Polyhydroxyalkanoate biosynthesis by oxalotrophic bacteria from high Andean soil

    Directory of Open Access Journals (Sweden)

    Roger David Castillo-Arteaga

    2018-02-01

    Full Text Available Oxalate is a highly oxidized organic acid anion used as a carbon and energy source by oxalotrophic bacteria. Oxalogenic plants convert atmospheric CO2 into oxalic acid and oxalic salts. Oxalate-salt formation acts as a carbon sink in terrestrial ecosystems via the oxalate-carbonate pathway (OCP. Oxalotrophic bacteria might be implicated in other carbon-storage processes, including the synthesis of polyhydroxyalkanoates (PHAs. More recently, a variety of bacteria from the Andean region of Colombia in Nariño have been reported for their PHA-producing abilities. These species can degrade oxalate and participate in the oxalate-carbonate pathway. The aim of this study was to isolate and characterize oxalotrophic bacteria with the capacity to accumulate PHA biopolymers. Plants of the genus Oxalis were collected and bacteria were isolated from the soil adhering to the roots. The isolated bacterial strains were characterized using biochemical and molecular biological methods. The consumption of oxalate in culture was quantified, and PHA production was monitored in batch fermentation. The polymeric composition was characterized using gas chromatography. Finally, a biosynthetic pathway based on our findings and on those from published sources is proposed. Strains of Bacillus spp. and Serratia sp. were found to metabolize calcium oxalate and synthesize PHA.

  6. Start a Research on Biopolymer Polyhydroxyalkanoate (PHA: A Review

    Directory of Open Access Journals (Sweden)

    Giin-Yu Amy Tan

    2014-03-01

    Full Text Available With the impending fossil fuel crisis, the search for and development of alternative chemical/material substitutes is pivotal in reducing mankind’s dependency on fossil resources. One of the potential substitute candidates is polyhydroxyalkanoate (PHA. PHA is a carbon-neutral and valuable polymer that could be produced from many renewable carbon sources by microorganisms, making it a sustainable and environmental-friendly material. At present, PHA is not cost competitive compared to fossil-derived products. Encouraging and intensifying research work on PHA is anticipated to enhance its economic viability in the future. The development of various biomolecular and chemical techniques for PHA analysis has led to the identification of many PHA-producing microbial strains, some of which are deposited in culture collections. Research work on PHA could be rapidly initiated with these ready-to-use techniques and microbial strains. This review aims to facilitate the start-up of PHA research by providing a summary of commercially available PHA-accumulating microbial cultures, PHA biosynthetic pathways, and methods for PHA detection, extraction and analysis.

  7. Synthesis of Diblock copolymer poly-3-hydroxybutyrate -block-poly-3-hydroxyhexanoate [PHB-b-PHHx] by a β-oxidation weakened Pseudomonas putida KT2442

    DEFF Research Database (Denmark)

    Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun

    2012-01-01

    ), thermo- and mechanical analysis. NMR confirmed the existence of diblock copolymers consisting of 58 mol% PHB as the short chain length block with 42 mol% PHHx as the medium chain length block. The block copolymers had two glass transition temperatures (Tg) at 2.7°C and -16.4°C, one melting temperature...... (Tm) at 172.1°C and one cool crystallization temperature (Tc) at 69.1°C as revealed by differential scanning calorimetry (DSC), respectively. This is the first microbial short-chain-length (scl) and medium-chain-length (mcl) PHA block copolymer reported. CONCLUSIONS: It is possible to produce PHA......BACKGROUND: Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB...

  8. Polyhydroxyalkanoate (PHA) Granules Have no Phospholipids

    Science.gov (United States)

    Bresan, Stephanie; Sznajder, Anna; Hauf, Waldemar; Forchhammer, Karl; Pfeiffer, Daniel; Jendrossek, Dieter

    2016-01-01

    Polyhydroxybutyrate (PHB) granules, also designated as carbonosomes, are supra-molecular complexes in prokaryotes consisting of a PHB polymer core and a surface layer of structural and functional proteins. The presence of suspected phospholipids in the surface layer is based on in vitro data of isolated PHB granules and is often shown in cartoons of the PHB granule structure in reviews on PHB metabolism. However, the in vivo presence of a phospholipid layer has never been demonstrated. We addressed this topic by the expression of fusion proteins of DsRed2EC and other fluorescent proteins with the phospholipid-binding domain (LactC2) of lactadherin in three model organisms. The fusion proteins specifically localized at the cell membrane of Ralstonia eutropha but did not co-localize with PHB granules. The same result was obtained for Pseudomonas putida, a species that accumulates another type of polyhydroxyalkanoate (PHA) granules related to PHB. Notably, DsRed2EC-LactC2 expressed in Magnetospirillum gryphiswaldense was detected at the position of membrane-enclosed magnetosome chains and at the cytoplasmic membrane but not at PHB granules. In conclusion, the carbonosomes of representatives of α-proteobacteria, β-proteobacteria and γ-proteobacteria have no phospholipids in vivo and we postulate that the PHB/PHA granule surface layers in natural producers generally are free of phospholipids and consist of proteins only. PMID:27222167

  9. Fungal degradation of polyhydroxyalkanoates and a semiquantitative assay for screening their degradation by terrestrial fungi.

    Science.gov (United States)

    Matavulj, M; Molitoris, H P

    1992-12-01

    The current problems with decreasing fossile resources and increasing environmental pollution by petrochemical-based plastics have stimulated investigations to find biosynthetic materials which are also biodegradable. Bacterial reserve materials such as polyhydroxyalkanoates (PHA) have been discovered to possess thermoplastic properties and can be synthesized from renewable resources. Poly-beta-hydroxybutyric acid (PHB) is at present the most promising PHA; and BIOPOL, its copolymer with poly-beta-hydroxy-valerate (PHV), is already industrially produced (ICI, UK), and used as packaging material (WELLA, FRG). According to the literature, PHA degradation has so far mainly been observed in bacteria; only under certain environmental conditions has fungal degradation of PHAs been indicated. Since fungi constitute an important part of microbial populations participating in degradation processes, a simple screening method for fungal degradation of BIOPOL, a PHA-based plastic, was developed. Several media with about 150 fungal strains from different terrestrial environments and belonging to different systematic and ecological groups were used. PHA depolymerization was tested on three PHB-based media, each with 0.1% BIOPOL or PHB homopolymer causing turbidity of the medium. The media contained either a comparatively low or high content of organic carbon (beside PHA) or were based on mineral medium with PHA as the principal source of carbon. The degradation activity was detectable due to formation of a clear halo around the colony (Petri plates) or a clear zone under the colony (test tubes).(ABSTRACT TRUNCATED AT 250 WORDS)

  10. Polyethylene-Based Tadpole Copolymers

    KAUST Repository

    Alkayal, Nazeeha

    2017-02-15

    Novel well-defined polyethylene-based tadpole copolymers ((c-PE)-b-PS, PE: polyethylene, PS: polystyrene) with ring PE head and linear PS tail are synthesized by combining polyhomologation, atom transfer radical polymerization (ATRP), and Glaser coupling reaction. The -OH groups of the 3-miktoarm star copolymers (PE-OH)-b-PS, synthesized by polyhomologation and ATRP, are transformed to alkyne groups by esterification with propiolic acid, followed by Glaser cyclization and removal of the unreacted linear with Merrifield\\'s resin-azide. The characterization results of intermediates and final products by high-temperature size exclusion chromatography, H NMR spectroscopy, and differential scanning calorimetry confirm the tadpole topology.

  11. Isolation and Screening of Polyhydroxyalkanoates Producing Bacteria from Pulp, Paper, and Cardboard Industry Wastes

    Directory of Open Access Journals (Sweden)

    Anish Kumari Bhuwal

    2013-01-01

    Full Text Available Background. Polyhydroxyalkanoates (PHAs are storage materials that accumulate by various bacteria as energy and carbon reserve materials. They are biodegradable, environmentally friendly, and also biocompatible bioplastics. Unlike petrochemical-based plastics that take several decades to fully degrade, PHAs can be completely degraded within a year by variety of microorganisms into CO2 and water. In the present study, we aim to utilize pulp, paper, and cardboard industry sludge and waste water for the isolation and screening of polyhydroxyalkanoates (PHAs accumulating bacteria and production of cost-effective PHB using cardboard industry waste water. Results. A total of 42 isolates showed black-blue coloration when stained with Sudan black B, a preliminary screening agent for lipophilic compounds, and a total of 15 isolates showed positive result with Nile blue A staining, a more specific dye for PHA granules. The isolates NAP11 and NAC1 showed maximum PHA production 79.27% and 77.63% with polymer concentration of 5.236 g/L and 4.042 g/L with cardboard industry waste water. Both of the selected isolates, NAP11 and NAC1, were classified up to genus level by studying their morphological and biochemical characteristics and were found to be Enterococcus sp., Brevundimonas sp. and, respectively. Conclusion. The isolates Enterococcus sp. NAP11 and Brevundimonas sp. NAC1 can be considered as good candidates for industrial production of PHB from cardboard industry waste water. We are reporting for the first time the use of cardboard industry waste water as a cultivation medium for the PHB production.

  12. Isolation and Screening of Polyhydroxyalkanoates Producing Bacteria from Pulp, Paper, and Cardboard Industry Wastes

    Science.gov (United States)

    Bhuwal, Anish Kumari; Singh, Gulab; Aggarwal, Neeraj Kumar; Goyal, Varsha; Yadav, Anita

    2013-01-01

    Background. Polyhydroxyalkanoates (PHAs) are storage materials that accumulate by various bacteria as energy and carbon reserve materials. They are biodegradable, environmentally friendly, and also biocompatible bioplastics. Unlike petrochemical-based plastics that take several decades to fully degrade, PHAs can be completely degraded within a year by variety of microorganisms into CO2 and water. In the present study, we aim to utilize pulp, paper, and cardboard industry sludge and waste water for the isolation and screening of polyhydroxyalkanoates (PHAs) accumulating bacteria and production of cost-effective PHB using cardboard industry waste water. Results. A total of 42 isolates showed black-blue coloration when stained with Sudan black B, a preliminary screening agent for lipophilic compounds, and a total of 15 isolates showed positive result with Nile blue A staining, a more specific dye for PHA granules. The isolates NAP11 and NAC1 showed maximum PHA production 79.27% and 77.63% with polymer concentration of 5.236 g/L and 4.042 g/L with cardboard industry waste water. Both of the selected isolates, NAP11 and NAC1, were classified up to genus level by studying their morphological and biochemical characteristics and were found to be Enterococcus sp., Brevundimonas sp. and, respectively. Conclusion. The isolates Enterococcus sp. NAP11 and Brevundimonas sp. NAC1 can be considered as good candidates for industrial production of PHB from cardboard industry waste water. We are reporting for the first time the use of cardboard industry waste water as a cultivation medium for the PHB production. PMID:24288534

  13. Olefin–Styrene Copolymers

    OpenAIRE

    Nunzia Galdi; Antonio Buonerba; Leone Oliva

    2016-01-01

    In this review are reported some of the most relevant achievements in the chemistry of the ethylene–styrene copolymerization and in the characterization of the copolymer materials. Focus is put on the relationship between the structure of the catalyst and that of the obtained copolymer. On the other hand, the wide variety of copolymer architecture is related to the properties of the material and to the potential utility.

  14. Benzene containing polyhydroxyalkanoates homo- and copolymers synthesized by genome edited Pseudomonas entomophila

    DEFF Research Database (Denmark)

    Shen, Rui; Cai, Longwei; Meng, Dechuan

    2014-01-01

    Microbial synthesis of functional polymers has become increasingly important for industrial biotechnology. For the first time, it became possible to synthesize controllable composition of poly(3-hydroxyalkanoate) (P3HA) consisting of 3-hydroxydodecanoate (3HDD) and phenyl group on the side......HPhV) and 3-hydroxydodecanoate (3HDD) were synthesized when the strain was grown on mixtures of PVA and dodecanoic acid (DDA). Compositions of 3HPhV in P(3HPhV-co-3HDD) were controllable ranging from 3% to 32% depending on DDDA/PVA ratios. Nuclear magnetic resonance (NMR) spectra clearly indicated...

  15. Block Copolymers: Synthesis and Applications in Nanotechnology

    Science.gov (United States)

    Lou, Qin

    This study is focused on the synthesis and study of (block) copolymers using reversible deactivation radical polymerizations (RDRPs), including atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. In particular, two primary areas of study are undertaken: (1) a proof-of-concept application of lithographic block copolymers, and (2) the mechanistic study of the deposition of titania into block copolymer templates for the production of well-ordered titania nanostructures. Block copolymers have the ability to undergo microphase separation, with an average size of each microphase ranging from tens to hundreds of nanometers. As such, block copolymers have been widely considered for nanotechnological applications over the past two decades. The development of materials for various nanotechnologies has become an increasingly studied area as improvements in many applications, such as those found in the semiconductor and photovoltaic industries are constantly being sought. Significant growth in developments of new synthetic methods ( i.e. RDRPs) has allowed the production of block copolymers with molecular (and sometimes atomic) definition. In turn, this has greatly expanded the use of block copolymers in nanotechnology. Herein, we describe the synthesis of statistical and block copolymers of 193 nm photolithography methacrylate and acrylate resist monomers with norbornyl and adamantyl moieties using RAFT polymerization.. For these resist (block) copolymers, the phase separation behaviors were examined by atomic force microscopy (AFM). End groups were removed from the polymers to avoid complications during the photolithography since RAFT end groups absorb visible light. Poly(glycidyl methacrylate-block-polystyrene) (PGMA-b-PS) was synthesize by ATRP and demonstrated that this block copolymer acts as both a lithographic UV (365 nm) photoresist and a self-assembly material. The PGMA segments can undergo cationic

  16. Silicon containing copolymers

    CERN Document Server

    Amiri, Sahar; Amiri, Sanam

    2014-01-01

    Silicones have unique properties including thermal oxidative stability, low temperature flow, high compressibility, low surface tension, hydrophobicity and electric properties. These special properties have encouraged the exploration of alternative synthetic routes of well defined controlled microstructures of silicone copolymers, the subject of this Springer Brief. The authors explore the synthesis and characterization of notable block copolymers. Recent advances in controlled radical polymerization techniques leading to the facile synthesis of well-defined silicon based thermo reversible block copolymers?are described along with atom transfer radical polymerization (ATRP), a technique utilized to develop well-defined functional thermo reversible block copolymers. The brief also focuses on Polyrotaxanes and their great potential as stimulus-responsive materials which produce poly (dimethyl siloxane) (PDMS) based thermo reversible block copolymers.

  17. Advances in the Applications of Polyhydroxyalkanoate Nanoparticles for Novel Drug Delivery System

    Directory of Open Access Journals (Sweden)

    Anupama Shrivastav

    2013-01-01

    Full Text Available Drug delivery technology is emerging as an interdisciplinary science aimed at improving human health. The controlled delivery of pharmacologically active agents to the specific site of action at the therapeutically optimal rate and dose regimen has been a major goal in designing drug delivery systems. Over the past few decades, there has been considerable interest in developing biodegradable drug carriers as effective drug delivery systems. Polymeric materials from natural sources play an important role in controlled release of drug at a particular site. Polyhydroxyalkanoates, due to their origin from natural sources, are given attention as candidates for drug delivery materials. Biodegradable and biocompatible polyhydroxyalkanoates are linear polyesters produced by microorganisms under unbalanced growth conditions, which have emerged as potential polymers for use as biomedical materials for drug delivery due to their unique physiochemical and mechanical properties. This review summarizes many of the key findings in the applications of polyhydroxyalkanoates and polyhydroxyalkanoate nanoparticles for drug delivery system.

  18. Biodegradable and Biocompatible Polyhydroxy-alkanoates (PHA: Auspicious Microbial Macromolecules for Pharmaceutical and Therapeutic Applications

    Directory of Open Access Journals (Sweden)

    Martin Koller

    2018-02-01

    Full Text Available Polyhydroxyalkanoates (PHA are bio-based microbial biopolyesters; their stiffness, elasticity, crystallinity and degradability are tunable by the monomeric composition, selection of microbial production strain, substrates, process parameters during production, and post-synthetic processing; they display biological alternatives for diverse technomers of petrochemical origin. This, together with the fact that their monomeric and oligomeric in vivo degradation products do not exert any toxic or elsewhere negative effect to living cells or tissue of humans or animals, makes them highly stimulating for various applications in the medical field. This article provides an overview of PHA application in the therapeutic, surgical and tissue engineering area, and reviews strategies to produce PHA at purity levels high enough to be used in vivo. Tested applications of differently composed PHA and advanced follow-up products as carrier materials for controlled in vivo release of anti-cancer drugs or antibiotics, as scaffolds for tissue engineering, as guidance conduits for nerve repair or as enhanced sutures, implants or meshes are discussed from both a biotechnological and a material-scientific perspective. The article also describes the use of traditional processing techniques for production of PHA-based medical devices, such as melt-spinning, melt extrusion, or solvent evaporation, and emerging processing techniques like 3D-printing, computer-aided wet-spinning, laser perforation, and electrospinning.

  19. Accumulation of a Polyhydroxyalkanoate Containing Primarily 3-Hydroxydecanoate from Simple Carbohydrate Substrates by Pseudomonas sp. Strain NCIMB 40135

    OpenAIRE

    Haywood, Geoffrey W.; Anderson, Alistair J.; Ewing, David F.; Dawes, Edwin A.

    1990-01-01

    A number of Pseudomonas species have been identified which accumulate a polyhydroxyalkanoate containing mainly 3-hydroxydecanoate monomers from sodium gluconate as the sole carbon source. One of these, Pseudomonas sp. strain NCIMB 40135, was further investigated and shown to accumulate such a polyhydroxyalkanoate from a wide range of carbon sources (C2 to C6); however, when supplied with octanoic acid it produced a polyhydroxyalkanoate containing mainly 3-hydroxyoctanoate monomers. Polymer sy...

  20. Evaluation of short-chain-length polyhydroxyalkanoate accumulation in Bacillus aryabhattai

    Directory of Open Access Journals (Sweden)

    Aneesh Balakrishna Pillai

    Full Text Available Abstract This study was focused on the polyhydroxybutyrate (PHB accumulation property of Bacillus aryabhattai isolated from environment. Twenty-four polyhydroxyalkanoate (PHA producers were screened out from sixty-two environmental bacterial isolates based on Sudan Black B colony staining. Based on their PHA accumulation property, six promising isolates were further screened out. The most productive isolate PHB10 was identified as B. aryabhattai PHB10. The polymer production maxima were 3.264 g/L, 2.181 g/L, 1.47 g/L, 1.742 g/L and 1.786 g/L in glucose, fructose, maltose, starch and glycerol respectively. The bacterial culture reached its stationary and declining phases at 18 h and 21 h respectively and indicated growth-associated PHB production. Nuclear Magnetic Resonance (NMR spectra confirmed the material as PHB. The material has thermal stability between 30 and 140 °C, melting point at 170 °C and maximum thermal degradation at 287 °C. The molecular weight and poly dispersion index of the polymer were found as 199.7 kDa and 2.67 respectively. The bacterium B. aryabhattai accumulating PHB up to 75% of cell dry mass utilizing various carbon sources is a potential candidate for large scale production of bacterial polyhydroxybutyrate.

  1. Polyhydroxyalkanoates: A way to sustainable development of bioplastics

    Directory of Open Access Journals (Sweden)

    Roopesh Jain

    2010-01-01

    Full Text Available This paper reviews role of polyhydroxyalkanoates (PHAs for sustainable development of bioplastics. PHAs are polyesters of hydroxyalkanoates with the general structural and have been investigated by biologists, chemists, engineers and other experts over the past many years. Bio-based and biodegradable plastics can form the basis for environmentally referable and sustainable alternative to current materials based exclusively on petroleum feed stocks. The result of the efforts made by scientist sought solution in form of biopolymer obtained either from microorganism or plants source and likely to replace currently used synthetic polymers as bioplastic. Applications of PHA as bioplastics, fine chemicals, implant biomaterials, and medicines have been developed. The PHA polymers promise to extend significantly the range of biomaterials as suitable alternative of plastic.

  2. Increasing polyhydroxyalkanoate (PHA) yields from Cupriavidus necator by using filtered digestate liquors.

    Science.gov (United States)

    Passanha, Pearl; Esteves, Sandra R; Kedia, Gopal; Dinsdale, Richard M; Guwy, Alan J

    2013-11-01

    The production of polyhydroxyalkanoates (PHAs) using digestate liquor as culture media is a novel application to extend the existing uses of digestates. In this study, two micro-filtered digestates (0.22 μm) were evaluated as a source of complex culture media for the production of PHA by Cupriavidus necator as compared to a conventional media. Culture media using a mixture of micro-filtered liquors from food waste and from wheat feed digesters showed a maximum PHA accumulation of 12.29 g/l PHA, with 90% cell dry weight and a yield of 0.48 g PHA/g VFA consumed, the highest reported to date for C. necator studies. From the analysis of the starting and residual media, it was concluded that ammonia, potassium, magnesium, sulfate and phosphate provided in the digestate liquors were vital for the initial growth of C. necator whereas copper, iron and nickel may have played a significant role in PHA accumulation. Copyright © 2013 Elsevier Ltd. All rights reserved.

  3. Low frequency sonic waves assisted cloud point extraction of polyhydroxyalkanoate from Cupriavidus necator.

    Science.gov (United States)

    Murugesan, Sivananth; Iyyaswami, Regupathi

    2017-08-15

    Low frequency sonic waves, less than 10kHz were introduced to assist cloud point extraction of polyhydroxyalkanoate from Cupriavidus necator present within the crude broth. Process parameters including surfactant system variables and sonication parameters were studied for their effect on extraction efficiency. Introduction of low frequency sonic waves assists in the dissolution of microbial cell wall by the surfactant micelles and release of cellular content, polyhydroxyalkanoate granules released were encapsulated by the micelle core which was confirmed by crotonic acid assay. In addition, sonic waves resulted in the separation of homogeneous surfactant and broth mixture into two distinct phases, top aqueous phase and polyhydroxyalkanoate enriched bottom surfactant rich phase. Mixed surfactant systems showed higher extraction efficiency compared to that of individual Triton X-100 concentrations, owing to increase in the hydrophobicity of the micellar core and its interaction with polyhydroxyalkanoate. Addition of salts to the mixed surfactant system induces screening of charged surfactant head groups and reduces inter-micellar repulsion, presence of ammonium ions lead to electrostatic repulsion and weaker cation sodium enhances the formation of micellar network. Addition of polyethylene glycol 8000 resulted in increasing interaction with the surfactant tails of the micelle core there by reducing the purity of polyhydroxyalkanoate. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Marine sponge-associated bacteria as a potential source for polyhydroxyalkanoates.

    Science.gov (United States)

    Sathiyanarayanan, Ganesan; Saibaba, Ganesan; Kiran, George Seghal; Yang, Yung-Hun; Selvin, Joseph

    2017-05-01

    Marine sponges are filter feeding porous animals and usually harbor a remarkable array of microorganisms in their mesohyl tissues as transient and resident endosymbionts. The marine sponge-microbial interactions are highly complex and, in some cases, the relationships are thought to be truly symbiotic or mutualistic rather than temporary associations resulting from sponge filter-feeding activity. The marine sponge-associated bacteria are fascinating source for various biomolecules that are of potential interest to several biotechnological industries. In recent times, a particular attention has been devoted to bacterial biopolymer (polyesters) such as intracellular polyhydroxyalkanoates (PHAs) produced by sponge-associated bacteria. Bacterial PHAs act as an internal reserve for carbon and energy and also are a tremendous alternative for fossil fuel-based polymers mainly due to their eco-friendliness. In addition, PHAs are produced when the microorganisms are under stressful conditions and this biopolymer synthesis might be exhibited as one of the survival mechanisms of sponge-associated or endosymbiotic bacteria which exist in a highly competitive and stressful sponge-mesohyl microenvironment. In this review, we have emphasized the industrial prospects of marine bacteria for the commercial production of PHAs and special importance has been given to marine sponge-associated bacteria as a potential resource for PHAs.

  5. Polyhydroxyalkanoate (PHA: Review of synthesis, characteristics, processing and potential applications in packaging

    Directory of Open Access Journals (Sweden)

    E. Bugnicourt

    2014-11-01

    Full Text Available Polyhydroxyalkanoates (PHAs are gaining increasing attention in the biodegradable polymer market due to their promising properties such as high biodegradability in different environments, not just in composting plants, and processing versatility. Indeed among biopolymers, these biogenic polyesters represent a potential sustainable replacement for fossil fuel-based thermoplastics. Most commercially available PHAs are obtained with pure microbial cultures grown on renewable feedstocks (i.e. glucose under sterile conditions but recent research studies focus on the use of wastes as growth media. PHA can be extracted from the bacteria cell and then formulated and processed by extrusion for production of rigid and flexible plastic suitable not just for the most assessed medical applications but also considered for applications including packaging, moulded goods, paper coatings, non-woven fabrics, adhesives, films and performance additives. The present paper reviews the different classes of PHAs, their main properties, processing aspects, commercially available ones, as well as limitations and related improvements being researched, with specific focus on potential applications of PHAs in packaging.

  6. Block coordination copolymers

    Science.gov (United States)

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2012-11-13

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  7. Emerging bone tissue engineering via Polyhydroxyalkanoate (PHA)-based scaffolds.

    Science.gov (United States)

    Lim, Janice; You, Mingliang; Li, Jian; Li, Zibiao

    2017-10-01

    Polyhydroxyalkanoates (PHAs) are a class of biodegradable polymers derived from microorganisms. On top of their biodegradability and biocompatibility, different PHA types can contribute to varying mechanical and chemical properties. This has led to increasing attention to the use of PHAs in numerous biomedical applications over the past few decades. Bone tissue engineering refers to the regeneration of new bone through providing mechanical support while inducing cell growth on the PHA scaffolds having a porous structure for tissue regeneration. This review first introduces the various properties PHA scaffold that make them suitable for bone tissue engineering such as biocompatibility, biodegradability, mechanical properties as well as vascularization. The typical fabrication techniques of PHA scaffolds including electrospinning, salt-leaching and solution casting are further discussed, followed by the relatively new technology of using 3D printing in PHA scaffold fabrication. Finally, the recent progress of using different types of PHAs scaffold in bone tissue engineering applications are summarized in intrinsic PHA/blends forms or as composites with other polymeric or inorganic hybrid materials. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. [Preparation and characterization of polyhydroxyalkanoate bioplastics with antibacterial activity].

    Science.gov (United States)

    Lou, Qiuli; Ma, Yiming; Che, Xuemei; Zhong, Jin; Sun, Xiaoxia; Zhang, Haoqian

    2016-08-25

    Polyhydroxyalkanoates (PHAs), as a novel class of biopolymer, are attracting more attention due to their diverse material properties and environment-independent biodegradability. Here we report the preparation of PHA exhibiting efficient antibacterial activity by embedding Nisin, a food additive generally recognized as safe, into poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx), a type of PHA with high biocompatibility. We first prepared Nisin-containing PHBHHx films using solvent casting method. Confocal laser scanning microscopy analysis showed that a well-mixed integrated structure of the films with an even distribution of the Nisin particles in the PHBHHx matrices. Then the antimicrobial activity of PHBHHx/Nisin films against Micrococcus luteus was quantified on agar plate by measuring the size of inhibition zone. Cultivation in liquid media further confirmed the releasing of Nisin from the films and the long-time antibacterial activity. Results showed that the threshold of Nisin concentration for long-time and effective inhibition against bacteria growth is 25 μg/g. These results altogether establish a technological foundation for the application of PHA in biomedicine and food industry.

  9. Block copolymer battery separator

    Science.gov (United States)

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

    The invention herein described is the use of a block copolymer/homopolymer blend for creating nanoporous materials for transport applications. Specifically, this is demonstrated by using the block copolymer poly(styrene-block-ethylene-block-styrene) (SES) and blending it with homopolymer polystyrene (PS). After blending the polymers, a film is cast, and the film is submerged in tetrahydrofuran, which removes the PS. This creates a nanoporous polymer film, whereby the holes are lined with PS. Control of morphology of the system is achieved by manipulating the amount of PS added and the relative size of the PS added. The porous nature of these films was demonstrated by measuring the ionic conductivity in a traditional battery electrolyte, 1M LiPF.sub.6 in EC/DEC (1:1 v/v) using AC impedance spectroscopy and comparing these results to commercially available battery separators.

  10. Increased radiation degradation in methyl methacrylate copolymers

    International Nuclear Information System (INIS)

    Helbert, J.N; Wagner, G.E.; Caplan, P.J.; Poindexter, E.H.

    1975-01-01

    The effect of polar substituents at the quaternary carbon on degradation processes in several polymers and 10 to 20 percent copolymers of methyl methacrylate was explored. EPR was used to monitor radiation degradation products and to determine radiation G values. Irradiations were carried out at 77 0 K in a gamma irradiator at a dose rate of 0.3 Mrad/hr. (U.S.)

  11. Poly(hydroxyalkanoates for Food Packaging: Application and Attempts towards Implementation

    Directory of Open Access Journals (Sweden)

    M. Koller

    2014-09-01

    Full Text Available Plastics are well-established for convenient and safe packaging and distribution of food and feed goods. At present, this special sector of the plastic market displays remarkably increasing quantities of its annual production. Caused by the ongoing limitation and strongly fluctuating prices of fossil feedstocks, classically used for plastic production, there is an evident trend to switch towards so-called “bio-plastics”. Especially for bulk applications such as food packaging, a broad implementation of “bio-plastics” constitutes a future-oriented strategy to restrict the dependence of global industry on fossil feedstocks, and to diminish current problematic environmental issues arising from plastic disposal. However, food packaging demands a great deal of the utilized packaging material. This encompasses tailored mechanical properties such as low brittleness and adequate tensile strength, a sufficient barrier for oxygen, CO2, and aromatic flavors, high UV-resistance, and high water retention-capacity to block the food´s moisture content, or to prevent humidity, respectively. Due to their hydrophobic character and the broad flexibility of their mechanical features, prokaryotic poly(hydroxyalkanoates (PHAs are considered as promising materials to compete with petro-plastics on the food-packaging market. Nevertheless, short-comings in particular aspects of their material performance and economics of their biosynthesis and purification constitute stumbling blocks on the long way towards broad implementation of PHAs for food packaging. This article discusses advantages and drawbacks of PHAs as food packaging materials, and demonstrates how desired properties can be improved by the designing of novel composite materials, and also encompassing techniques by applying nanoparticles.

  12. Intracellular organisation of polyhydroxyalkanoate inclusion bodies: a role for small angle neutron scattering?

    International Nuclear Information System (INIS)

    Foster, L.J.R.; Holden, P.J.; Garvey, C.J.; Russell, R.A.; Stone, D.J.M.

    2003-01-01

    Full text: Polyhydroxyalkanoates (PHAs) are a diverse family of bacterially produced biopolyesters. Their biodegradability, and in some cases biocompatibility, suggest applications ranging from bioplastics to biomedical implantation devices. Despite extensive interest in their production and potential applications, little is known about their intracellular organisation. Microbial PHAs are synthesised by microorganisms under conditions of nutrient stress and can comprise up to 90% of the dry cell mass. The formation and organisation of these PHA inclusion bodies requires clarification. Such investigations have important implications for the biotechnological production of PHAs in microbes and other organisms, for downstream processing and in vitro precision polymerisation. Morphological and biochemical evidence supports two different models for the intracellular organisation of PHAs. Steinbuchel and coworkers propose a simple model of amorphous PHA enclosed by a single protein membrane consisting of structural proteins (PHAsins) and enzymes responsible for synthesis and degradation. In contrast, Fuller and coworkers have theorised a more complex system of PHA encompassed by a PHAsin bilayer separated by phospholipid. The polymerase and depolymerase enzymes are proposed to be associated with an incomplete inner PHAsin layer. It may be that such models are genera or species specific, since both proposals were derived from research on different species producing different types of PHA. Our initial investigations have focussed on in vivo deuteration of polyhydroxyoctanoate, produced by Pseudomonas oleovorans, both in fermentation on natural and deuterated substrates and during Small Angle Neutron Scattering by whole cells using AUSANS. The nature of the structural questions and our preliminary findings including contrast variation data will be discussed

  13. Renewable alkenes from the hydrothermal treatment of polyhydroxyalkanoates-containing sludge

    NARCIS (Netherlands)

    Torri, Cristian; Detert Oude Weme, Tom; Samorì, Chiara; Kiwan, Alisar; Brilman, Derk W.F.

    2017-01-01

    Polyhydroxyalkanoates (PHA) are a key constituent of excess sludge produced by Aerobic Sewage Sludge Treatment plants. The accumulation of significant amount of PHA inside aerobic microbial cells occurs when a surplus of an easily degradable carbon source (e.g., volatile fatty acids, VFA) is found

  14. Polyether/Polyester Graft Copolymers

    Science.gov (United States)

    Bell, Vernon L., Jr.; Wakelyn, N.; Stoakley, D. M.; Proctor, K. M.

    1986-01-01

    Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

  15. Synthesis of Diblock copolymer poly-3-hydroxybutyrate -block-poly-3-hydroxyhexanoate [PHB-b-PHHx] by a β-oxidation weakened Pseudomonas putida KT2442.

    Science.gov (United States)

    Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun; Chen, Guo-Qiang

    2012-04-05

    Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB) block covalently bonded with poly-3-hydroxyhexanoate (PHHx) block were for the first time produced successfully by a recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. The chloroform extracted polymers were characterized by nuclear magnetic resonance (NMR), thermo- and mechanical analysis. NMR confirmed the existence of diblock copolymers consisting of 58 mol% PHB as the short chain length block with 42 mol% PHHx as the medium chain length block. The block copolymers had two glass transition temperatures (Tg) at 2.7°C and -16.4°C, one melting temperature (Tm) at 172.1°C and one cool crystallization temperature (Tc) at 69.1°C as revealed by differential scanning calorimetry (DSC), respectively. This is the first microbial short-chain-length (scl) and medium-chain-length (mcl) PHA block copolymer reported. It is possible to produce PHA block copolymers of various kinds using the recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. In comparison to a random copolymer poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P(HB-co-HHx)) and a blend sample of PHB and PHHx, the PHB-b-PHHx showed improved structural related mechanical properties.

  16. Accumulation of a Polyhydroxyalkanoate Containing Primarily 3-Hydroxydecanoate from Simple Carbohydrate Substrates by Pseudomonas sp. Strain NCIMB 40135.

    Science.gov (United States)

    Haywood, G W; Anderson, A J; Ewing, D F; Dawes, E A

    1990-11-01

    A number of Pseudomonas species have been identified which accumulate a polyhydroxyalkanoate containing mainly 3-hydroxydecanoate monomers from sodium gluconate as the sole carbon source. One of these, Pseudomonas sp. strain NCIMB 40135, was further investigated and shown to accumulate such a polyhydroxyalkanoate from a wide range of carbon sources (C(2) to C(6)); however, when supplied with octanoic acid it produced a polyhydroxyalkanoate containing mainly 3-hydroxyoctanoate monomers. Polymer synthesis occurred in batch culture after cessation of growth due to exhaustion of nitrogen. In continuous culture under nitrogen limitation up to 16.9% (wt/wt) polyhydroxyalkanoate was synthesized from glucose as the carbon source. The monomer units are mainly of the R-(-) configuration. Nuclear magnetic resonance studies confirmed the composition of the polymer. Differential scanning calorimetry suggested that the solvent-extracted polymer contained a significant proportion of crystalline material. The weight-average molecular weight of the polymer from glucose-grown cells was 143,000.

  17. Optimization of critical factors to enhance polyhydroxyalkanoates (PHA) synthesis by mixed culture using Taguchi design of experimental methodology.

    Science.gov (United States)

    Venkata Mohan, S; Venkateswar Reddy, M

    2013-01-01

    Optimizing different factors is crucial for enhancement of mixed culture bioplastics (polyhydroxyalkanoates (PHA)) production. Design of experimental (DOE) methodology using Taguchi orthogonal array (OA) was applied to evaluate the influence and specific function of eight important factors (iron, glucose concentration, VFA concentration, VFA composition, nitrogen concentration, phosphorous concentration, pH, and microenvironment) on the bioplastics production. Three levels of factor (2(1) × 3(7)) variation were considered with symbolic arrays of experimental matrix [L(18)-18 experimental trails]. All the factors were assigned with three levels except iron concentration (2(1)). Among all the factors, microenvironment influenced bioplastics production substantially (contributing 81%), followed by pH (11%) and glucose concentration (2.5%). Validation experiments were performed with the obtained optimum conditions which resulted in improved PHA production. Good substrate degradation (as COD) of 68% was registered during PHA production. Dehydrogenase and phosphatase enzymatic activities were monitored during process operation. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. Biosynthesis and characterization of polyhydroxyalkanoates copolymers produced by Pseudomonas putida Bet001 isolated from palm oil mill effluent.

    Directory of Open Access Journals (Sweden)

    Ahmad Mohammed Gumel

    Full Text Available The biosynthesis and characterization of medium chain length poly-3-hydroxyalkanoates (mcl-PHA produced by Pseudomonas putida Bet001 isolated from palm oil mill effluent was studied. The biosynthesis of mcl-PHA in this newly isolated microorganism follows a growth-associated trend. Mcl-PHA accumulation ranging from 49.7 to 68.9% on cell dry weight (CDW basis were observed when fatty acids ranging from octanoic acid (C(8:0 to oleic acid (C(18:1 were used as sole carbon and energy source. Molecular weight of the polymer was found to be ranging from 55.7 to 77.7 kDa. Depending on the type of fatty acid used, the (1H NMR and GCMSMS analyses of the chiral polymer showed a composition of even and odd carbon atom chain with monomer length of C4 to C14 with C8 and C10 as the principal monomers. No unsaturated monomer was detected. Thermo-chemical analyses showed the accumulated PHA to be semi-crystalline polymer with good thermal stability, having a thermal degradation temperature (T(d of 264.6 to 318.8 (± 0.2 (oC, melting temperature (T(m of 43. (± 0.2 (oC, glass transition temperature (T(g of -1.0 (± 0.2 (oC and apparent melting enthalpy of fusion (ΔH(f of 100.9 (± 0.1 J g(-1.

  19. Biosynthesis and characterization of polyhydroxyalkanoates copolymers produced by Pseudomonas putida Bet001 isolated from palm oil mill effluent.

    Science.gov (United States)

    Gumel, Ahmad Mohammed; Annuar, Mohamad Suffian Mohamad; Heidelberg, Thorsten

    2012-01-01

    The biosynthesis and characterization of medium chain length poly-3-hydroxyalkanoates (mcl-PHA) produced by Pseudomonas putida Bet001 isolated from palm oil mill effluent was studied. The biosynthesis of mcl-PHA in this newly isolated microorganism follows a growth-associated trend. Mcl-PHA accumulation ranging from 49.7 to 68.9% on cell dry weight (CDW) basis were observed when fatty acids ranging from octanoic acid (C(8:0)) to oleic acid (C(18:1)) were used as sole carbon and energy source. Molecular weight of the polymer was found to be ranging from 55.7 to 77.7 kDa. Depending on the type of fatty acid used, the (1)H NMR and GCMSMS analyses of the chiral polymer showed a composition of even and odd carbon atom chain with monomer length of C4 to C14 with C8 and C10 as the principal monomers. No unsaturated monomer was detected. Thermo-chemical analyses showed the accumulated PHA to be semi-crystalline polymer with good thermal stability, having a thermal degradation temperature (T(d)) of 264.6 to 318.8 (± 0.2) (o)C, melting temperature (T(m)) of 43. (± 0.2) (o)C, glass transition temperature (T(g)) of -1.0 (± 0.2) (o)C and apparent melting enthalpy of fusion (ΔH(f)) of 100.9 (± 0.1) J g(-1).

  20. Polyethylene-Based Tadpole Copolymers

    KAUST Repository

    Alkayal, Nazeeha; Zhang, Zhen; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikolaos

    2017-01-01

    Novel well-defined polyethylene-based tadpole copolymers ((c-PE)-b-PS, PE: polyethylene, PS: polystyrene) with ring PE head and linear PS tail are synthesized by combining polyhomologation, atom transfer radical polymerization (ATRP), and Glaser

  1. Secondary Structural Models (16S rRNA of Polyhydroxyalkanoates Producing Bacillus Species Isolated from Different Rhizospheric Soil: Phylogenetics and Chemical Analysis

    Directory of Open Access Journals (Sweden)

    Swati Mohapatra

    2016-09-01

    Full Text Available Polyhydroxyalkanoates (PHAs producing bacterial isolates are gaining more importance over the world due to the synthesis of a biodegradable polymer which is extremely desirable to substitute synthetic plastics. PHAs are produced by various microorganisms under certain stress conditions. In this study, sixteen bacterial isolates characterized previously by partial 16S rRNA gene sequencing (NCBI Accession No. KF626466 to KF626481 were again stained by Nile red after three years of preservation in order to confirm their ability to accumulate PHAs. Also, phylogenetic analysis carried out in the present investigation evidenced that the bacterial species belonging to genus Bacillus are the dominant flora of the rhizospheric region, with a potentiality of biodegradable polymer (PHAs production. Again, RNA secondary structure prediction hypothesized that there is no direct correlation between RNA folding pattern stability with a rate of PHAs production among the selected isolates of genus Bacillus.

  2. Application of Poly(hydroxyalkanoate) In Food Packaging: Improvements by Nanotechnology

    OpenAIRE

    Khosravi-Darani, K.; Bucci, D. Z.

    2015-01-01

    The environmental impact of plastic usage is of critical concern and too great to repair. A shift toward biodegradable food packaging is one option. The aim of this review paper is the study of the potential of biodegradable materials for food packaging. The main characteristics in relation to food usage can be narrowed down to mass transfer (gas and water vapor), thermal and mechanical properties. Among several kinds of biodegradable polymers, poly(hydroxyalkanoate) is one of the favorable c...

  3. Quantitative Raman Spectroscopy Analysis of Polyhydroxyalkanoates Produced by Cupriavidus necator H16

    Czech Academy of Sciences Publication Activity Database

    Samek, Ota; Obruča, S.; Šiler, Martin; Sedláček, P.; Benešová, P.; Kučera, D.; Márová, I.; Ježek, Jan; Bernatová, Silvie; Zemánek, Pavel

    2016-01-01

    Roč. 16, č. 11 (2016), 1808:1-7 ISSN 1424-8220 R&D Projects: GA ČR(CZ) GA15-20645S; GA MŠk(CZ) LO1212; GA MŠk ED0017/01/01 Institutional support: RVO:68081731 Keywords : Raman spectroscopy * Cupriavidus necator H16 * polyhydroxyalkanoates Subject RIV: BH - Optics, Masers, Lasers Impact factor: 2.677, year: 2016

  4. Up-cycling of PET (polyethylene terephthalate) to the biodegradable plastic PHA (polyhydroxyalkanoate).

    Science.gov (United States)

    Kenny, Shane T; Runic, Jasmina Nikodinovic; Kaminsky, Walter; Woods, Trevor; Babu, Ramesh P; Keely, Chris M; Blau, Werner; O'Connor, Kevin E

    2008-10-15

    The conversion of the petrochemical polymer polyethylene terephthalate (PET) to a biodegradable plastic polyhydroxyal-kanoate (PHA) is described here. PET was pyrolised at 450 degrees C resulting in the production of a solid, liquid, and gaseous fraction. The liquid and gaseous fractions were burnt for energy recovery, whereas the solid fraction terephthalic acid (TA) was used as the feedstock for bacterial production of PHA. Strains previously reported to grow on TA were unable to accumulate PHA. We therefore isolated bacteria from soil exposed to PET granules at a PET bottle processing plant From the 32 strains isolated, three strains capable of accumulation of medium chain length PHA (mclPHA) from TA as a sole source of carbon and energy were selected for further study. These isolates were identified using 16S rDNA techniques as P. putida (GO16), P. putida (GO19), and P. frederiksbergensis (GO23). P. putida GO16 and GO19 accumulate PHA composed predominantly of a 3-hydroxydecanoic acid monomer while P. frederiksbergensis GO23 accumulates 3-hydroxydecanoic acid as the predominant monomer with increased amounts of 3-hydroxydodecanoic acid and 3-hydroxydodecenoic acid compared to the other two strains. PHA was detected in all three strains when nitrogen depleted below detectable levels in the growth medium. Strains GO16 and GO19 accumulate PHA at a maximal rate of approximately 8.4 mg PHA/l/h for 12 h before the rate of PHA accumulation decreased dramatically. Strain GO23 accumulates PHA at a lower maximal rate of 4.4 mg PHA/l/h but there was no slow down in the rate of PHA accumulation over time. Each of the PHA polymers is a thermoplastic with the onset of thermal degradation occurring around 308 degrees C with the complete degradation occurring by 370 degrees C. The molecular weight ranged from 74 to 123 kDa. X-ray diffraction indicated crystallinity of the order of 18-31%. Thermal analysis shows a low glass transition (-53 degrees C) with a broad melting

  5. PREPARATION AND PROPERTIES OF MMA/1-PROPYLMETHACRYLATE-POSS COPOLYMER WITH ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    He-xin Zhang; Ho-young Lee; Young-jun Shin; Dong-ho Lee; Seok Kyun Noh

    2008-01-01

    The methyl methacrylate(MMA)/1-propylmethacrylate-polyhedral oligomeric silsesquioxane(PM-POSS) copolymers were synthesized via atom transfer radical polymerization with CuBr as catalyst.The unreacted PM-POSS monomer could be removed completely by washing the copolymerization product with n-hexane.The copolymers were characterized with 1H-NMR,X-ray diffraction,difierential scanning calorimetry,thermogravimetric analysis and gel permeatlon chromatography.With increasing PM-POSS feed ratio.the total conversion increased while the glass transition temperatures of copolymer decreased.The thermogravimetric analysis demonstrated that the thermal stability of copolymer improved slightly with PM-POSS addition.The molecular weight of copolymers increased with incorporation of PM-POSS.

  6. Sustainable multistage process for enhanced productivity of bioplastics from waste remediation through aerobic dynamic feeding strategy: Process integration for up-scaling.

    Science.gov (United States)

    Amulya, K; Jukuri, Srinivas; Venkata Mohan, S

    2015-01-01

    Polyhydroxyalkanoates (PHA) production was evaluated in a multistage operation using food waste as a renewable feedstock. The first step involved the production of bio-hydrogen (bio-H2) via acidogenic fermentation. Volatile fatty acid (VFA) rich effluent from bio-H2 reactor was subsequently used for PHA production, which was carried out in two stages, Stage II (culture enrichment) and Stage III (PHA production). PHA-storing microorganisms were enriched in a sequencing batch reactor (SBR), operated at two different cycle lengths (CL-24; CL-12). Higher polymer recovery as well as VFA removal was achieved in CL-12 operation both in Stage II (16.3% dry cell weight (DCW); VFA removal, 84%) and Stage III (23.7% DCW; VFA removal, 88%). The PHA obtained was a co-polymer [P(3HB-co-3HV)] of PHB and PHV. The results obtained indicate that this integrated multistage process offers new opportunities to further leverage large scale PHA production with simultaneous waste remediation in the framework of biorefinery. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Effect of co-substrate on production of poly-β- hydroxybutyrate (PHB and copolymer PHBV from newly identified mutant Rhodobacter sphaeroides U7 cultivated under aerobic-dark condition

    Directory of Open Access Journals (Sweden)

    Kemarajt Kemavongse

    2007-07-01

    Full Text Available Photosynthetic bacterial mutant strain U7 was identified using both classical and molecular (16S rDNA techniques to be Rhodobacter sphaeroides. The glutamate-acetate (GA medium containing sodium acetate and sodium glutamate as carbon and nitrogen sources was used for production of poly-β-hydroxybutyrate (PHB from R. sphaeroides U7 cultivated under aerobic-dark condition (200 rpm at 37oC. Effect of auxiliary carbon sources (propionate and valerate and concentrations (molar ratio of 40/0, 40/20, 40/40 and 40/80 on copolymer production were studied. Both combinations of acetate with valerate and acetate with propionate were found to induce the accumulation of poly-β-hydroxybutyrate-co-β-hydroxyvalerate (PHBV within the cell. Acetate with propionate in the molar ratio of 40/40 gave the highest poly-β-hydroxyalkanoates (PHA content (77.68%, followed by acetate with valerate at the same molar ratio (77.42%. Although their polymer contents were similar, the presence of 40 mM valerate gave more than 4 times higher hydroxyvalerate (HV fraction (84.77% than in the presence of 40 mM propionate (19.12% HV fraction.

  8. Lignin poly(lactic acid) copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Olsson, Johan Vilhelm; Chung, Yi-Lin; Li, Russell Jingxian; Waymouth, Robert; Sattely, Elizabeth; Billington, Sarah; Frank, Curtis W.

    2017-02-14

    Provided herein are graft co-polymers of lignin and poly(lactic acid) (lignin-g-PLA copolymer), thermoset and thermoplastic polymers including them, methods of preparing these polymers, and articles of manufacture including such polymers.

  9. Investigation on ultrasonication mediated biosurfactant disintegration method in sludge flocs for enhancing hydrolytic enzymes activity and polyhydroxyalkanoates.

    Science.gov (United States)

    Sethupathy, A; Sivashanmugam, P

    2018-06-04

    In this study, a novel biosurfactant potential bacterial strain Pseudomonas pachastrellae RW43 was isolated from pulp and paper sludge and the biosurfactant namely rhamnolipid produced by Pseudomonas pachastrellae RW43 was investigated by varying pH and incubation time in batch liquid fermentation process. The maximal yield of rhamnolipid was found to be 12.1 g/L at an optimized condition of pH 7 and incubation time of 168 h. NMR analysis was performed for identification of molecular structure of produced rhamnolipid and its results concluded that the product was identified as di rhamnolipid. Then, statistically the global optimum conditions for hydrolytic enzymes extraction parameters (sonication power (100 W), extraction time (15 min) and rhamnolipid dosage (2% v/v)) were established. At 30,456 kJ/kg TS specific energy, ultrasonication with rhamnolipid disintegration method extracted maximal consortium activity of hydrolytic enzymes from mixed sludge (municipal and pulp & paper sludge) and the maximum observed were found to be 42.22, 51.75, 34.26, 24.21, 11.35 Units/g VSS respectively for protease, α-amylase, cellulase, lipase and α-glucosidase. Polyhydroxyalkanoates was recovered from enzymes extracted sludge using various solvents namely chloroform, sodium hypochlorite with chloroform and sodium lauryl sulfate with sodium hypochlorite. The maximum recovery was found to be 74 g/kg using sodium hypochlorite and chloroform extraction solvents.

  10. Detection of the enzymatically-active polyhydroxyalkanoate synthase subunit gene, phaC, in cyanobacteria via colony PCR.

    Science.gov (United States)

    Lane, Courtney E; Benton, Michael G

    2015-12-01

    A colony PCR-based assay was developed to rapidly determine if a cyanobacterium of interest contains the requisite genetic material, the PHA synthase PhaC subunit, to produce polyhydroxyalkanoates (PHAs). The test is both high throughput and robust, owing to an extensive sequence analysis of cyanobacteria PHA synthases. The assay uses a single detection primer set and a single reaction condition across multiple cyanobacteria strains to produce an easily detectable positive result - amplification via PCR as evidenced by a band in electrophoresis. In order to demonstrate the potential of the presence of phaC as an indicator of a cyanobacteria's PHA accumulation capabilities, the ability to produce PHA was assessed for five cyanobacteria with a traditional in vivo PHA granule staining using an oxazine dye. The confirmed in vivo staining results were then compared to the PCR-based assay results and found to be in agreement. The colony PCR assay was capable of successfully detecting the phaC gene in all six of the diverse cyanobacteria tested which possessed the gene, while exhibiting no undesired product formation across the nine total cyanobacteria strains tested. The colony PCR quick prep provides sufficient usable DNA template such that this assay could be readily expanded to assess multiple genes of interest simultaneously. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. A screening method for the isolation of polyhydroxyalkanoate-producing purple non-sulfur photosynthetic bacteria from natural seawater

    Directory of Open Access Journals (Sweden)

    Mieko Higuchi-Takeuchi

    2016-09-01

    Full Text Available Polyhydroxyalkanoates (PHAs are a family of biopolyesters accumulated by a variety of microorganisms as carbon and energy storage under starvation conditions. We focused on marine purple non-sulfur photosynthetic bacteria as host microorganisms for PHA production and developed a method for their isolation from natural seawater. To identify novel PHA-producing marine purple non-sulfur photosynthetic bacteria, natural seawaters were cultured in nutrient-rich medium for purple non-sulfur photosynthetic bacteria, and twelve pink- or red-pigmented colonies were picked up. Gas chromatography mass spectrometry analysis revealed that four isolates synthesized PHA at levels ranging from 0.5 to 24.4 wt% of cell dry weight. The 16S ribosomal RNA sequence analysis revealed that one isolate (HM2 showed 100% identity to marine purple non-sulfur photosynthetic bacteria. In conclusion, we have demonstrated in this study that PHA-producing marine purple non-sulfur photosynthetic bacteria can be isolated from natural seawater under nutrient-rich conditions.

  12. Mixed Culture PHA Production With Alternating Feedstocks

    DEFF Research Database (Denmark)

    Oliveira, C.S.S.; Duque, A.F.; Carvalho, Gilda

    Polyhydroxyalkanoates (PHA) are a sustainable alternative to conventional plastics that can be obtained from industrial wastes/by-products using mixed microbial cultures (MMC). MMC PHA production is commonly carried out in a 3-stage process consisting of an acidogenic stage, a PHA producing cultu...

  13. Metallo-supramolecular block copolymer micelles

    NARCIS (Netherlands)

    Gohy, J.M.W.

    2009-01-01

    Supramolecular copolymers have become of increasing interest in recent years in the search for new materials with tunable properties. In particular, metallo-supramolecular block copolymers in which metal-ligand complexes are introduced in block copolymer architectures, have known important progress,

  14. Main-chain supramolecular block copolymers.

    Science.gov (United States)

    Yang, Si Kyung; Ambade, Ashootosh V; Weck, Marcus

    2011-01-01

    Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

  15. Burkholderia sacchari DSM 17165: A source of compositionally-tunable block-copolymeric short-chain poly(hydroxyalkanoates) from xylose and levulinic acid

    Science.gov (United States)

    Burkholderia sacchari DSM 17165 was used as a biocatalyst for the production of poly-3-hydroxybutyrate-co-3-hydroxyvalerate block copolymers (Poly-3HB-block-3HV) from xylose and levulinic acid. Among the carbon source mixtures, levulinic acid was preferred and was consumed early in the fermentations...

  16. The radiation crosslinking of ethylene copolymers

    International Nuclear Information System (INIS)

    Burns, N.M.

    1979-01-01

    The enhanced radiation crosslinking tendency of ethylene-vinyl acetate and ethylene-ethyl acrylate copolymers over ethylene homopolymer is proportional to the comonomer content. This is caused by an increase in the amorphous polymer content and by structure-related factors. The copolymers crosslink by a random process that for ethylene-vinyl acetate copolymer involves some crosslinking through the acetoxy group of the comonomer. While knowledge of the process for the crosslinking of ethylene-ethyl acrylate copolymer is less certain, it is currently believed to occur primarily at the branch point on the polymer backbone. Data relating comonomer content and the molecular weight of the copolymers to the radiation crosslinking levels realized were developed to aid in resin selection by the formulator. Triallyl cyanurate cure accelerator was found to be less effective in ethylene-vinyl acetate copolymer than in homopolymer and to have no effect on gel development in ethylene-ethyl acrylate copolymer. (author)

  17. Modeling of emulsion copolymer microstructure

    NARCIS (Netherlands)

    van Doremaele, G.H.J.; Herk, van A.M.; German, A.L.

    1992-01-01

    A model is developed to describe stages II and III of batch emulsion copolymn., and its predictive capabilities are investigated by application to the system styrene-Me acrylate. The main reaction site is the monomer-swollen polymer particle. Copolymn. rate and copolymer microstructure (molar

  18. Polyether-polyester graft copolymer

    Science.gov (United States)

    Bell, Vernon L. (Inventor)

    1987-01-01

    Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

  19. Thermo-responsive block copolymers

    NARCIS (Netherlands)

    Mocan Cetintas, Merve

    2017-01-01

    Block copolymers (BCPs) are remarkable materials because of their self-assembly behavior into nano-sized regular structures and high tunable properties. BCPs are in used various applications such as surfactants, nanolithography, biomedicine and nanoporous membranes. In these thesis, we aimed to

  20. Specific character of bacterial biodegradation of polyhydroxyalkanoates with different chemical structure in soil.

    Science.gov (United States)

    Prudnikova, S V; Vinogradova, O N; Trusova, M Y

    2017-03-01

    The study addresses the influence of the physicochemical properties of the reserve cellular macromolecules (polyhydroxyalkanoates, PHA) with different chemical composition on their biodegradation in the agro-transformed field soil of the Siberian region (Krasnoyarsk Territory, Russia). It was shown that the degradation of the PHA samples depends on the degree of polymer crystallinity (C x ). For the first time, it was shown that the range of PHA-degrading microorganisms differs for each of PHA types. The study defines the primary degraders specific to each PHA type and common to all types of examined polymers.

  1. Molecular changes in copolymers of styrene and methyl methacrylate caused by radiation

    International Nuclear Information System (INIS)

    Busfield, W.K.; O'Donnell, J.H.; Smith, C.A.

    1976-01-01

    Homopolymers of styrene and methyl methacrylate and copolymers of these monomers were irradiated in vacuo at room temperature using 60 Co γ-radiation to various doses. The gaseous radiolysis products of the polymers were analysed by gas chromatography. The radiation chemical yield, G values, of the gaseous and liquid products were calculated for the homopolymers and copolymers. The G values obtained for the homopolymers were compared with those obtained by previous workers. The graphs of G value versus composition (% Styrene) showed a marked deviation from linearity which indicated that the styrene in the copolymer had a greater effect on the behaviour than did the methyl methacrylate units. It has been postulated that the benzene ring on the styrene unit acts in some way as an energy sink, and hence protects the copolymer from radiation damage in an analogous way to that suggested for hydrocarbon mixtures. Mechanisms for the process are discussed. (author)

  2. Structure reveals regulatory mechanisms of a MaoC-like hydratase from Phytophthora capsici involved in biosynthesis of polyhydroxyalkanoates (PHAs).

    Science.gov (United States)

    Wang, Huizheng; Zhang, Kai; Zhu, Jie; Song, Weiwei; Zhao, Li; Zhang, Xiuguo

    2013-01-01

    Polyhydroxyalkanoates (PHAs) have attracted increasing attention as "green plastic" due to their biodegradable, biocompatible, thermoplastic, and mechanical properties, and considerable research has been undertaken to develop low cost/high efficiency processes for the production of PHAs. MaoC-like hydratase (MaoC), which belongs to (R)-hydratase involved in linking the β-oxidation and the PHA biosynthetic pathways, has been identified recently. Understanding the regulatory mechanisms of (R)-hydratase catalysis is critical for efficient production of PHAs that promise synthesis an environment-friendly plastic. We have determined the crystal structure of a new MaoC recognized from Phytophthora capsici. The crystal structure of the enzyme was solved at 2.00 Å resolution. The structure shows that MaoC has a canonical (R)-hydratase fold with an N-domain and a C-domain. Supporting its dimerization observed in structure, MaoC forms a stable homodimer in solution. Mutations that disrupt the dimeric MaoC result in a complete loss of activity toward crotonyl-CoA, indicating that dimerization is required for the enzymatic activity of MaoC. Importantly, structure comparison reveals that a loop unique to MaoC interacts with an α-helix that harbors the catalytic residues of MaoC. Deletion of the loop enhances the enzymatic activity of MaoC, suggesting its inhibitory role in regulating the activity of MaoC. The data in our study reveal the regulatory mechanism of an (R)-hydratase, providing information on enzyme engineering to produce low cost PHAs.

  3. Structure reveals regulatory mechanisms of a MaoC-like hydratase from Phytophthora capsici involved in biosynthesis of polyhydroxyalkanoates (PHAs.

    Directory of Open Access Journals (Sweden)

    Huizheng Wang

    Full Text Available Polyhydroxyalkanoates (PHAs have attracted increasing attention as "green plastic" due to their biodegradable, biocompatible, thermoplastic, and mechanical properties, and considerable research has been undertaken to develop low cost/high efficiency processes for the production of PHAs. MaoC-like hydratase (MaoC, which belongs to (R-hydratase involved in linking the β-oxidation and the PHA biosynthetic pathways, has been identified recently. Understanding the regulatory mechanisms of (R-hydratase catalysis is critical for efficient production of PHAs that promise synthesis an environment-friendly plastic.We have determined the crystal structure of a new MaoC recognized from Phytophthora capsici. The crystal structure of the enzyme was solved at 2.00 Å resolution. The structure shows that MaoC has a canonical (R-hydratase fold with an N-domain and a C-domain. Supporting its dimerization observed in structure, MaoC forms a stable homodimer in solution. Mutations that disrupt the dimeric MaoC result in a complete loss of activity toward crotonyl-CoA, indicating that dimerization is required for the enzymatic activity of MaoC. Importantly, structure comparison reveals that a loop unique to MaoC interacts with an α-helix that harbors the catalytic residues of MaoC. Deletion of the loop enhances the enzymatic activity of MaoC, suggesting its inhibitory role in regulating the activity of MaoC.The data in our study reveal the regulatory mechanism of an (R-hydratase, providing information on enzyme engineering to produce low cost PHAs.

  4. PHA Production in Aerobic Mixed Microbial Cultures

    NARCIS (Netherlands)

    Johnson, K.

    2010-01-01

    Polyhydroxyalkanoate (PHA) is a common intracellular energy and carbon storage material in bacteria, which is considered as a bioplastic due to its plastic like properties. PHAs are versatile materials which are biodegradable and made from renewable resources. Commercial production of PHAs is

  5. Cloning and heterologous expression of a novel subgroup of class IV polyhydroxyalkanoate synthase genes from the genus Bacillus.

    Science.gov (United States)

    Mizuno, Kouhei; Kihara, Takahiro; Tsuge, Takeharu; Lundgren, Benjamin R; Sarwar, Zaara; Pinto, Atahualpa; Nomura, Christopher T

    2017-01-01

    Many microorganisms harbor genes necessary to synthesize biodegradable plastics known as polyhydroxyalkanoates (PHAs). We surveyed a genomic database and discovered a new cluster of class IV PHA synthase genes (phaRC). These genes are different in sequence and operon structure from any previously reported PHA synthase. The newly discovered PhaRC synthase was demonstrated to produce PHAs in recombinant Escherichia coli.

  6. Blends of Styrene-Butadiene-Styrene Triblock Copolymer with Random Styrene-Maleic Anhydride Copolymers

    NARCIS (Netherlands)

    Piccini, Maria Teresa; Ruggeri, Giacomo; Passaglia, Elisa; Picchioni, Francesco; Aglietto, Mauro

    2002-01-01

    Blends of styrene-butadiene-styrene triblock copolymer (SBS) with random styrene-maleic anhydride copolymers (PS-co-MA), having different MA content, were prepared in a Brabender Plastigraph mixer. The presence of polystyrene (PS) blocks in the SBS copolymer and the high styrene content (93 and 86

  7. Polyketones as alternating copolymers of carbon monoxide

    International Nuclear Information System (INIS)

    Belov, Gennady P; Novikova, Elena V

    2004-01-01

    Characteristic features of the catalytic synthesis of alternating copolymers of carbon monoxide with various olefins, dienes, styrene and its derivatives are considered. The diversity of catalyst systems used for the copolymerisation of carbon monoxide is demonstrated and their influence on the structure and the molecular mass of the resulting copolymers is analysed. The data on the structure and physicochemical and mechanical properties of this new generation of functional copolymers are generalised and described systematically for the first time.

  8. Study on the production of kanvas shoes adhesive from natural rubber latex grafted with methyl methacrylate (NRL-g PMMA) copolymer

    International Nuclear Information System (INIS)

    Utama, Marga; Sudirman; Setyowati, Penny

    2002-01-01

    The optimation condition of radiation copolymerization of MMA into natural rubber latex at the doses of radiation : 5; 7.5 and 10 kGy with concentration of MMA 25; 50; 75; and 100 phr (Part Hundred Ratio of Rubber) expectially and optimazation condition of the adhesive process all the production of canvas shoes have been carried out. The properties of NRL-g-MMA and its rubber such as total solid contain, viscosity, pH, modulus, tensile, strenght, hardnes, elongation at break, and adhesive strenght for producting canvas shoes where evaluated. The at adhesive results show that NRL-g-MMA with the 75 phr of MMA and iradiation dose 5 kGy is adhesive will good stability during storage. The adhesive strenght of shoes its 16-18 N/6mm, more here than SNI 1-0172-1987 with the value 10N/6mm. Besic there is a tendency that adhesive strengt of product shoes at rome temperature (30-50 o C). stronger than at high temperature (100 o C)

  9. The conversion of BTEX compounds by single and defined mixed cultures to medium-chain-length polyhydroxyalkanoate.

    Science.gov (United States)

    Nikodinovic, Jasmina; Kenny, Shane T; Babu, Ramesh P; Woods, Trevor; Blau, Werner J; O'Connor, Kevin E

    2008-09-01

    Here, we report the use of petrochemical aromatic hydrocarbons as a feedstock for the biotechnological conversion into valuable biodegradable plastic polymers--polyhydroxyalkanoates (PHAs). We assessed the ability of the known Pseudomonas putida species that are able to utilize benzene, toluene, ethylbenzene, p-xylene (BTEX) compounds as a sole carbon and energy source for their ability to produce PHA from the single substrates. P. putida F1 is able to accumulate medium-chain-length (mcl) PHA when supplied with toluene, benzene, or ethylbenzene. P. putida mt-2 accumulates mcl-PHA when supplied with toluene or p-xylene. The highest level of PHA accumulated by cultures in shake flask was 26% cell dry weight for P. putida mt-2 supplied with p-xylene. A synthetic mixture of benzene, toluene, ethylbenzene, p-xylene, and styrene (BTEXS) which mimics the aromatic fraction of mixed plastic pyrolysis oil was supplied to a defined mixed culture of P. putida F1, mt-2, and CA-3 in the shake flasks and fermentation experiments. PHA was accumulated to 24% and to 36% of the cell dry weight of the shake flask and fermentation grown cultures respectively. In addition a three-fold higher cell density was achieved with the mixed culture grown in the bioreactor compared to shake flask experiments. A run in the 5-l fermentor resulted in the utilization of 59.6 g (67.5 ml) of the BTEXS mixture and the production of 6 g of mcl-PHA. The monomer composition of PHA accumulated by the mixed culture was the same as that accumulated by single strains supplied with single substrates with 3-hydroxydecanoic acid occurring as the predominant monomer. The purified polymer was partially crystalline with an average molecular weight of 86.9 kDa. It has a thermal degradation temperature of 350 degrees C and a glass transition temperature of -48.5 degrees C.

  10. Homologous functional expression of cryptic phaG from Pseudomonas oleovorans establishes the transacylase-mediated polyhydroxyalkanoate biosynthetic pathway.

    Science.gov (United States)

    Hoffmann, N; Steinbüchel, A; Rehm, B H

    2000-11-01

    Various pseudomonads are capable of the synthesis of polyhydroxyalkanoate (PHA), composed of medium chain length (MCL) 3-hydroxy fatty acids (C6-C14), when grown on simple carbon sources such as, for example, gluconate or acetate. In Pseudomonas putida, the fatty acid de novo synthesis and PHA synthesis are linked by the transacylase PhaG. Southern hybridization experiments with digoxigenin-labeled phaG(Pp) from P. putida and genomic DNA from various pseudomonads indicate that phaG homologues are present in various other pseudomonads. Although P. oleovorans does not accumulate PHA(MCL) from non-related carbon sources, its genomic DNA reveals a strong hybridization signal. We employed PCR to amplify this phaG homologue. The respective PCR product comprising the coding region of phaG(Po) was cloned into pBBR1MCS-2, resulting in plasmid pBHR84. DNA sequencing revealed that putative PhaG(Po) from P. oleovorans exhibited about 95% amino acid sequence identity to PhaG(Pp) from P. putida. Reverse transcriptase-PCR analysis demonstrated that phaG(Po) was not transcribed even tinder inducing conditions, i.e. in the presence of gluconate as carbon source, whereas induction of phaG(Pp) transcription was obtained in P. putida. When octanoate was used as sole carbon source, only low levels of phaG mRNA were detected in P. putida. Plasmid pBHR84 complemented the phaG-negative mutant PhaG(N)-21 from P. putida. Interestingly, reintroduction of phaG(Po) under lac promoter control into the natural host P. oleovorans established PHA(MCL) synthesis from non-related carbon sources in this bacterium. These data indicated that phaG(Po) in P. oleovorans is not functionally expressed and does not exert its original function.

  11. Copolymers of fluorinated polydienes and sulfonated polystyrene

    Science.gov (United States)

    Mays, Jimmy W [Knoxville, TN; Gido, Samuel P [Hadley, MA; Huang, Tianzi [Knoxville, TN; Hong, Kunlun [Knoxville, TN

    2009-11-17

    Copolymers of fluorinated polydienes and sulfonated polystyrene and their use in fuel cell membranes, batteries, breathable chemical-biological protective materials, and templates for sol-gel polymerization.

  12. Living cationic polymerization and polyhomologation: an ideal combination to synthesize functionalized polyethylene–polyisobutylene block copolymers

    KAUST Repository

    Zhang, Hefeng

    2015-12-17

    A series of hydroxyl-terminated polyisobutylene-b-polyethylene (PIB-b-PE-OH) copolymers were synthesized by combining living cationic polymerization and polyhomologation. Allyl-terminated PIBs, synthesized by living cationic polymerization, were hydroborated with BH3·THF to produce 3-arm boron-linked stars, PIB3B, which served as macroinitiators for the in situ polyhomologation of dimethylsulfoxonium methylide. The resulting 3-arm star block copolymers, (PIB-b-PE)3B, were oxidized/hydrolysed to afford PIB-b-PE-OH. Characterization of all intermediates and final products by high temperature gel permeation chromatography (HT-GPC) and proton nuclear magnetic resonance spectroscopy (1H NMR) revealed the well-defined character of the copolymers. The thermal properties of the copolymers were studied by differential scanning calorimetry (DSC).

  13. Study of the therapeutic benefit of cationic copolymer administration to vascular endothelium under mechanical stress

    Science.gov (United States)

    Giantsos-Adams, Kristina; Lopez-Quintero, Veronica; Kopeckova, Pavla; Kopecek, Jindrich; Tarbell, John M.; Dull, Randal

    2015-01-01

    Pulmonary edema and the associated increases in vascular permeability continue to represent a significant clinical problem in the intensive care setting, with no current treatment modality other than supportive care and mechanical ventilation. Therapeutic compound(s) capable of attenuating changes in vascular barrier function would represent a significant advance in critical care medicine. We have previously reported the development of HPMA-based copolymers, targeted to endothelial glycocalyx that are able to enhance barrier function. In this work, we report the refinement of copolymer design and extend our physiological studies todemonstrate that the polymers: 1) reduce both shear stress and pressure-mediated increase in hydraulic conductivity, 2) reduce nitric oxide production in response to elevated hydrostatic pressure and, 3) reduce the capillary filtration coefficient (Kfc) in an isolated perfused mouse lung model. These copolymers represent an important tool for use in mechanotransduction research and a novel strategy for developing clinically useful copolymers for the treatment of vascular permeability. PMID:20932573

  14. Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization

    Science.gov (United States)

    Kermagoret, Anthony; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe

    2014-03-01

    The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials.

  15. Synthesis of biodegradable styrene copolymers

    OpenAIRE

    Gevers, Dries; Kobben, Stephan; Junkers, Tanja; Copinet, Alain; Buntinx, Mieke; Peeters, Roos

    2017-01-01

    Polystyrene (PS), a versatile polymer with many applications (e.g. packaging) representing about 10% of the total annual polymer consumption, shows practically no biodegradability. In this study a styrene (ST) based copolymer is synthesized and examined regarding its ability to degrade in a composting test. As second monomer, to introduce biodegradable ester groups, 5,6-benzo-2-metylene-dioxepane (BMDO) has been used in radical copolymerization reactions performed in inert and stirred 10 m...

  16. 21 CFR 177.2470 - Polyoxymethylene copolymer.

    Science.gov (United States)

    2010-04-01

    ... Components of Articles Intended for Repeated Use § 177.2470 Polyoxymethylene copolymer. Polyoxymethylene copolymer identified in this section may be safely used as an article or component of articles intended for... are available from the Center for Food Safety and Applied Nutrition (HFS-200), Food and Drug...

  17. Radiation resistance of ethylene-styrene copolymers

    International Nuclear Information System (INIS)

    Matsumoto, Kaoru; Ikeda, Masaaki; Ohki, Yoshimichi; Kusama, Yasuo; Harashige, Masahiro; Yazaki, Fumihiko.

    1988-01-01

    In this paper, the radiation resistance of ethylene-styrene copolymer, a polymeric resin developed newly by the authors, is reported. Resin examined were five kinds of ethylene-styrene copolymers: three random and two graft copolymers with different styrene contents. Low-density polyethylene was used as a reference. The samples were irradiated by 60 Co γ-rays to total absorbed doses up to 10 MGy. The mechanical properties of the smaples were examined. Infrared spectroscopy, differential scanning calorimetry and X-ray scattering techniques were used to examine the morphology of the samples. The random copolymers are soft and easy to extend, because benzene rings which exisist highly at random hinder the crystallization. As for the radiation resistance, they are highly resistant to γ-rays in the aspects of carbonyl group formation, gel formation, and elongation. Further, they show even better radiation resistance when proper additives were compounded in. The graft copolymers are hard to extend, because they consist of segregated polystyrene and polyethylene regions which are connected with each other. The tensile strength of irradiated graft copolymers does not decrease below that of unirradiated copolymers, up to a total dose of 10 MGy. As a consequence, it can be said that ethylene-styrene copolymers have good radiation resistance owing to the so-called 'sponge' effect of benzene rings. (author)

  18. Copolymers at the solid - liquid interface

    NARCIS (Netherlands)

    Wijmans, C.M.

    1994-01-01

    Copolymers consisting of both adsorbing and nonadsorbing segments can show an adsorption behaviour which is very different from that of homopolymers. We have mainly investigated the adsorption of AB diblock copolymers, which have one adsorbing block (anchor) and one nonadsorbing block

  19. Amphiphilic copolymers for fouling-release coatings

    DEFF Research Database (Denmark)

    Noguer, Albert Camós; Olsen, Stefan Møller; Hvilsted, Søren

    of the coatings [9,10,11]. This work shows the effect of an amphiphilic copolymer that induces hydrophilicity on the surface of the silicone-based fouling release coatings. The behaviour of these copolymers within the coating upon immersion and the interaction of these surface-active additives with other...

  20. Poly(ferrocenylsilane)-block-Polylactide Block Copolymers

    NARCIS (Netherlands)

    Roerdink, M.; van Zanten, Thomas S.; Hempenius, Mark A.; Zhong, Zhiyuan; Feijen, Jan; Vancso, Gyula J.

    2007-01-01

    A PFS/PLA block copolymer was studied to probe the effect of strong surface interactions on pattern formation in PFS block copolymer thin films. Successful synthesis of PFS-b-PLA was demonstrated. Thin films of these polymers show phase separation to form PFS microdomains in a PLA matrix, and

  1. Effects of carbon sources on the enrichment of halophilic polyhydroxyalkanoate-storing mixed microbial culture in an aerobic dynamic feeding process

    Science.gov (United States)

    Cui, You-Wei; Zhang, Hong-Yu; Lu, Peng-Fei; Peng, Yong-Zhen

    2016-08-01

    Microbial polyhydroxyalkanoate (PHA) production serves as a substitute for petroleum-based plastics. Enriching mixed microbial cultures (MMCs) with the capacity to store PHA is a key precursor for low-cost PHA production. This study investigated the impact of carbon types on enrichment outcomes. Three MMCs were separately fed by acetate sodium, glucose, and starch as an enriching carbon source, and were exposed to long-term aerobic dynamic feeding (ADF) periods. The PHA production capacity, kinetics and stoichiometry of the enrichments, the PHA composition, and the microbial diversity and community composition were explored to determine carbon and enrichment correlations. After 350-cycle enriching periods under feast-famine (F-F) regimes, the MMCs enriched by acetate sodium and glucose contained a maximum PHA content of 64.7% and 60.5% cell dry weight (CDW). The starch-enriched MMC only had 27.3% CDW of PHA. High-throughput sequencing revealed that non-PHA bacteria survived alongside PHA storing bacteria, even under severe F-F selective pressure. Genus of Pseudomonas and Stappia were the possible PHA accumulating bacteria in acetate-enriched MMC. Genus of Oceanicella, Piscicoccus and Vibrio were found as PHA accumulating bacteria in glucose-enriched MMC. Vibrio genus was the only PHA accumulating bacteria in starch-enriched MMC. The community diversity and composition were regulated by the substrate types.

  2. Copolymers for soft hydrophilic contact lenses: development and investigations

    International Nuclear Information System (INIS)

    Schwach, G.W.

    1978-05-01

    Low esters of methacrylic acid which may be polymerized by different methods are used predominantly for producing soft hydrophilic contact lenses. Compounds of the vinyl-type often are added to improve the optical and mechanical qualities. Composition as well as possibilities of polymerization by irradiation were tested so long until copolymers were found which finally allowed the production of soft hydrophilic contact lenses. Swelling characteristics and permeability of the different elastomeres are to be investigated in order to guarantee sufficient compatibility of contact lenses. Contamination of the lens materials by microorganisms is also a point of special interest. The effects on the hydrophilic contact lens-copolymers by different substances used for cleaning and storage solutions have been investigated as well. (author)

  3. Synthesis and thermal behavior of polyacrylonitrile/vinylidene chloride copolymer

    Directory of Open Access Journals (Sweden)

    Robson Fleming

    2014-06-01

    Full Text Available Polyacrylonitrile fiber encompasses a broad range of products based on acrylonitrile (AN which is readily copolymerized with a wide range of ethylenic unsaturated monomers giving rise to polymers with different characteristics and applications. Such products can be designed for cost-effective, flame and heat resistant solutions for the textile industry, aircraft and automotive markets. In the present work acrylonitrile was copolymerized with vinylidene chloride (VDC by conventional suspension polymerization process via redox system, with an initial content of 10%/mass of the VDC monomer. The copolymer average molecular weight was obtained by Gel Permeation Chromatography (GPC and by intrinsic viscosity analysis. To control the polymerization process continuously, qualitative and quantitative analysis of the chloride content in the PAN AN/VDC copolymer structure was accomplished by using X-ray fluorescence and potentiometric titration techniques. A good correlation was found between these two techniques, leading to a straightforward verification of VDC in the polymer structure. The thermal behavior of PAN AN/VDC copolymer was performed by Differential Scanning Calorimetry (DSC and Thermogravimetric Analysis (TGA. The results showed that VDC monomers exhibited a nearly stoichiometric reaction with acrylonitrile, copolymerizing about 90% of its initial mass. VDC changed significantly the polyacrylonitrile thermal behavior, decreasing the polymer degradation temperature by about 40-50°C.

  4. Crystallization and initial X-ray analysis of polyhydroxyalkanoate granule-associated protein from Aeromonas hydrophila

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Minglian; Li, Zhenguo; Zheng, Wei; Lou, Zhiyong [MOE Key Laboratory of Protein Science, Department of Biological Sciences and Biotechnology, Tsinghua University, Beijing 100084 (China); Chen, Guo-Qiang, E-mail: chengq@stu.edu.cn [MOE Key Laboratory of Protein Science, Department of Biological Sciences and Biotechnology, Tsinghua University, Beijing 100084 (China); Multidisciplinary Research Center, Shantou University, Shantou 515063, Guangdong (China)

    2006-08-01

    The phasin PhaP{sub Ah} from A. hydrophila strain 4AK4 was crystallized using the hanging-drop vapour-diffusion method. Polyhydroxyalkanoate (PHA) granule-associated proteins (phasins) were discovered in PHA-accumulating bacteria. They play a crucial role as a structural protein during initial PHA-granule formation and granule growth and also serve as interfaces for granule stabilization in vivo. The phasin PhaP{sub Ah} from Aeromonas hydrophila strain 4AK4 was crystallized using the hanging-drop vapour-diffusion method. Single crystals were cryocooled for X-ray diffraction analysis. The phasin crystals belonged to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 80.8, b = 108.9, c = 134.4 Å.

  5. ACCUMULATION OF POLYHYDROXYALKANOIC ACIDS BY AZOTOBACTER CHROOCOCCUM MAL-201 FROM ORGANIC WASTE

    Directory of Open Access Journals (Sweden)

    Soma Pal Saha

    2013-08-01

    Full Text Available Azotobacter chroococcum MAL-201 (MTCC 3853, a free-living nitrogen-fixing bacterium accumulated intracellular poly(3-hydroxybutyric acid [P(3HB] accounting 69% of cell dry weight (CDW when grown in nitrogrn-free Stockdale medium containing 2% (w/v glucose. It also produced copolymer of poly(3-hydroxybutyrate co-3-hydroxyvalerate [P(3HB-co-3HV] using glucose as primary carbon source and valerate cas cosubstrate. To make the polymer production cost effective four types of waste material of different origin were tested for growth and polymer production. Stockdale medium supplemented with 1% (w/v waste materials failed to yield good growth and polymer accumulation. Two–step cultivation was adopted for better growth and enhanced polymer accumulation. The candy factory waste was most suitable for synthesis of P(3HB accounting 17.8 and 40.58% using single and two-step cultivation conditions respectively. Wastes of domestic and poultry origin produced P(3HB-co-3HV with 3HV content 28.8 and 21.5 mol% respectively in two-step cultivation. Increase concentration of these wastes resulted in further upliftment of 3HV content of polymer with reduced growth and polymer accumulation. However, at optimum incubation the strain MAL-201 cells accumulated P(3HB 48.5% of CDW (at 40h from candy factory waste and P(3HB-co-3HV 24.75 % of CDW with 3HV 34.65 mol % from domestic waste. Intrinsic viscosity, molecular weight and thermal degradation of the polymers accumulated in the cells grown in glucose, glucose with valerate and glucose with waste were compared.

  6. Rapid self-assembly of block copolymers to photonic crystals

    Science.gov (United States)

    Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

    2016-07-05

    The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

  7. Characterization of a Bio-Based, Biodegradable Class of Copolymers, Poly[(R)-3-Hydroxybutyrate-Co-(R)-3- Hydroxyhexanoate], and Application Development

    Science.gov (United States)

    Sobieski, Brian

    As modern society begins to focus on sustainability and renewable resources there is a growing need for the polymer industry to develop more environmentally friendly materials and practices. Part of this movement can be seen in the use of recycled materials in new products and in the development of bio-based, biodegradable polymers. Bio-based, biodegradable polymers are produced from renewable carbon sources, such as vegetable oils, typically polymerized using fermentation reactions via bacteria, and are able to be consumed by bacteria in landfills to completely convert the polymers to water and CO2. One class of such polymers are poly(hydroxyalkanoate)'s (PHAs), which are chiral, aliphatic polyesters. Within this class of polyesters are poly(hydroxybutyrate) (PHB) and the copolymer poly[(R)-3-hydroxybutyrate- co-(R)-3-hydroxyhexanoate] (PHBHx), which have received extensive study due to their material properties as thermoplastics. Although the properties of PHB have been widely explored, much still remains to be understood about these promising biodegradable polymers. Specifically, PHB and its copolymers exhibit physical gelation in most solvents, yet the origin and mechanism of gelation and the properties of the resulting gel state are unknown. This research effort was primarily focused on investigating the physical gel state of PHBHx. Five goals were laid out and completed: determining the origin of gelation, the mechanism of gelation, the structure of the gel state, the properties of the gel state, and the effects of gelation on electrospun fibers of PHBHx. These goals were achieved through material characterization of the gel state utilizing infrared spectroscopy/two-dimensional correlation spectroscopy, differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, and many other analysis methods. Crystallization of the polymer in solution was found to cause gelation in PHBHx solutions, where the polymer crystals act as tie points forming

  8. Morphological investigation of polydisperse asymmetric block copolymer systems of poly(styrene) and poly(methacrylic acid) in the strong segregation regime

    DEFF Research Database (Denmark)

    Asad Ayoubi, Mehran; Zhu, Kaizheng; Nyström, Bo

    2013-01-01

    Samples of compositionally (highly) asymmetric diblock copolymers and, also, mixtures of diblock and triblock copolymers (the latter obtained as end-coupling products of two diblock molecules of the mixture), composed of (a) monodisperse majority block(s) of poly(styrene) (PS) and a polydisperse...

  9. Copolymer Production From Poly(Vinyl Alcohol

    Directory of Open Access Journals (Sweden)

    Jaleel Kareem Ahmed

    2018-03-01

    Full Text Available  The treatment of PVA with concentrated hydrochloric acid using a reflex technique for several days to transfer some of PVA to PVC as co-polmer. Black material formed with very high ability to absorb water (approximately 220% which indicates large voids formed in the new structure which confirmed by many tests. The new structure is a good water storage  which is interested in agriculture applications 

  10. Block copolymer membranes for aqueous solution applications

    KAUST Repository

    Nunes, Suzana Pereira

    2016-03-22

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  11. Block copolymer membranes for aqueous solution applications

    KAUST Repository

    Nunes, Suzana Pereira

    2016-01-01

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  12. Distribution of short block copolymer chains in Binary Blends of Block Copolymers Having Hydrogen Bonding

    Science.gov (United States)

    Kwak, Jongheon; Han, Sunghyun; Kim, Jin Kon

    2014-03-01

    A binary mixture of two block copolymers whose blocks are capable of forming the hydrogen bonding allows one to obtain various microdomains that could not be expected for neat block copolymer. For instance, the binary blend of symmetric polystyrene-block-poly(2-vinylpyridine) copolymer (PS-b-P2VP) and polystyrene-block-polyhydroxystyrene copolymer (PS-b-PHS) blends where the hydrogen bonding occurred between P2VP and PHS showed hexagonally packed (HEX) cylindrical and body centered cubic (BCC) spherical microdomains. To know the exact location of short block copolymer chains at the interface, we synthesized deuterated polystyrene-block-polyhydroxystyrene copolymer (dPS-b-PHS) and prepared a binary mixture with PS-b-P2VP. We investigate, via small angle X-ray scattering (SAXS) and neutron reflectivity (NR), the exact location of shorter dPS block chain near the interface of the microdomains.

  13. Micellization and Dynamics of a Block Copolymer

    DEFF Research Database (Denmark)

    Hvidt, Søren

    2006-01-01

    and copolymer mixtures, and evidence in favor of a multi-equilibria unimer-micelle model will be presented. Results obtained by liquid chromatographic methods will be shown and it will be demonstrated that commercial EPE copolymers are inhomogeneous at several levels and many of their unusual properties reflect...... ratios and temperature. The micellization process with increasing temperature has been followed by a number of techniques including differential scanning calorimetry, liquid chromatography, and surface tension measurements. Different micellization models have been tested for purified copolymers...

  14. PEO-related block copolymer surfactants

    DEFF Research Database (Denmark)

    Mortensen, K.

    2001-01-01

    Non-ionic block copolymer systems based on hydrophilic poly(ethylene oxide) and more hydrophobic co-polymer blocks are used intensively in a variety of industrial and personal applications. A brief description on the applications is presented. The physical properties of more simple model systems...... of such PEG-based block copolymers in aqueous suspensions are reviewed. Based on scattering experiments using either X-ray or neutrons, the phase behavior is characterized, showing that the thermo-reversible gelation is a result of micellar ordering into mesoscopic crystalline phases of cubic, hexagonal...

  15. Graft copolymers of ethyl methacrylate on waxy maize starch derivatives as novel excipients for matrix tablets: physicochemical and technological characterisation.

    Science.gov (United States)

    Marinich, J A; Ferrero, C; Jiménez-Castellanos, M R

    2009-05-01

    Nowadays, graft copolymers are being used as an interesting option when developing a direct compression excipient for controlled release matrix tablets. New graft copolymers of ethyl methacrylate (EMA) on waxy maize starch (MS) and hydroxypropylstarch (MHS) were synthesised by free radical polymerization and alternatively dried in a vacuum oven (OD) or freeze-dried (FD). This paper evaluates the performance of these new macromolecules and discusses the effect of the carbohydrate nature and drying process on their physicochemical and technological properties. Grafting of EMA on the carbohydrate backbone was confirmed by IR and NMR spectroscopy, and the grafting yields revealed that graft copolymers present mainly a hydrophobic character. The graft copolymerization also leads to more amorphous materials with larger particle size and lower apparent density and water content than carbohydrates (MS, MHS). All the products show a lack of flow, except MHSEMA derivatives. MSEMA copolymers underwent much plastic flow and less elastic recovery than MHSEMA copolymers. Concerning the effect of drying method, FD derivatives were characterised by higher plastic deformation and less elasticity than OD derivatives. Tablets obtained from graft copolymers showed higher crushing strength and disintegration time than tablets obtained from raw starches. This behaviour suggests that these copolymers could be used as excipients in matrix tablets obtained by direct compression and with a potential use in controlled release.

  16. Biodegradation of starch–graft–polystyrene and starch–graft–poly(methacrylic acid copolymers in model river water

    Directory of Open Access Journals (Sweden)

    Nikolić Vladimir

    2013-01-01

    Full Text Available In this paper the biodegradation study of grafted copolymers of polystyrene (PS and corn starch and poly(methacrylic acid and corn starch in model river water is described. These copolymers were obtained in the presence of different amine activators. The synthesized copolymers and products of degradation were characterized by Fourier Transform Infrared Spectroscopy (FTIR and Scanning Electron Microscopy (SEM. Biodegradation was monitored by mass decrease and number of microorganisms by Koch’s method. Biodegradation of both copolymers advanced with time, poly(methacrylic acid-graft-starch copolymers completely degraded after 21 day, and polystyrene-graft-starch partially degraded (45.78-93.09 % of total mass after 27 days. Differences in the degree of biodegradation are consequences of different structure of the samples, and there is a significant negative correlation between the share of polystyrene in copolymer and degree of biodegradation. The grafting degree of PS necessary to prevent biodegradation was 54 %. Based on experimental evidence, mechanisms of both biodegradation processes are proposed, and influence of degree of starch and synthetic component of copolymers on degradation were established. [Projekat Ministarstva nauke Republike Srbije, br. 172001 i br. 172062

  17. Barite formation in the presence of a commercial copolymer

    Science.gov (United States)

    Ruiz-Agudo, Cristina; Putnis, Christine; Ruiz-Agudo, Encarnacion; Putnis, Andrew

    2015-04-01

    Fluid composition can significantly modify the mechanisms of mineral formation. Particularly, the presence of organic additives in the aqueous media has been shown to alter the precipitation of minerals substantially (e.g. calcium carbonate, barium carbonate and barium sulfate). Despite the numerous studies dealing with barite precipitation and the influence of organic additives (e.g. Benton et al. 1993, Qi et al., 2000, Wang and Cölfen, 2006, Mavredaki et al., 2011), the details of the mechanism of barite formation in the presence of organic additives, particularly at the early stages of this process, are yet to be fully resolved. Here, we present observations on the initial stages of barite formation from aqueous solutions, as well as the alterations induced by a commercial copolymer (maleic acid/allyl sulfonic acid copolymer with phosphonate groups), commonly used as a scale inhibitor in oil recovery. Most synthetic commercial additives contain the same functional groups (e.g. carboxylate, phosphonate and/or sulfonate groups). Thus our work may help to understand the mechanism by which copolymers modify crystallization processes and aid in the selection of the most appropriate inhibitors for hindering or controlling barite scale formation. Barite scaling is one of the main problems in many industrial processes (such as, paper-making, chemical manufacturing, cement operations, off-shore oil extraction, geothermal energy production). Using Atomic Force Microscopy (AFM), we show that barite growth is significantly influenced by the presence of the copolymer. In its absence, barium sulfate growth occurs by 2D island nucleation and spreading. The addition of small amounts (0.1 ppm and 0.5 ppm) of the copolymer enhances 2D nucleation but blocks growth. Just 1 ppm of inhibitor is enough to block barite nucleation and growth by adsorption of a copolymer layer onto the barite surface. Transmission electron microscopy (TEM) was also used to gain better insights into the

  18. Synthesis, Characterization and Application of Thermoresponsive Polyhydroxyalkanoate-graft-Poly(N-isopropylacrylamide)

    DEFF Research Database (Denmark)

    Ma, Yi-Ming; Wei, Dai-Xu; Yao, Hui

    2016-01-01

    (3HDD-co-3H10U), a random copolymer of 3-hydroxydodecanoate (3HDD) and 3-hydroxy-10-undecylenate (3H10U), via a thiol–ene click reaction. Enhanced hydrophilicity and thermoresponsive property of the resulted PHA-g-PNIPAm were confirmed by water contact angle studies. The biocompatibility of PHA...

  19. Microbial synthesis of functional homo-, random, and block polyhydroxyalkanoates by β-oxidation deleted Pseudomonas entomophila

    DEFF Research Database (Denmark)

    Li, Shijun; Cai, Longwei; Wu, Linping

    2014-01-01

    -link with other PHA polymer chains. However, it has been very difficult to obtain structurally controllable functional homo-, random, or block PHA. For the first time, a β-oxidation deleted Pseudomonas entomophila was used to successfully synthesize random copolymers of 3-hydroxydodecanoate (3HDD) and 3-hydroxy-9...... be controlled to meet various requirements....

  20. Rapid selection of glucose-utilizing variants of the polyhydroxyalkanoate producer Ralstonia eutropha H16 by incubation with high substrate levels.

    Science.gov (United States)

    Franz, A; Rehner, R; Kienle, A; Grammel, H

    2012-01-01

    The application of Ralstonia eutropha H16 for producing polyhydroxyalkanoates as bioplastics is limited by the incapability of the bacterium to utilize glucose as a growth substrate. This study aims in characterizing glucose-utilizing strains that arose after incubation with high glucose levels, in comparison with previously published mutants, generated either by mutagenesis or by metabolic engineering. Cultivations on solid and liquid media showed that the application of high substrate concentrations rapidly induced a glucose-positive phenotype. The time span until the onset of growth and the frequency of glucose-utilizing colonies were correlated to the initial glucose concentration. All mutants exhibited elevated activities of glucose-6-phosphate dehydrogenase. The glucose-positive phenotype was abolished after deleting genes for the N-acetylglucosamine phosphotransferase system. A procedure is provided for selecting glucose-utilizing R. eutropha H16 in an unprecedented short time period and without any mutagenic treatment. An altered N-acetylglucosamine phosphotransferase system appears to be a common motif in all glucose-utilizing mutants examined so far. The correlation of the applied glucose concentration and the appearance of glucose-utilizing mutants poses questions about the randomness or the specificity of adaptive mutations in general. Furthermore, glucose-adapted strains of R. eutropha H16 could be useful for the production of bioplastics. © 2011 The Authors. Letters in Applied Microbiology ©2011 The Society for Applied Microbiology.

  1. Functional Nanoporous Polymers from Block Copolymer Precursors

    DEFF Research Database (Denmark)

    Guo, Fengxiao

    Abstract Self-assembly of block copolymers provides well-defined morphologies with characteristic length scales in the nanometer range. Nanoporous polymers prepared by selective removal of one block from self-assembled block copolymers offer great technological promise due to their many potential...... functionalities remains a great challenge due to the limitation of available polymer synthesis and the nanoscale confinement of the porous cavities. The main topic of this thesis is to develop methods for fabrication of functional nanoporous polymers from block copolymer precursors. A method has been developed......, where living anionic polymerization and atom transfer radical polymerization (ATRP) are combined to synthesize a polydimethylsiloxane-b-poly(tert-butyl acrylate)-b-polystyrene (PDMS-b-PtBA-b-PS) triblock copolymer precursor. By using either anhydrous hydrogen fluoride or trifluoroacetic acid, PtBA block...

  2. Hydrophilic block copolymer-directed growth of lanthanum hydroxide nano-particles

    Energy Technology Data Exchange (ETDEWEB)

    Bouyer, F.; Sanson, N.; Gerardin, C. [Laboratoire de Materiaux Catalytiques et Catalyse en Chimie Organique, UMR 5618 CNRS-ENSCM-UM1, FR 1878, Institut Gerhardt, 34 - Montpellier (France); Destarac, M. [Centre de Recherches Rhodia Aubervilliers, 93 - Aubervilliers (France)

    2006-03-15

    Stable hairy lanthanum hydroxide nano-particles were synthesized in water by performing hydrolysis and condensation reactions of lanthanum cations in the presence of double hydrophilic poly-acrylic acid-b-polyacrylamide block copolymers (PAA-b-PAM). In the first step, the addition of asymmetric PAA-b-PAM copolymers (M{sub w,PAA} {<=} M{sub w,PAM}) to lanthanum salt solutions, both at pH = 5.5, induces the formation of monodispersed micellar aggregates, which are predominantly isotropic. The core of the hybrid aggregates is constituted of a lanthanum polyacrylate complex whose formation is due to bidentate coordination bonding between La{sup 3+} and acrylate groups, as shown by ATR-FTIR experiments and pH measurements. The size of the micellar aggregates depends on the molecular weight of the copolymer but is independent of the copolymer to metal ratio in solution. In the second step, the hydrolysis of lanthanum ions is induced by addition of a strong base such as sodium hydroxide. Either flocculated suspensions or stable anisotropic or spherical nano-particles of lanthanum hydrolysis products were obtained depending on the metal complexation ratio [acrylate]/[La]. The variation of that parameter also enables the control of the size of the core-corona nano-particles obtained by lanthanum hydroxylation. The asymmetry degree of the copolymer was shown to influence both the size and the shape of the particles. Elongated particles with a high aspect ratio, up to 10, were obtained with very asymmetric copolymers (M{sub w,PAM}/M{sub w,PAA}{>=}10) while shorter rice grain-like particles were obtained with a less asymmetric copolymer. The asymmetry degree also influences the value of the critical metal complexation degree required to obtain stable colloidal suspensions of polymer-stabilized lanthanum hydroxide. (authors)

  3. Responsive Copolymers for Enhanced Petroleum Recovery

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.

    2001-02-27

    The objectives of this work was to: synthesize responsive copolymer systems; characterize molecular structure and solution behavior; measure rheological properties of aqueous fluids in fixed geometry flow profiles; and to tailor final polymer compositions for in situ rheology control under simulated conditions. This report focuses on the synthesis and characterization of novel stimuli responsive copolymers, the investigation of dilute polymer solutions in extensional flow and the design of a rheometer capable of measuring very dilute aqueous polymer solutions at low torque.

  4. Reactivity Ratios for Organotin Copolymer Systems

    Directory of Open Access Journals (Sweden)

    Mohamed H. El-Newehy

    2010-04-01

    Full Text Available Di(tri-n-butyltin itaconate (DTBTI and monoethyl tributyltin fumarate (METBTF were synthesized as organotin monomers. The organotin monomers were copolymerized with styrene (ST and methyl methacrylate (MMA via a free radical polymerization technique. The overall conversion was kept low (£15% wt/wt for all studied samples and the copolymer composition was determined from tin analysis. The synthesized monomers and copolymers were characterized by elemental analysis, 1H- and 13C-NMR, and FTIR spectroscopy.

  5. The influence of chain stretching on the phase behavior of multiblock copolymer and comb copolymer melts

    NARCIS (Netherlands)

    Angerman, HJ; ten Brinke, G

    The subject of this paper is inspired by microphase-separated copolymer melts in which a small-scale structure is present inside one of the phases of a large-scale structure. Such a situation can arise in a diblock copolymer melt, if one of the blocks of the diblock is in itself a multiblock

  6. Solid radiation curable polyene compositions containing liquid polythiols and solid styrene-allyl copolymer based polyenes

    International Nuclear Information System (INIS)

    Morgan, C.R.

    1977-01-01

    Novel styrene-allyl alcohol copolymer based solid polyene compositions which when mixed with liquid polythiols can form solid curable polyene-polythiol systems are claimed. These solid polyenes, containing at least two reactive carbon-to-carbon unsaturated bonds, are urethane or ester derivatives of styrene-allyl alcohol copolymers. The solid polyenes are prepared by treating the hydroxyl groups of a styrene-allyl alcohol copolymer with a reactive unsaturated isocyanate, e.g., allyl isocyanate or a reactive unsaturated carboxylic acid, e.g., acrylic acid. Upon exposure to a free radical generator, e.g., actinic radiation, the solid polyene-polythiol compositions cure to solid, insoluble, chemically resistant, cross-linked polythioether products. Since the solid polyene-liquid polythiol composition can be cured in a solid state, such a curable system finds particular use in preparation of coatings, imaged surfaces such as photoresists, particularly solder-resistant photoresists, printing plates, etc

  7. Synthesis of an amphiphilic dendrimer-like block copolymer and its application on drug delivery

    KAUST Repository

    Wang, Shuaipeng

    2014-10-27

    Dendrimer-like amphiphilic copolymer is a kind of three-dimensional spherical structure polymer. An amphiphilic dendrimer-like diblock copolymer, PEEGE-G2-b-PEO(OH)12, constituted of a hydrophobic poly(ethoxyethyl glycidol ether) inner core and a hydrophilic poly(ethylene oxide) outer layer, has been successfully synthesized by the living anionic ring-opening polymerization method. The intermediates and targeted products were characterized with 1H NMR spectroscopy and gel permeation chromatography. The application on drug delivery of dendrimer-like diblock copolymer PEEGE-G2-b-PEO(OH)12 using DOX as a model drug was also studied. The drug loading content and encapsulation efficiency were found at 13.07% and 45.75%, respectively. In vitro release experiment results indicated that the drug-loaded micelles exhibited a sustained release behavior under acidic media.

  8. Biomechanics of Polyhydroxyalkanoate Mesh-Augmented Single-Row Rotator Cuff Repairs.

    Science.gov (United States)

    Tashjian, Robert Z; Kolz, Christopher W; Suter, Thomas; Henninger, Heath B

    Polyhydroxyalkanoate (PHA) mesh is a bioresorbable scaffold used to reinforce the suture-tendon interface in rotator cuff repairs (RCRs). We conducted a study of cyclic and ultimate failure properties of PHA mesh-augmented single-row RCRs and nonaugmented RCRs. Eight pairs of fresh-frozen cadaver humeri (6 male, 2 female) were tested. Mean (SD) age was 61 (9) years. The supraspinatus tendon was resected and reattached in a single-row configuration using 2 triple-loaded suture anchors and 6 simple stitches. The opposite humerus underwent RCR augmented with 2 strips of 13-mm × 23-mm PHA mesh. Humeri were mounted in an Instron load frame, cycled 1000 times to 1.0 MPa of effective stress, and loaded to failure. Construct gapping and ultimate failure loads/displacements were recorded. Paired t tests compared augmented and nonaugmented RCRs (P ≤ .05 was significant). There was no difference in gapping over 1000 cycles (P = .879). Mean (SD) failure load was higher for PHA mesh-augmented RCRs, 571 (173) N, than for nonaugmented (control) RCRs, 472 (120) N (P = .042), and failures were consistent within pairs because of tissue failure at the knots or anchor pullout. This technique for arthroscopic augmentation can be used to improve initial biomechanical repair strength in tears at risk for failure.

  9. Development and Characterization of a Metal Injection Molding Bio Sourced Inconel 718 Feedstock Based on Polyhydroxyalkanoates

    Directory of Open Access Journals (Sweden)

    Alexandre Royer

    2016-04-01

    Full Text Available The binder plays the most important role in the metal injection molding (MIM process. It provides fluidity of the feedstock mixture and adhesion of the powder to keep the molded shape during injection molding. The binder must provide strength and cohesion for the molded part and must be easy to remove from the molded part. Moreover, it must be recyclable, environmentally friendly and economical. Also, the miscibility between polymers affects the homogeneity of the injected parts. The goal of this study is to develop a feedstock of superalloy Inconel 718 that is environmentally friendly. For these different binders, formulations based on polyethylene glycol (PEG, because of his water solubility property, and bio sourced polymers were studied. Polyhydroxyalkanoates (PHA were investigated as a bio sourced polymer due to its miscibility with the PEG. The result is compared to a standard formulation using polypropylene (PP. The chemical and rheological behavior of the binder formulation during mixing, injection and debinding process were investigated. The feedstock was characterized in the same way as the binders and the interactions between the powder and the binders were also studied. The results show the well adapted formulation of polymer binder to produce a superalloy Inconel 718 feedstock.

  10. Modelling of microbial polyhydroxyalkanoate surface binding protein PhaP for rational mutagenesis.

    Science.gov (United States)

    Zhao, Hongyu; Yao, Zhenyu; Chen, Xiangbin; Wang, Xinquan; Chen, Guo-Qiang

    2017-11-01

    Phasins are unusual amphiphilic proteins that bind to microbial polyhydroxyalkanoate (PHA) granules in nature and show great potential for various applications in biotechnology and medicine. Despite their remarkable diversity, only the crystal structure of PhaP A h from Aeromonas hydrophila has been solved to date. Based on the structure of PhaP A h , homology models of PhaP A z from Azotobacter sp. FA-8 and PhaP TD from Halomonas bluephagenesis TD were successfully established, allowing rational mutagenesis to be conducted to enhance the stability and surfactant properties of these proteins. PhaP A z mutants, including PhaP A z Q38L and PhaP A z Q78L, as well as PhaP TD mutants, including PhaP TD Q38M and PhaP TD Q72M, showed better emulsification properties and improved thermostability (6-10°C higher melting temperatures) compared with their wild-type homologues under the same conditions. Importantly, the established PhaP homology-modelling approach, based on the high-resolution structure of PhaP A h , can be generalized to facilitate the study of other PhaP members. © 2017 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

  11. In-silico-driven metabolic engineering of Pseudomonas putida for enhanced production of poly-hydroxyalkanoates

    NARCIS (Netherlands)

    Poblete-Castro, I.; Binger, D.; Rodrigues, A.; Becker, J.; Martins Dos Santos, V.A.P.; Wittmann, C.

    2013-01-01

    Here, we present systems metabolic engineering driven by in-silico modeling to tailor Pseudomonas putida for synthesis of medium chain length PHAs on glucose. Using physiological properties of the parent wild type as constraints, elementary flux mode analysis of a large-scale model of the metabolism

  12. Preparation of polystyrene-poly(ethylene glycol) diblock copolymer by "living" free radical polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Gao, Bo; Kops, Jørgen

    1998-01-01

    terminated with a TEMPO unit (MPEG-TEMPO), which was further used to prepare the diblock copolymer PS-b-PEG by 'living' free radical polymerisation of styrene. The product was purified and identified by H-1 n.m.r. and GPC. However, large amounts of homopolystyrene was also formed by simultaneous thermal...

  13. Asymmetric block copolymer membranes with ultrahigh porosity and hierarchical pore structure by plain solvent evaporation

    KAUST Repository

    Yu, H.

    2016-09-14

    Membranes with a hierarchical porous structure could be manufactured from a block copolymer blend by pure solvent evaporation. Uniform pores in a 30 nm thin skin layer supported by a macroporous structure were formed. This new process is attractive for membrane production because of its simplicity and the lack of liquid waste.

  14. Asymmetric block copolymer membranes with ultrahigh porosity and hierarchical pore structure by plain solvent evaporation

    KAUST Repository

    Yu, H.; Qiu, Xiaoyan; Behzad, Ali Reza; Musteata, Valentina-Elena; Smilgies, D.-M.; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2016-01-01

    Membranes with a hierarchical porous structure could be manufactured from a block copolymer blend by pure solvent evaporation. Uniform pores in a 30 nm thin skin layer supported by a macroporous structure were formed. This new process is attractive for membrane production because of its simplicity and the lack of liquid waste.

  15. Self-assembled block copolymer membranes: From basic research to large-scale manufacturing

    KAUST Repository

    Nunes, Suzana Pereira

    2013-09-24

    Order and porosity of block copolymer membranes have been controlled by solution thermodynamics, self-assembly, and macrophase separation. We have demonstrated how the film manufacture with long-range order can be up-scaled with the use of conventional membrane production technology.

  16. Multiblock copolymers synthesized in aqueous dispersions using multifunctional RAFT agents

    NARCIS (Netherlands)

    Bussels, R.; Bergman-Göttgens, C.M.; Meuldijk, J.; Koning, C.E.

    2005-01-01

    Triblock copolymers were synthesized in aqueous dispersions in two polymerization steps using a low molar mass difunctional dithiocarbamate-based RAFT agent, and in merely one polymerization step using a macromolecular difunctional dithiocarbamate-based RAFT agent. Segmented block copolymers

  17. Polyamide copolymers having 2,5-furan dicarboxamide units

    Science.gov (United States)

    Chisholm, Bret Ja; Samanta, Satyabrata

    2017-09-19

    Polyamide copolymers, and methods of making and using polyamide copolymers, having 2,5-furan dicarboxamide units are disclosed herein. Such polymers can be useful for engineering thermoplastics having advantageous physical and/or chemical properties.

  18. Screening of polyhydroxyalkanoate-producing bacteria and PhaC-encoding genes in two hypersaline microbial mats from Guerrero Negro, Baja California Sur, Mexico

    Directory of Open Access Journals (Sweden)

    Carolina A. Martínez-Gutiérrez

    2018-05-01

    Full Text Available Hypersaline microbial mats develop through seasonal and diel fluctuations, as well as under several physicochemical variables. Hence, resident microorganisms commonly employ strategies such as the synthesis of polyhydroxyalkanoates (PHAs in order to resist changing and stressful conditions. However, the knowledge of bacterial PHA production in hypersaline microbial mats has been limited to date, particularly in regard to medium-chain length PHAs (mcl-PHAs, which have biotechnological applications due to their plastic properties. The aim of this study was to obtain evidence for PHA production in two hypersaline microbial mats of Guerrero Negro, Mexico by searching for PHA granules and PHA synthase genes in isolated bacterial strains and environmental samples. Six PHA-producing strains were identified by 16S rRNA gene sequencing; three of them corresponded to a Halomonas sp. In addition, Paracoccus sp., Planomicrobium sp. and Staphylococcus sp. were also identified as PHA producers. Presumptive PHA granules and PHA synthases genes were detected in both sampling sites. Moreover, phylogenetic analysis showed that most of the phylotypes were distantly related to putative PhaC synthases class I sequences belonging to members of the classes Alphaproteobacteria and Gammaproteobacteria distributed within eight families, with higher abundances corresponding mainly to Rhodobacteraceae and Rhodospirillaceae. This analysis also showed that PhaC synthases class II sequences were closely related to those of Pseudomonas putida, suggesting the presence of this group, which is probably involved in the production of mcl-PHA in the mats. According to our state of knowledge, this study reports for the first time the occurrence of phaC and phaC1 sequences in hypersaline microbial mats, suggesting that these ecosystems may be a novel source for the isolation of short- and medium-chain length PHA producers.

  19. Oil recovery with vinyl sulfonic acid-acrylamide copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Norton, C.J.; Falk, D.O.

    1973-12-18

    An aqueous polymer flood containing sulfomethylated alkali metal vinyl sulfonate-acrylamide copolymers was proposed for use in secondary or tertiary enhanced oil recovery. The sulfonate groups on the copolymers sustain the viscosity of the flood in the presence of brine and lime. Injection of the copolymer solution into a waterflooded Berea core, produced 30.5 percent of the residual oil. It is preferred that the copolymers are partially hydrolyzed.

  20. Photo-Induced Micellization of Block Copolymers

    Directory of Open Access Journals (Sweden)

    Satoshi Kuwayama

    2010-11-01

    Full Text Available We found novel photo-induced micellizations through photolysis, photoelectron transfer, and photo-Claisen rearrangement. The photolysis-induced micellization was attained using poly(4-tert-butoxystyrene-block-polystyrene diblock copolymer (PBSt-b-PSt. BSt-b-PSt showed no self-assembly in dichloromethane and existed as isolated copolymers. Dynamic light scattering demonstrated that the copolymer produced spherical micelles in this solvent due to irradiation with a high-pressure mercury lamp in the presence of photo-acid generators, such as bis(alkylphenyliodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, and triphenylsulfonium triflate. The 1H NMR analysis confirmed that PBSt-b-PSt was converted into poly(4-vinylphenol-block-PSt by the irradiation, resulting in self-assembly into micelles. The irradiation in the presence of the photo-acid generator also induced the micellization of poly(4-pyridinemethoxymethylstyrene-block-polystyrene diblock copolymer (PPySt-b-PSt. Micellization occurred by electron transfer from the pyridine to the photo-acid generator in their excited states and provided monodispersed spherical micelles with cores of PPySt blocks. Further, the photo-Claisen rearrangement caused the micellization of poly(4-allyloxystyrene-block-polystyrene diblock copolymer (PASt-b-PSt. Micellization was promoted in cyclohexane at room temperature without a catalyst. During micellization, the elimination of the allyl groups competitively occurred along with the photorearrangement of the 4-allyloxystyrene units into the 3-allyl-4-hydroxystyrene units.

  1. Nanoparticles based on novel amphiphilic polyaspartamide copolymers

    International Nuclear Information System (INIS)

    Craparo, Emanuela Fabiola; Teresi, Girolamo; Ognibene, Maria Chiara; Casaletto, Maria Pia; Bondi, Maria Luisa; Cavallaro, Gennara

    2010-01-01

    In this article, the synthesis of two amphiphilic polyaspartamide copolymers, useful to obtain polymeric nanoparticles without using surfactants or stabilizing agents, is described. These copolymers were obtained starting from α,β-poly-(N-2-hydroxyethyl)-dl-aspartamide (PHEA) by following a novel synthetic strategy. In particular, PHEA and its pegylated derivative (PHEA-PEG 2000 ) were functionalized with poly(lactic acid) (PLA) through 1,1'-carbonyldiimidazole (CDI) activation to obtain PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers, respectively. These copolymers were properly purified and characterized by 1 H-NMR, FT-IR, and Size Exclusion Chromatography (SEC) analyses, which confirmed that derivatization reactions occurred. Nanoparticles were obtained from PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers by using the high pressure homogenization-solvent evaporation method, avoiding the use of surfactants or stabilizing agents. Polymeric nanoparticles were characterized by dimensional analysis, before and after freeze-drying process, and Scanning Electron Microscopy (SEM). Zeta potential measurements and X-ray Photoelectron Spectroscopy (XPS) analysis demonstrated the presence of PEG and/or PHEA onto the PHEA-PEG 2000 -PLA and PHEA-PLA nanoparticle surface, respectively.

  2. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-acrylic acid copolymers. 177.1310 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid copolymers identified in paragraph (a) of this section may be safely...

  3. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-carbon monoxide copolymers. 177.1312... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1312 Ethylene-carbon monoxide copolymers. The ethylene-carbon monoxide copolymers identified in paragraph (a) of this section may be safely...

  4. 21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate copolymers. 177.1350 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymers may be safely used as articles or components of articles...

  5. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-ethyl acrylate copolymers. 177.1320... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1320 Ethylene-ethyl acrylate copolymers. Ethylene-ethyl acrylate copolymers may be safely used to produce packaging materials, containers...

  6. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-ethylene copolymers. 177.1950... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1950 Vinyl chloride-ethylene copolymers. The vinyl chloride-ethylene copolymers identified in paragraph (a) of this section may be safely...

  7. Functionalization of Block Copolymer Vesicle Surfaces

    Directory of Open Access Journals (Sweden)

    Wolfgang Meier

    2011-01-01

    Full Text Available In dilute aqueous solutions certain amphiphilic block copolymers self-assemble into vesicles that enclose a small pool of water with a membrane. Such polymersomes have promising applications ranging from targeted drug-delivery devices, to biosensors, and nanoreactors. Interactions between block copolymer membranes and their surroundings are important factors that determine their potential biomedical applications. Such interactions are influenced predominantly by the membrane surface. We review methods to functionalize block copolymer vesicle surfaces by chemical means with ligands such as antibodies, adhesion moieties, enzymes, carbohydrates and fluorophores. Furthermore, surface-functionalization can be achieved by self-assembly of polymers that carry ligands at their chain ends or in their hydrophilic blocks. While this review focuses on the strategies to functionalize vesicle surfaces, the applications realized by, and envisioned for, such functional polymersomes are also highlighted.

  8. Amphiphilic block copolymers for biomedical applications

    Science.gov (United States)

    Zupancich, John Andrew

    Amphiphilic block copolymer self-assembly provides a versatile means to prepare nanoscale objects in solution. Control over aggregate shape is granted through manipulation of amphiphile composition and the synthesis of well-defined polymers offers the potential to produce micelles with geometries optimized for specific applications. Currently, polymer micelles are being investigated as vehicles for the delivery of therapeutics and attempts to increase efficacy has motivated efforts to incorporate bioactive ligands and stimuli-responsive character into these structures. This thesis reports the synthesis and self-assembly of biocompatible, degradable polymeric amphiphiles. Spherical, cylindrical, and bilayered vesicle structures were generated spontaneously by the direct dispersion of poly(ethylene oxide)-b-poly(gamma-methyl-ε-caprolactone) block copolymers in water and solutions were characterized with cryogenic transmission electron microscopy (cryo-TEM). The dependence of micelle structure on diblock copolymer composition was examined through the systematic variation of the hydrophobic block molecular weight. A continuous evolution of morphology was observed with coexistence of aggregate structures occurring in windows of composition intermediate to that of pure spheres, cylinders and vesicles. A number of heterobifunctional poly(ethylene oxide) polymers were synthesized for the preparation of ligand-functionalized amphiphilic diblock copolymers. The effect of ligand conjugation on block copolymer self-assembly and micelle morphology was also examined. An RGD-containing peptide sequence was efficiently conjugated to a set of well characterized poly(ethylene oxide)-b-poly(butadiene) copolymers. The reported aggregate morphologies of peptide-functionalized polymeric amphiphiles deviated from canonical structures and the micelle clustering, cylinder fragmentation, network formation, and multilayer vesicle generation documented with cryo-TEM was attributed to

  9. Dynamics of Block Copolymer Nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Mochrie, Simon G. J.

    2014-09-09

    A detailed study of the dynamics of cadmium sulfide nanoparticles suspended in polystyrene homopolymer matrices was carried out using X-ray photon correlation spectroscopy for temperatures between 120 and 180 °C. For low molecular weight polystyrene homopolymers, the observed dynamics show a crossover from diffusive to hyper-diffusive behavior with decreasing temperatures. For higher molecular weight polystyrene, the nanoparticle dynamics appear hyper-diffusive at all temperatures studied. The relaxation time and characteristic velocity determined from the measured hyper-diffusive dynamics reveal that the activation energy and underlying forces determined are on the order of 2.14 × 10-19 J and 87 pN, respectively. We also carried out a detailed X-ray scattering study of the static and dynamic behavior of a styrene– isoprene diblock copolymer melt with a styrene volume fraction of 0.3468. At 115 and 120 °C, we observe splitting of the principal Bragg peak, which we attribute to phase coexistence of hexagonal cylindrical and cubic double- gyroid structure. In the disordered phase, above 130 °C, we have characterized the dynamics of composition fluctuations via X-ray photon correlation spectroscopy. Near the peak of the static structure factor, these fluctuations show stretched-exponential relaxations, characterized by a stretching exponent of about 0.36 for a range of temperatures immediately above the MST. The corresponding characteristic relaxation times vary exponentially with temperature, changing by a factor of 2 for each 2 °C change in temperature. At low wavevectors, the measured relaxations are diffusive with relaxation times that change by a factor of 2 for each 8 °C change in temperature.

  10. Co-polymer Films for Sensors

    Science.gov (United States)

    Ryan, Margaret A. (Inventor); Jewell, April D. (Inventor); Taylor, Charles (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Manatt, Kenneth S. (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor); Homer, Margie L. (Inventor); Shevade, Abhijit V. (Inventor)

    2012-01-01

    Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

  11. Ordering phenomena in ABA triblock copolymer gels

    DEFF Research Database (Denmark)

    Reynders, K.; Mischenko, N.; Kleppinger, R.

    1997-01-01

    Temperature and concentration dependencies of the degree of order in ABA triblock copolymer gels are discussed. Two factors can influence the ordering phenomena: the conformation of the midblocks (links of the network) and the polydispersity of the endblock domains (nodes of the network). The lat......Temperature and concentration dependencies of the degree of order in ABA triblock copolymer gels are discussed. Two factors can influence the ordering phenomena: the conformation of the midblocks (links of the network) and the polydispersity of the endblock domains (nodes of the network...

  12. Molecular Interaction Control in Diblock Copolymer Blends and Multiblock Copolymers with Opposite Phase Behaviors

    Science.gov (United States)

    Cho, Junhan

    2014-03-01

    Here we show how to control molecular interactions via mixing AB and AC diblock copolymers, where one copolymer exhibits upper order-disorder transition and the other does lower disorder-order transition. Linear ABC triblock copolymers possessing both barotropic and baroplastic pairs are also taken into account. A recently developed random-phase approximation (RPA) theory and the self-consistent field theory (SCFT) for general compressible mixtures are used to analyze stability criteria and morphologies for the given systems. It is demonstrated that the copolymer systems can yield a variety of phase behaviors in their temperature and pressure dependence upon proper mixing conditions and compositions, which is caused by the delicate force fields generated in the systems. We acknowledge the financial support from National Research Foundation of Korea and Center for Photofunctional Energy Materials.

  13. Synthesis of polyaniline catalysed by Cu(I), Ni(II) and Fe(II) supported on the polyethylene-i-acrylic acid copolymer

    International Nuclear Information System (INIS)

    Hernandez, L.; Urena, F.; Lopez, R.

    1997-01-01

    In this study the active sites of acrylic acid (AA) were grafted in low density polyethylene (PEBD) using gamma radiation. Subsequently, the graft copolymer PEBD-i-AA was coordinated with different metals such as copper, nickel and iron. The organometallic copolymers so formed were used as catalysts in the aniline polymerization reaction. Finally, it was realized the characterization of the obtained products, determining their thermal properties, copolymer graft percentage, quantification of the metal contained in the complex as well as polymerization and electric conductivity percentages of the poly aniline film. (Author)

  14. Shear instability of a gyroid diblock copolymer

    DEFF Research Database (Denmark)

    Eskimergen, Rüya; Mortensen, Kell; Vigild, Martin Etchells

    2005-01-01

    -induced destabilization is discussed in relation to analogous observations on shear-induced order-to-order and disorder-to-order transitions observed in related block copolymer systems and in microemulsions. It is discussed whether these phenomena originate in shear-reduced fluctuations or shear-induced dislocations....

  15. CONJUGATED BLOCK-COPOLYMERS FOR ELECTROLUMINESCENT DIODES

    NARCIS (Netherlands)

    Hilberer, A; Gill, R.E; Herrema, J.K; Malliaras, G.G; Wildeman, J.; Hadziioannou, G

    In this article we review results obtained in our laboratory on the design and study of new light-emitting polymers. We are interested in the synthesis and characterisation of block copolymers with regularly alternating conjugated and non conjugated sequences. The blocks giving rise to luminescence

  16. Substrate tolerant direct block copolymer nanolithography

    DEFF Research Database (Denmark)

    Li, Tao; Wang, Zhongli; Schulte, Lars

    2016-01-01

    Block copolymer (BC) self-assembly constitutes a powerful platform for nanolithography. However, there is a need for a general approach to BC lithography that critically considers all the steps from substrate preparation to the final pattern transfer. We present a procedure that significantly sim...... plasma treatment enables formation of the oxidized PDMS hard mask, PS block removal and polymer or graphene substrate patterning....

  17. Micellization and Characterization of Block Copolymer Detergents

    DEFF Research Database (Denmark)

    Hvidt, Søren

    and different models have been proposed. Results obtained by a range of liquid chromatographic methods will be shown and it will be demonstrated that commercial EPE copolymers are inhomogeneous at several levels and many of their unusual properties reflect the presence of impurities....

  18. Cyclic olefin copolymer-silica nanocomposites foams

    Czech Academy of Sciences Publication Activity Database

    Pegoretti, A.; Dorigato, A.; Biani, A.; Šlouf, Miroslav

    2016-01-01

    Roč. 51, č. 8 (2016), s. 3907-3916 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : cyclic olefin copolymer * nanocomposites * silica Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.599, year: 2016

  19. Research Update: Triblock copolymers as templates to synthesize inorganic nanoporous materials

    OpenAIRE

    Yunqi Li; Bishnu Prasad Bastakoti; Yusuke Yamauchi

    2016-01-01

    This review focuses on the application of triblock copolymers as designed templates to synthesize nanoporous materials with various compositions. Asymmetric triblock copolymers have several advantages compared with symmetric triblock copolymers and diblock copolymers, because the presence of three distinct domains can provide more functional features to direct the resultant nanoporous materials. Here we clearly describe significant contributions of asymmetric triblock copolymers, especially p...

  20. Process for producing a new copolymer. [Patent in Japanese

    Energy Technology Data Exchange (ETDEWEB)

    Tojima, M; Matsumoto, K; Sasaki, H

    1970-12-11

    A new process for copolymerization is given by using either a diaryl oxalate single polymer or a diaryl oxalate copolymer with at least one vinyl monomer as a source of free radicals, and adding a conventional radical initiator to them when irradiated with light or particle radiations. The function of the free radicals generated from the diaryl oxalate monomer is quite different from the free radicals generated from the conventional initiators. The addition of the conventional radical initiators is to accelerate the copolymerization reaction. The advantage of this process is that low energy light at room temperature can be used like high energy radiation. In one of the examples, 500 g of diaryl oxalate monomer, 1200ml of benzene and 0.2 mol/l of benzoil peroxide were mixed and underwent a polymerization reaction in nitrogen gas at 70/sup 0/C for 8 hrs. A polymer was isolated from their methanol solution. The polymer had an iodine value of 77.7 and a yield of 35%. The polymer was dissolved in vinyl acetate, methacrylate or acrylic acid with or without benzoil peroxides. The produced viscous solutions were molded and irradiated with a 450 Watt mercury lamp. Experiments revealed that the products obtained in the presence of benzoil peroxides could reduce by as much as one half to one third the time required to harden the copolymer.

  1. Polyhydroxyalkanoate synthesis by mixed microbial consortia cultured on fermented dairy manure: Effect of aeration on process rates/yields and the associated microbial ecology.

    Science.gov (United States)

    Coats, Erik R; Watson, Benjamin S; Brinkman, Cynthia K

    2016-12-01

    Polyhydroxyalkanoates (PHAs) are biodegradable polymers that can substitute for petroleum-based plastics in a variety of applications. One avenue to commercial PHA production involves coupling waste-based synthesis with the use of mixed microbial consortia (MMC). In this regard, production requires maximizing the enrichment of a MMC capable of feast-famine PHA synthesis, with the metabolic response induced through imposition of aerobic-dynamic feeding (ADF) conditions. However, the concept of PHA production in complex matrices remains unrefined; process operational improvements are needed, along with an enhanced understanding of the MMC. Research presented herein investigated the effect of aeration on feast-famine PHA synthesis, with four independent aeration state systems studied; MMC were fed volatile fatty acid (VFA)-rich fermented dairy manure. Regardless of the aeration state, all MMC exhibited a feast-famine response based on observed carbon cycling. Moreover, there was no statistical difference in PHA synthesis rates, with q PHA ranging from 0.10 to 0.19 CmmolPHA gVSS -1 min -1 ; VFA uptake rates exhibited similar statistical indifferences. PHA production assessments on the enriched MMC resulted in maximum intracellular concentrations ranging from 22.5 to 90.7% (mgPHA mgVSS -1 ); at maximum concentration, the mean hydroxyvalerate mol content was 73 ± 0.6%. While a typical feast-famine dissolved oxygen (DO) pattern was observed at maximum aeration, less resolution was observed at decreasing aeration rates, suggesting that DO may not be an optimal process monitoring parameter. At lower aeration states, nitrogen cycling patterns, supported by molecular investigations targeting AOBs and NOBs, indicate that NO 2 and NO 3 sustained feast-famine PHA synthesis. Next-generation sequencing analysis of the respective MMC revealed numerous and diverse genera exhibiting the potential to achieve PHA synthesis, suggesting functional redundancy embedded in the diverse

  2. Synthesis of a gamma irradiation grafted polytetrafluoroethylene (PTFE) based olefinic copolymer

    International Nuclear Information System (INIS)

    Ferreto, Helio Fernando Rodrigues

    2006-01-01

    The extrusion of linear low density polyethylene (LLDPE) is limited by a process related defect known as 'melt fracture' or 'sharkskin', which is a surface defect of the extruded polymer. This defect results in a product with a rough surface that lacks luster and in alterations of specific surface properties. The aim of this study was to obtain a recycled polytetrafluoroethylene polymer with an olefin that could improve the extrudability of the LLDPE. The copolymer was obtained by irradiating recycled PTFE in an inert atmosphere followed by the addition of an olefinic monomer to graft the latter in the polymeric matrix (PTFE). After a certain time of contact, the copolymer was heat treated to permit recombination and elimination of the radicals, both in a reactive and/or inert atmosphere. Three olefinic monomers were used, namely; acetylene, ethylene and 1,3-butadiene. The 1,3-butadiene monomer was found to be more effective with respect to grafting. The specimens were studied using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). 0.2-2.0 wt% of the copolymer that was obtained was mixed with LLDPE. The rheological properties of the mixture were determined with a torque rheometer. The results indicated that the process used rendered a copolymer which when added to LLDPE, improved the extrusion process and eliminated the defect 'melt fracture'. (author)

  3. Synthesis and Characterization of Solution and Melt Processible Poly(Acrylonitrile-Co-Methyl Acrylate) Statistical Copolymers

    Science.gov (United States)

    Pisipati, Padmapriya

    Polyacrylonitrile (PAN) and its copolymers are used in a wide variety of applications ranging from textiles to purification membranes, packaging material and carbon fiber precursors. High performance polyacrylonitrile copolymer fiber is the most dominant precursor for carbon fibers. Synthesis of very high molecular weight poly(acrylonitrile-co-methyl acrylate) copolymers with weight average molecular weights of at least 1.7 million g/mole were synthesized on a laboratory scale using low temperature, emulsion copolymerization in a closed pressure reactor. Single filaments were spun via hybrid dry-jet gel solution spinning. These very high molecular weight copolymers produced precursor fibers with tensile strengths averaging 954 MPa with an elastic modulus of 15.9 GPa (N = 296). The small filament diameters were approximately 5 im. Results indicated that the low filament diameter that was achieved with a high draw ratio, combined with the hybrid dry-jet gel spinning process lead to an exponential enhancement of the tensile properties of these fibers. Carbon fibers for polymer matrix composites are currently derived from polyacrylonitrile copolymer fiber precursors where solution spinning accounts for ˜40 % of the total fiber production cost. To expand carbon fiber applications into the automotive industry, the cost of the carbon fiber needs to be reduced from 8 to ˜3-5. In order to develop an alternative melt processing route several benign plasticizers have been investigated. A low temperature, persulfate-metabisulfite initiated emulsion copolymerization was developed to synthesize poly(acrylonitrile-co-methyl acrylate) copolymers with acrylonitrile contents between 91-96 wt% with a molecular weight range of 100-200 kg/mol. This method was designed for a potential industrial scale up. Furthermore, water was investigated as a potential melting point depressant for these copolymers. Twenty-five wt% water lead to a decrease in the Tm of a 93/7 wt/wt % poly

  4. Characterisation of copolymer, poly (hydroxybutyrate-co-hydroxyvalerate) (PHB-co-PHV) produced by Halomonas campisalis (MCM B-1027), its biodegradability and potential application.

    Science.gov (United States)

    Kulkarni, Snehal O; Kanekar, Pradnya P; Jog, Jyoti P; Patil, Prashant A; Nilegaonkar, Smita S; Sarnaik, Seema S; Kshirsagar, Pranav R

    2011-06-01

    Characterisation of polyhydroxyalkanoate (PHA) film produced by haloalkalitolerant Halomonas campisalis (MCM B-1027) in 14L SS fermenter revealed it to have composition of monomer units, HB:HV as 96:4 as analysed by (1)H NMR indicating the PHA as a co-polymer of PHB-co-PHV, molecular weight by gel permeation chromatography as 2.08 × 10(6), melting temperature 166.51°C, tensile strength 18.8 MPa; two relaxations namely beta transition corresponding to the glass rubber transition and alpha transition corresponding to crystalline relaxation by Dynamic Mechanical Thermal analysis and only one relaxation corresponding to MWS interfacial polarisation with activation energy of 129 kJ/mol by broadband dielectric spectroscopy. Optical microscopic studies showed typical Maltese-cross pattern of spherulites. The PHA film was found to be biodegradable by standard ASTM method as well as by soil burial method. The leak proof polymer bags prepared from the film could be used as a packaging material. Copyright © 2011 Elsevier Ltd. All rights reserved.

  5. Phase behavior of model ABC triblock copolymers

    Science.gov (United States)

    Chatterjee, Joon

    The phase behavior of poly(isoprene-b-styrene- b-ethylene oxide) (ISO), a model ABC triblock copolymer has been studied. This class of materials exhibit self-assembly, forming a large array of ordered morphologies at length scales of 5-100 nm. The formation of stable three-dimensionally continuous network morphologies is of special interest in this study. Since these nanostructures considerably impact the material properties, fundamental knowledge for designing ABC systems have high technological importance for realizing applications in the areas of nanofabrication, nanoporous media, separation membranes, drug delivery and high surface area catalysts. A comprehensive framework was developed to describe the phase behavior of the ISO triblock copolymers at weak to intermediate segregation strengths spanning a wide range of composition. Phases were characterized through a combination of characterization techniques, including small angle x-ray scattering, dynamic mechanical spectroscopy, transmission electron microscopy, and birefringence measurements. Combined with previous investigations on ISO, six different stable ordered state symmetries have been identified: lamellae (LAM), Fddd orthorhombic network (O70), double gyroid (Q230), alternating gyroid (Q214), hexagonal (HEX), and body-centered cubic (BCC). The phase map was found to be somewhat asymmetric around the fI = fO isopleth. This work provides a guide for theoretical studies and gives insight into the intricate effects of various parameters on the self-assembly of ABC triblock copolymers. Experimental SAXS data evaluated with a simple scattering intensity model show that local mixing varies continuously across the phase map between states of two- and three-domain segregation. Strategies of blending homopolymers with ISO triblock copolymer were employed for studying the swelling properties of a lamellar state. Results demonstrate that lamellar domains swell or shrink depending upon the type of homopolymer that

  6. Renewable Pentablock Copolymers Containing Bulky Natural Rosin for Tough Bioplastics

    Science.gov (United States)

    Rahman, Md Anisur; Ganewatta, Mitra S.; Lokupitiya, Hasala N.; Liang, Yuan; Stefik, Morgan; Tang, Chuanbing

    Renewable polymers have received significant attention due to environmental concerns on petrochemical counterparts. One of the most abundant natural biomass is resin acids. However, most polymers derived from resin acids are low molecular weight and brittle because of the high chain entanglement molecular weight resulted from the bulky hydrophenanthrene pendant group. It is well established that the brittleness can be overcome by synthesizing multi-block copolymers with low entanglement molecular weight components. We investigated the effects of chain architecture and microdomain orientation on mechanical properties of both tri and pentablock copolymers. We synthesized rosin-containing A-B-A-B-A type pentablock and A-B-A type triblock copolymers to improve their mechanical properties. Pentablock copolymers showed higher strength and better toughness as compared to triblock copolymers, both superior to homopolymers. The greater toughness of pentablock copolymers is due to the presence of the rosin based midblock chains that act as bridging chains between two polynorbornene blocks.

  7. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    OpenAIRE

    Hoarfrost, Megan Lane

    2012-01-01

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the additio...

  8. Hybrid, Nanoscale Phospholipid/Block Copolymer Vesicles

    Directory of Open Access Journals (Sweden)

    Bo Liedberg

    2013-09-01

    Full Text Available Hybrid phospholipid/block copolymer vesicles, in which the polymeric membrane is blended with phospholipids, display interesting self-assembly behavior, incorporating the robustness and chemical versatility of polymersomes with the softness and biocompatibility of liposomes. Such structures can be conveniently characterized by preparing giant unilamellar vesicles (GUVs via electroformation. Here, we are interested in exploring the self-assembly and properties of the analogous nanoscale hybrid vesicles (ca. 100 nm in diameter of the same composition prepared by film-hydration and extrusion. We show that the self-assembly and content-release behavior of nanoscale polybutadiene-b-poly(ethylene oxide (PB-PEO/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC hybrid phospholipid/block copolymer vesicles can be tuned by the mixing ratio of the amphiphiles. In brief, these hybrids may provide alternative tools for drug delivery purposes and molecular imaging/sensing applications and clearly open up new avenues for further investigation.

  9. Rapid ordering of block copolymer thin films

    International Nuclear Information System (INIS)

    Majewski, Pawel W; Yager, Kevin G

    2016-01-01

    Block-copolymers self-assemble into diverse morphologies, where nanoscale order can be finely tuned via block architecture and processing conditions. However, the ultimate usage of these materials in real-world applications may be hampered by the extremely long thermal annealing times—hours or days—required to achieve good order. Here, we provide an overview of the fundamentals of block-copolymer self-assembly kinetics, and review the techniques that have been demonstrated to influence, and enhance, these ordering kinetics. We discuss the inherent tradeoffs between oven annealing, solvent annealing, microwave annealing, zone annealing, and other directed self-assembly methods; including an assessment of spatial and temporal characteristics. We also review both real-space and reciprocal-space analysis techniques for quantifying order in these systems. (topical review)

  10. Nanostructured Polysulfone-Based Block Copolymer Membranes

    KAUST Repository

    Xie, Yihui

    2016-05-01

    The aim of this work is to fabricate nanostructured membranes from polysulfone-based block copolymers through self-assembly and non-solvent induced phase separation. Block copolymers containing polysulfone are novel materials for this purpose providing better mechanical and thermal stability to membranes than polystyrene-based copolymers, which have been exclusively used now. Firstly, we synthesized a triblock copolymer, poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) through polycondensation and reversible addition-fragmentation chain-transfer polymerization. The obtained membrane has a highly porous interconnected skin layer composed of elongated micelles with a flower-like arrangement, on top of the graded finger-like macrovoids. Membrane surface hydrolysis was carried out in a combination with metal complexation to obtain metal-chelated membranes. The copper-containing membrane showed improved antibacterial capability. Secondly, a poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) triblock copolymer obtained by hydrolyzing poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) formed a thin film with cylindrical poly(acrylic acid) microdomains in polysulfone matrix through thermal annealing. A phase inversion membrane was prepared from the same polymer via self-assembly and chelation-assisted non-solvent induced phase separation. The spherical micelles pre-formed in a selective solvent mixture packed into an ordered lattice in aid of metal-poly(acrylic acid) complexation. The space between micelles was filled with poly(acrylic acid)-metal complexes acting as potential water channels. The silver0 nanoparticle-decorated membrane was obtained by surface reduction, having three distinct layers with different particle sizes. Other amphiphilic copolymers containing polysulfone and water-soluble segments such as poly(ethylene glycol) and poly(N-isopropylacrylamide) were also synthesized through coupling reaction and copper0-mediated

  11. A Cationic Smart Copolymer for DNA Binding

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro

    2017-11-01

    Full Text Available A new block copolymer with a temperature-responsive block and a cationic block was prepared by reversible addition-fragmentation chain transfer (RAFT polymerization, with good control of its size and composition. The first block is composed by di(ethylene glycol methyl ether methacrylate (DEGMA and oligo(ethylene glycol methyl ether methacrylate (OEGMA, with the ratio DEGMA/OEGMA being used to choose the volume phase transition temperature of the polymer in water, tunable from ca. 25 to above 90 °C. The second block, of trimethyl-2-methacroyloxyethylammonium chloride (TMEC, is positively charged at physiological pH values and is used for DNA binding. The coacervate complexes between the block copolymer and a model single strand DNA are characterized by fluorescence correlation spectroscopy and fluorescence spectroscopy. The new materials offer good prospects for biomedical application, for example in controlled gene delivery.

  12. Analysis of polyhydroxyalkanoates granuales in bacillus Sp. MFD11 and enterobacter Sp. SEL2

    International Nuclear Information System (INIS)

    Naheed, N.; Jamil, N.

    2016-01-01

    Bacillus sp. MFD11 (JF901809) and Enterobacter sp. SEL2 (JF901810) were isolated from agriculture waste contaminated sites. When fed with 2% glucose as a carbon source, these bacteria produced 75.26±0.45% and 76.61±0.28% PHA of their wet weight respectively. The accumulated PHA was extracted by direct addition of sodium dodysyl sulphate in the culture medium, which yielded 52.3±0.56 micro g/l and 136.21±0.45 micro g/l PHA respectively when assayed with Crotonic acid. The PHA detection medium (PDM) provided nutrient limitation condition which favored accumulation of PHA granules. A tremendous increase in cell size was observed when strain MFD11 was grown in PDM. The size of the granules as revealed by TEM micrographs spanned from 0.1 to 1.5 micro m which is quite large as compared to the size reported in the literature 0.2 to 0.5 micro m 18). (PHA polymer was analyzed by FTIR, GC/MS and proton Nuclear magnetic resonance. The intense absorption band in the spectrum at 1724-1740 cm -1 and 1215 cm -1 to 1280 corresponding to C=O and C-O stretching group, respectively, indicated that the both strains were PHA producers. GC/MS analysis indicated that the polymer produced were copolymers of PHB-co-PHV. NMR also suggested that the extracted PHA was not a homopolymer but was the blend of copolymers with 3HV in lower abundance. Differential calorimetric thermal analysis showed melting temperature of 163 and 169 degree C for PHA produced by both strains, respectively. However, the observed melting temperature was found to be lower than the standard PHB (Signa-aldrich). (author)

  13. SANS study of coated block copolymer micelles

    Czech Academy of Sciences Publication Activity Database

    Pleštil, Josef; Kříž, Jaroslav; Koňák, Čestmír; Pospíšil, Herman; Kadlec, Petr; Sedláková, Zdeňka; Grillo, I.; Cubitt, R.

    2005-01-01

    Roč. 206, č. 12 (2005), s. 1206-1215 ISSN 1022-1352 R&D Projects: GA ČR GA203/03/0600; GA AV ČR IAA1050201; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z40500505 Keywords : block copolymer micelles * core-shell polymers * nanoparticles Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.111, year: 2005

  14. Burkholderia sacchari DSM 17165: A source of compositionally-tunable block-copolymeric short-chain poly(hydroxyalkanoates) from xylose and levulinic acid.

    Science.gov (United States)

    Ashby, Richard D; Solaiman, Daniel K Y; Nuñez, Alberto; Strahan, Gary D; Johnston, David B

    2018-04-01

    Burkholderia sacchari was used to produce poly-3-hydroxybutyrate-co-3-hydroxyvalerate block copolymers from xylose and levulinic acid. Levulinic acid was the preferred substrate resulting in 3-hydroxyvalerate (3HV) contents as high as 95 mol% at 24 h. The 3HB:3HV ratios were controlled by the initial levulinic acid media concentration and fermentation length. Higher levulinic acid concentrations and longer durations, resulted in polymers with two glass transition temperatures, each approximating those associated with poly-3HB and poly-3HV. 13 C NMR confirmed the presence of high concentrations of 3HB-3HB and 3HV-3HV homopolymeric dyads, while mass spectrometry of the partial hydrolysis products did not conform to Bernoullian statistics for randomness, confirming block sequences. MS/MS analysis of specific oligomers showed the mass-loss of 86 amu (a 3HB unit) and 100 amu (a 3HV unit) attesting to some randomness within the polymers. This study verifies the potential for producing Poly-3HB-block-3HV copolymers from inexpensive biorenewable feedstocks without sequential addition of carbon sources. Published by Elsevier Ltd.

  15. Ultraporous films with uniform nanochannels by block copolymer micelles assembly

    KAUST Repository

    Nunes, Suzana Pereira

    2010-10-12

    Films with high pore density and regularity that are easy to manufacture by conventional large-scale technology are key components aimed for fabrication of new generations of magnetic arrays for storage media, medical scaffolds, and artificial membranes. However, potential manufacture strategies like the self-assembly of block copolymers, which lead to amazing regular patterns, could be hardly reproduced up to now using commercially feasible methods. Here we report a unique production method of nanoporous films based on the self-assembly of copper(II) ion-polystyrene-b-poly(4-vinylpyridine) complexes and nonsolvent induced phase separation. Extremely high pore densities and uniformity were achieved. Water fluxes of 890 L m-2 h-1 bar-1 were obtained, which are at least 1 order of magnitude higher than those of commercially available membranes with comparable pore size. The pores are also stimuli (pH)-responsive. © 2010 American Chemical Society.

  16. N-containing carbons from styrene-divinylbenzene copolymer by urea treatment

    Energy Technology Data Exchange (ETDEWEB)

    Zhuravsky, Sergey V.; Kartel, Mykola T.; Tarasenko, Yuriy O. [Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine, 17 General Naumov Street, Kiev, 03164 (Ukraine); Villar-Rodil, Silvia [Instituto Nacional del Carbon, INCAR-CSIC, Apartado 73, 33080 Oviedo (Spain); Dobos, Gabor [Department of Atomic Physics, Budapest University of Technology and Economics, H-1521 Budapest (Hungary); Toth, Ajna [Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, H-1521 Budapest, PO Box 92 (Hungary); Tascon, Juan M.D. [Instituto Nacional del Carbon, INCAR-CSIC, Apartado 73, 33080 Oviedo (Spain); Laszlo, Krisztina, E-mail: klaszlo@mail.bme.hu [Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, H-1521 Budapest, PO Box 92 (Hungary)

    2012-01-15

    N-containing synthetic carbons with narrow porosity were prepared from a chlorinated styrene and divinylbenzene copolymer by a multistep method with a yield of 34 wt%. Surface chemical treatment and thermal carbonization of the starting copolymer was monitored by urea impregnation. Steam activation, oxidation and an additional heat treatment gave the final product. The synthesis route was designed in a cost-effective way. The porosity and the concentration of the introduced nitrogen atoms were determined at each step. The final product has a surface area of 1135 m{sup 2}/g. More than 70% of the pore volume comes from micropores with an average width of 0.7 nm. The 2.3 at.% surface nitrogen atoms are distributed among five detectable species, of which about 44% is quaternary nitrogen.

  17. Pseudomonas putida KT2442 as a platform for the biosynthesis of polyhydroxyalkanoates with adjustable monomer contents and compositions

    DEFF Research Database (Denmark)

    Tripathi, Lakshmi; Wu, Lin-Ping; Dechuan, Meng

    2013-01-01

    of P(3HHx-co-3HD) consisting of 3-hydroxyhexanoate (3HHx) and 3-hydroxydecanoate (3HD), the monomer fraction of 3HHx ranged from 16 mol% to 63 mol%. The comonomer compositions were easily regulated by varying the fatty acid concentrations. P. putida KTQQ20 produced a novel diblock copolymer P3HHx-b-P(3......6), random copolymers of P(3HB-co-3HHx) consisting of 3-hydroxybutyrate (3HB), 3-hydroxyhexanoate (3HHx), were accumulated with 3HHx content ranged from 19 mol% to 75 mol%. While recombinant P. putida KTQQ20 grown on mixtures of sodium hexanoate and decanoic acid (C6:C10), produced random copolymers......HD-co-3HDD) consisting of 49 mol% P3HHx and 51 mol% P(3HD-co-3HDD) [35.25 mol% 3HDD (3-hydroxydodecanoate)], which was characterized by (13)C NMR, HMBC NMR, DSC, GPC and universal testing machine....

  18. Silk-collagen-like block copolymers with charged blocks : self-assembly into nanosized ribbons and macroscopic gels

    NARCIS (Netherlands)

    Martens, A.A.

    2008-01-01

    The research described in this thesis concerns the design, biotechnological production, and physiochemical study of large water-soluble (monodisperse) protein triblock-copolymers with sequential blocks, some of which are positively or negatively charged and self-assemble in response to a change in

  19. Surface morphology of PS-PDMS diblock copolymer films

    DEFF Research Database (Denmark)

    Andersen, T.H.; Tougaard, S.; Larsen, N.B.

    2001-01-01

    Spin coated thin films (∼400 Å) of poly(styrene)–poly(dimethylsiloxane) (PS–PDMS) diblock copolymers have been investigated using X-ray Photoelectron Spectroscopy and Atomic Force Microscopy. Surface segregation of the poly(dimethylsiloxane) blocks was studied for five diblock copolymers which ra...

  20. Rheological Behavior of Entangled Polystyrene-Polyhedral Oligosilsesquioxane (POSS) Copolymer

    National Research Council Canada - National Science Library

    Wu, Jian; Mather, Patrick T; Haddad, Timothy S; Kim, Gyeong-Man

    2006-01-01

    ...: random copolymers of polystyrene (PS) and styryl-based polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(C6H4CH=CH2), with R = isobutyl (iBu). A series of styrene-styryl POSS random copolymers with 0, 6, 15, 30, 50 wt...

  1. Adsorption of charged diblock copolymers : effect on colloidal stability

    NARCIS (Netherlands)

    Israels, R.

    1994-01-01

    In this thesis we present Scheutjens-Fleer (SF) calculations on the adsorption of diblock copolymers. More specifically, we restrict ourselves to adsorption at uncharged surfaces, while the specific type of block copolymers we consider have one uncharged adsorbing "anchor" block and one

  2. Amphiphilic brushes from metallo-supramolecular block copolymers

    NARCIS (Netherlands)

    Guillet, P.; Fustin, C.A.; Wouters, D.; Höppener, S.; Schubert, U.S.; Gohy, J.M.W.

    2009-01-01

    A novel strategy to control the formation of amphiphilic brushes from metallo-supramol. block copolymers is described. The investigated copolymer consists of a polystyrene block linked to a poly(ethylene oxide) one via a charged bis-terpyridine ruthenium(ii) complex (PS-[Ru]-PEO). The initial

  3. Polyether based segmented copolymers with uniform aramid units

    NARCIS (Netherlands)

    Niesten, M.C.E.J.

    2000-01-01

    Segmented copolymers with short, glassy or crystalline hard segments and long, amorphous soft segments (multi-block copolymers) are thermoplastic elastomers (TPE’s). The hard segments form physical crosslinks for the amorphous (rubbery) soft segments. As a result, this type of materials combines

  4. Morphological studies on block copolymer modified PA 6 blends

    Energy Technology Data Exchange (ETDEWEB)

    Poindl, M., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de [Institut für Kunststofftechnik, University of Stuttgart (Germany)

    2014-05-15

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  5. Antimicrobial activity of poly(acrylic acid) block copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Gratzl, Günther, E-mail: guenther.gratzl@jku.at [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Paulik, Christian [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Hild, Sabine [Johannes Kepler University Linz, Institute of Polymer Science, Altenberger Str. 69, 4040 Linz (Austria); Guggenbichler, Josef P.; Lackner, Maximilian [AMiSTec GmbH and Co. KG, Leitweg 13, 6345 Kössen, Tirol (Austria)

    2014-05-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed.

  6. Antimicrobial activity of poly(acrylic acid) block copolymers

    International Nuclear Information System (INIS)

    Gratzl, Günther; Paulik, Christian; Hild, Sabine; Guggenbichler, Josef P.; Lackner, Maximilian

    2014-01-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed

  7. Radiation crosslinked block copolymer blends with improved impact resistance

    International Nuclear Information System (INIS)

    Saunders, F.L.; Pelletier, R.R.

    1976-01-01

    Polymer blends having high impact resistance after mechanical working are produced by blending together a non-elastomeric monovinylidene aromatic polymer such as polystyrene with an elastomeric copolymer, such as a block copolymer of styrene and butadiene, in the form of crosslinked, colloidal size particles

  8. Characteristics of immobilized aminoacylase from Aspergillus oryzae on macroporous copolymers.

    Science.gov (United States)

    He, B L; Jiang, P; Qiu, Y B

    1990-01-01

    Aminoacylase from Aspergillus oryzae was adsorbed on functionallized macroporous copolymers where the enzyme showed excellent catalyzing activity and operation stability. Various factors which effect the activity of the immobilized aminoacylase such as temperature, pH and ionic strength were investigated. The continuous operation of the enzyme immobilized on macroporous copolymers was compared with that of the enzyme immobilized on DEAE-Sephadex.

  9. Simultaneous determination of the styrene unit content and assessment of molecular weight of triblock copolymers in adhesives by a size exclusion chromatography method.

    Science.gov (United States)

    Wang, Mingfang; Wang, Yuerong; Luo, Pei; Zhang, Hongyang; Zhang, Min; Hu, Ping

    2017-10-01

    The content of styrene units in nonhydrogenated and hydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers significantly influences product performance. A size exclusion chromatography method was developed to determine the average styrene content of triblock copolymers blended with tackifier in adhesives. A complete separation of the triblock copolymer from the other additives was realized with size exclusion chromatography. The peak area ratio of the UV and refraction index signals of the copolymers at the same effective elution volume was correlated to the average styrene unit content using nuclear magnetic resonance spectroscopy with commercial copolymers as standards. The obtained calibration curves showed good linearity for both the hydrogenated and nonhydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers (r = 0.974 for styrene contents of 19.3-46.3% for nonhydrogenated ones and r = 0.970 for the styrene contents of 23-58.2% for hydrogenated ones). For copolymer blends, the developed method provided more accurate average styrene unit contents than nuclear magnetic resonance spectroscopy provided. These results were validated using two known copolymer blends consisting of either styrene-isoprene-styrene or hydrogenated styrene-butadiene-styrene and a hydrocarbon tackifying resin as well as an unknown adhesive with styrene-butadiene-styrene and an aromatic tackifying resin. The methodology can be readily applied to styrene-containing polymers in blends such as poly(acrylonitrile-butadiene styrene). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Advanced analytical methods for the structure elucidation of polystyrene-b-poly(n-butyl acrylate) block copolymers prepared by reverse iodine transfer polymerisation

    Energy Technology Data Exchange (ETDEWEB)

    Wright, Trevor Gavin; Pfukwa, Helen; Pasch, Harald, E-mail: hpasch@sun.ac.za

    2015-09-10

    Reverse iodine transfer polymerisation (RITP) is a living radical polymerisation technique that has shown to be feasible in synthesising segmented styrene-acrylate copolymers. Polymers synthesised via RITP are typically only described regarding their bulk properties using nuclear magnetic resonance spectroscopy and size exclusion chromatography. To fully understand the complex composition of the polymerisation products and the RITP reaction mechanism, however, it is necessary to use a combination of advanced analytical methods. In the present RITP procedure, polystyrene was synthesised first and then used as a macroinitiator to synthesise polystyrene-block-poly(n-butyl acrylate) (PS-b-PBA) block copolymers. For the first time, these PS-b-PBA block copolymers were analysed by a combination of SEC, in situ{sup 1}H NMR and HPLC. {sup 1}H NMR was used to determine the copolymer composition and the end group functionality of the samples, while SEC and HPLC were used to confirm the formation of block copolymers. Detailed information on the living character of the RITP process was obtained. - Highlights: • Comprehensive analysis of novel block copolymers. • Polymers were prepared for the first time by reverse iodine transfer polymerisation. • Combination of SEC, NMR, kinetic NMR, HPLC and comprehensive 2D-HPLC was used. • Detailed information about complex molecular composition and polymerisation kinetics was obtained.

  11. Synthesis and characterization of waterborne polyurethane acrylate copolymers

    International Nuclear Information System (INIS)

    Sultan, Misbah; Bhatti, Haq Nawaz; Zuber, Mohammad; Barikani, Mehdi

    2013-01-01

    Polyurethane acrylate copolymers were synthesized by emulsion polymerization process. To reduce the environmental hazards, organic solvents were replaced by eco-friendly aqueous system. Concentration of polyurethane and acrylate monomer was varied to investigate the effect of chemical composition on performance properties of copolymers. FTIR spectroscopy was used as a key tool to record the chemical synthesis route. The synthesized copolymer emulsions were characterized by evaluating their particle size, viscosity, dry weight content, chemical and water resistance. Thermal decomposition was studied by thermogravimetric analysis. Scanning electron microscope was used to visualize the morphological structure of copolymers. The experimental results indicate better polyurethane acrylate compatibility till the ratio of 30/70. However, these copolymers exhibited synergistic effects between the two polymers and revealed a remarkable improvement in numerous coating properties

  12. Sulfomethylated graft copolymers of xanthan gum and polyacrylamide

    Energy Technology Data Exchange (ETDEWEB)

    Cottrell, I.W.; Empey, R.A.; Racciato, J.S.

    1978-08-08

    A water-soluble anionic graft copolymer of xanthan gum and polyacrylamide is described in which at least part of the amide function of the acrylamide portion of the copolymer is sulfomethylated and the xanthan gum portion of the copolymer is unreacted with formaldehyde. The copolymer is sulfomethylated by reaction with formaldehyde and sodium metabisulfite. The formaldehyde does not cause any appreciable cross-linking between hydroxyl groups of the xanthan moieties. The sulfomethylation of the acrylamido group takes place at temperatures from 35 to 70 C. The pH is 10 or higher, typically from 12 to 13. The degree of anionic character may be varied by adjusting the molar ratio of formaldehyde and sodium metabisulfite with respect to the copolymer. 10 claims.

  13. Photoisomerization study of p-phenylazoacrylanilide and its homo- and copolymers

    Science.gov (United States)

    Rachkov, A.; Minoura, N.; Shimizu, T.

    2003-01-01

    To develop materials possessing intrinsic photoresponsive properties, a polymerizable derivative of azobenzene was synthesized. Condensation of acryloyl chloride with 4-phenylazoaniline was performed in THF with 100% conversion to the final product p-phenylazoacrylanilide. Its homopolymers and copolymers with methacrylic acid were prepared by free radical polymerization using 2,2 '-azobis (2,4-dimethylvaleronitrile) as an initiator. Copolymerization reactivity ratios showed clear preference to form short sequences of polymethacrylic acid alternated by individual p-phenylazoacrylanilide residues. Photochemical interconversion between trans and cis isomers of p-phenylazoacrylanilide under UV or visible light irradiation was shown to be reversible and reproducible for the monomer as well as for the homopolymers and the copolymers with methacrylic acid.

  14. Investigation of free-radical processes in low temperature radiolysis of copolymers of ethylene with styrene

    International Nuclear Information System (INIS)

    Mal'tseva, A.P.; Golikov, V.P.; Leshchenko, S.S.; Karpov, V.L.; Muromtsev, V.I.

    1977-01-01

    Free radical processes during γ-radiolysis of statistical ethylene-styrene copolimers (ESC) have been investigated. The presence of styrene links in the ESC has been shown to reduce both radical yields and their reaction ability as compared with low density polyethylene irradiated under the same conditions. The character of radical processes in ESC sighificantly depends both on styrene concentration in them and on the dose absorbed. The most pronounced decrease in radical yield is found in the copolymer having 5 mol % styrene. This effect seems to be caused by the accumulation in the irradiated copolymer of products which are capable of more effective dissipation of absorbed energy than only styrene links alone

  15. Comb-like temperature-responsive polyhydroxyalkanoate-graft-poly(2-dimethylamino-ethylmethacrylate) for controllable protein adsorption

    DEFF Research Database (Denmark)

    Yao, Hui; Wei, Daixu; Che, Xuemei

    2016-01-01

    %. Graft copolymer PHA-g-PDMAEMA showed enhanced thermal stability, biocompatibility and controllable hydrophilicity compared with non-grafted P(3HDD-co-3H9D). The grafted material presented an obvious tendency of increasing protein adsorptions over the lower critical solution temperature (LCST 47.5 °C...... controllable protein adsorption for biomedical usages....

  16. Ionization of amphiphilic acidic block copolymers.

    Science.gov (United States)

    Colombani, Olivier; Lejeune, Elise; Charbonneau, Céline; Chassenieux, Christophe; Nicolai, Taco

    2012-06-28

    The ionization behavior of an amphiphilic diblock copolymer poly(n-butyl acrylate(50%)-stat-acrylic acid(50%))(100)-block-poly(acrylic acid)(100) (P(nBA(50%)-stat-AA(50%))(100)-b-PAA(100), DH50) and of its equivalent triblock copolymer P(nBA(50%)-stat-AA(50%))(100)-b-PAA(200)-b-P(nBA(50%)-stat-AA(50%))(100) (TH50) were studied by potentiometric titration either in pure water or in 0.5 M NaCl. These polymers consist of a hydrophilic acidic block (PAA) connected to a hydrophobic block, P(nBA(50%)-stat-AA(50%))(100), whose hydrophobic character has been mitigated by copolymerization with hydrophilic units. We show that all AA units, even those in the hydrophobic block could be ionized. However, the AA units within the hydrophobic block were less acidic than those in the hydrophilic block, resulting in the preferential ionization of the latter block. The preferential ionization of PAA over that of P(nBA(50%)-stat-AA(50%))(100) was stronger at higher ionic strength. Remarkably, the covalent bonds between the PAA and P(nBA(50%)-stat-AA(50%))(100) blocks in the diblock or the triblock did not affect the ionization of each block, although the self-association of the block copolymers into spherical aggregates modified the environment of the PAA blocks compared to when PAA was molecularly dispersed.

  17. Amphiphilic block copolymers for drug delivery.

    Science.gov (United States)

    Adams, Monica L; Lavasanifar, Afsaneh; Kwon, Glen S

    2003-07-01

    Amphiphilic block copolymers (ABCs) have been used extensively in pharmaceutical applications ranging from sustained-release technologies to gene delivery. The utility of ABCs for delivery of therapeutic agents results from their unique chemical composition, which is characterized by a hydrophilic block that is chemically tethered to a hydrophobic block. In aqueous solution, polymeric micelles are formed via the association of ABCs into nanoscopic core/shell structures at or above the critical micelle concentration. Upon micellization, the hydrophobic core regions serve as reservoirs for hydrophobic drugs, which may be loaded by chemical, physical, or electrostatic means, depending on the specific functionalities of the core-forming block and the solubilizate. Although the Pluronics, composed of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide), are the most widely studied ABC system, copolymers containing poly(L-amino acid) and poly(ester) hydrophobic blocks have also shown great promise in delivery applications. Because each ABC has unique advantages with respect to drug delivery, it may be possible to choose appropriate block copolymers for specific purposes, such as prolonging circulation time, introduction of targeting moieties, and modification of the drug-release profile. ABCs have been used for numerous pharmaceutical applications including drug solubilization/stabilization, alteration of the pharmacokinetic profile of encapsulated substances, and suppression of multidrug resistance. The purpose of this minireview is to provide a concise, yet detailed, introduction to the use of ABCs and polymeric micelles as delivery agents as well as to highlight current and past work in this area. Copyright 2003 Wiley-Liss, Inc. and the American Pharmacists Association

  18. 21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Poly-1-butene resins and butene/ethylene copolymers... resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers identified... the catalytic polymerization of 1-butene liquid monomer. Butene/ethylene copolymers are produced by...

  19. Anomalous Micellization of Pluronic Block Copolymers

    Science.gov (United States)

    Leonardi, Amanda; Ryu, Chang Y.

    2014-03-01

    Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

  20. Responsive linear-dendritic block copolymers.

    Science.gov (United States)

    Blasco, Eva; Piñol, Milagros; Oriol, Luis

    2014-06-01

    The combination of dendritic and linear polymeric structures in the same macromolecule opens up new possibilities for the design of block copolymers and for applications of functional polymers that have self-assembly properties. There are three main strategies for the synthesis of linear-dendritic block copolymers (LDBCs) and, in particular, the emergence of click chemistry has made the coupling of preformed blocks one of the most efficient ways of obtaining libraries of LDBCs. In these materials, the periphery of the dendron can be precisely functionalised to obtain functional LDBCs with self-assembly properties of interest in different technological areas. The incorporation of stimuli-responsive moieties gives rise to smart materials that are generally processed as self-assemblies of amphiphilic LDBCs with a morphology that can be controlled by an external stimulus. Particular emphasis is placed on light-responsive LDBCs. Furthermore, a brief review of the biomedical or materials science applications of LDBCs is presented. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Bactericidal and Hemocompatible Coating via the Mixed-Charged Copolymer.

    Science.gov (United States)

    Fan, Xiao-Li; Hu, Mi; Qin, Zhi-Hui; Wang, Jing; Chen, Xia-Chao; Lei, Wen-Xi; Ye, Wan-Ying; Jin, Qiao; Ren, Ke-Feng; Ji, Jian

    2018-03-28

    Cationic antibacterial coating based on quaternary ammonium compounds, with an efficient and broad spectrum bactericidal property, has been widely used in various fields. However, the high density of positive charges tends to induce weak hemocompatibility, which hinders the application of the cationic antibacterial coating in blood-contacting devices and implants. It has been reported that a negatively charged surface can reduce blood coagulation, showing improved hemocompatibility. Here, we describe a strategy to combine the cationic and anionic groups by using mixed-charged copolymers. The copolymers of poly (quaternized vinyl pyridine- co- n-butyl methacrylate- co-methacrylate acid) [P(QVP- co- nBMA- co-MAA)] were synthesized through free radical copolymerization. The cationic group of QVP, the anionic group of MAA, and the hydrophobic group of nBMA were designed to provide bactericidal capability, hemocompatibility, and coating stability, respectively. Our findings show that the hydrophilicity of the copolymer coating increased, and its zeta potential decreased from positive charge to negative charge with the increase of the anionic/cationic ratio. Meanwhile, the bactericidal property of the copolymer coating was kept around a similar level compared with the pure quaternary ammonium copolymer coating. Furthermore, the coagulation time, platelet adhesion, and hemolysis tests revealed that the hemocompatibility of the copolymer coating improved with the addition of the anionic group. The mixed-charged copolymer combined both bactericidal property and hemocompatibility and has a promising potential in blood-contacting antibacterial devices and implants.

  2. Block copolymer systems: from single chain to self-assembled nanostructures.

    Science.gov (United States)

    Giacomelli, Cristiano; Schmidt, Vanessa; Aissou, Karim; Borsali, Redouane

    2010-10-19

    Recent advances in the field of macromolecular engineering applied to the fabrication of nanostructured materials using block copolymer chains as elementary building blocks are described in this feature article. By highlighting some of our work in the area and accounting for the contribution of other groups, we discuss the relationship between the physical-chemical properties of copolymer chains and the characteristics of nano-objects originating from their self-assembly in solution and in bulk, with emphasis on convenient strategies that allow for the control of composition, functionality, and topology at different levels of sophistication. In the case of micellar nanoparticles in solution, in particular, we present approaches leading to morphology selection via macromolecular architectural design, the functionalization of external solvent-philic shells with biomolecules (polysaccharides and proteins), and the maximization of micelle loading capacity by the suitable choice of solvent-phobic polymer segments. The fabrication of nanomaterials mediated by thin block copolymer films is also discussed. In this case, we emphasize the development of novel polymer chain manipulation strategies that ultimately allow for the preparation of precisely positioned nanodomains with a reduced number of defects via block-selective chemical reactivity. The challenges facing the soft matter community, the urgent demand to convert huge public and private investments into consumer products, and future possible directions in the field are also considered herein.

  3. Development of Graft Copolymer Flocculant Based on Acrylamide and Acrylic Acid for the dewatering of coal

    International Nuclear Information System (INIS)

    Mahmoud, G.A.; Abdel Khalek, M.A

    2012-01-01

    Most coal preparation processes were carried out in water medium. The water content of coal product has a negative impact on handling and specific energy value. The moisture content may be attributed to the proportion of fine coal, which presents the greatest dewatering problem. A novel polymeric flocculant has been developed by graft copolymerization of acrylamide (AAm) with acrylic acid (AAc) using gamma irradiation technique. The grafted copol621621ymer P(AAm/AAc) was characterized by Fourier-transform infrared spectroscopy (FTIR), and thermo-gravimetric analysis (TGA). The effects of reaction parameters, such as total absorbed dose, and monomer concentration on grafting yield were investigated. The flocculation performance of the graft copolymer P(AAm/AAc) was investigated in coal suspension. It was observed that the grafting ratio was one of the key factors for the flocculating effects. The copolymers with various grafting ratios showed different flocculating properties. It was found that as the grafting ratio increased, the flocculating effect also increased. The flocculation performance of the grafted copolymer was better than that of the commercial flocculant, poly-acrylamide (Magnafloc 1011).

  4. The metabolic response of P. putida KT2442 producing high levels of polyhydroxyalkanoate under single- and multiple-nutrient-limited growth: Highlights from a multi-level omics approach

    Directory of Open Access Journals (Sweden)

    Poblete-Castro Ignacio

    2012-03-01

    Full Text Available Abstract Background Pseudomonas putida KT2442 is a natural producer of polyhydroxyalkanoates (PHAs, which can substitute petroleum-based non-renewable plastics and form the basis for the production of tailor-made biopolymers. However, despite the substantial body of work on PHA production by P. putida strains, it is not yet clear how the bacterium re-arranges its whole metabolism when it senses the limitation of nitrogen and the excess of fatty acids as carbon source, to result in a large accumulation of PHAs within the cell. In the present study we investigated the metabolic response of KT2442 using a systems biology approach to highlight the differences between single- and multiple-nutrient-limited growth in chemostat cultures. Results We found that 26, 62, and 81% of the cell dry weight consist of PHA under conditions of carbon, dual, and nitrogen limitation, respectively. Under nitrogen limitation a specific PHA production rate of 0.43 (g·(g·h-1 was obtained. The residual biomass was not constant for dual- and strict nitrogen-limiting growth, showing a different feature in comparison to other P. putida strains. Dual limitation resulted in patterns of gene expression, protein level, and metabolite concentrations that substantially differ from those observed under exclusive carbon or nitrogen limitation. The most pronounced differences were found in the energy metabolism, fatty acid metabolism, as well as stress proteins and enzymes belonging to the transport system. Conclusion This is the first study where the interrelationship between nutrient limitations and PHA synthesis has been investigated under well-controlled conditions using a system level approach. The knowledge generated will be of great assistance for the development of bioprocesses and further metabolic engineering work in this versatile organism to both enhance and diversify the industrial production of PHAs.

  5. Magnetic silica hybrids modified with guanidine containing co-polymers for drug delivery applications

    Energy Technology Data Exchange (ETDEWEB)

    Timin, Alexander S., E-mail: a_timin@mail.ru [Inorganic Chemistry Department, Ivanovo State University of Chemistry and Technology (ISUCT), 7, Sheremetevsky prosp., 153000 Ivanovo (Russian Federation); RASA Center in Tomsk, Tomsk Polytechnic University, 30, Lenin Avenue, 634500 Tomsk (Russian Federation); Khashirova, Svetlana Yu. [Kabardino-Balkar State University, ul. Chernyshevskogo 173, Nal' chik, 360004 Kabardino-Balkaria (Russian Federation); Rumyantsev, Evgeniy V.; Goncharenko, Alexander A. [Inorganic Chemistry Department, Ivanovo State University of Chemistry and Technology (ISUCT), 7, Sheremetevsky prosp., 153000 Ivanovo (Russian Federation)

    2016-07-01

    Guanidine containing co-polymers grafted onto silica nanoparticles to form core-shell structure were prepared by sol-gel method in the presence of γ-Fe{sub 2}O{sub 3} nanoparticles. The morphological features for uncoated and coated silica particles have been characterized with scanning electron microscopy. The results show that the polymer coated silicas exhibit spherical morphology with rough polymeric surface covered by γ-Fe{sub 2}O{sub 3} nanoparticles. The grafting amount of guanidine containing co-polymers evaluated by thermogravimetric analysis was in the range from 17 to 30%. Then, the drug loading properties and cumulative release of silica hybrids modified with guanidine containing co-polymers were evaluated using molsidomine as a model drug. It was shown that after polymer grafting the loading content of molsidomine could reach up to 3.42 ± 0.21 and 2.34 ± 0.14 mg/g respectively. The maximum drug release of molsidomine is achieved at pH 1.6 (approximately 71–75% release at 37 °C), whereas at pH 7.4 drug release is lower (50.4–59.6% release at 37 °C). These results have an important implication that our magneto-controlled silica hybrids modified with guanidine containing co-polymers are promising as drug carriers with controlled behaviour under influence of magnetic field. - Highlights: • Polymer coated silica hybrids containing γ-Fe{sub 2}O{sub 3} were prepared via sol–gel method. • Polymer grafting influences pH-response and surface properties of final products. • Molsidomine as a model drug was effectively loaded into polymer coated silicas. • The drug loading depends on the nature of grafted polymer and its content.

  6. Incorporation of fluconazole in copolymer PMMA-g-PEG derivatives

    International Nuclear Information System (INIS)

    Silveira, B.M.; Santos, V.M.R. dos; Novack, K.M.; Lopes, S.A.

    2014-01-01

    The graft copolymer PMMA-g-PEG went through chemical transformations in its chain through acetylation, halogenation, methylation and esterification followed by hydrolysis reactions. Subsequently, the copolymer PMMA-g-PEG derivatives passed through the process of emulsification and incorporation of the drug fluconazole. Derivatives copolymers were characterized by infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) after incorporation in order to evaluate their effectiveness. The efficiency of incorporation was observed and it was also verified that the complexity of polymer chain influence in the incorporated fluconazole content. (author)

  7. Patchy micelles based on coassembly of block copolymer chains and block copolymer brushes on silica particles.

    Science.gov (United States)

    Zhu, Shuzhe; Li, Zhan-Wei; Zhao, Hanying

    2015-04-14

    Patchy particles are a type of colloidal particles with one or more well-defined patches on the surfaces. The patchy particles with multiple compositions and functionalities have found wide applications from the fundamental studies to practical uses. In this research patchy micelles with thiol groups in the patches were prepared based on coassembly of free block copolymer chains and block copolymer brushes on silica particles. Thiol-terminated and cyanoisopropyl-capped polystyrene-block-poly(N-isopropylacrylamide) block copolymers (PS-b-PNIPAM-SH and PS-b-PNIPAM-CIP) were synthesized by reversible addition-fragmentation chain transfer polymerization and chemical modifications. Pyridyl disulfide-functionalized silica particles (SiO2-SS-Py) were prepared by four-step surface chemical reactions. PS-b-PNIPAM brushes on silica particles were prepared by thiol-disulfide exchange reaction between PS-b-PNIPAM-SH and SiO2-SS-Py. Surface micelles on silica particles were prepared by coassembly of PS-b-PNIPAM-CIP and block copolymer brushes. Upon cleavage of the surface micelles from silica particles, patchy micelles with thiol groups in the patches were obtained. Dynamic light scattering, transmission electron microscopy, and zeta-potential measurements demonstrate the preparation of patchy micelles. Gold nanoparticles can be anchored onto the patchy micelles through S-Au bonds, and asymmetric hybrid structures are formed. The thiol groups can be oxidized to disulfides, which results in directional assembly of the patchy micelles. The self-assembly behavior of the patchy micelles was studied experimentally and by computer simulation.

  8. Mechanical properties of weakly segregated block copolymers : 1. Synergism on tensile properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers

    NARCIS (Netherlands)

    Weidisch, R.; Michler, G.H.; Fischer, H.; Arnold, M.; Hofmann, S.; Stamm, M.

    1999-01-01

    Mechanical properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers, PS-b-PBMA, with different lengths of the polystyrene block were investigated. The copolymers display a composition range where the tensile strength of the block copolymers exceeds the values of the corresponding

  9. Synthesis of graft copolymers onto starch and its semiconducting properties

    Directory of Open Access Journals (Sweden)

    Nevin Çankaya

    Full Text Available Literature review has revealed that, although there are studies about grafting on natural polymers, especially on starch, few of them are about electrical properties of graft polymers. Starch methacrylate (St.met was obtained by esterification of OH groups on natural starch polymer for this purpose. Grafting of synthesized N-cyclohexyl acrylamide (NCA and commercial methyl methacrylate (MMA monomers with St.met was done by free radical polymerization method. The graft copolymers were characterized with FT-IR spectra, thermal and elemental analysis. Thermal stabilities of the graft copolymers were determined by TGA (thermo gravimetric analysis method and thermal stability of the copolymers is decreased via grafting. The electrical conductivity of the polymers was measured as a function of temperature and it has been observed that electrical conductivity increases with increasing temperature. The absorbance and transmittance versus wavelength of the polymers have been measured. Keywords: Starch, Graft copolymer, Semiconducting, Thermal stability, Starch methacrylate

  10. HPMA and HEMA copolymer bead interactions with eukaryotic cells

    Directory of Open Access Journals (Sweden)

    Cristina D. Vianna-Soares

    2004-09-01

    Full Text Available Two different hydrophilic acrylate beads were prepared via aqueous suspension polymerization. Beads produced of a hydroxypropyl methacrylate (HPMA and ethyleneglycol methacrylate (EDMA copolymer were obtained using a polyvinyl alcohol suspending medium. Copolymers of 2hydroxyethyl methacrylate (HEMA, methyl methacrylate (MMA and ethyleneglycol methacrylate (EDMA beads were obtained using magnesium hydroxide as the suspending agent. Following characterization by scanning electron microscopy (SEM, nitrogen sorption analysis (NSA and mercury intrusion porosimetry (MIP, the beads were cultured with monkey fibroblasts (COS7 to evaluate their ability to support cell growth, attachment and adhesion. Cell growth behavior onto small HPMA/EDMA copolymer beads and large HEMA/MMA/EDMA copolymer beads is evaluated regarding their hidrophilicity/hidrophobicity and surface roughness.

  11. Controlled Synthesis of Fluorinated Copolymers with Pendant Sulfonates

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Jankova Atanasova, Katja; Hvilsted, Søren

    2008-01-01

    Novel fluorinated copolymers of different architectures and bearing sulfopropyl groups were synthesized by atom transfer radical polymerization (ATRP) of aromatic fluorinated monomers and two modification reactions performed on the polymer chain - demethylation followed by sulfopropylation. As a ...

  12. Fast & scalable pattern transfer via block copolymer nanolithography

    DEFF Research Database (Denmark)

    Li, Tao; Wang, Zhongli; Schulte, Lars

    2015-01-01

    A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin-casting of s......A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin...... on long range lateral order, including fabrication of substrates for catalysis, solar cells, sensors, ultrafiltration membranes and templating of semiconductors or metals....

  13. Self-Assembly of Rod-Coil Block Copolymers

    National Research Council Canada - National Science Library

    Jenekhe, S

    1999-01-01

    ... the self-assembly of new rod-coil diblock, rod- coil-rod triblock, and coil-rod-coil triblock copolymers from solution and the resulting discrete and periodic mesostmctares with sizes in the 100...

  14. Design of block copolymer membranes using segregation strength trend lines

    KAUST Repository

    Sutisna, Burhannudin; Polymeropoulos, Georgios; Musteata, Valentina-Elena; Peinemann, Klaus-Viktor; Avgeropoulos, Apostolos; Smilgies, Detlef-M.; Hadjichristidis, Nikolaos; Nunes, Suzana Pereira

    2016-01-01

    composition, polymer molecular weights, casting solution concentration, and evaporation time. We propose here an effective method for designing new block copolymer membranes. The method consists of predetermining a trend line for the preparation of isoporous

  15. Opto-electronic devices from block copolymers and their oligomers.

    NARCIS (Netherlands)

    Hadziioannou, G

    1997-01-01

    This paper presents research activities towards the development of polymer materials and devices for optoelectronics, An approach to controlling the conjugation length and transferring the luminescence properties of organic molecules to polymers through black copolymers containing well-defined

  16. Blends of caprolactam/caprolactone copolymers and chlorinated polymers

    NARCIS (Netherlands)

    Alberda van Ekenstein, G.O.R.; Deuring, H.; ten Brinke, G.; Ellis, T.S.

    The phase behaviour of blends of chlorinated polyethylene, polyvinyl chloride (PVC) and chlorinated PVC with random copolymers of caprolactone and caprolactam has been investigated and the results correlated with a binary interaction model. The known miscibility of polycaprolactone in the

  17. Molecular weight and its distribution of tetrafluoroethylene and propylene copolymer

    International Nuclear Information System (INIS)

    Watanabe, Hiromasa; Okamoto, Jiro; Yamaguchi, Koichi.

    1978-04-01

    In comparison of molecular structure of tetrafluoroethylene and propylene copolymer produced by radiation and chemical initiators respectively, both were fractionated by elution method and fine structure was examined. For the fractionated sample by radiation, the relation between molecular weight anti Mn and intrinsic viscosity ( eta] is ( eta] = 3.97 x 10 -4 anti Mnsup(0.630) The result is not in agreement with that of the unfractionated sample by radiation, and similar to those of samples by chemical initiators. There is no difference, however, in the elution method of GPC between both these copolymers; the elution behavior agrees with that of standard polystyrene. Long chain branching thus exists little in the copolymer of tetrafluoroethylene and propylene. To reveal the relations between reaction conditions and molecular weight and its distribution of the copolymer produced by flow apparatus, the molecular weight distribution was measured by GPC. The method of analysis could evaluate molecular weight distribution changing constantly. (auth.)

  18. Designing block copolymer architectures for targeted membrane performance

    KAUST Repository

    Dorin, Rachel Mika; Phillip, William A.; Sai, Hiroaki; Werner, Jö rg; Elimelech, Menachem; Wiesner, Ulrich

    2014-01-01

    Using a combination of block copolymer self-assembly and non-solvent induced phase separation, isoporous ultrafiltration membranes were fabricated from four poly(isoprene-b-styrene-b-4-vinylpyridine) triblock terpolymers with similar block volume

  19. Block copolymer/homopolymer dual-layer hollow fiber membranes

    KAUST Repository

    Hilke, Roland; Neelakanda, Pradeep; Behzad, Ali Reza; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2014-01-01

    We manufactured the first time block copolymer dual-layer hollow fiber membranes and dual layer flat sheet membranes manufactured by double solution casting and phase inversion in water. The support porous layer was based on polystyrene

  20. Fluctuations, conformational asymmetry and block copolymer phase behaviour

    DEFF Research Database (Denmark)

    Bates, F.S.; Schulz, M.F.; Khandpur, A.K.

    1994-01-01

    Phase behaviour near the order-disorder transition (ODT) of 58 model hydrocarbon diblock copolymers, representing four different systems, is summarized. Six distinct ordered-state microstructures are reported, including hexagonally modulated lamellae (HML), hexagonally perforated layers (HPL) and...

  1. Surface dynamics of micellar diblock copolymer films

    Science.gov (United States)

    Song, Sanghoon; Cha, Wonsuk; Kim, Hyunjung; Jiang, Zhang; Narayanan, Suresh

    2011-03-01

    We studied the structure and surface dynamics of poly(styrene)-b-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer films with micellar PDMS surrounded by PS shells. By `in-situ' high resolution synchrotron x-ray reflectivity and diffuse scattering, we obtained exact thickness, electron density and surface tension. A segregation layer near the top surface was appeared with increasing temperature Surface dynamics were measured as a function of film thickness and temperature by x-ray photon correlation spectroscopy. The best fit to relaxation time constants as a function of in-plane wavevectors were analyzed with a theory based on capillary waves with hydrodynamics with bilayer model Finally the viscosities for the top segregated layer as well as for the bottom layer are obtained at given temperatures This work was supported by National Research Foundation of Korea (R15-2008-006-01001-0), Seoul Research and Business Development Program (10816), and Sogang University Research Grant (2010).

  2. Restructuring in block copolymer thin films

    DEFF Research Database (Denmark)

    Posselt, Dorthe; Zhang, Jianqi; Smilgies, Detlef-M.

    2017-01-01

    Block copolymer (BCP) thin films have been proposed for a number of nanotechnology applications, such as nanolithography and as nanotemplates, nanoporous membranes and sensors. Solvent vapor annealing (SVA) has emerged as a powerful technique for manipulating and controlling the structure of BCP...... thin films, e.g., by healing defects, by altering the orientation of the microdomains and by changing the morphology. Due to high time resolution and compatibility with SVA environments, grazing-incidence small-angle X-ray scattering (GISAXS) is an indispensable technique for studying the SVA process......, providing information of the BCP thin film structure both laterally and along the film normal. Especially, state-of-the-art combined GISAXS/SVA setups at synchrotron sources have facilitated in situ and real-time studies of the SVA process with a time resolution of a few seconds, giving important insight...

  3. Thin Film Assembly of Spider Silk-like Block Copolymers

    Science.gov (United States)

    2011-01-01

    Shipley, N. H.; Lewis, R. V. Int. J. Biol.Macromol. 1999, 24, 271. (c) Thiel, B. L.; Guess, K. B.; Viney, C. Biopolymers 1997, 41, 703. (13) Silk ...Film Assembly of Spider Silk -like Block Copolymers Sreevidhya T. Krishnaji,†,‡ Wenwen Huang,§ Olena Rabotyagova,†,‡ Eugenia Kharlampieva, ) Ikjun Choi...Received November 26, 2010 We report the self-assembly of monolayers of spider silk -like block copolymers. Langmuir isotherms were obtained for a series of

  4. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers

    OpenAIRE

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N. V.; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-01-01

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affiniti...

  5. Biodegradable copolymers carrying cell-adhesion peptide sequences.

    Science.gov (United States)

    Proks, Vladimír; Machová, Lud'ka; Popelka, Stepán; Rypácek, Frantisek

    2003-01-01

    Amphiphilic block copolymers are used to create bioactive surfaces on biodegradable polymer scaffolds for tissue engineering. Cell-selective biomaterials can be prepared using copolymers containing peptide sequences derived from extracellular-matrix proteins (ECM). Here we discuss alternative ways for preparation of amphiphilic block copolymers composed of hydrophobic polylactide (PLA) and hydrophilic poly(ethylene oxide) (PEO) blocks with cell-adhesion peptide sequences. Copolymers PLA-b-PEO were prepared by a living polymerisation of lactide in dioxane with tin(II)2-ethylhexanoate as a catalyst. The following approaches for incorporation of peptides into copolymers were elaborated. (a) First, a side-chain protected Gly-Arg-Gly-Asp-Ser-Gly (GRGDSG) peptide was prepared by solid-phase peptide synthesis (SPPS) and then coupled with delta-hydroxy-Z-amino-PEO in solution. In the second step, the PLA block was grafted to it via a controlled polymerisation of lactide initiated by the hydroxy end-groups of PEO in the side-chain-protected GRGDSG-PEO. Deprotection of the peptide yielded a GRGDSG-b-PEO-b-PLA copolymer, with the peptide attached through its C-end. (b) A protected GRGDSG peptide was built up on a polymer resin and coupled with Z-carboxy-PEO using a solid-phase approach. After cleavage of the delta-hydroxy-PEO-GRGDSG copolymer from the resin, polymerisation of lactide followed by deprotection of the peptide yielded a PLA-b-PEO-b-GRGDSG block copolymer, in which the peptide is linked through its N-terminus.

  6. Novel block, graft and random copolymers for biomedical applications

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Jankova Atanasova, Katja; Tanaka, Masaru

    Despite the simple structure, poly(2-methoxyethyl acrylate) (PMEA) shows excellent blood compatibility [1]. Both the freezing-bound water (intermediate water: preventing the biocomponents from directly contacting the polymer surface) and non-freezing water on the polymer surface play important...... copolymers with MMA [4] utilizing ATRP. Here we present other block, graft and random copolymers of MEA intended for biomedical applications. These macromolecular architectures have been constructed by employing controlled radical polymerization methods such as RAFT and ATRP....

  7. Synthesis and Characterization of Novel Magnetite Nanoparticle Block Copolymer Complexes

    OpenAIRE

    Zhang, Qian

    2007-01-01

    Superparamagnetic Magnetite (Fe3O4) nanoparticles were synthesized and complexed with carboxylate-functionalized block copolymers, and aqueous dispersions of the complexes were investigated as functions of their chemical and morphological structures. The block copolymer dispersants possessed either poly(ethylene oxide), poly(ethylene oxide-co-propylene oxide), or poly(ethylene oxide-b-propylene oxide) outer blocks, and all contained a polyurethane center block with pendant carboxylate functi...

  8. Electrorheological Properties of Suspensions Prepared from Polystyrene- Block- Polyisoprene Copolymer

    OpenAIRE

    YAVUZ, Mustafa

    2014-01-01

    Considerable scientific and industrial interest is currently being focused on a class of materials known as electrorheological (ER) fluids, which display remarkable rheological behaviour, being able to convert rapidly and repeatedly from a liquid to solid when an electric field (E) is applied or removed. In this article, the synthesis, characterization, partial hydrolysis and ER properties of polystyrene- block}-polyisoprene copolymer (COP) were investigated. The block copolymer was ...

  9. Self-assembled Block Copolymer Membranes with Bioinspired Artificial Channels

    KAUST Repository

    Sutisna, Burhannudin

    2018-04-01

    Nature is an excellent design that inspires scientists to develop smart systems. In the realm of separation technology, biological membranes have been an ideal model for synthetic membranes due to their ultrahigh permeability, sharp selectivity, and stimuliresponse. In this research, fabrications of bioinspired membranes from block copolymers were studied. Membranes with isoporous morphology were mainly prepared using selfassembly and non-solvent induced phase separation (SNIPS). An effective method that can dramatically shorten the path for designing new isoporous membranes from block copolymers via SNIPS was first proposed by predetermining a trend line computed from the solvent properties, interactions and copolymer block sizes of previously-obtained successful systems. Application of the method to new copolymer systems and fundamental studies on the block copolymer self-assembly were performed. Furthermore, the manufacture of bioinspired membranes was explored using (1) poly(styrene-b-4-hydroxystyrene-b-styrene) (PS-b-PHS-b-PS), (2) poly(styrene-bbutadiene- b-styrene) (PS-b-PB-b-PS) and (3) poly(styrene-b-γ-benzyl-L-glutamate) (PSb- PBLG) copolymers via SNIPS. The structure formation was investigated using smallangle X-ray scattering (SAXS) and time-resolved grazing-Incidence SAXS. The PS-b- PHS-b-PS membranes showed preferential transport for proteins, presumably due to the hydrogen bond interactions within the channels, electrostatic attraction, and suitable pore dimension. Well-defined nanochannels with pore sizes of around 4 nm based on PS-b- PB-b-PS copolymers could serve as an excellent platform to fabricate bioinspired channels due to the modifiable butadiene blocks. Photolytic addition of thioglycolic acid was demonstrated without sacrificing the self-assembled morphology, which led to a five-fold increase in water permeance compared to that of the unmodified. Membranes with a unique feather-like structure and a lamellar morphology for dialysis and

  10. Microbial Community Composition of Polyhydroxyalkanoate-Accumulating Organisms in Full-Scale Wastewater Treatment Plants Operated in Fully Aerobic Mode

    Science.gov (United States)

    Oshiki, Mamoru; Onuki, Motoharu; Satoh, Hiroyasu; Mino, Takashi

    2013-01-01

    The removal of biodegradable organic matter is one of the most important objectives in biological wastewater treatments. Polyhydroxyalkanoate (PHA)-accumulating organisms (PHAAOs) significantly contribute to the removal of biodegradable organic matter; however, their microbial community composition is mostly unknown. In the present study, the microbial community composition of PHAAOs was investigated at 8 full-scale wastewater treatment plants (WWTPs), operated in fully aerobic mode, by fluorescence in situ hybridization (FISH) analysis and post-FISH Nile blue A (NBA) staining techniques. Our results demonstrated that 1) PHAAOs were in the range of 11–18% in the total number of cells, and 2) the microbial community composition of PHAAOs was similar at the bacterial domain/phylum/class/order level among the 8 full-scale WWTPs, and dominant PHAAOs were members of the class Alphaproteobacteria and Betaproteobacteria. The microbial community composition of α- and β-proteobacterial PHAAOs was examined by 16S rRNA gene clone library analysis and further by applying a set of newly designed oligonucleotide probes targeting 16S rRNA gene sequences of α- or β-proteobacterial PHAAOs. The results demonstrated that the microbial community composition of PHAAOs differed in the class Alphaproteobacteria and Betaproteobacteria, which possibly resulted in a different PHA accumulation capacity among the WWTPs (8.5–38.2 mg-C g-VSS−1 h−1). The present study extended the knowledge of the microbial diversity of PHAAOs in full-scale WWTPs operated in fully aerobic mode. PMID:23257912

  11. Whole genome amplification approach reveals novel polyhydroxyalkanoate synthases (PhaCs) from Japan Trench and Nankai Trough seawater.

    Science.gov (United States)

    Foong, Choon Pin; Lau, Nyok-Sean; Deguchi, Shigeru; Toyofuku, Takashi; Taylor, Todd D; Sudesh, Kumar; Matsui, Minami

    2014-12-24

    Special features of the Japanese ocean include its ranges of latitude and depth. This study is the first to examine the diversity of Class I and II PHA synthases (PhaC) in DNA samples from pelagic seawater taken from the Japan Trench and Nankai Trough from a range of depths from 24 m to 5373 m. PhaC is the key enzyme in microorganisms that determines the types of monomer units that are polymerized into polyhydroxyalkanoate (PHA) and thus affects the physicochemical properties of this thermoplastic polymer. Complete putative PhaC sequences were determined via genome walking, and the activities of newly discovered PhaCs were evaluated in a heterologous host. A total of 76 putative phaC PCR fragments were amplified from the whole genome amplified seawater DNA. Of these 55 clones contained conserved PhaC domains and were classified into 20 genetic groups depending on their sequence similarity. Eleven genetic groups have undisclosed PhaC activity based on their distinct phylogenetic lineages from known PHA producers. Three complete DNA coding sequences were determined by IAN-PCR, and one PhaC was able to produce poly(3-hydroxybutyrate) in recombinant Cupriavidus necator PHB-4 (PHB-negative mutant). A new functional PhaC that has close identity to Marinobacter sp. was discovered in this study. Phylogenetic classification for all the phaC genes isolated from uncultured bacteria has revealed that seawater and other environmental resources harbor a great diversity of PhaCs with activities that have not yet been investigated. Functional evaluation of these in silico-based PhaCs via genome walking has provided new insights into the polymerizing ability of these enzymes.

  12. Integrated systems for biopolymers and bioenergy production from organic waste and by-products: a review of microbial processes.

    Science.gov (United States)

    Pagliano, Giorgia; Ventorino, Valeria; Panico, Antonio; Pepe, Olimpia

    2017-01-01

    Recently, issues concerning the sustainable and harmless disposal of organic solid waste have generated interest in microbial biotechnologies aimed at converting waste materials into bioenergy and biomaterials, thus contributing to a reduction in economic dependence on fossil fuels. To valorize biomass, waste materials derived from agriculture, food processing factories, and municipal organic waste can be used to produce biopolymers, such as biohydrogen and biogas, through different microbial processes. In fact, different bacterial strains can synthesize biopolymers to convert waste materials into valuable intracellular (e.g., polyhydroxyalkanoates) and extracellular (e.g., exopolysaccharides) bioproducts, which are useful for biochemical production. In particular, large numbers of bacteria, including Alcaligenes eutrophus , Alcaligenes latus , Azotobacter vinelandii , Azotobacter chroococcum , Azotobacter beijerincki , methylotrophs, Pseudomonas spp., Bacillus spp., Rhizobium spp., Nocardia spp., and recombinant Escherichia coli , have been successfully used to produce polyhydroxyalkanoates on an industrial scale from different types of organic by-products. Therefore, the development of high-performance microbial strains and the use of by-products and waste as substrates could reasonably make the production costs of biodegradable polymers comparable to those required by petrochemical-derived plastics and promote their use. Many studies have reported use of the same organic substrates as alternative energy sources to produce biogas and biohydrogen through anaerobic digestion as well as dark and photofermentation processes under anaerobic conditions. Therefore, concurrently obtaining bioenergy and biopolymers at a reasonable cost through an integrated system is becoming feasible using by-products and waste as organic carbon sources. An overview of the suitable substrates and microbial strains used in low-cost polyhydroxyalkanoates for biohydrogen and biogas

  13. Suspension polymerization a process for the production of beaded polymer supports and derived ion exchangers

    International Nuclear Information System (INIS)

    Malik, M.A.

    1995-01-01

    Suspension polymerization techniques for production of beaded polymers are discussed with special reference to styrene divinylbenzene copolymers. Methods to control particle size and size distribution of final copolymer beads are given. Mechanism of copolymerization and constituents of aqueous and oil phase are discussed. Mechanism of porous structure formation and control of porosity are also discussed. Chemical conversion of base copolymers into ion exchange resins is also discussed. (author) 16 figs

  14. Controlled radical copolymerization of styrene and maleic anhydride and the synthesis of novel polyolefin-based block copolymers by reversible addition-fragmentation chain-transfer (RAFT) polymerization

    NARCIS (Netherlands)

    Brouwer, de J.A.M.; Schellekens, M.A.J.; Klumperman, B.; Monteiro, M.J.; German, A.L.

    2000-01-01

    Reversible addn.-fragmentation chain transfer (RAFT) was applied to the copolymn. of styrene and maleic anhydride. The product had a low polydispersity and a predetd. molar mass. Novel, well-defined polyolefin-based block copolymers were prepd. with a macromol. RAFT agent prepd. from a com.

  15. A Study on Copolymer Systems of Styrene with Diethanolamine Side Group and Methyl Methacrylate

    Directory of Open Access Journals (Sweden)

    Aslisah Acikses

    2018-01-01

    Full Text Available 4-Diethanolaminomethyl styrene (DEAMSt monomer was prepared by the modification of 4-chloromethyl styrene with diethanolamine. The copolymers in different combinations (0.11, 0.19, and 0.30 by mole of DEAMSt and methyl methacrylate (MMA were prepared by free radical polymerization method at 60°C in the presence of 1,4-dioxane and AIBN as initiator. The structures of DEAMSt and DEAMSt-MMA copolymer were characterized by FT-IR and 1H-NMR. The glass transition temperature (Tg of the copolymers was measured by DSC. Thermal decomposition behavior of the copolymers was investigated by TGA. The average molecular weights of the copolymers were determined by GPC. The dye uptaking properties of the copolymers were investigated using bromocresol green. Then, the dielectric constant, dielectric loss factor, and conductivity of copolymers were investigated as a function of temperature and frequency. The activation energies (Ea of the copolymers were determined by impedance analyzer.

  16. Tuning the Optoelectronic Properties of Vinylene-Linked Donor−Acceptor Copolymers for Organic Photovoltaics

    KAUST Repository

    Ko, Sangwon; Mondal, Rajib; Risko, Chad; Lee, Jung Kyu; Hong, Sanghyun; McGehee, Michael D.; Brédas, Jean-Luc; Bao, Zhenan

    2010-01-01

    -property relationships in organic photovoltaic devices. Both alternating (P) and random copolymers (P1-P4) were prepared via Suzuki and Stille polycondensations, respectively. The cyclopentadithiophene copolymers (P2 and P4) have smaller electrochemical band gaps (1

  17. Monte Carlo simulations of the phase separation of a copolymer blend in a thin film

    KAUST Repository

    Wang, Zhexiao

    2014-12-11

    Monte Carlo simulations were carried out to study the phase separation of a copolymer blend comprising an alternating copolymer and/or block copolymer in a thin film, and a phase diagram was constructed with a series of composed recipes. The effects of composition and segregation strength on phase separation were discussed in detail. The chain conformation of the block copolymer and alternating copolymer were investigated with changes of the segregation strength. Our simulations revealed that the segment distribution along the copolymer chain and the segregation strength between coarse-grained beads are two important parameters controlling phase separation and chain conformation in thin films of a copolymer blend. A well-controlled phase separation in the copolymer blend can be used to fabricate novel nanostructures.

  18. Triplet State Formation in Photovoltaic Blends of DPP-Type Copolymers and PC71BM

    KAUST Repository

    Ochsmann, Julian R.; Chandran, Deepak; Gehrig, Dominik W.; Anwar, Husna; Madathil, Pramod Kandoth; Lee, Kwang-Sup; Laquai, Fré dé ric

    2015-01-01

    The exciton dynamics in pristine films of two structurally related low-bandgap diketopyrrolopyrrole (DPP)-based donor–acceptor copolymers and the photophysical processes in bulk heterojunction solar cells using DPP copolymer:PC71BM blends

  19. CO2-Philic Thin Film Composite Membranes: Synthesis and Characterization of PAN-r-PEGMA Copolymer

    KAUST Repository

    Karunakaran, Madhavan; Kumar, Mahendra; Shevate, Rahul; Akhtar, Faheem Hassan; Peinemann, Klaus-Viktor

    2017-01-01

    amounts of PEG content was synthesized by free radical polymerization in presence of AIBN initiator and the obtained copolymers were used for the fabrication of composite membranes. The synthesized copolymers show high molecular weights in the range of 44

  20. A poly(ether-ester) copolymer for the preparation of nanocarriers with improved degradation and drug delivery kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Gagliardi, M., E-mail: mariacristina.gagliardi@iit.it [Center for Micro Bio-Robotics @SSSA, Istituto Italiano di Tecnologia, Viale Rinaldo Piaggio 34, 56025 Pontedera (Italy); Bertero, A. [Department of Biology, Unit of Cellular and Developmental Biology, University of Pisa, S.S.12 Abetone e Brennero 4, 56127 Pisa (Italy); Center for Neuroscience and Cognitive Systems @UNITN, Istituto Italiano di Tecnologia, Corso Bettini 31, 38068 Rovereto (Italy); Bardi, G. [Center for Bio-Molecular Nanotechnologies @UniLe, Istituto Italiano di Tecnologia, Via Barsanti, 73010 Arnesano (Italy); Bifone, A. [Center for Neuroscience and Cognitive Systems @UNITN, Istituto Italiano di Tecnologia, Corso Bettini 31, 38068 Rovereto (Italy)

    2016-02-01

    This paper reports the synthesis and the physicochemical, functional and biological characterisations of nanocarriers made of a novel di-block biodegradable poly(ether-ester) copolymer. This material presents tunable, fast biodegradation rates, but its products are less acidic than those of other biosorbable polymers like PLGA, thus presenting a better biocompatibility profile and the possibility to carry pH-sensitive payloads. A method for the production of monodisperse and spherical nanoparticles is proposed; drug delivery kinetics and blood protein adsorption were measured to evaluate the functional properties of these nanoparticles as drug carriers. The copolymer was labelled with a fluorescent dye for internalisation tests, and rhodamine B was used as a model cargo to study transport and release inside cultured cells. Biological tests demonstrated good cytocompatibility, significant cell internalisation and the possibility to vehiculate non-cell penetrating moieties into endothelial cells. Taken together, these results support the potential use of this nanoparticulate system for systemic administration of drugs. - Highlights: • We propose a novel biodegradable nanocarrier for intracellular drug delivery. • Biodegradation rates can be finely tuned by controlling copolymer composition. • Degradation products are less acidic, thus enabling delivery of pH-sensitive cargoes. • We demonstrate intracellular delivery of a non-cell-penetrating model drug. • No significant membrane damage by the polymer nanocarriers is observed.

  1. A poly(ether-ester) copolymer for the preparation of nanocarriers with improved degradation and drug delivery kinetics

    International Nuclear Information System (INIS)

    Gagliardi, M.; Bertero, A.; Bardi, G.; Bifone, A.

    2016-01-01

    This paper reports the synthesis and the physicochemical, functional and biological characterisations of nanocarriers made of a novel di-block biodegradable poly(ether-ester) copolymer. This material presents tunable, fast biodegradation rates, but its products are less acidic than those of other biosorbable polymers like PLGA, thus presenting a better biocompatibility profile and the possibility to carry pH-sensitive payloads. A method for the production of monodisperse and spherical nanoparticles is proposed; drug delivery kinetics and blood protein adsorption were measured to evaluate the functional properties of these nanoparticles as drug carriers. The copolymer was labelled with a fluorescent dye for internalisation tests, and rhodamine B was used as a model cargo to study transport and release inside cultured cells. Biological tests demonstrated good cytocompatibility, significant cell internalisation and the possibility to vehiculate non-cell penetrating moieties into endothelial cells. Taken together, these results support the potential use of this nanoparticulate system for systemic administration of drugs. - Highlights: • We propose a novel biodegradable nanocarrier for intracellular drug delivery. • Biodegradation rates can be finely tuned by controlling copolymer composition. • Degradation products are less acidic, thus enabling delivery of pH-sensitive cargoes. • We demonstrate intracellular delivery of a non-cell-penetrating model drug. • No significant membrane damage by the polymer nanocarriers is observed.

  2. Incomplete copolymer degradation of in situ chemotherapy.

    Science.gov (United States)

    Bourdillon, Pierre; Boissenot, Tanguy; Goldwirt, Lauriane; Nicolas, Julien; Apra, Caroline; Carpentier, Alexandre

    2018-02-17

    In situ carmustine wafers containing 1,3-bis(2-chloroethyl)-1-nitrosourea (BCNU) are commonly used for the treatment of recurrent glioblastoma to overcome the brain-blood barrier. In theory, this chemotherapy diffuses into the adjacent parenchyma and the excipient degrades in maximum 8 weeks but no clinical data confirms this evolution, because patients are rarely operated again. A 75-year-old patient was operated twice for recurrent glioblastoma, and a carmustine wafer was implanted during the second surgery. Eleven months later, a third surgery was performed, revealing unexpected incomplete degradation of the wafer. 1H-Nuclear Magnetic Resonance was performed to compare this wafer to pure BCNU and to an unused copolymer wafer. In the used wafer, peaks corresponding to hydrophobic units of the excipient were no longer noticeable, whereas peaks of the hydrophilic units and traces of BCNU were still present. These surprising results could be related to the formation of a hydrophobic membrane around the wafer, thus interfering with the expected diffusion and degradation processes. The clinical benefit of carmustine wafers in addition to the standard radio-chemotherapy remains limited, and in vivo behavior of this treatment is not completely elucidated yet. We found that the wafer may remain after several months. Alternative strategies to deal with the blood-brain barrier, such as drug-loaded liposomes or ultrasound-opening, must be explored to offer larger drug diffusion or allow repetitive delivery.

  3. Design of block copolymer membranes using segregation strength trend lines

    KAUST Repository

    Sutisna, Burhannudin

    2016-05-18

    Block copolymer self-assembly and non-solvent induced phase separation are now being combined to fabricate membranes with narrow pore size distribution and high porosity. The method has the potential to be used with a broad range of tailor-made block copolymers to control functionality and selectivity for specific separations. However, the extension of this process to any new copolymer is challenging and time consuming, due to the complex interplay of influencing parameters, such as solvent composition, polymer molecular weights, casting solution concentration, and evaporation time. We propose here an effective method for designing new block copolymer membranes. The method consists of predetermining a trend line for the preparation of isoporous membranes, obtained by computing solvent properties, interactions and copolymer block sizes for a set of successful systems and using it as a guide to select the preparation conditions for new membranes. We applied the method to membranes based on poly(styrene-b-ethylene oxide) diblocks and extended it to newly synthesized poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) terpolymers. The trend line method can be generally applied to other new systems and is expected to dramatically shorten the path of isoporous membrane manufacture. The PS-b-P2VP-b-PEO membrane formation was investigated by in situ Grazing Incident Small Angle X-ray Scattering (GISAXS), which revealed a hexagonal micelle order with domain spacing clearly correlated to the membrane interpore distances.

  4. SANS and SAXS study of block copolymer/homopolymer mixtures

    International Nuclear Information System (INIS)

    Hasegawa, Hirokazu; Tanaka, Hideaki; Hashimoto, Takeji; Han, C.C.

    1991-01-01

    The lateral and vertical components of the radius of gyration for a single block copolymer chain and those of a single homopolymer chain in the lamellar microdomain space formed by a mixture of diblock copolymers and homopolymers were investigated by means of small-angle neutron scattering (SANS) and the microdomain structures by small-angle X-ray scattering (SAXS). The homopolymers whose molecular weights are much smaller than that of the corresponding chains of the block copolymers were used so that the homopolymers were uniformly solubilized in the corresponding microdomains. The SANS result suggests that the homopolymer chains in the microdomain space as well as the block copolymer chains are more compressed in the direction parallel to the interface and more stretched in the direction perpendicular to the interface than the corresponding unperturbed polymer chains with the same molecular weight. On increasing the volume fraction of the homopolymers the thickness of the lamellar microdomains increases. The block copolymer chains were found to undergo an isochoric affine deformation on addition of the homopolymers or with the change of the thickness of the lamellar microdomains. (orig.)

  5. Relaxation processes in a lower disorder order transition diblock copolymer

    International Nuclear Information System (INIS)

    Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora; Hernández, Rebeca; Sprung, Michael

    2015-01-01

    The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition T ODT , the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chain segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system

  6. Highly conductive side chain block copolymer anion exchange membranes.

    Science.gov (United States)

    Wang, Lizhu; Hickner, Michael A

    2016-06-28

    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

  7. Synthesis, characterization and antimicrobial activity of important heterocyclic acrylic copolymers

    Directory of Open Access Journals (Sweden)

    2008-10-01

    Full Text Available The acrylate monomer, 7-acryloyloxy-4-methyl coumarin (AMC has been synthesized by reacting 7-hydroxy-4-methyl coumarin, with acryloyl chloride in the presence of NaOH at 0–5°C. Copolymers of 7-acryloyloxy-4-methyl coumarin (AMC with vinyl acetate (VAc were synthesized in DMF (dimethyl formamide solution at 70±1°C using 2,2′-azobisisobutyronitrile (AIBN as an initiator with different monomer-to-monomer ratios in the feed. The copolymers were characterized by Fourier transform infra red (FTIR spectroscopy. The copolymer composition was evaluated by 1H-NMR (proton nuclear magnetic resonance and was further used to determine reactivity ratios. The monomer reactivity ratios for AMC (M1-VAc (M2 pair were determined by the application of conventional linearization methods such as Fineman-Ross (r1 = 0.6924; r2 = 0.6431, Kelen-Tüdõs (r1 = 0.6776; r2 = 0.6374 and extended Kelen-Tüdõs (r1 = 0.6657; r2 = 0.6256. Thermo gravimetric analysis showed that thermal decomposition of the copolymers occurred in single stage in the temperature range of 263–458°C. The molecular weights of the polymers were determined using gel permeation chromatography. The homo and copolymers were tested for their antimicrobial properties against selected microorganisms.

  8. Controlling block copolymer phase behavior using ionic surfactant

    Energy Technology Data Exchange (ETDEWEB)

    Ray, D.; Aswal, V. K. [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India E-mail: debes.phys@gmail.com (India)

    2016-05-23

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO{sub 26}PO{sub 39}EO{sub 26})] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle–surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at higher temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.

  9. Polystyrene-b-polyethylene oxide block copolymer membranes, methods of making, and methods of use

    KAUST Repository

    Peinemann, Klaus-Viktor; Karunakaran, Madhavan

    2015-01-01

    Embodiments of the present disclosure provide for polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer nanoporous membranes, methods of making a PS-b-PEO block copolymer nanoporous membrane, methods of using PS-b-PEO block copolymer nanoporous membranes, and the like.

  10. 78 FR 20032 - Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption

    Science.gov (United States)

    2013-04-03

    ...-Ethylene-Propylene Block Copolymer; Tolerance Exemption AGENCY: Environmental Protection Agency (EPA... for residues of styrene-ethylene-propylene block copolymer (CAS Reg. No. 108388-87-0) when used as an...-ethylene-propylene block copolymer on food or feed commodities. DATES: This regulation is effective April 3...

  11. 21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate-vinyl alcohol copolymers... for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1360 Ethylene-vinyl acetate-vinyl alcohol copolymers. Ethylene-vinyl acetate-vinyl alcohol copolymers (CAS Reg. No. 26221-27-2...

  12. 21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-methyl acrylate copolymer resins. 177.1340... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1340 Ethylene-methyl acrylate copolymer resins. Ethylene-methyl acrylate copolymer resins may be safely used as articles or components of...

  13. Realization of an integrated VDF/TrFE copolymer-on-silicon pyroelectric sensor

    NARCIS (Netherlands)

    Setiadi, D.; Setiadi, D.; Regtien, Paulus P.L.; Sarro, P.M.

    1995-01-01

    An integrated pyroelectric sensor based on a vinylidene fluoride trifluoroethylene (VDF/TrFE) copolymer is presented. A silicon substrate that contains FET readout electronics is coated with the VDF/TrFE copolymer film using a spin-coating technique. On-chip poling of the copolymer has been applied

  14. 40 CFR 180.1162 - Acrylate polymers and copolymers; exemption from the requirement of a tolerance.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Acrylate polymers and copolymers... RESIDUES IN FOOD Exemptions From Tolerances § 180.1162 Acrylate polymers and copolymers; exemption from the requirement of a tolerance. (a) Acrylate polymers and copolymers are exempt from the requirement of a...

  15. Polystyrene-b-polyethylene oxide block copolymer membranes, methods of making, and methods of use

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-04-16

    Embodiments of the present disclosure provide for polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer nanoporous membranes, methods of making a PS-b-PEO block copolymer nanoporous membrane, methods of using PS-b-PEO block copolymer nanoporous membranes, and the like.

  16. 21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances.../butadiene/sty-rene co-polymer. Acrylonitrile/butadiene/styrene copolymer identified in this section may be...

  17. [Prediction of Encapsulation Temperatures of Copolymer Films in Photovoltaic Cells Using Hyperspectral Imaging Techniques and Chemometrics].

    Science.gov (United States)

    Lin, Ping; Chen, Yong-ming; Yao, Zhi-lei

    2015-11-01

    A novel method of combination of the chemometrics and the hyperspectral imaging techniques was presented to detect the temperatures of Ethylene-Vinyl Acetate copolymer (EVA) films in photovoltaic cells during the thermal encapsulation process. Four varieties of the EVA films which had been heated at the temperatures of 128, 132, 142 and 148 °C during the photovoltaic cells production process were used for investigation in this paper. These copolymer encapsulation films were firstly scanned by the hyperspectral imaging equipment (Spectral Imaging Ltd. Oulu, Finland). The scanning band range of hyperspectral equipemnt was set between 904.58 and 1700.01 nm. The hyperspectral dataset of copolymer films was randomly divided into two parts for the training and test purpose. Each type of the training set and test set contained 90 and 10 instances, respectively. The obtained hyperspectral images of EVA films were dealt with by using the ENVI (Exelis Visual Information Solutions, USA) software. The size of region of interest (ROI) of each obtained hyperspectral image of EVA film was set as 150 x 150 pixels. The average of reflectance hyper spectra of all the pixels in the ROI was used as the characteristic curve to represent the instance. There kinds of chemometrics methods including partial least squares regression (PLSR), multi-class support vector machine (SVM) and large margin nearest neighbor (LMNN) were used to correlate the characteristic hyper spectra with the encapsulation temperatures of of copolymer films. The plot of weighted regression coefficients illustrated that both bands of short- and long-wave near infrared hyperspectral data contributed to enhancing the prediction accuracy of the forecast model. Because the attained reflectance hyperspectral data of EVA materials displayed the strong nonlinearity, the prediction performance of linear modeling method of PLSR declined and the prediction precision only reached to 95%. The kernel-based forecast models were

  18. Block copolymer/homopolymer dual-layer hollow fiber membranes

    KAUST Repository

    Hilke, Roland

    2014-12-01

    We manufactured the first time block copolymer dual-layer hollow fiber membranes and dual layer flat sheet membranes manufactured by double solution casting and phase inversion in water. The support porous layer was based on polystyrene and the selective layer with isopores was formed by micelle assembly of polystyrene-. b-poly-4-vinyl pyridine. The dual layers had an excellent interfacial adhesion and pore interconnectivity. The dual membranes showed pH response behavior like single layer block copolymer membranes with a low flux for pH values less than 3, a fast increase between pH4 and pH6 and a constant high flux level for pH values above 7. The dry/wet spinning process was optimized to produce dual layer hollow fiber membranes with polystyrene internal support layer and a shell block copolymer selective layer.

  19. Morphologies of precise polyethylene-based acid copolymers and ionomers

    Science.gov (United States)

    Buitrago, C. Francisco

    Acid copolymers and ionomers are polymers that contain a small fraction of covalently bound acidic or ionic groups, respectively. For the specific case of polyethylene (PE), acid and ionic pendants enhance many of the physical properties such as toughness, adhesion and rheological properties. These improved properties result from microphase separated aggregates of the polar pendants in the non-polar PE matrix. Despite the widespread industrial use of these materials, rigorous chemical structure---morphology---property relationships remain elusive due to the inevitable structural heterogeneities in the historically-available acid copolymers and ionomers. Recently, precise acid copolymers and ionomers were successfully synthesized by acyclic diene metathesis (ADMET) polymerization. These precise materials are linear, high molecular weight PEs with pendant acid or ionic functional groups separated by a precisely controlled number of carbon atoms. The morphologies of nine precise acid copolymers and eleven precise ionomers were investigated by X-ray scattering, solid-state 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). For comparison, the morphologies of linear PEs with pseudo-random placement of the pendant groups were also studied. Previous studies of precise copolymers with acrylic acid (AA) found that the microstructural precision produces a new morphology in which PE crystals drive the acid aggregates into layers perpendicular to the chain axes and presumably at the interface between crystalline and amorphous phases. In this dissertation, a second new morphology for acid copolymers is identified in which the aggregates arrange on cubic lattices. The fist report of a cubic morphology was observed at room and elevated temperatures for a copolymer functionalized with two phosphonic acid (PA) groups on every 21st carbon atom. The cubic lattice has been identified as face-centered cubic (FCC). Overall, three morphology types have been

  20. Low molecular weight block copolymers as plasticizers for polystyrene

    DEFF Research Database (Denmark)

    Hansen, Kristoffer Karsten; Nielsen, Charlotte Juel; Hvilsted, Søren

    2005-01-01

    /mol and minimum polystyrene content of 50 w/w%, which by us is predicted as the limits for solubility of polystyrene-b-alkyl in polystyrene. DSC showed polystyrene was plasticized, as seen by a reduction in glass transition temperature, by block copolymers consisting of a polystyrene block with molecular weight...... of approximately 1 kg/mol and an alkyl block with a molecular weight of approximately of 0.3 kg/mol. The efficiency of the block copolymers as plasticizers increases with decreasing molecular weight and polystyrene content. In addition, polystyrene-b-alkyl is found to be an efficient plasticizer also...... for polystyrene-b-polyisoprene-b-polystyrene (SIS) block copolymers. The end use properties of SIS plasticized with polystyrene-b-alkyl, measured as tensile strength, is higher than for SIS plasticized with dioctyl adipate. The polystyrene-b-polybutadiene-b-polystyrene and polystyrene-bpoly(propylene glycol...

  1. Water stale and structure analysis of Konjac irradiation copolymer

    International Nuclear Information System (INIS)

    Geng Shengrong; Xia Hezhou; Chen Xueling; Ye Lixiu; Hua Yuejin

    2011-01-01

    To study the absorption performance of Konjac-AA copolymer prepared by using irradiation, the water absorption capacity, sorbent speed and water keeping ability were determined, DSC and TEM analysis were used to investigate the water content and structure characters. The results showed that the largest water absorption speed was 16 g · -1 · min -1 at room temperature, and the largest water absorption was 400 times within 60 minutes. The water absorption was affected by granularity, temperature, ion content and ion type, especially the ion type. The water keeping ability was affected by temperature and time, which was up to 35% of absorbed water when the fully water absorbed copolymer was kept under room temperature for 15 d. The free and bounder water content which could be assimilated by the plants was 99.617%. The water stale copolymer has a three-dimensional spiral structure. (authors)

  2. Thermoresponsive behavior of chitosan-g-N-isopropylacrylamide copolymer solutions.

    Science.gov (United States)

    Recillas, Maricarmen; Silva, Luisa L; Peniche, Carlos; Goycoolea, Francisco M; Rinaudo, Marguerite; Argüelles-Monal, Waldo M

    2009-06-08

    Chitosan-g-N-isopropylacrylamide (NIPAm) water-soluble copolymers were synthesized and characterized by FTIR and (1)H NMR spectroscopies combined with conductometric and potentiometric titrations. Their thermoresponsive, fully reversible, behavior in aqueous solutions was characterized by means of microcalorimetry and rheology. During heating of copolymer solutions there is a well-known endothermic effect, which coincides with a marked increase in G' and a moderate decrement in G'' due to the formation of a hydrophobic network at the expense of the net amount of sol fraction. It was also found that a straight dependence between the values of G' above the LCST and the enthalpies associated with the transition reflecting that the connectivity in the gel network is governed by the net number of formed enthalpic-hydrophobic driven-junctions. Both the LCST and the enthalpy change vary with the ionic strength of copolymer solutions, but no dependence was found with the neutralization of the polyelectrolyte chain.

  3. Pressure and temperature effects in homopolymer blends and diblock copolymers

    DEFF Research Database (Denmark)

    Frielinghaus, H.; Schwahn, D.; Mortensen, K.

    1997-01-01

    Thermal composition fluctuations in a homogeneous binary polymer blend and in a diblock copolymer were measured by small-angle neutron scattering as a function of temperature and pressure. The experimental data were analyzed with theoretical expressions, including the important effect of thermal...... fluctuations. Phase boundaries, the Flory-Huggins interaction parameter and the Ginzburg number were obtained. The packing of the molecules changes with pressure. Therefore, the degree of thermal fluctuation as a function of packing and temperature was studied. While in polymer blends packing leads, in some...... respects, to a universal behaviour, such behaviour is not found in diblock copolymers. It is shown that the Ginzburg number decreases with pressure sensitively in blends, while it is constant in diblock copolymers. The Ginzburg number is an estimation of the transition between the universality classes...

  4. Characterization of Lithium Polysulfide Salts in Homopolymers and Block Copolymers

    Science.gov (United States)

    Wang, Dunyang; Wujcik, Kevin; Balsara, Nitash

    Ion-conducting polymers are important for solid-state batteries due to the promise of better safety and the potential to produce higher energy density batteries. Nanostructured block copolymer electrolytes can provide high ionic conductivity and mechanical strength through microphase separation. One of the potential use of block copolymer electrolytes is in lithium-sulfur batteries, a system that has high theoretical energy density wherein the reduction of sulfur leads to the formation of lithium polysulfide intermediates. In this study we investigate the effect of block copolymer morphology on the speciation and transport properties of the polysulfides. The morphology and conductivities of polystyrene-b-poly(ethylene oxide) (SEO) containing lithium polysulfides were studies using small-angle X-ray scattering and ac impedance spectroscopy. UV-vis spectroscopy is being used to determine nature of the polysulfide species in poly(ethylene oxide) and SEO. Department of Energy, Soft Matter Electron Microscopy Program and Battery Materials Research Program.

  5. ABC triblock copolymer vesicles with mesh-like morphology.

    Science.gov (United States)

    Zhao, Wei; Chen, Dian; Hu, Yunxia; Grason, Gregory M; Russell, Thomas P

    2011-01-25

    Polymer vesicles made from poly(isoprene-b-styrene-b-2-vinyl pyridine) (PI-b-PS-b-P2VP) triblock copolymer confined within the nanopores of an anodic aluminum oxide (AAO) membrane are studied. It was found that these vesicles have well-defined, nanoscopic size, and complex microphase-separated hydrophobic membranes, comprised of the PS and PI blocks, while the coronas are formed by the P2VP block. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the membrane at a well-defined composition of the three blocks that can be tuned by changing the copolymer composition. The nanoscale confinement, copolymer composition, and subtle molecular interactions contribute to the generation of these vesicles with such unusual morphologies.

  6. Modification of ethylene-norbornene copolymer by Gamma irradiation

    Directory of Open Access Journals (Sweden)

    Kačarević-Popović Zorica M.

    2006-01-01

    Full Text Available The possibility of modifying polyethylene and many other polymers with high energy radiation has led to many useful applications. Due to their new combination of properties and the shortage of experimental data, the radiolysis of a new class of materials, cyclo-olefin copolymers (COC, polymerised from norbornene and ethylene using metallocene catalysts, is of great interest to the study of radiation chemistry and the physics of polymeric systems. Ethylenenorbornene copolymer, pristine and containing an antioxidant were subjected to gamma irradiation in the presence of air and in water. The irradiated copolymer was studied using IR and UV-vis spectrophotometric analysis. The radiation-induced changes in the molecular structure were correlated to changes in the glass transition temperature measured by the DSC method.

  7. Preparation and icephobic properties of polymethyltrifluoropropylsiloxane–polyacrylate block copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiaohui; Zhao, Yunhui [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China); Li, Hui [School of Chemistry and Chemical Engineering, Shandong Key Laboratory of Fluorine Chemistry and Chemical Engineering Materials, University of Jinan, Jinan 250022 (China); Yuan, Xiaoyan, E-mail: xyuan28@yahoo.com [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China)

    2014-10-15

    Highlights: • PMTFPS–b-polyacrylate copolymers in five different compositions were synthesized. • Enrichment of PMTFPS amounts at the surface made high F/Si value. • Icing delay time was related to the surface roughness. • Ice shear strength was decreased by the synergistic effect of silicone and fluorine. - Abstract: Five polymethyltrifluoropropylsiloxane (PMTFPS)–polyacrylate block copolymers (PMTFPS–b-polyacrylate) were synthesized by free radical polymerization of methyl methacrylate, n-butyl acrylate and hydroxyethyl methacrylate using PMTFPS macroazoinitiator (PMTFPS-MAI) in range of 10–50 mass percentages. The morphology, surface chemical composition and wettability of the prepared copolymer films were investigated by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle measurement. Delayed icing time and ice shear strength of the films were also detected for the icephobic purpose. The surface morphologies of the copolymers were different from those of the bulk because of the migration of the PMTFPS segments to the air interface during the film formation. Maximal delayed icing time (186 s at −15 °C) and reduction of the ice shear strength (301 ± 10 kPa) which was significantly lower than that of polyacrylates (804 ± 37 kPa) were achieved when the content of PMTFPS-MAI was 20 wt%. The icephobicity of the copolymers was attributed primarily to the enrichment of PMTFPS on the film surface and synergistic effect of both silicone and fluorine. Thus, the results show that the PMTFPS–b-polyacrylate copolymer can be used as icephobic coating materials potentially.

  8. Responsive copolymers for enhanced petroleum recovery. Second annual report

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.

    1995-05-01

    The authors describe second year efforts in synthesis, characterization, and rheology to develop polymers with significantly improved efficiency in mobility control and conformance. These advanced polymer systems would maintain high viscosities or behave as virtual gels under low shear conditions and at elevated electrolyte concentrations. At high fluid shear rates, associates would deaggregate yielding low viscosity solutions, reducing problems of shear degradation or face plugging during injection. Polymeric surfactants were also developed with potential for use in higher salt, higher temperature reservoirs for mobilization of entrapped oil. Chapters include: Ampholytic terpolymers of acrylamide with sodium 3-acrylamido-3-methylbutanoate and 2-acrylamido-2-methylpropanetrimethylammonium chloride; Hydrophilic sulfobetaine copolymers of acrylamide and 3-(2-acrylamido-methylpropane-dimethylammonio)-1-propanesulfonate; Copolymerization of maleic anhydride and N-vinylformamide; Reactivity ratio of N-vinylformamide with acrylamide, sodium acrylate, and n-butyl acrylate; Effect of the distribution of the hydrophobic cationic monomer dimethyldodecyl(2-acrylamidoethyl)ammonium bromide on the solution behavior of associating acrylamide copolymers; Effect of surfactants on the solution properties of amphipathic copolymers of acrylamide and N,N-dimethyl-N-dodecyl-N-(2-acrylamidoethyl)ammonium bromide; Associative interactions and photophysical behavior of amphiphilic terpolymers prepared by modification of maleic anhydride/ethyl vinyl ether copolymers; Copolymer compositions of high-molecular-weight functional acrylamido water-soluble polymers using direct-polarization magic-angle spinning {sup 13}C NMR; Use of factorial experimental design in static and dynamic light scattering characterization of water soluble polymers; and Porous medium elongational rheometer studies of NaAMB/AM copolymer solutions.

  9. Multiblock Copolymers of Styrene and Butyl Acrylate via Polytrithiocarbonate-Mediated RAFT Polymerization

    Directory of Open Access Journals (Sweden)

    Bastian Ebeling

    2011-03-01

    Full Text Available When linear polytrithiocarbonates as Reversible Addition-Fragmentation chain Transfer (RAFT agents are employed in a radical polymerization, the resulting macromolecules consist of several homogeneous polymer blocks, interconnected by the functional groups of the respective RAFT agent. Via a second polymerization with another monomer, multiblock copolymers—polymers with alternating segments of both monomers—can be prepared. This strategy was examined mechanistically in detail based on subsequent RAFT polymerizations of styrene and butyl acrylate. Size-exclusion chromatography (SEC of these polymers showed that the examined method yields low-disperse products. In some cases, resolved peaks for molecules with different numbers of blocks (polymer chains separated by the trithiocarbonate groups could be observed. Cleavage of the polymers at the trithiocarbonate groups and SEC analysis of the products showed that the blocks in the middle of the polymers are longer than those at the ends and that the number of blocks corresponds to the number of functional groups in the initial RAFT agent. Furthermore, the produced multiblock copolymers were analyzed via differential scanning calorimetry (DSC. This work underlines that the examined methodology is very well suited for the synthesis of well-defined multiblock copolymers.

  10. Synthesis and Characterization of Organotin Containing Copolymers: Reactivity Ratio Studies

    Directory of Open Access Journals (Sweden)

    Mohamed H. El-Newehy

    2010-03-01

    Full Text Available Organotin monomers containing dibutyltin groups – dibutyltin citraconate (DBTC as a new monomer and dibutyltin maleate (DBTM – were synthesized. Free radical copolymerizations of the organotin monomers with styrene (ST and butyl acrylate (BA were performed. The overall conversion was kept low (≤15% wt/wt for all studied samples and the copolymers composition was determined from tin analysis using the Gillman and Rosenberg method. The reactivity ratios were calculated from the copolymer composition using the Fineman-Ross (FR method. The synthesized monomers were characterized by elemental analysis, 1H-, 13C-NMR and FTIR spectroscopy.

  11. Thin Films of Novel Linear-Dendritic Diblock Copolymers

    Science.gov (United States)

    Iyer, Jyotsna; Hammond, Paula

    1998-03-01

    A series of diblock copolymers with one linear block and one dendrimeric block have been synthesized with the objective of forming ultrathin film nanoporous membranes. Polyethyleneoxide serves as the linear hydrophilic portion of the diblock copolymer. The hyperbranched dendrimeric block consists of polyamidoamine with functional end groups. Thin films of these materials made by spin casting and the Langmuir-Blodgett techniques are being studied. The effect of the polyethylene oxide block size and the number and chemical nature of the dendrimer end group on the nature and stability of the films formed willbe discussed.

  12. Polymers and block copolymers of fluorostyrenes by ATRP

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Borkar, Sachin; Abildgaard, Lillian

    2002-01-01

    Fully or partly fluorinated polymers have many desirable and intriguing properties. In the framework of a larger program on design and control of new functional block copolymers we recently employed the Atom Transfer Radical Polymerization (ATRP) protocol on 2,3,4,5,6-pentafluorostyrene (FS). We...... materials based on 2,3,5,6-tetrafiuoro-4-methoxy-styrene (TFMS). TFMS homopolymers as well as diblock copolymers with FS are produced by ATRP. Both types of novel polymers were subsequently demethylated and different side chains introduced on the resulting hydroxy sites....

  13. Chemical etching of fission tracks in ethylene-tetrafluoroethylene copolymer

    International Nuclear Information System (INIS)

    Komaki, Y.; Tsujimura, S.; Seguchi, T.

    1979-01-01

    The chemical etching of fission tracks in ethylene-tetrafluoroethylene copolymer was studied. Etched holes 3000 to 4000 A in diameter were recognized by electron microscopy for a film bombarded by fission fragments in oxygen and etched in a 12N sodium hydroxide solution at 125 0 C. The radial etching rate at 125 0 C was 6 to 8 A/hr, which is less than 17 A/hr for polyvinylidene fluoride in the same sodium hydroxide concentration at 85 0 C. The smaller rate is a reflection of the larger chemical resistivity of ethylene-tetrafluoroethylene copolymer than polyvinylidene fluoride. (author)

  14. Organisation and shape of micellar solutions of block copolymers

    Science.gov (United States)

    Gaspard, J. P.; Creutz, S.; Bouchat, Ph.; Jérôme, R.; Cohen Stuart, M.

    1997-02-01

    Diblock copolymers of polymethacrylic acid sodium salt, forming the hair, and styrene derivatives have been studied in aqueous solutions by SANS and SAXS. The influence of both the chemical nature and the length of the hydrophobic bloxk on the size and shape of micelles have been investigated. The micellar core size is in agreement with the theoretical evaluation for copolymers with a short hydrophobic sequence. In contrast, in case of larger hydrophobic blocks, the measured size is incompatible with a star-like model. Various hypotheses are presented for the latter.

  15. Thermal and radiochemical degradation of some PAN copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Jipa, S. [INCDIE, ICPE CA, 313 Splaiul Unirii, P.O. Box 149, Bucharest 030138 (Romania); ' Valachia' University of Targoviste, 18-22 Unirii Av., Targoviste 130082 (Romania); Zaharescu, T. [' Valachia' University of Targoviste, 18-22 Unirii Av., Targoviste 130082 (Romania)], E-mail: traian_zaharescu@yahoo.com; Setnescu, R. [INCDIE, ICPE CA, 313 Splaiul Unirii, P.O. Box 149, Bucharest 030138 (Romania); ' Valachia' University of Targoviste, 18-22 Unirii Av., Targoviste 130082 (Romania); Dragan, E.S.; Dinu, M.V. [' Petru Poni' Institute of Macromolecular Chemistry, Iasi 700487 (Romania)

    2008-12-01

    Polyacrylonitrile (PAN) and some copolymers of acrylonitrile with divinylbenzene (AN-DVB) were investigated by the characterization of their thermal and radiation stabilities. The contribution of DVB to the thermal stability of PAN by the modification in the amount of unsaturated hydrocarbon between 6 and 20% was revealed by the evaluation of oxidation induction periods and required activation energies. The exposure of these materials to the action of {gamma}-radiation points out the higher stability of copolymers (AN-DVB) in comparison to the relative stability of PAN.

  16. Nanoporous Crosslinked Polyisoprene from Polyisoprene-Polydimethylsiloxane Block Copolymer

    DEFF Research Database (Denmark)

    Hansen, Michael Steffen; Vigild, Martin Etchells; Berg, Rolf Henrik

    2004-01-01

    The polyisoprene block of a polyisoprene-polydimethylsiloxane (PI-PDMS) diblock copolymer with 0.68 volume fraction of PI was tightly crosslinked with dicumylperoxide. The PDMS part of the obtained glassy material was subsequently quantitatively etched with anhydrous hydrogen fluoride or tetrabut......The polyisoprene block of a polyisoprene-polydimethylsiloxane (PI-PDMS) diblock copolymer with 0.68 volume fraction of PI was tightly crosslinked with dicumylperoxide. The PDMS part of the obtained glassy material was subsequently quantitatively etched with anhydrous hydrogen fluoride...

  17. POLYCAPROLACTONE-POLY (ETHYLENE GLYCOL) BLOCK COPOLYMER Ⅲ DRUG RELEASE BEHAVIOR

    Institute of Scientific and Technical Information of China (English)

    BEI Jianzhong; WANG Zhifeng; WANG Shenguo

    1995-01-01

    The drug release behavior of degradable polymer - polycaprolactone-poly (ethylene glycol)block copolymer(PCE) in vitro was investigated by using 5-Fluoro-uracil (5-Fu) as a model drug under a condition of pH 7.4 at 37℃. It is found that the release rate of 5-Fu from PCE increased with increasing polyether content of the copolymer. The results show that the increasing polyether content of the copolymer caused increasing hydrophilicity and decreasing crystallinity of the PCE copolymer. Thus, the drug release behavior and the degradable property of the PCE can be controlled by adjusting the composition of the copolymer.

  18. STUDIES ON POLY (ETHYLENE TEREPHTHALATE)- POLY ( TETRAMETHYLENE ETHER ) MULTIBLOCK COPOLYMER.Ⅰ. COM POSITIONAL HOMOGENEITY

    Institute of Scientific and Technical Information of China (English)

    ZHAN Yongjian; YING Qicong; WU Meiyan; QIAN Renyuan

    1991-01-01

    The compositional homogeneity of a poly (ethylene terephthalate )-poly (tetramethylene ether)multiblock copolymer sample with low content of hard segment was examined by GPC, TLC, and solubility method. The copolymer sample was found to have a uniform composition as a function of elution volume over the major portion of sample from GPC method. However within one elution fraction, the copolymer chains, although having the same hydrodynamic volume, may have some difference in composition. Two fractions with different composition were obtained by precipitation in ethanol. Some low molar mass copolymers were also separated by a TLC technique from the copolymer sample.

  19. SYNTHESIS OF STYRENE-METHYL METHACRYLATE BLOCK COPOLYMER BY POLYAZOAMIDE AS INITIATOR

    Institute of Scientific and Technical Information of China (English)

    WANG Zhongyi; WEI Jeqing

    1996-01-01

    Polyazoamide(PAA) was used as initiator to prepare block copolymer P(MMA-b-St) by free radical polymerization. The fraction of block copolymer was about 50%. The structure of the block-copolymer was characterized by IR and the results of 1H-NMR and GPC showed that the content of the block and the molecular weight (-Mw) of the prepolymer and block copolymer could be controlled by varying the mol ratio of styrene/PAA and MMA/prepolymer. DSC and TEM results revealed that the block copolymer has two separated glass transition temperatures and phase separation within the domain structure.

  20. Research Update: Triblock copolymers as templates to synthesize inorganic nanoporous materials

    Directory of Open Access Journals (Sweden)

    Yunqi Li

    2016-04-01

    Full Text Available This review focuses on the application of triblock copolymers as designed templates to synthesize nanoporous materials with various compositions. Asymmetric triblock copolymers have several advantages compared with symmetric triblock copolymers and diblock copolymers, because the presence of three distinct domains can provide more functional features to direct the resultant nanoporous materials. Here we clearly describe significant contributions of asymmetric triblock copolymers, especially polystyrene-block-poly(2-vinylpyridine-block-poly(ethylene oxide (abbreviated as PS-b-P2VP-b-PEO.

  1. Morphology and electrical properties of electrochemically synthesized pyrrole–formyl pyrrole copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Gholami, Mehrdad, E-mail: mehrdad897@um.edu.my [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Department of Chemistry, Marvdasht Branch, Islamic Azad University, P.O. Box 465, Marvdasht (Iran, Islamic Republic of); Nia, Pooria Moozarm, E-mail: pooriamn@yahoo.com [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Alias, Yatimah, E-mail: yatimah70@um.edu.my [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia)

    2015-12-01

    Graphical abstract: - Highlights: • The (Py–co-FPy) copolymer was synthesized electrochemically. • This copolymer has 1.6 times higher surface coverage compared to polypyrrole. • This copolymer showed 2.5 times lower resistance compared to polypyrrole. • The conjugated structure between Py and FPy causes enhancement of conductivity. • This conducting copolymer has a strong potential to be used in various applications. - Abstract: A direct electrochemical copolymerization of pyrrole–formyl pyrrole (Py–co-FPy) was carried out by oxidative copolymerization of formyl pyrrole and pyrrole in LiClO{sub 4} aqueous solution through galvanostatic method. The (Py–co-FPy) copolymer was characterized using Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FESEM), energy-filtering transmission electron microscope (EFTEM), thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The FESEM images showed that the synthesized copolymer had a hollow whelk-like helixes structure, which justifies the enhancement of charge transportation through the copolymer film. Cyclic voltammetry studies revealed that the electrocatalytic activity of synthesized copolymer has improved and the surface coverage in copolymer enhanced 1.6 times compared to polypyrrole alone. Besides, (Py–co-FPy) copolymer showed 2.5 times lower electrochemical charge transfer resistance (R{sub ct}) value in impedance spectroscopy. Therefore, this copolymer has a strong potential to be used in several applications such as sensor applications.

  2. Anhydric maleic functionalization and polyethylene glycol grafting of lactide-co-trimethylene carbonate copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Díaz, A.; Valle, L.; Franco, L. del [Departament d' Enginyeria Química, Universitat Politècnica de Catalunya, Av. Diagonal 647, Barcelona E-08028 (Spain); Sarasua, J.R. [Department of Mining-Metallurgy Engineering and Materials Science, University of the Basque Country (UPV/EHU), Bilbao (Spain); Estrany, F. [Departament d' Enginyeria Química, Universitat Politècnica de Catalunya, Av. Diagonal 647, Barcelona E-08028 (Spain); Puiggalí, J., E-mail: Jordi.Puiggali@upc.es [Department of Mining-Metallurgy Engineering and Materials Science, University of the Basque Country (UPV/EHU), Bilbao (Spain)

    2014-09-01

    Lactide and trimethylene carbonate copolymers were successfully grafted with polyethylene glycol via previous functionalization with maleic anhydride and using N,N′-diisopropylcarbodiimide as condensing agent. Maleinization led to moderate polymer degradation. Specifically, the weight average molecular weight decreased from 36,200 to 30,200 g/mol for the copolymer having 20 mol% of trimethylene carbonate units. Copolymers were characterized by differential scanning calorimetry, thermogravimetry and X-ray diffraction. Morphology of spherulites and lamellar crystals was evaluated with optical and atomic force microscopies, respectively. The studied copolymers were able to crystallize despite the randomness caused by the trimethylene carbonate units and the lateral groups. Contact angle measurements indicated that PEG grafted copolymers were more hydrophilic than parent copolymers. This feature justified that enzymatic degradation in lipase medium and proliferation of both epithelial-like and fibroblast-like cells were enhanced. Grafted copolymers were appropriate to prepare regular drug loaded microspheres by the oil-in-water emulsion method. Triclosan release from loaded microspheres was evaluated in two media. - Highlights: • Pegylated copolymers of lactide and trimethylene carbonate have been synthesized. • Grafting with polyethylene glycol was able via maleic anhydride functionalization. • Drug-loaded microspheres could be prepared from new pegylated copolymers. • Hydrophilicity of lactide/trimethylene carbonate copolymers increased by pegylation. • New pegylated copolymers supported cell adhesion and proliferation.

  3. Amphiphilic star block copolymers as gene carrier Part I: Synthesis via ATRP using calix[4]resorcinarene-based initiators and characterization

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Anna; Xue, Yan; Wei, Dafu [Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Guan, Yong, E-mail: yguan@ecust.edu.cn [Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Xiao, Huining [Department of Chemical Engineering, University of New Brunswick, Fredericton, New Brunswick, Canada E3B 5A3 (Canada)

    2013-01-01

    In this work, a cationic star polymer [poly(2-dimethylamino)ethyl methacrylate (PDMAEMA)] was prepared via atom transfer radical polymerization (ATRP), using brominated calix[4]resorcinarene as an initiator. Hydrophobic moieties, methyl methacrylate (MMA) and butyl acrylate (BA), were further incorporated via 'one-pot' method. Well-defined eight-armed star block copolymers bearing hydrophilic blocks inside and hydrophobic blocks outside were synthesized. The molecular weight, particle size, electrophoretic mobility and apparent charge density were determined by gel permeation chromatography (GPC), dynamic light scattering (DLS), phase analysis light scattering (PALS) and colloidal titration, respectively. The zeta potentials and apparent charge densities of the products exhibited the characteristics of polyelectrolyte. The incorporation of hydrophobic moieties generated electrostatic screening effect. The as-synthesized amphiphilic star copolymer is promising as a thermo-sensitive gene carrier for gene therapy. Highlights: Black-Right-Pointing-Pointer Amphiphilic cationic star block copolymers with well-controlled structures were prepared via ATRP. Black-Right-Pointing-Pointer The molecular structures and properties of the initiator and copolymers were systematically characterized. Black-Right-Pointing-Pointer The products exhibited the positive charged character, and hydrophobic moieties generated electrostatic screening effect.

  4. Inhomogeneity of block copolymers at the interface of an immiscible polymer blend

    Science.gov (United States)

    Ryu, Ji Ho; Kim, YongJoo; Lee, Won Bo

    2018-04-01

    We present the effects of structure and stiffness of block copolymers on the interfacial properties of an immiscible homopolymer blend. Diblock and two-arm grafted copolymers with variation in stiffness are modeled using coarse-grained molecular dynamics to compare the compatibilization efficiency, i.e., reduction of interfacial tension. Overall, grafted copolymers are located more compactly at the interface and show better compatibilization efficiency than diblock copolymers. In addition, an increase in the stiffness for one of the blocks of the diblock copolymers causes unusual inhomogeneous interfacial coverage due to bundle formation. However, an increase in the stiffness for one of blocks of the grafted copolymers prevents the bundle formation due to the branched chain. As a result, homogeneous interfacial coverage of homopolymer blends is realized with significant reduction of interfacial tension which makes grafted copolymer a better candidate for the compatibilizer of immiscible homopolymer blend.

  5. Synthesis of polyaniline catalysed by Cu(I), Ni(II) and Fe(II) supported on the polyethylene-i-acrylic acid copolymer; Sintesis de polianilina catalizada por Cu(I), Ni(II) y Fe(II), soportados en el copolimero polietileno-i-acido acrilico

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez, L.; Urena, F.; Lopez, R. [Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

    1997-07-01

    In this study the active sites of acrylic acid (AA) were grafted in low density polyethylene (PEBD) using gamma radiation. Subsequently, the graft copolymer PEBD-i-AA was coordinated with different metals such as copper, nickel and iron. The organometallic copolymers so formed were used as catalysts in the aniline polymerization reaction. Finally, it was realized the characterization of the obtained products, determining their thermal properties, copolymer graft percentage, quantification of the metal contained in the complex as well as polymerization and electric conductivity percentages of the poly aniline film. (Author)

  6. Influence of sludge retention time on tolerance of copper toxicity for polyphosphate accumulating organisms linked to polyhydroxyalkanoates metabolism and phosphate removal.

    Science.gov (United States)

    Tsai, Yung-Pin; Chen, Hsiu-Ting

    2011-12-01

    This study explored the influence of sludge retention time (SRT) on tolerance of copper invasion for polyphosphate accumulating organisms (PAOs) in an enhanced biological phosphorus removal (EBPR). The experimental data showed the anaerobic polyhydroxyalkanoates (PHA) storage for the sludge at 10d SRT was less influenced by copper invasion than those at 5d and 15d SRTs. The reaction of PAOs aerobically taking up phosphate for the sludge at 5d or 15d SRT almost ceased at 2 mg Cu L(-1), whereas PAOs in the sludge at 10d SRT retained half of the ability to take up phosphate. Both the PHAs degradation and synthesis rates decreased with increasing copper concentration, regardless of the SRTs. However, the copper inhibition of the former was greater than that of the later. Copyright © 2011 Elsevier Ltd. All rights reserved.

  7. Enhancing the stability of colloidal silver nanoparticles using polyhydroxyalkanoates (PHA) from Bacillus circulans (MTCC 8167) isolated from crude oil contaminated soil.

    Science.gov (United States)

    Phukon, Pinkee; Saikia, Jyoti Prasad; Konwar, Bolin Kumar

    2011-09-01

    Polyhydroxyalkanoate (PHA) was produced by growing Bacillus circulans (MTCC 8167) in the specific detection medium. The identification of the polymer as PHA was confirmed by fluorescence microscopy. The PHA was purified and characterized using FT-IR. The silver nanoparticles (SNP) were synthesized from AgNO3 in the dispersed colloids of PHA (0.085%) using NaBH4 (sodium borohydrate as reducing agent). The stability was tested using wave length scanning with a UV-Vis spectrophotometer and finally with transmission electron microscopy. The PHA stabilized solution was found to be stable for 30 days as against the low stability of silver nanoparticles (SNP) solution alone. Copyright © 2011 Elsevier B.V. All rights reserved.

  8. Monte Carlo simulation of AB-copolymers with saturating bonds

    DEFF Research Database (Denmark)

    Chertovich, A.C.; Ivanov, V.A.; Khokhlov, A.R.

    2003-01-01

    Structural transitions in a single AB-copolymer chain where saturating bonds can be formed between A- and B-units are studied by means of Monte Carlo computer simulations using the bond fluctuation model. Three transitions are found, coil-globule, coil-hairpin and globule-hairpin, depending...

  9. Asymmetric block copolymers confined in a thin film

    NARCIS (Netherlands)

    Huinink, HP; Brokken-Zijp, JCM; van Dijk, MA; Sevink, GJA

    2000-01-01

    We have used a dynamic density functional theory (DDFT) for polymeric systems, to simulate the formation of micro phases in a melt of an asymmetric block copolymer, A(n)B(m)(f(A) = 1/3), both in the bulk and in a thin film. In the DDFT model a polymer is represented as a chain of springs and beads.

  10. Diblock Copolymer/Layered Silicate Nanocomposite Thin Film Stability

    Science.gov (United States)

    Limary, Ratchana; Green, Peter

    2000-03-01

    The stability of thin film symmetric diblock copolymers blended with layered silicate nanocomposites were examined using a combination of optical microscopy, atomic force microscopy (AFM), and X-ray diffraction (XRD). Two cases were examined PS-b-PMMA (polystyrene-b-polymethylacrylate) blended with montmorillonite stoichiometrically loaded with alkyl ammonium ions, OLS(S), and PS-b-PMMA blended with montmorillonite loaded with excess alkyl ammonium ions, OLS(E). XRD spectra show an increase in the gallery spacing of the OLSs, indicating that the copolymer chains have intercalated the layered silicates. AFM images reveal a distinct difference between the two nanocomposite thin films: regions in the vicinity of OLS(S) aggregates were depleted of material, while in the vicinity of OLS(E) aggregates, dewetting of the substrate occurred. We show that the stability of the copolymer/OLS nanocomposite films is determined by the enthalpic driving force associated with intercalation of the copolymer chains into the galleries of the modified OLS layers and by the substrate/organic modifier interactions.

  11. Functional (co)polymers from carbenes: scope, mechanism & polymer properties

    NARCIS (Netherlands)

    Franssen, N.M.G.

    2012-01-01

    Polymerization of carbenes is a valuable alternative to traditional olefin polymerization with regard to the formation of high molecular-weight functional copolymers in a stereoregular way. The versatility of this reaction with respect to different carbene precursors allows the formation of a large

  12. Linear low density polyethylene/cycloolefin copolymer blends

    Czech Academy of Sciences Publication Activity Database

    Dorigato, A.; Pegoretti, A.; Fambri, L.; Lonardi, C.; Šlouf, Miroslav; Kolařík, Jan

    2011-01-01

    Roč. 5, č. 1 (2011), s. 23-37 ISSN 1788-618X R&D Projects: GA ČR GA106/09/1348 Institutional research plan: CEZ:AV0Z40500505 Keywords : polymer blends * cycloolefin copolymer * creep Subject RIV: JI - Composite Materials Impact factor: 1.769, year: 2011

  13. Epoxy-crosslinked sulfonated poly (phenylene) copolymer proton exchange membranes

    Science.gov (United States)

    Hibbs, Michael; Fujimoto, Cy H.; Norman, Kirsten; Hickner, Michael A.

    2010-10-19

    An epoxy-crosslinked sulfonated poly(phenylene) copolymer composition used as proton exchange membranes, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cell, in electrode casting solutions and electrodes, and in sulfur dioxide electrolyzers. These improved membranes are tougher, have higher temperature capability, and lower SO.sub.2 crossover rates.

  14. Tough, semiconducting polyethylene-poly(3-hexylthiophene) diblock copolymers

    DEFF Research Database (Denmark)

    Müller, C.; Goffri, S.; Breiby, Dag Werner

    2007-01-01

    Semiconducting diblock copolymers of polyethylene (PE) and regioregular poly(3-hexylthiophene) (P3HT) are demonstrated to exhibit a rich phase behaviour, judicious use of which permitted us to fabricate field-effect transistors that show saturated charge carrier mobilities, mu(FET), as high as 2 x...

  15. Poly(bisphenol A carbonate) - poly(dimethylsiloxane) multiblock copolymers

    NARCIS (Netherlands)

    Aert, van H.A.M.; Nelissen, L.N.I.H.; Lemstra, P.J.; Brunelle, D.J.

    2001-01-01

    A versatile technique for the synthesis of multiblock copolymers of polydimethylsiloxane (PDMS) and poly(bisphenol A carbonate) (PC) is described. Specific reaction of the phenol end groups of a,¿-bis(bisphenol A)-terminated PDMS with the activated end groups of

  16. Isotropic Lifshitz behavior in block copolymer-homopolymer blends

    DEFF Research Database (Denmark)

    Bates, F.S.; Maurer, W.; Lodge, T.P.

    1995-01-01

    A series of mixtures composed of a symmetric A-B diblock copolymer and a symmetric blend of A and B homopolymers was investigated by small-angle neutron scattering. Mean-field theory predicts that a line of lamellar-disorder transitions with wave-vector instability q* > 0 will meet a line of crit...

  17. 21 CFR 175.210 - Acrylate ester copolymer coating.

    Science.gov (United States)

    2010-04-01

    ... ester copolymer coating may safely be used as a food-contact surface of articles intended for packaging..., and methacrylic acid applied in emulsion form to molded virgin fiber and heat-cured to an insoluble... application of the emulsion may include substances named in this paragraph, in an amount not to exceed that...

  18. Block copolymer-nanoparticle hybrid self-assembly

    KAUST Repository

    Hoheisel, Tobias N.; Hur, Kahyun; Wiesner, Ulrich B.

    2015-01-01

    © 2014 Published by Elsevier Ltd. Polymer-inorganic hybrid materials provide exciting opportunities as they may display favorable properties from both constituents that are desired in applications including catalysis and energy conversion and storage. For the preparation of hybrid materials with well-defined morphologies, block copolymer-directed nanoparticle hybrids present a particularly promising approach. As will be described in this review, once the fundamental characteristics for successful nanostructure formation at or close to the thermodynamic equilibrium of these nanocomposites are identified, the approach can be generalized to various materials classes. In addition to the discussion of recent materials developments based on the use of AB diblock copolymers as well as ABC triblock terpolymers, this review will therefore emphasize progress in the fundamental understanding of the underlying formation mechanisms of such hybrid materials. To this end, critical experiments for, as well as theoretical progress in the description of these nanostructured block copolymer-based hybrid materials will be discussed. Rather than providing a comprehensive overview, the review will emphasize work by the Wiesner group at Cornell University, US, on block copolymer-directed nanoparticle assemblies as well as their use in first potential application areas. The results provide powerful design criteria for wet-chemical synthesis methodologies for the generation of functional nanomaterials for applications ranging from microelectronics to catalysis to energy conversion and storage.

  19. Spectral Signatures of Polarons in Conjugated Co-polymers

    NARCIS (Netherlands)

    Wiebeler, Christian; Tautz, Raphael; Feldmann, Jochen; von Hauff, Elizabeth; Da Como, Enrico; Schumacher, Stefan

    2013-01-01

    We study electronic and optical properties of the low-bandgap co-polymer PCPDT-BT (poly-cyclopentadithiophene-co-benzothiadiazole) and compare it with the corresponding homo-polymer PCPDT (poly-cyclopentadithiophene). We investigate the linear absorptivity in these systems for neutral molecules and

  20. Influence of Chirality in Ordered Block Copolymer Phases

    Science.gov (United States)

    Prasad, Ishan; Grason, Gregory

    2015-03-01

    Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

  1. Fast assembly of ordered block copolymer nanostructures through microwave annealing.

    Science.gov (United States)

    Zhang, Xiaojiang; Harris, Kenneth D; Wu, Nathanael L Y; Murphy, Jeffrey N; Buriak, Jillian M

    2010-11-23

    Block copolymer self-assembly is an innovative technology capable of patterning technologically relevant substrates with nanoscale precision for a range of applications from integrated circuit fabrication to tissue interfacing, for example. In this article, we demonstrate a microwave-based method of rapidly inducing order in block copolymer structures. The technique involves the usage of a commercial microwave reactor to anneal block copolymer films in the presence of appropriate solvents, and we explore the effect of various parameters over the polymer assembly speed and defect density. The approach is applied to the commonly used poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) and poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) families of block copolymers, and it is found that the substrate resistivity, solvent environment, and anneal temperature all critically influence the self-assembly process. For selected systems, highly ordered patterns were achieved in less than 3 min. In addition, we establish the compatibility of the technique with directed assembly by graphoepitaxy.

  2. Oriented Structure of Pentablock Copolymers Induced by Solution Extrusion

    Science.gov (United States)

    Harada, Tamotsu; Bates, Frank S.; Lodge, Timothy P.

    2002-03-01

    Highly oriented structure of a poly(styrene-co-butadiene) pentablock copolymer (Mw; 104,700 g/mol, weight percentage of polybutadiene blocks; 29 wt of concentrated solutions. The pentablock copolymer was dissolved into mixtures of toluene and heptane, and the polymer concentration ranged from 40 wt extrusion, the pentablock copolymer was solidified either by coagulation in methanol or by evaporation of the solvent. Interestingly, a highly oriented lamellar structure was confirmed through the small angle X-ray scattering over a specific range of heptane composition, which is a good solvent for polybutadiene, although the hexagonal cylinder morphology was identified for the melt sample. The transition from the oriented lamellar to highly oriented cylinder structure was observed by annealing the samples at temperatures above the glass transition temperature of polystyrene. Moreover, a transition from parallel to perpendicular orientation in the lamellar state was observed with an increase of the extrusion shear rate. A comparison between pentablock and triblock copolymers will be also discussed.

  3. Protein resistance of dextran and dextran-PEG copolymer films

    Science.gov (United States)

    Kozak, Darby; Chen, Annie; Bax, Jacinda; Trau, Matt

    2011-01-01

    The protein resistance of dextran and dextran-poly(ethylene glycol) (PEG) copolymer films was examined on an organosilica particle-based assay support. Comb-branched dextran-PEG copolymer films were synthesized in a two step process using the organosilica particle as a solid synthetic support. Particles modified with increasing amounts (0.1-1.2 mg m−2) of three molecular weights (10 000, 66 900, 400 000 g mol−1) of dextran were found to form relatively poor protein-resistant films compared to dextran-PEG copolymers and previously studied PEG films. The efficacy of the antifouling polymer films was found to be dependent on the grafted amount and its composition, with PEG layers being the most efficient, followed by dextran-PEG copolymers, and dextran alone being the least efficient. Immunoglobulin gamma (IgG) adsorption decreased from ~ 5 to 0.5 mg m−2 with increasing amounts of grafted dextran, but bovine serum albumin (BSA) adsorption increased above monolayer coverage (to ~2 mg m−2) indicating ternary adsorption of the smaller protein within the dextran layer. PMID:21614699

  4. Nanoporous Network Channels from Self-Assembled Triblock Copolymer Supramolecules

    NARCIS (Netherlands)

    du Sart, Gerrit Gobius; Vukovic, Ivana; Vukovic, Zorica; Polushkin, Evgeny; Hiekkataipale, Panu; Ruokolainen, Janne; Loos, Katja; ten Brinke, Gerrit

    2011-01-01

    Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded

  5. Resonant soft x-ray GISAXS on block copolymer films

    Science.gov (United States)

    Wang, Cheng; Araki, T.; Watts, B.; Ade, H.; Hexemer, A.; Park, S.; Russell, T. P.; Schlotter, W. F.; Stein, G. E.; Tang, C.; Kramer, E. J.

    2008-03-01

    Ordered block copolymer thin films may have important applications in modern device fabrication. Current characterization methods such as conventional GISAXS have fixed electron density contrast that can be overwhelmed by surface scattering. However, soft x-rays have longer wavelength, energy dependent contrast and tunable penetration, making resonant GISAXS a very promising tool for probing nanostructured polymer thin films. Our preliminary investigation was performed using PS-b-P2VP block copolymer films on beam-line 5-2 SSRL, and beam-line 6.3.2 at ALS, LBNL. The contrast/sensitivity of the scattering pattern varies significantly with photon energy close to the C K-edge (˜290 eV). Also, higher order peaks are readily observed, indicating hexagonal packing structure in the sample. Comparing to the hard x-ray GISAXS data of the same system, it is clear that resonant GISAXS has richer data and better resolution. Beyond the results on the A-B diblock copolymers, results on ABC block copolymers are especially interesting.

  6. Multiple ordered phases in a block copolymer melt

    DEFF Research Database (Denmark)

    Almdal, K.; Koppi, K.A.; Bates, F.S.

    1992-01-01

    A poly(ethylenepropylene)-poly(ethylethylene) (PEP-PEE) diblock copolymer containing 65% by volume PEP was investigated using small-angle neutron scattering (SANS) and rheological measurements. Four distinct phases have been identified as a function of temperature: three ordered phases at low...

  7. Copolymer adsorption and the effect on colloidal stability

    NARCIS (Netherlands)

    Bijsterbosch, H.D.

    1998-01-01

    The main aim of the work described in this thesis is to study the effect of different types of copolymers on the stability of aqueous oxide dispersions. Such dispersions are a major component in water-borne paints. In order to obtain a better insight in steric stabilisation we first investigated the

  8. Responsive copolymers for enhanced petroleum recovery. Annual report

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.

    1994-08-01

    A coordinated research program involving synthesis, characterization, and rheology has been undertaken to develop advanced polymer system which should be significantly more efficient than polymers presently used for mobility control and conformance. Unlike the relatively inefficient, traditional EOR polymers, these advanced polymer systems possess microstructural features responsive to temperature, electrolyte concentration, and shear conditions. Contents of this report include the following chapters. (1) First annual report responsive copolymers for enhanced oil recovery. (2) Copolymers of acrylamide and sodium 3-acrylamido-3-methylbutanoate. (3) Terpolymers of NaAMB, Am, and n-decylacrylamide. (4) Synthesis and characterization of electrolyte responsive terpolymers of acrylamide, N-(4-butyl)phenylacrylamide, and sodium acrylate, sodium-2-acrylamido-2-methylpropanesulphonate or sodium-3-acrylamido-3-methylbutanoate. (5) Synthesis and solution properties of associative acrylamido copolymers with pyrensulfonamide fluorescence labels. (6) Photophysical studies of the solution behavior of associative pyrenesulfonamide-labeled polyacrylamides. (7) Ampholytic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate with [2-(acrylamido)-2-methypropyl]trimethylammonium chloride. (8) Ampholytic terpolymers of acrylamide with sodium 2-acrylamido-2-methylpropanesulphoante and 2-acrylamido-2-methylpropanetrimethyl-ammonium chloride and (9) Polymer solution extensional behavior in porous media.

  9. Electrochromic properties of a novel low band gap conductive copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Yigitsoy, Basak; Varis, Serhat; Tanyeli, Cihangir; Akhmedov, Idris M.; Toppare, Levent [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey)

    2007-07-10

    A copolymer of 2,5-di(thiophen-2-yl)-1-p-tolyl-1H-pyrrole (DTTP) with 3,4-ethylene dioxythiophene (EDOT) was electrochemically synthesized. The resultant copolymer P(DTTP-co-EDOT) was characterized via cyclic voltammetry, FTIR, SEM, conductivity measurements and spectroelectrochemistry. Copolymer film has distinct electrochromic properties. It has four different colors (chestnut, khaki, camouflage green, and blue). At the neutral state {lambda}{sub max} due to the {pi}-{pi}{sup *} transition was found to be 487 nm and E{sub g} was calculated as 1.65 eV. Double potential step chronoamperometry experiment shows that copolymer film has good stability, fast switching time (less than 1 s) and good optical contrast (20%). An electrochromic device based on P(DTTP-co-EDOT) and poly(3,4-ethylenedioxythiophene) (PEDOT) was constructed and characterized. The device showed reddish brown color at -0.6 V when the P(DTTP-co-EDOT) layer was in its reduced state; whereas blue color at 2.0 V when PEDOT was in its reduced state and P(DTTP-co-EDOT) layer was in its oxidized state. At 0.2 V intermediate green state was observed. Maximum contrast (%{delta}T) and switching time of the device were measured as 18% and 1 s at 615 nm. ECD has good environmental and redox stability. (author)

  10. Optical fibre Bragg grating recorded in TOPAS cyclic olefin copolymer

    DEFF Research Database (Denmark)

    Johnson, I.P.; Yuan, Scott Wu; Stefani, Alessio

    2011-01-01

    A report is presented on the inscription of a fibre Bragg grating into a microstructured polymer optical fibre fabricated from TOPAS cyclic olefin copolymer. This material offers two important advantages over poly (methyl methacrylate), which up to now has formed the basis for polymer fibre Bragg...

  11. Segmented block copolymers with monodisperse aramide end-segments

    NARCIS (Netherlands)

    Araichimani, A.; Gaymans, R.J.

    2008-01-01

    Segmented block copolymers were synthesized using monodisperse diaramide (TT) as hard segments and PTMO with a molecular weight of 2 900 g · mol-1 as soft segments. The aramide: PTMO segment ratio was increased from 1:1 to 2:1 thereby changing the structure from a high molecular weight multi-block

  12. Synthesis and characterization of a star shaped supramolecular block copolymer

    NARCIS (Netherlands)

    Meier, M.A.R.; Schubert, U.S.

    2004-01-01

    A novel 5-arm star shaped block copolymer consisting of an poly(ethylene glycol) inner block and an poly(e-caprolactone) outer block was prepd. by utilizing an 5-arm star shaped poly(ethylene glycol) macroinitiator for the controlled ring opening polymn. of e-caprolactone. Furthermore, the resulting

  13. 21 CFR 177.1830 - Styrene-methyl methacrylate copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene-methyl methacrylate copolymers. 177.1830 Section 177.1830 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Us...

  14. Synthesis and photooxidation of styrene copolymer bearing camphorquinone pendant groups

    Science.gov (United States)

    Moszner, Norbert; Lukáč, Ivan

    2012-01-01

    Summary (±)-10-Methacryloyloxycamphorquinone (MCQ) was synthesized from (±)-10-camphorsulfonic acid either by a known seven-step synthetic route or by a novel, shorter five-step synthetic route. MCQ was copolymerized with styrene (S) and the photochemical behavior of the copolymer MCQ/S was compared with that of a formerly studied copolymer of styrene with monomers containing the benzil (BZ) moiety (another 1,2-dicarbonyl). Irradiation (λ > 380 nm) of aerated films of styrene copolymers with monomers containing the BZ moiety leads to the insertion of two oxygen atoms between the carbonyl groups of BZ and to the formation of benzoyl peroxide (BP) as pendant groups on the polymer backbone. An equivalent irradiation of MCQ/S led mainly to the insertion of only one oxygen atom between the carbonyl groups of camphorquinone (CQ) and to the formation of camphoric anhydride (11) covalently bound to the polymer backbone. While the decomposition of pendant BP groups formed in irradiated films of styrene copolymers with pendant BZ groups leads to crosslinking, only small molecular-weight changes in irradiated MCQ/S were observed. PMID:22509202

  15. Styrene-divinylbenzene copolymer grafted with phosphonic acid dialkylesters

    Directory of Open Access Journals (Sweden)

    SMARANDA ILIESCU

    2004-12-01

    Full Text Available The functionalization of a crosslinked chloromethylated polystyrene 8% divinylbenzene copolymer with phosphonic ester groups is detailed. The reacton conditions were studied in order to determine the optimal conditions for obtaining only diesters. A statistical method for the calculation of the fraction of repetive units for the inited and final resin is proposed.

  16. Features of radiation chemical processes in ethylene-styrene copolymers

    International Nuclear Information System (INIS)

    Leshchenko, S.S.; Mal'tseva, A.P.; Iskakov, L.I.; Karpov, V.L.

    1976-01-01

    A study was made of statistical copolymers of ethylene with styrene to determine their structure and properties and radio-chemical transformations. The styrene content of the copolymers ranged from 1 to 85 mole%. The investigation covered non-irradiated copolymers and those irradiated with doses of 1-1000Mrad at room temperature and at liquid nitrogen temperature. It is shown that styrene units present in the CES inhibited all radio-chemical processes compared with PE irradiated under similar conditions. It is suggested that the radiation resistance of CES with styrene contents up to 10 mole % increases in the course of irradiation as a result of the formation of structures with a high degree of conjugation which are more capable of scattering absorbed energy than in the case of phenyl rings by themselves. The most promising of the CES examined is the one with a styrene content of 5 mole %. The mechanical properties of this copolymer are similar to those of PE, and its radiation resistance rises under service conditions in the presence of ionizing radiation

  17. 21 CFR 177.1820 - Styrene-maleic anhydride copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene-maleic anhydride copolymers. 177.1820 Section 177.1820 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use...

  18. Engineering new polypropylene copolymer for asphalt modification. Progettazione di un polimero a base polipropilenica adatto per la modifica dei bitumi

    Energy Technology Data Exchange (ETDEWEB)

    Giavarini, C.; Santarelli, M.L. (Rome Univ. (Italy). Dipt. di Ingegneria Chimica); Braga, V. (Himont Centro Ricerche ' G. Natta' , Ferrara (Italy))

    1993-04-01

    Polypropylene polymers: isotactic PP, random, heterophasic copolymer, ethylene-propylene rubber, are suitable as modifiers for road bitumens. Among the advantages of PP polymers, such as heterophasic polymers, prepared via synthesis, are good thermal and ageing resistance, and the fact that they can be easily tailored to the specific application. Various types of PP and EPR polymers, possibly blended, prepared or modified for this purpose, were mixed with bitumens to study the dispersion of the polymer, segregation characteristics, ageing and viscoelastic properties. The experimental results gave indications on the characteristics of a polyolefinic copolymer for bitumen modification. The PP based products applicable as bitumen modifiers are the heterophasic copolymers containing a substantial amounts of EPR, possibly modified to increase branching. For road bitumens with a penetration between 100 and 200 dmm, the average molecular weight of the polymer should be arranged to reach an intrinsic viscosity between about 1.5 and 2.0 dl/g. Partial branching (or partial crosslinking) of the chains in the PP-phase is helpful when not followed by EPR-phase crosslinking.

  19. Biodegradable blends of poly (lactic acid) (PLA) / polyhydroxybutrate (PHB) copolymer and its effects on rheological, thermal and mechanical properties

    Science.gov (United States)

    Sood, Nitin K.

    Poly (Lactic acid) is the most important plastic derived from the renewable resources. PLA based products have extensively been used in the medical industry. However, PLA has a few disadvantages such as inherent brittleness and low toughness despite a high modulus. A focus of this experiment was to study the improvement in toughness of PLA and to study the changes in thermal and rheological properties by blending PLA with a PHB copolymer. Where, PLA and PHB copolymer were melt blended using a twin screw Brabender extruder in the ratios of 100/0, 70/30, 50/50, 30/70, 0/100. Further, the blends were injection molded into tensile bar and impact bars for mechanical testing. Rheological properties were studied using a Galaxy capillary rheometer for melt viscosities and temperature dependence indicated a shear-thinning behavior along with power law model and consistency index. Blends were characterized to study the phase model using a differential scanning calorimetric (DSC), showed two separate phases. Mechanical properties were analyzed using a Tensile and Izod impact test indicating decrease in elastic modulus with increase in toughness and elongation as the PHB copolymer content was increased in the blend.

  20. Mechanism of co-nanoprecipitation of organic actives and block copolymers in a microfluidic environment

    International Nuclear Information System (INIS)

    Capretto, Lorenzo; Cheng Wei; Carugo, Dario; Katsamenis, Orestis L; Zhang Xunli; Hill, Martyn

    2012-01-01

    Microreactors have been shown to be a powerful tool for the production of nanoparticles (NPs); however, there is still a lack of understanding of the role that the microfluidic environment plays in directing the nanoprecipitation process. Here we investigate the mechanism of nanoprecipitation of block copolymer stabilized organic NPs using a microfluidic-based reactor in combination with computational fluid dynamics (CFD) modelling of the microfluidic implementation. The latter also accounts for the complex interplay between molecular and hydrodynamic phenomena during the nanoprecipitation process, in order to understand the hydrodynamics and its influence on the NP formation process. It is demonstrated that the competitive reactions result in the formation of two types of NPs, i.e., either with or without loading organic actives. The obtained results are interpreted by taking into consideration a new parameter representing the mismatching between the aggregations of the polymers and actives, which plays a decisive role in determining the size and polydispersity of the prepared hybrid NPs. These results expand the current understanding of the co-nanoprecipitation mechanism of active and block copolymer stabilizer, and on the role exerted by the microfluidic environment, giving information that could be translated to the emerging fields of microfluidic formation of NPs and nanomedicine. (paper)

  1. FTIR spectroscopy as an alternative tool for high gamma dose dosimetry using P(VDF-TrFE) fluorinated copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, Adriana S.; Liz, Otavio S., E-mail: asm@cdtn.b [Universidade Federal de Minas Gerais (DEN/UFMG), Belo Horizonte, MG (Brazil). Dept. de Engenharia Nuclear; Faria, Luiz O., E-mail: farialo@cdtn.b [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2011-07-01

    Poly(vinylidene fluoride) [PVDF] is a semicrystalline homopolymer and some of its fluorinated copolymer has demonstrated to have sensitiveness to high doses of ionizing radiation. We have recently proposed a semicrystalline fluorinated PVDF copolymer, the poly(vinylidene-trifluorethylene) [P(VDF-TrFE], as a candidate for measuring larger dose ranges. In fact, in these copolymers the optical absorption peak at 274 nm has been used to measure gamma doses ranging from 1.0 to 100.0 kGy and the melting latent heat, collected by differential scanning calorimetry (DSC), have been used to measure gamma doses from 1.0 to 1,000.0 kGy. In this paper, the infrared stretching vibration of radio-induced in-chain unsaturations (CH=CF) in P(VDF-TrFE) copolymers has been considered as an alternative tool for high dose dosimetric purposes. FTIR spectroscopic data revealed two optical absorption bands at 1754 cm{sup -1} and 1854 cm{sup -1} whose intensities are unambiguously related to gamma delivered doses ranging from 100.0 kGy to 1,000.0 kGy. Fading was evaluated one month after irradiation. The results indicate that the sample dose evaluation should be performed in the first two hours after being exposed to the radiation beam. The radio-induced formation of unsaturations was also investigated by ultraviolet and visible spectroscopy, which has confirmed the gradual increase of conjugated C=C bonds with the absorbed dose. Our results indicate that quantitative analysis of FTIR absorption bands is a useful tool to perform a product end-point dosimetry in radiation processing facilities that use high gamma dose irradiation. (author)

  2. Pyrolysis gas chromatographic study of homo polymers and copolymers of chlorotrifluoroethylene and styrene

    International Nuclear Information System (INIS)

    Rizvi, M.; Munir, A.

    1993-01-01

    Polymer degradation reactions have always been important for the development of thermally stable polymers. Among different available techniques, pyrolysis gas chromatography (PGC) has been used frequently to establish thermal stability and the plausible mechanism of degradation reactions. In the present work, homo polymers of chlorotrifluoroethylene (CTFE) and styrene and their copolymers were studied by PGC/IR for separation and identification of degraded products and to understand the degradation mechanism. Besides monomers, C/sub 2/H/sub 4/, C/sub 2/H/sub 2/, SiF/sub 4/, C/sub 6/H/sub 6/ C/sub 3/F/sub 5/Cl, C/sub 7/H sub 8/, C/sub 8/H/sub 10/ are the observed pyrolysis products. Mechanism for different degradation reactions have also been studied. (author)

  3. Characterization of a Novel Subgroup of Extracellular Medium-Chain-Length Polyhydroxyalkanoate Depolymerases from Actinobacteria

    Science.gov (United States)

    Gangoiti, Joana; Santos, Marta; Prieto, María Auxiliadora; de la Mata, Isabel; Llama, María J.

    2012-01-01

    Nineteen medium-chain-length (mcl) poly(3-hydroxyalkanoate) (PHA)-degrading microorganisms were isolated from natural sources. From them, seven Gram-positive and three Gram-negative bacteria were identified. The ability of these microorganisms to hydrolyze other biodegradable plastics, such as short-chain-length (scl) PHA, poly(ε-caprolactone) (PCL), poly(ethylene succinate) (PES), and poly(l-lactide) (PLA), has been studied. On the basis of the great ability to degrade different polyesters, Streptomyces roseolus SL3 was selected, and its extracellular depolymerase was biochemically characterized. The enzyme consisted of one polypeptide chain of 28 kDa with a pI value of 5.2. Its maximum activity was observed at pH 9.5 with chromogenic substrates. The purified enzyme hydrolyzed mcl PHA and PCL but not scl PHA, PES, and PLA. Moreover, the mcl PHA depolymerase can hydrolyze various substrates for esterases, such as tributyrin and p-nitrophenyl (pNP)-alkanoates, with its maximum activity being measured with pNP-octanoate. Interestingly, when poly(3-hydroxyoctanoate-co-3-hydroxyhexanoate [11%]) was used as the substrate, the main hydrolysis product was the monomer (R)-3-hydroxyoctanoate. In addition, the genes of several Actinobacteria strains, including S. roseolus SL3, were identified on the basis of the peptide de novo sequencing of the Streptomyces venezuelae SO1 mcl PHA depolymerase by tandem mass spectrometry. These enzymes did not show significant similarity to mcl PHA depolymerases characterized previously. Our results suggest that these distinct enzymes might represent a new subgroup of mcl PHA depolymerases. PMID:22865072

  4. Dynamic photoinduced realignment processes in photoresponsive block copolymer films: effects of the chain length and block copolymer architecture.

    Science.gov (United States)

    Sano, Masami; Shan, Feng; Hara, Mitsuo; Nagano, Shusaku; Shinohara, Yuya; Amemiya, Yoshiyuki; Seki, Takahiro

    2015-08-07

    A series of block copolymers composed of an amorphous poly(butyl methacrylate) (PBMA) block connected with an azobenzene (Az)-containing liquid crystalline (PAz) block were synthesized by changing the chain length and polymer architecture. With these block copolymer films, the dynamic realignment process of microphase separated (MPS) cylinder arrays of PBMA in the PAz matrix induced by irradiation with linearly polarized light was studied by UV-visible absorption spectroscopy, and time-resolved grazing incidence small angle X-ray scattering (GI-SAXS) measurements using a synchrotron beam. Unexpectedly, the change in the chain length hardly affected the realignment rate. In contrast, the architecture of the AB-type diblock or the ABA-type triblock essentially altered the realignment feature. The strongly cooperative motion with an induction period before realignment was characteristic only for the diblock copolymer series, and the LPL-induced alignment change immediately started for triblock copolymers and the PAz homopolymer. Additionally, a marked acceleration in the photoinduced dynamic motions was unveiled in comparison with a thermal randomization process.

  5. Poly(Lactic Acid) Hemodialysis Membranes with Poly(Lactic Acid)-block-Poly(2-Hydroxyethyl Methacrylate) Copolymer As Additive: Preparation, Characterization, and Performance.

    Science.gov (United States)

    Zhu, Lijing; Liu, Fu; Yu, Xuemin; Xue, Lixin

    2015-08-19

    Poly(lactic acid) (PLA) hemodialysis membranes with enhanced antifouling capability and hemocompatibility were developed using poly(lactic acid)-block-poly(2-hydroxyethyl methacrylate) (PLA-PHEMA) copolymers as the blending additive. PLA-PHEMA block copolymers were synthesized via reversible addition-fragmentation (RAFT) polymerization from aminolyzed PLA. Gel permeation chromatography (GPC) and (1)H-nuclear magnetic resonance ((1)H NMR) were applied to characterize the synthesized products. By blending PLA with the amphiphilic block copolymer, PLA/PLA-PHEMA membranes were prepared by nonsolvent induced phase separation (NIPS) method. Their chemistry and structure were characterized with X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and atomic force microscopy (AFM). The results revealed that PLA/PLA-PHEMA membranes with high PLA-PHEMA contents exhibited enhanced hydrophilicity, water permeability, antifouling and hemocompatibility. Especially, when the PLA-PHEMA concentration was 15 wt %, the water flux of the modified membrane was about 236 L m(-2) h(-1). Its urea and creatinine clearance was more than 0.70 mL/min, lysozyme clearance was about 0.50 mL/min, BSA clearance was as less as 0.31 mL/min. All the results suggest that PLA-PHEMA copolymers had served as effective agents for optimizing the property of PLA-based membrane for hemodialysis applications.

  6. Production of polyhydroxybutyrate in switchgrass

    Energy Technology Data Exchange (ETDEWEB)

    Somleva, Mariya N.; Snell, Kristi D.; Beaulieu, Julie; Peoples, Oliver P.; Garrison, Bradley; Patterson, Nii

    2013-07-16

    Transgenic plants, plant material, and plant cells for synthesis of polyhydroxyalkanoates, preferably poly(3-hydroxybutyrate) (also referred to a as PHB) are provided. Preferred plants that can be genetically engineered to produce PHB include plants that do not normally produce storage products such as oils and carbohydrates, and plants that have a C.sub.4 NAD-malic enzyme photosynthetic pathway. Such plants also advantageously produce lignocellulosic biomass that can be converted into biofuels. An exemplary plant that can be genetically engineered to produce PHB and produce lignocellulosic biomass is switchgrass, Panicum virgatum L. A preferred cultivar of switchgrass is Alamo. Other suitable cultivars of switchgrass include but are not limited to Blackwell, Kanlow, Nebraska 28, Pathfinder, Cave-in-Rock, Shelter and Trailblazer.

  7. Anomalous Behaviors of Block Copolymers at the Interface of an Immiscible Polymer Blend

    Science.gov (United States)

    Ryu, Ji Ho; Lee, Won Bo

    We investigate the effects of structure and stiffness of block copolymers on the interface of an immiscible polymer blend using coarse-grained molecular dynamics (CGMD) simulation. The diblock and grafted copolymers, which are described by Kremer and Grest bead spring model, are used to compare the compatibilization efficiency, that is, reduction of the interfacial tension. It is found that, overall, the grafted copolymers are located more compactly at the interface and show better compatibilization efficiency than diblock copolymers. In addition, it is noted that an increase in the stiffness of one block of diblock copolymer causes inhomogeneous interfacial coverage due to bundle formation among the stiff blocks and orientational constraint on bundled structures near the interface, which makes copolymers poor compatibilizers. The dependence of anomalous orientational constraint on the chain length of homopolymers is also investigated. Theoretical and Computational Soft Matters Lab.

  8. Topology and Shape Control for Assemblies of Block Copolymer Blends in Solution

    KAUST Repository

    Moreno Chaparro, Nicolas; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor; Calo, Victor M.

    2015-01-01

    We study binary blends of asymmetric diblock copolymers (AB/AC) in selective solvents with a mesoscale model. We investigate the morphological transitions induced by the concentration of the AC block copolymer and the difference in molecular weight between the AB and AC copolymers, when segments B and C exhibit hydrogen-bonding interactions. To the best of our knowledge, this is the first work modeling mixtures of block copolymers with large differences in molecular weight. The coassembly mechanism localizes the AC molecules at the interface of A and B domains and induces the swelling of the B-rich domains. The coil size of the large molecular weight block copolymer depends only on the concentration of the short block copolymer (AC or AB), regardless of the B–C interactions. However, the B–C interactions control the morphological transitions that occur in these blends.

  9. Microtome Sliced Block Copolymers and Nanoporous Polymers as Masks for Nanolithography

    DEFF Research Database (Denmark)

    Shvets, Violetta; Schulte, Lars; Ndoni, Sokol

    2014-01-01

    Introduction. Block copolymers self-assembling properties are commonly used for creation of very fine nanostructures [1]. Goal of our project is to test new methods of the block-copolymer lithography mask preparation: macroscopic pieces of block-copolymers or nanoporous polymers with cross...... PDMS can be chemically etched from the PB matrix by tetrabutylammonium fluoride in tetrahydrofuran and macroscopic nanoporous PB piece is obtained. Both block-copolymer piece and nanoporous polymer piece were sliced with cryomicrotome perpendicular to the axis of cylinder alignment and flakes...... of etching patterns appear only under the certain parts of thick flakes and are not continuous. Although flakes from block copolymer are thinner and more uniform in thickness than flakes from nanoporous polymer, quality of patterns under nanoporous flakes appeared to be better than under block copolymer...

  10. Topology and Shape Control for Assemblies of Block Copolymer Blends in Solution

    KAUST Repository

    Moreno Chaparro, Nicolas

    2015-10-27

    We study binary blends of asymmetric diblock copolymers (AB/AC) in selective solvents with a mesoscale model. We investigate the morphological transitions induced by the concentration of the AC block copolymer and the difference in molecular weight between the AB and AC copolymers, when segments B and C exhibit hydrogen-bonding interactions. To the best of our knowledge, this is the first work modeling mixtures of block copolymers with large differences in molecular weight. The coassembly mechanism localizes the AC molecules at the interface of A and B domains and induces the swelling of the B-rich domains. The coil size of the large molecular weight block copolymer depends only on the concentration of the short block copolymer (AC or AB), regardless of the B–C interactions. However, the B–C interactions control the morphological transitions that occur in these blends.

  11. Immobilization of trichoderma REESEI (QM 9414) cells with paper covered with ionic copolymer by radiation polymerization

    International Nuclear Information System (INIS)

    Lu Zhaoxin

    1992-01-01

    Cationic-hydrophobic copolymer and anionic-hydrophobic copolymer was covered onto surface of paper by radiation polymerization. The paper covered with ionic copolymer was used as carrier of immobilizing Trichoderma reesei cells. Results showed that the cells were immobilized firmly on the carriers and not dislocated from the carriers by shaking. All of FPA of the cells immobilized with the carriers covered with cationic copolymer were higher than that of un-immobilized free cells. The carriers covered with anionic copolymer showed good effect on immobilization of the cells. The weight of immobilized cells increase as increasing the component of DEAEMA in poly (DEAEMA-ATMPT) or decreasing the component of AA in poly (AA-ATMPT). It also increase with the increase of water absorption in poly (DEAEMA-ATMPT) or decrease of water absorption in poly (AA-ATMPT). It shows the static interaction play an important role in the immobilization of cells with ionic copolymer materials

  12. SYNTHESIS OF AMPHIPHILIC COMB-SHAPED COPOLYMERS USED FOR SURFACE MODIFICATION OF PVDF MEMBRANES

    Institute of Scientific and Technical Information of China (English)

    徐又一

    2009-01-01

    The synthesis of a novel amphiphilic comb-shaped copolymer consisting of a main chain of styrene-(N-(4- hydroxyphenyl) maleimide)(SHMI) copolymer and poly(ethylene glycol) methyl ether methacrylate(PEGMA) side groups was achieved by atom transfer radical polymerization(ATRP).The amphiphilic copolymers were characterized by ~1H-NMR, Fourier transform infrared(FTIR) spectroscopy and gel permeation chromatography(GPC).From thermogravimetric analysis (TGA),the decomposition temperature of SHMI-g-PEGMA is low...

  13. Phase Separation and Elastic Properties of Poly(Trimethylene Terephthalate)-block-poly(Ethylene Oxide) Copolymers

    OpenAIRE

    Elżbieta Piesowicz; Sandra Paszkiewicz; Anna Szymczyk

    2016-01-01

    A series of poly(trimethylene terephthalate)-block-poly(ethylene oxide) (PTT-b-PEOT) copolymers with different compositions of rigid PTT and flexible PEOT segments were synthesized via condensation in the melt. The influence of the block length and the block ratio on the micro-separated phase structure and elastic properties of the synthesized multiblock copolymers was studied. The PEOT segments in these copolymers were kept constant at 1130, 2130 or 3130 g/mol, whereas the PTT content varied...

  14. Oxidation effect on templating of metal oxide nanoparticles within block copolymers

    International Nuclear Information System (INIS)

    Akcora, Pinar; Briber, Robert M.; Kofinas, Peter

    2009-01-01

    Amphiphilic norbornene-b-(norbornene dicarboxylic acid) diblock copolymers with different block ratios were prepared as templates for the incorporation of iron ions using an ion exchange protocol. The disordered arrangement of iron oxide particles within these copolymers was attributed to the oxidation of the iron ions and the strong interactions between iron oxide nanoparticles, particularly at high iron ion concentrations, which was found to affect the self-assembly of the block copolymer morphologies.

  15. Directed self-assembly of poly(styrene)-block-poly(acrylic acid) copolymers for sub-20nm pitch patterning

    Science.gov (United States)

    Cheng, Jing; Lawson, Richard A.; Yeh, Wei-Ming; Jarnagin, Nathan D.; Peters, Andrew; Tolbert, Laren M.; Henderson, Clifford L.

    2012-03-01

    Directed self-assembly (DSA) of block copolymers is a promising technology for extending the patterning capability of current lithographic exposure tools. For example, production of sub-40 nm pitch features using 193nm exposure technologies is conceivably possible using DSA methods without relying on time consuming, challenging, and expensive multiple patterning schemes. Significant recent work has focused on demonstration of the ability to produce large areas of regular grating structures with low numbers of defects using self-assembly of poly(styrene)-b-poly(methyl methacrylate) copolymers (PS-b-PMMA). While these recent results are promising and have shown the ability to print pitches approaching 20 nm using DSA, the ability to advance to even smaller pitches will be dependent upon the ability to develop new block copolymers with higher χ values and the associated alignment and block removal processes required to achieve successful DSA with these new materials. This paper reports on work focused on identifying higher χ block copolymers and their associated DSA processes for sub-20 nm pitch patterning. In this work, DSA using polystyrene-b-polyacid materials has been explored. Specifically, it is shown that poly(styrene)-b-poly(acrylic acid) copolymers (PS-b-PAA) is one promising material for achieving substantially smaller pitch patterns than those possible with PS-b-PMMA while still utilizing simple hydrocarbon polymers. In fact, it is anticipated that much of the learning that has been done with the PS-b-PMMA system, such as development of highly selective plasma etch block removal procedures, can be directly leveraged or transferred to the PS-b-PAA system. Acetone vapor annealing of PS-b-PAA (Mw=16,000 g/mol with 50:50 mole ratio of PS:PAA) and its self-assembly into a lamellar morphology is demonstrated to generate a pattern pitch size (L0) of 21 nm. The χ value for PS-b-PAA was estimated from fingerprint pattern pitch data to be approximately 0.18 which

  16. Structural and chemical aspects of HPMA copolymers as drug carriers.

    Science.gov (United States)

    Ulbrich, Karel; Subr, Vladimír

    2010-02-17

    Synthetic strategies and chemical and structural aspects of the synthesis of HPMA copolymer conjugates with various drugs and other biologically active molecules are described and discussed in this chapter. The discussion is held from the viewpoint of design and structure of the polymer backbone and biodegradable spacer between a polymer and drug, structure and methods of attachment of the employed drugs to the carrier and structure and methods of conjugation with targeting moieties. Physicochemical properties of the water-soluble polymer-drug conjugates and polymer micelles including mechanisms of drug release are also discussed. Detailed description of biological behavior of the polymer-drug conjugates as well as application of the copolymers for surface modification and targeting of gene delivery vectors are not included, they are presented and discussed in separate chapters of this issue. Copyright 2009 Elsevier B.V. All rights reserved.

  17. Pathway-engineering for highly-aligned block copolymer arrays.

    Science.gov (United States)

    Choo, Youngwoo; Majewski, Paweł W; Fukuto, Masafumi; Osuji, Chinedum O; Yager, Kevin G

    2017-12-21

    While the ultimate driving force in self-assembly is energy minimization and the corresponding evolution towards equilibrium, kinetic effects can also play a very strong role. These kinetic effects, such as trapping in metastable states, slow coarsening kinetics, and pathway-dependent assembly, are often viewed as complications to be overcome. Here, we instead exploit these effects to engineer a desired final nano-structure in a block copolymer thin film, by selecting a particular ordering pathway through the self-assembly energy landscape. In particular, we combine photothermal shearing with high-temperature annealing to yield hexagonal arrays of block copolymer cylinders that are aligned in a single prescribed direction over macroscopic sample dimensions. Photothermal shearing is first used to generate a highly-aligned horizontal cylinder state, with subsequent thermal processing used to reorient the morphology to the vertical cylinder state in a templated manner. Finally, we demonstrate the successful transfer of engineered morphologies into inorganic replicas.

  18. Cylindrical-confinement-induced phase behaviours of diblock copolymer melts

    International Nuclear Information System (INIS)

    Mei-Jiao, Liu; Shi-Ben, Li; Lin-Xi, Zhang; Xiang-Hong, Wang

    2010-01-01

    The phase behaviours of diblock copolymers under cylindrical confinement are studied in two-dimensional space by using the self-consistent field theory. Several phase parameters are adjusted to investigate the cylindrical-confinement-induced phase behaviours of diblock copolymers. A series of lamella-cylinder mixture phases, such as the mixture of broken-lamellae and cylinders and the mixture of square-lamellae and cylinders, are observed by varying the phase parameters, in which the behaviours of these mixture phases are discussed in the corresponding phase diagrams. Furthermore, the free energies of these mixture phases are investigated to illustrate their evolution processes. Our results are compared with the available observations from the experiments and simulations respectively, and they are in good agreement and provide an insight into the phase behaviours under cylindrical confinement. (cross-disciplinary physics and related areas of science and technology)

  19. Thermosensitive Self-Assembling Block Copolymers as Drug Delivery Systems

    Directory of Open Access Journals (Sweden)

    Giovanni Filippo Palmieri

    2011-04-01

    Full Text Available Self-assembling block copolymers (poloxamers, PEG/PLA and PEG/PLGA diblock and triblock copolymers, PEG/polycaprolactone, polyether modified poly(Acrylic Acid with large solubility difference between hydrophilic and hydrophobic moieties have the property of forming temperature dependent micellar aggregates and, after a further temperature increase, of gellifying due to micelle aggregation or packing. This property enables drugs to be mixed in the sol state at room temperature then the solution can be injected into a target tissue, forming a gel depot in-situ at body temperature with the goal of providing drug release control. The presence of micellar structures that give rise to thermoreversible gels, characterized by low toxicity and mucomimetic properties, makes this delivery system capable of solubilizing water-insoluble or poorly soluble drugs and of protecting labile molecules such as proteins and peptide drugs.

  20. Biocompatibility of epoxidized styrene-butadiene-styrene block copolymer membrane

    International Nuclear Information System (INIS)

    Yang, Jen Ming; Tsai, Shih Chang

    2010-01-01

    Styrene-butadiene-styrene block copolymer (SBS) membrane was prepared by solution casting method and then was epoxidized with peroxyformic acid generated in situ to yield the epoxidized styrene-butadiene-styrene block copolymer membrane (ESBS). The structure and properties of ESBS were characterized with infrared spectroscopy, Universal Testing Machine, differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA). The performances of contact angle, water content, protein adsorption, and water vapor transmission rate on ESBS membrane were determined. After epoxidation, the hydrophilicity of the membrane increased. The water vapor transmission rate of ESBS membrane is similar to human skin. The biocompatibility of ESBS membrane was evaluated with the cell culture of fibroblasts on the membrane. It revealed that the cells not only remained viable but also proliferated on the surface of the various ESBS membranes and the population doubling time for fibroblast culture decreased.

  1. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers.

    Science.gov (United States)

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N V; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-12-31

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affinities of the donor and the acceptor, the triplet-triplet state can have a stronger oscillator strength than the charge-transfer exciton. We discuss the possibility of intramolecular singlet fission from the triplet-triplet state, and how such fission can be detected experimentally.

  2. Metallic nickel nanorod arrays embedded into ordered block copolymer templates

    International Nuclear Information System (INIS)

    Seifarth, O.; Krenek, R.; Tokarev, I.; Burkov, Y.; Sidorenko, A.; Minko, S.; Stamm, M.; Schmeisser, D.

    2007-01-01

    We report on metallic Nickel nanorods prepared by utilizing a mask of ordered nanostructured hollow channels in a block copolymer matrix. These polymeric templates were formed by a self organized process in block copolymer supramolecular assemblies. Nickel was filled into with two different techniques, electrodeposition and washing in. We monitor the formation process of these nanorods by means of atomic force microscopy and synchrotron radiation soft X-ray based photoelectron emission microscopy. The oxidation state of the nickelrods is evaluated with X-ray absorption spectroscopy and X-ray photoelectron spectroscopy at the Ni L edges and lateral distributions of the Ni nanorods were detected with micrometer resolved X-ray absorption spectroscopy. The finding is that the Ni rods were metallic despite their preparation under ambient conditions, inside the particles no hints for NiO complexes were found. This indicates that the polymer protects Ni nanoparticles against oxidation

  3. Synthesis and characterization of acrylate copolymer containing fluorescein functional group

    Energy Technology Data Exchange (ETDEWEB)

    Hui, Guodong; Huang, Weiyun; Song, Yunzhao; Chen, Deben; Zhong, Anyong [Sichuan University, Chengdu (China)

    2013-08-15

    We report a novel method to fabricate fluorescent polymer (F-CPA) based on the esterification between acrylate copolymer (CPA) and fluorescein using N, N-dicyclohexylcarbodiimide (DCC)/4-dimethylaminopyridine (DMAP) as catalyst. The resulting copolymer was characterized by Fourier transform-infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), ultraviolet-visible spectroscopy (UV-Vis) and fluorescence spectroscopy. In addition, the influences of concentration, solvents, pH and metal cations (Cu{sup 2+}, Fe{sup 3+} and Zn{sup 2+}) on the fluorescent behaviors of F-CPA are discussed in detail. All those observations suggest that the synthesized F-CPA is an excellent luminescent macromolecular material with simple synthesis method and excellent solubility. Moreover, its sensitive fluorescence response behaviors to solvents, pH and metal cations make it to become a polymer-based probe.

  4. Synthesis and characterization of acrylate copolymer containing fluorescein functional group

    International Nuclear Information System (INIS)

    Hui, Guodong; Huang, Weiyun; Song, Yunzhao; Chen, Deben; Zhong, Anyong

    2013-01-01

    We report a novel method to fabricate fluorescent polymer (F-CPA) based on the esterification between acrylate copolymer (CPA) and fluorescein using N, N-dicyclohexylcarbodiimide (DCC)/4-dimethylaminopyridine (DMAP) as catalyst. The resulting copolymer was characterized by Fourier transform-infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), ultraviolet-visible spectroscopy (UV-Vis) and fluorescence spectroscopy. In addition, the influences of concentration, solvents, pH and metal cations (Cu"2"+, Fe"3"+ and Zn"2"+) on the fluorescent behaviors of F-CPA are discussed in detail. All those observations suggest that the synthesized F-CPA is an excellent luminescent macromolecular material with simple synthesis method and excellent solubility. Moreover, its sensitive fluorescence response behaviors to solvents, pH and metal cations make it to become a polymer-based probe

  5. Magnetic Alignment of Block Copolymer Microdomains by Intrinsic Chain Anisotropy.

    Science.gov (United States)

    Rokhlenko, Yekaterina; Gopinadhan, Manesh; Osuji, Chinedum O; Zhang, Kai; O'Hern, Corey S; Larson, Steven R; Gopalan, Padma; Majewski, Paweł W; Yager, Kevin G

    2015-12-18

    We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δχ, that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δχ≈2×10^{-8}. From field-dependent scattering data, we estimate that grains of ≈1.2  μm are present during alignment. These results demonstrate that intrinsic anisotropy is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.

  6. Water state and TEM analysis of Konjac irradiation copolymer

    International Nuclear Information System (INIS)

    Geng Shengrong; Xia Hezhou; Chen Xueling; Ye Lixiu; Hua Yuejin

    2012-01-01

    To study the absorption performance of Konjac-AA copolymer prepared by irradiation, the water absorbent capacity, sorbent speed and water keeping ability was determined and DSC and TEM analysis were used to explore the water content and structure characters. The results showed that on room temperature the largest water absorption speed was 16 g · g -1 · min -1 at, and the largest water absorption was 400 times at 60 min. The water absorption was affected by granularity, temperature, ion content and ion type, especially the ion type, the water keeping ability was affected by temperature and time, which was up to 35% while the fully water absorbed copolymer was kept under room temperature for 15 d. The free and bounder water content which was assimilated by the plants was 99.617%. The gel stale co polymer has a three-dimensional structure of spiral, which was constituted by spherical objects of varying sizes. (authors)

  7. Radiation degradation of α-substituted acrylate polymers and copolymers

    International Nuclear Information System (INIS)

    Helbert, J.N.; Caplan, P.J.; Poindexter, E.H.

    1977-01-01

    Radiation degradation is observed in poly(methyl α-chloroacrylate), poly(methyl α-cyanoacrylate), and poly (α-chloroacrylonitrile) homopolymers and their respective MMA copolymers when γ-irradiated in vacuo. Polymer degradation susceptibilities are quantified in terms of G(scission radicals) and G(scission) -- G(crosslinks), measured by EPR and membrane osmometry, respectively; values by these two methods are compared. Higher G(rads) values ranging from 2 to 6 and [G(s) -- G(x)] values ranging from 2 to 11 are obtained for the substituted polymers and copolymers relative to the values for PMMA (1.6; 1.9), a standard e-beam positive resist, which suggests that these modified polymers are more sensitive e-beam resists than PMMA

  8. Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes

    Science.gov (United States)

    Meador, Mary Ann B.; Tigelaar, Dean M.

    2009-01-01

    Polyimide-PEO copolymers (PEO signifies polyethylene oxide) that have branched rod-coil molecular structures and that can be cured into film form at room temperature have been invented for use as gel electrolytes for lithium-ion electric-power cells. These copolymers offer an alternative to previously patented branched rod-coil polyimides that have been considered for use as polymer electrolytes and that must be cured at a temperature of 200 C. In order to obtain sufficient conductivity for lithium ions in practical applications at and below room temperature, it is necessary to imbibe such a polymer with a suitable carbonate solvent or ionic liquid, but the high-temperature cure makes it impossible to incorporate and retain such a liquid within the polymer molecular framework. By eliminating the high-temperature cure, the present invention makes it possible to incorporate the required liquid.

  9. Creating surfactant nanoparticles for block copolymer composites through surface chemistry.

    Science.gov (United States)

    Kim, Bumjoon J; Bang, Joona; Hawker, Craig J; Chiu, Julia J; Pine, David J; Jang, Se Gyu; Yang, Seung-Man; Kramer, Edward J

    2007-12-04

    A simple strategy to tailor the surface of nanoparticles for their specific adsorption to and localization at block copolymer interfaces was explored. Gold nanoparticles coated by a mixture of low molecular weight thiol end-functional polystyrene (PS-SH) (Mn = 1.5 and 3.4 kg/mol) and poly(2-vinylpyridine) homopolymers (P2VP-SH) (Mn = 1.5 and 3.0 kg/mol) were incorporated into a lamellar poly(styrene-b-2-vinylpyridine) diblock copolymer (PS-b-P2VP) (Mn = 196 kg/mol). A library of nanoparticles with varying PS and P2VP surface compositions (FPS) and high polymer ligand areal chain densities was synthesized. The location of the nanoparticles in the PS-b-P2VP block copolymer was determined by transmission electron microscopy. Sharp transitions in particle location from the PS domain to the PS/P2VP interface, and subsequently to the P2VP domain, were observed at FPS = 0.9 and 0.1, respectively. This extremely wide window of FPS values where the polymer-coated gold nanoparticles adsorb to the interface suggests a redistribution of PS and P2VP polymers on the Au surface, inducing the formation of amphiphilic nanoparticles at the PS/P2VP interface. In a second and synthetically more challenging approach, gold nanoparticles were covered with a thiol terminated random copolymer of styrene and 2-vinylpyridine synthesized by RAFT polymerization. Two different random copolymers were considered, where the molecular weight was fixed at 3.5 kg/mol and the relative incorporation of styrene and 2-vinylpyridine repeat units varied (FPS = 0.52 and 0.40). The areal chain density of these random copolymers on Au is unfortunately not high enough to preclude any contact between the P2VP block of the block copolymer and the Au surface. Interestingly, gold nanoparticles coated by the random copolymer with FPS = 0.4 were dispersed in the P2VP domain, while those with FPS = 0.52 were located at the interface. A simple calculation for the adsorption energy to the interface of the nanoparticles

  10. Dynamics of interacting edge defects in copolymer lamellae

    Science.gov (United States)

    Dalnoki-Veress, Kari; McGraw, Joshua D.; Rowe, Ian D. W.

    2011-03-01

    It is known that terraces at the interface of lamella forming diblock copolymers do not make discontinuous jumps in height. Rather, their profiles are smoothly varying. The width of the transition region between two lamellar heights is typically several hundreds of nanometres, resulting from a balance between surface tension, chain stretching penalties, and the enthalpy of mixing. What is less well known in these systems is what happens when two transition regions approach one another. In this study, we show that time dependent experimental data of interacting copolymer lamellar edges is consistent with a model that assumes a repulsion between adjacent edges. The range of the interaction between edge defects is consistent with the profile width of noninteracting diblock terraces. Financial support from NSERC of Canada is gratefully acknowledged.

  11. Investigation of some copolymers based on acrylic salts as circulation loss control agents

    Directory of Open Access Journals (Sweden)

    Ahmed Mohamed Alsabagh

    2013-12-01

    The prepared copolymers were investigated as loss circulation control materials by measuring different filtration parameters such as; spurt loss, fluid loss and permeability plugging tester value according to the American Petroleum Institute (API standard. From the obtained data, it was found that the 0.6% from the poly[PA-co-AM](0.4:0.6 exhibited the best results of the filtration parameters among the other copolymers. At the same time all the studied copolymers enhanced the rheological properties of the drilling mud. These results were discussed on the light of the swelling capacity of the copolymers.

  12. Molecular architecture of electroactive and biodegradable copolymers composed of polylactide and carboxyl-capped aniline trimer.

    Science.gov (United States)

    Guo, Baolin; Finne-Wistrand, Anna; Albertsson, Ann-Christine

    2010-04-12

    Two-, four-, and six-armed branched copolymers with electroactive and biodegradable properties were synthesized by coupling reactions between poly(l-lactides) (PLLAs) with different architecture and carboxyl-capped aniline trimer (CCAT). The aniline oligomer CCAT was prepared from amino-capped aniline trimer and succinic anhydride. FT-IR, NMR, and SEC analyses confirmed the structure of the branched copolymers. UV-vis spectra and cyclic voltammetry of CCAT and copolymer solution showed good electroactive properties, similar to those of polyaniline. The water contact angle of the PLLAs was the highest, followed by the undoped copolymer and the doped copolymers. The values of doped four-armed copolymers were 54-63 degrees . Thermal properties of the polymers were studied by DSC and TGA. The copolymers had better thermal stability than the pure PLLAs, and the T(g) between 48-58 degrees C and T(m) between 146-177 degrees C of the copolymers were lower than those of the pure PLLA counterparts. This kind of electroactive and biodegradable copolymer has a great potential for applications in cardiovascular or neuronal tissue engineering.

  13. Infrared and ultraviolet spectroscopic studies of low-temperature radiolysis of ethylene - styrene copolymers

    International Nuclear Information System (INIS)

    Mal'tseva, A.P.; Golikov, V.P.; Leshchenko, S.S.; Karpov, V.L.

    1977-01-01

    Certain features of low-temperature radiolysis of statistic ethylene-styrene copolymers have been studied by infrared and ultraviolet spectroscopy. It is shown that the nature of the accumulation and decay of trans-vinylene, vinyl and vinylidene double bonds in an ethylene-styrene copolymer is essentially influenced by both the dose absorbed and copolymer composition. A suggestion is made that the ethylene-styrene copolymer is formed when structures are irradiated containing double bonds conjugated with the phenyl rings of styrene groups - which more effectively dissipate the absorbed energy than solitary phenyl rings

  14. Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

    Science.gov (United States)

    De Lisi, Rosario; Milioto, Stefania; Muratore, Nicola

    2009-01-01

    The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties. PMID:19742173

  15. Functional Block Copolymers as Compatibilizers for Nanoclays in Polypropylene Nanocomposites

    DEFF Research Database (Denmark)

    Jankova Atanasova, Katja; Daugaard, Anders Egede; Stribeck, Norbert

    2011-01-01

    With the aim of creating tough nanocomposits (NC) [1] based on polypropylene (PP) and nanoclay (NCl) in the framework of the 7th EU program NANOTOUGH we have designed amphiphilic block copolymers utilizing Atom Transfer Radical Polymerization (ATRP) [2]. They consist of a hydrophobic block...... crystallites) is replaced by alien-reinforcement (of the MMT). Furthermore, the results from the impact strength and cyclic test of the prepared PP nanocomposites [3] are promicing....

  16. Rapid transitions between defect configurations in a block copolymer melt.

    Science.gov (United States)

    Tsarkova, Larisa; Knoll, Armin; Magerle, Robert

    2006-07-01

    With in situ scanning force microscopy, we image the ordering of cylindrical microdomains in a thin film of a diblock copolymer melt. Tracking the evolution of individual defects reveals elementary steps of defect motion via interfacial undulations and repetitive transitions between distinct defect configurations on a time scale of tens of seconds. The velocity of these transitions suggests a cooperative movement of clusters of chains. The activation energy for the opening/closing of a connection between two cylinders is estimated.

  17. Styrene-Based Copolymer for Polymer Membrane Modifications

    OpenAIRE

    Harsha Srivastava; Harshad Lade; Diby Paul; G. Arthanareeswaran; Ji Hyang Kweon

    2016-01-01

    Poly(vinylidene fluoride) (PVDF) was modified with a styrene-based copolymer. The crystalline behavior, phase, thermal stability, and surface morphology of the modified membranes were analyzed. The membrane surface roughness showed a strong dependence on the styrene-acrylonitrile content and was reduced to 34% for a PVDF/styrene-acrylonitrile blend membrane with a 40/60 ratio. The thermal and crystalline behavior confirmed the blend miscibility of both polymers. It was observed in X-ray diffr...

  18. Poly(alkylene oxide) Copolymers for Nucleic Acid Delivery

    Science.gov (United States)

    2012-07-17

    Poly(alkylene oxide) Copolymers for Nucleic Acid Delivery Swati Mishra1,#, Lavanya Y. Peddada1,#, David I. Devore3,4, and Charles M. Roth1,2...Neil Raju for assistance with figures. Biographies Swati Mishra received her Ph.D. in Biomedical Engineering and Biotechnology from the University of...Kleiman N, Anderson RD, Gottlieb D, Karlsberg R, Snell J, Rocha- Singh K. Results from a phase II multicenter, double-blind placebo-controlled study of Del

  19. Process for producing a novel copolymer. [electron beams

    Energy Technology Data Exchange (ETDEWEB)

    Oiwa, M; Matsumoto, A; Tojima, M; Matsumoto, K; Sasaki, H

    1970-11-27

    Diaryl oxalate present in a polymer not only decomposes at lower temperatures, but also provides for stronger free radicals initiating polymerization than diaryl oxalate present in a monomer. A copolymer of vinyl monomers is produced by providing a diaryl oxalate polymer or a diaryl oxalate monomer-co-vinyl monomer, decomposing them to release the diaryl oxalate units by heating or irradiating with radiation thereby copolymerizing the vinyl monomer with the polymer radicals by utilizing the diaryl oxalate unit. For example, a single diaryl oxalate polymer or a copolymer containing the diaryl oxalate polymer as a constituent of the copolymer are irradiated or heated with a vinyl monomer, i.e. methyl methacrylate, acrylnitrile, vinyl acetate, styrene etc., to form a copolymer without difficulty. In one of the examples, 500 g of diaryl oxalate monomer, 1,200 ml of benzene and 0.2 mol/l of benzoil peroxide as an initiator were mixed and polymerized in nitrogen gas at 70/sup 0/C for 8 hrs. From this polymerized solution, a polymer was deposited in methanol. The produced polymer had an iodin value of 77.7 with a yield of 35%. The gel content of the produced polymer was 98.9% for 10 Mrad. This polymer was dissolved in methyl methacrylate, thereafter filled in a mold and irradiated with electron beams of 2 MeV in nitrogen gas to harden it. The advantage of this process is that the polymerization is effected with low energy radiations at room temperature without requiring any catalyst.

  20. Ethylene vinylacetate copolymer and nanographite composite as chemical vapour sensor

    International Nuclear Information System (INIS)

    Stepina, Santa; Sakale, Gita; Knite, Maris

    2013-01-01

    Polymer-nanostructured carbon composite as chemical vapour sensor is described, made by the dissolution method of a non-conductive polymer, ethylene vinylacetate copolymer, mixed with conductive nanographite particles (carbon black). Sensor exhibits relative electrical resistance change in chemical vapours, like ethanol and toluene. Since the sensor is relatively cheap, easy to fabricate, it can be used in air quality monitoring and at industries to control hazardous substance concentration in the air, for example, to protect workers from exposure to chemical spills

  1. Block copolymer micelles as switchable templates for nanofabrication

    OpenAIRE

    Krishnamoorthy, S; Pugin, R; Brugger, J; Heinzelmann, H; Hoogerwerf, A C; Hinderling, C

    2006-01-01

    Block copolymer inverse micelles from polystyrene-block-poly-2-vinylpyridine (PS-b-P2VP) deposited as monolayer films onto surfaces show responsive behavior and are reversibly switchable between two states of different topography and surface chemistry. The as-coated films are in the form of arrays of nanoscale bumps, which can be transformed into arrays of nanoscale holes by switching through exposure to methanol. The use of these micellar films to act as switchable etch masks for the structu...

  2. Block copolymer libraries: modular versatility of the macromolecular Lego system.

    Science.gov (United States)

    Lohmeijer, Bas G G; Wouters, Daan; Yin, Zhihui; Schubert, Ulrich S

    2004-12-21

    The synthesis and characterization of a new 4 x 4 library of block copolymers based on polystyrene and poly(ethylene oxide) connected by an asymmetrical octahedral bis(terpyridine) ruthenium complex at the block junction are described, while initial studies on the thin film morphology of the components of the library are presented by the use of Atomic Force Microscopy, demonstrating the impact of a library approach to derive structure-property relationships.

  3. Localization of a random copolymer at an interface

    International Nuclear Information System (INIS)

    Madras, N; Whittington, S G

    2003-01-01

    We investigate the nature of the phase diagram for a self-avoiding walk model of a random copolymer at an interface between two immiscible solvents, when one monomer prefers to be in one solvent, the other monomer prefers to be in the other solvent, and both types of monomer have an attractive or repulsive interaction with the interface. Our results are all rigorous, and extend previous work of Maritan et al (1999) and Martin et al (2000)

  4. Nanostructured Colloidal Particles by Confined Self-Assembly of Block Copolymers in Evaporative Droplets

    Directory of Open Access Journals (Sweden)

    Minsoo P. Kim

    2015-06-01

    Full Text Available Block copolymers (BCPs can create various morphology by self-assembly in bulk or film. Recently, using BCPs in confined geometries such as thin film (one-dimension, cylindrical template (two-dimension, or emulsion droplet (three-dimension, nanostructured BCP particles have been prepared, in which unique nanostructures of the BCP are formed via solvent annealing process and can be controlled depending on molecular weight ratio and interaction parameter of the BCPs, and droplet size. Moreover, by tuning interfacial property of the BCP particles, anisotropic particles with unique nanostructures have been prepared. Furthermore, for practical application such as drug delivery system, sensor, self-healing, metamaterial, and optoelectronic device, functional nanoparticles can be incorporated inside BCP particles. In this article, we summarize recent progress on the production of structured BCP particles and composite particles with metallic nanoparticles.

  5. Directed self-assembly of block copolymers for use in bit patterned media fabrication

    International Nuclear Information System (INIS)

    Griffiths, Rhys Alun; Vijayaraghavan, Aravind; Thomson, Thomas; Williams, Aled; Oakland, Chloe; Roberts, Jonathan

    2013-01-01

    Reduction of the bit size in conventional magnetic recording media is becoming increasingly difficult due to the superparamagnetic limit. Bit patterned media (BPM) has been proposed as a replacement technology as it will enable hard disk areal densities to increase past 1 Tb in −2 . Block copolymer directed self-assembly (BCP DSA) is the leading candidate for forming BPM due to its ability to create uniform patterns over macroscopic areas. Here we review the latest research into two different BCP DSA techniques: graphoepitaxy and chemoepitaxy (or chemical prepatterning). In addition to assessing their potential for forming high density bit patterns, we also review current approaches using these techniques for forming servo patterns, which are required for hard disk drive (HDD) operation. Finally, we review the current state of UV nanoimprint lithography, which is the favoured technique for enabling mass production of BPM HDDs. (topical review)

  6. Growing Embossed Nanostructures of Polymer Brushes on Wet-Etched Silicon Templated via Block Copolymers

    Science.gov (United States)

    Lu, Xiaobin; Yan, Qin; Ma, Yinzhou; Guo, Xin; Xiao, Shou-Jun

    2016-02-01

    Block copolymer nanolithography has attracted enormous interest in chip technologies, such as integrated silicon chips and biochips, due to its large-scale and mass production of uniform patterns. We further modified this technology to grow embossed nanodots, nanorods, and nanofingerprints of polymer brushes on silicon from their corresponding wet-etched nanostructures covered with pendent SiHx (X = 1-3) species. Atomic force microscopy (AFM) was used to image the topomorphologies, and multiple transmission-reflection infrared spectroscopy (MTR-IR) was used to monitor the surface molecular films in each step for the sequential stepwise reactions. In addition, two layers of polymethacrylic acid (PMAA) brush nanodots were observed, which were attributed to the circumferential convergence growth and the diffusion-limited growth of the polymer brushes. The pH response of PMAA nanodots in the same region was investigated by AFM from pH 3.0 to 9.0.

  7. Electrochemical Synthesis of Polyaniline/Poly-O-Aminophenol Copolymers in Chloride Medium

    Directory of Open Access Journals (Sweden)

    Lucia H. Mascaro

    2011-01-01

    Full Text Available The copolymerization of o-aminophenol (OAP and aniline (ANI on Pt and ITO electrodes was studied using cyclic voltammetry in 0.1 M HCl/0.4 M NaCl solution. The films were characterized by SEM, cyclic voltammetry, and UV-Vis spectroscopy. The properties of the copolymer were compared with PANI and POAP films. The results strongly suggest that the growth of PANI-POAP films does not consist of the simple buildup of layers of homopolymers on the electrode surface as a result of OAP or ANI oxidation products in the monomer mixture, but that a new conducting polymer is formed by copolymerization.

  8. Self-assembled Block Copolymer Membrane

    KAUST Repository

    Peinemann, Klaus-Viktor

    2012-12-20

    Embodiments of the invention include methods for the production of porous membranes. In certain aspects the methods are directed to producing polymeric porous membranes having a narrow pore size distribution.

  9. Self-assembled Block Copolymer Membrane

    KAUST Repository

    Peinemann, Klaus-Viktor; Nunes, Suzana Pereira

    2012-01-01

    Embodiments of the invention include methods for the production of porous membranes. In certain aspects the methods are directed to producing polymeric porous membranes having a narrow pore size distribution.

  10. Donor-Acceptor Block Copolymers: Synthesis and Solar Cell Applications

    Directory of Open Access Journals (Sweden)

    Kazuhiro Nakabayashi

    2014-04-01

    Full Text Available Fullerene derivatives have been widely used for conventional acceptor materials in organic photovoltaics (OPVs because of their high electron mobility. However, there are also considerable drawbacks for use in OPVs, such as negligible light absorption in the visible-near-IR regions, less compatibility with donor polymeric materials and high cost for synthesis and purification. Therefore, the investigation of non-fullerene acceptor materials that can potentially replace fullerene derivatives in OPVs is increasingly necessary, which gives rise to the possibility of fabricating all-polymer (polymer/polymer solar cells that can deliver higher performance and that are potentially cheaper than fullerene-based OPVs. Recently, considerable attention has been paid to donor-acceptor (D-A block copolymers, because of their promising applications as fullerene alternative materials in all-polymer solar cells. However, the synthesis of D-A block copolymers is still a challenge, and therefore, the establishment of an efficient synthetic method is now essential. This review highlights the recent advances in D-A block copolymers synthesis and their applications in all-polymer solar cells.

  11. Non-Classical Order in Sphere Forming ABAC Tetrablock Copolymers

    Science.gov (United States)

    Zhang, Jingwen; Sides, Scott; Bates, Frank

    2013-03-01

    AB diblock and ABC triblock copolymers have been studied thoroughly. ABAC tetrablock copolymers, representing the simplest variation from ABC triblock by breaking the molecular symmetry via inserting some of the A block in between B and C blocks, have been studied systematically in this research. The model system is poly(styrene-b-isoprene-b-styrene-b-ethylene oxide) (SISO) tetrablock terpolymers and the resulting morphologies were characterized by nuclear magnetic resonance, gel permeation chromatography, small-angle X-ray scattering, transmission electron microscopy, differential scanning calorimetry and dynamic mechanical spectroscopy. Two novel phases are first discovered in a single component block copolymers: hexagonally ordered spherical phase and tentatively identified dodecagonal quasicrystalline (QC) phase. In particular, the discovery of QC phase bridges the world of soft matters to that of metals. These unusual sets of morphologies will be discussed in the context of segregation under the constraints associated with the tetrablock molecular architecture. Theoretical calculations based on the assumption of Gaussian chain statistics provide valuable insights into the molecular configurations associated with these morphologies. the U.S. Department of Energy, Basic Energy Sciences, Division of Materials Science and Engineering, under contract number DEAC05-00OR22725 with UT-Battelle LLC at Oak Ridge National Lab.

  12. Molecular Mobility in Phase Segregated Bottlebrush Block Copolymer Melts

    Science.gov (United States)

    Yavitt, Benjamin; Gai, Yue; Song, Dongpo; Winter, H. Henning; Watkins, James

    We investigate the linear viscoelastic behavior of poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) brush block copolymer (BBCP) materials over a range of vol. fractions and with side chain lengths below the entanglement molecular weights. The high chain mobility of the brush architecture results in rapid micro-phase segregation of the brush copolymer segments, which occurs during thermal annealing at mild temperatures. Master curves of the dynamic moduli were obtained by time-temperature superposition. The reduced degree of chain entanglements leads to a unique liquid-like rheology similar to that of bottlebrush homopolymers, even in the phase segregated state. We also explore the alignment of phase segregated domains at exceptionally low strain amplitudes (γ = 0.01) and mild processing temperatures using small angle X-ray scattering (SAXS). Domain orientation occurred readily at strains within the linear viscoelastic regime without noticeable effect on the moduli. This interplay of high molecular mobility and rapid phase segregation that are exhibited simultaneously in BBCPs is in contrast to the behavior of conventional linear block copolymer (LBCP) analogs and opens up new possibilities for processing BBCP materials for a wide range of nanotechnology applications. NSF Center for Hierarchical Manufacturing at the University of Massachusetts, Amherst (CMMI-1025020).

  13. Controlled Assembly of Fibronectin Nanofibrils Triggered by Random Copolymer Chemistry.

    Science.gov (United States)

    Mnatsakanyan, Hayk; Rico, Patricia; Grigoriou, Eleni; Candelas, Aarón Maturana; Rodrigo-Navarro, Aleixandre; Salmeron-Sanchez, Manuel; Sabater i Serra, Roser

    2015-08-19

    Fibronectin fibrillogenesis is the physiological process by which cells elaborate a fibrous FN matrix. Poly(ethyl acrylate), PEA, has been described to induce a similar process upon simple adsorption of fibronectin (FN) from a protein solution-in the absence of cells-leading to the so-called material-driven fibronectin fibrillogenesis. Poly(methyl acrylate), PMA, is a polymer with very similar chemistry to PEA, on which FN is adsorbed, keeping the globular conformation of the protein in solution. We have used radical polymerization to synthesize copolymers with controlled EA/MA ratio, seeking to modulate the degree of FN fibrillogenesis. The physicochemical properties of the system were studied using dynamic-mechanical analysis, differential scanning calorimetry, and water contact angle. Both the degree of FN fibrillogenesis and the availability of the integrin binding region of FN directly depend on the percentage of EA in the copolymer, whereas the same total amount of FN was adsorbed regardless the EA/MA ratio. Cell morphology adhesion and differentiation of murine C2C12 were shown to depend on the degree of FN fibrillogenesis previously attained on the material surface. Myogenic differentiation was enhanced on the copolymers with higher EA content, i.e. more interconnected FN fibrils.

  14. Formation and Characterization of Anisotropic Block Copolymer Gels

    Science.gov (United States)

    Liaw, Chya Yan; Joester, Derk; Burghardt, Wesley; Shull, Kenneth

    2012-02-01

    Cylindrical micelles formed from block copolymer solutions closely mimic biological fibers that are presumed to guide mineral formation during biosynthesis of hard tissues like bone. The goal of our work is to use acrylic block copolymers as oriented templates for studying mineral formation reactions in model systems where the structure of the underlying template is well characterized and reproducible. Self-consistent mean field theory is first applied to investigate the thermodynamically stable micellar morphologies as a function of temperature and block copolymer composition. Small-angle x-ray scattering, optical birefringence and shear rheometry are used to study the morphology development during thermal processing. Initial experiments are based on a thermally-reversible alcohol-soluble system that can be converted to an aqueous gel by hydrolysis of a poly(t-butyl methacrylate) block to a poly(methacrylic acid) block. Aligned cylindrical domains are formed in the alcohol-based system when shear is applied in an appropriate temperature regime, which is below the critical micelle temperature but above the temperature at which the relaxation time of the gels becomes too large. Processing strategies for producing the desired cylindrical morphologies are being developed that account for both thermodynamic and kinetic effects.

  15. High-frequency ultrasound-responsive block copolymer micelle.

    Science.gov (United States)

    Wang, Jie; Pelletier, Maxime; Zhang, Hongji; Xia, Hesheng; Zhao, Yue

    2009-11-17

    Micelles of a diblock copolymer composed of poly(ethylene oxide) and poly(2-tetrahydropyranyl methacrylate) (PEO-b-PTHPMA) in aqueous solution could be disrupted by high-frequency ultrasound (1.1 MHz). It was found that, upon exposure to a high-intensity focused ultrasound (HIFU) beam at room temperature, the pH value of the micellar solution decreased over irradiation time. The infrared spectroscopic analysis of solid block copolymer samples collected from the ultrasound irradiated micellar solution revealed the formation of carboxylic acid dimers and hydroxyl groups. These characterization results suggest that the high-frequency HIFU beam could induce the hydrolysis reaction of THPMA at room temperature resulting in the cleavage of THP groups. The disruption of PEO-b-PTHPMA micelles by ultrasound was investigated by using dynamic light scattering, atomic force microscopy, and fluorescence spectroscopy. On the basis of the pH change, it was found that the disruption process was determined by a number of factors such as the ultrasound power, the micellar solution volume and the location of the focal spot of the ultrasound beam. This study shows the potential to develop ultrasound-sensitive block copolymer micelles by having labile chemical bonds in the polymer structure, and to use the high-frequency HIFU to trigger a chemical reaction for the disruption of micelles.

  16. Removal of Industrial Pollutants From Wastewater's By Graft Copolymers

    International Nuclear Information System (INIS)

    Hegazy El-Sayed, A.; El-Nagar Abdel-Wahab, M.; Senna Magdy, M.; Zahran Abdel-Hamid, H.

    1999-01-01

    Graft copolymers that obtained by radiation grafting of acrylic acid and acrylamide onto LDPE film were converted to N-hydroxy ethyl amide and hydroxamic acid derivatives respectively. The possible application for the different prepared chemical derivatives of LDPE graft copolymers in metal adsorption from solutions containing a single cation or simulated medium active waste has been investigated. The results showed that the adsorption of Cu(II) metal by different chemical derivatives was greatly affected by different factors such as graft yield, ph value, concentration of metal in the feed solution, immersion time and treatment temperature. The affinity of N-hydroxy ethyl amide derivative toward the different metals was found to be in the order of; Cu(II) >Pd(II) > Cd(II)> Co(II). However, for hydroxamic acid derivative , the affinity order was: Cd(II) > Cu(II) > Co(II). The ESR and IR analysis revealed that the metal ions are chelated through the lone pair of electrons on the -OH and -NH- groups forming a ring structure. The measured metal ion uptake from simulated medium active waste mixture by N-hydroxy ethyl amide derivative was found to follow the following order: Fe> U> Ni> Zr> Zn> Cr. On the other hand, the measured metal uptake by hydroxamic acid derivative was found to follow: Fe>U> Zr> Ca. It is concluded that the prepared grafted copolymers are of interest for metal chelation and could be applied in the field of waste treatment

  17. PTCR effect in carbon black/copolymer composites

    International Nuclear Information System (INIS)

    Costa, L.C.; Chakki, A.; Achour, M.E.; Graca, M.P.F.

    2011-01-01

    Some materials show an abrupt increase in resistivity when the temperature changes only over a few degrees. This phenomenon, known as PTCR effect (positive temperature coefficient of resistivity), has been largely studied in the last few years, due to its potential applications in industry. Particularly, it can be used in auto controlled heaters, temperature sensors, protection circuits and in security systems for power electronic circuits. In this work we present the study of the electrical properties of the percolating system carbon black particles filled with ethylene butylacrylate copolymer composite (EBA), in the temperature range from -100 to 100 o C and in frequencies between 10 Hz and 100 kHz. The PTCR effect was observed at temperatures slightly above the room temperature, for concentrations higher than that of the percolation critical concentration. The mechanism responsible for the change in resistivity, at this stage, is predominantly tunnelling, wherein the conductive filler particles are not in physical contact, and the electrons tunnel through the insulating gap between them. At low temperatures, such as below and close to the glass transition temperature, the DC conductivity obeys the Arrhenius law. The calculated activation energy values are independent of carbon black contents inside the copolymer matrix, suggesting that these particles do not interact significantly with the chain segments of the macromolecules in the EBA copolymer.

  18. PTCR effect in carbon black/copolymer composites

    Energy Technology Data Exchange (ETDEWEB)

    Costa, L.C., E-mail: kady@fis.ua.p [I3N and Physics Department, University of Aveiro, 3810-193 Aveiro (Portugal); Chakki, A.; Achour, M.E. [LASTID, Physics Department, Faculty of Sciences, Ibn Tofail University, BP 133, 14000 Kenitra (Morocco); Graca, M.P.F. [I3N and Physics Department, University of Aveiro, 3810-193 Aveiro (Portugal)

    2011-01-15

    Some materials show an abrupt increase in resistivity when the temperature changes only over a few degrees. This phenomenon, known as PTCR effect (positive temperature coefficient of resistivity), has been largely studied in the last few years, due to its potential applications in industry. Particularly, it can be used in auto controlled heaters, temperature sensors, protection circuits and in security systems for power electronic circuits. In this work we present the study of the electrical properties of the percolating system carbon black particles filled with ethylene butylacrylate copolymer composite (EBA), in the temperature range from -100 to 100 {sup o}C and in frequencies between 10 Hz and 100 kHz. The PTCR effect was observed at temperatures slightly above the room temperature, for concentrations higher than that of the percolation critical concentration. The mechanism responsible for the change in resistivity, at this stage, is predominantly tunnelling, wherein the conductive filler particles are not in physical contact, and the electrons tunnel through the insulating gap between them. At low temperatures, such as below and close to the glass transition temperature, the DC conductivity obeys the Arrhenius law. The calculated activation energy values are independent of carbon black contents inside the copolymer matrix, suggesting that these particles do not interact significantly with the chain segments of the macromolecules in the EBA copolymer.

  19. Application of Bottlebrush Block Copolymers as Photonic Crystals.

    Science.gov (United States)

    Liberman-Martin, Allegra L; Chu, Crystal K; Grubbs, Robert H

    2017-07-01

    Brush block copolymers are a class of comb polymers that feature polymeric side chains densely grafted to a linear backbone. These polymers display interesting properties due to their dense functionality, low entanglement, and ability to rapidly self-assemble to highly ordered nanostructures. The ability to prepare brush polymers with precise structures has been enabled by advancements in controlled polymerization techniques. This Feature Article highlights the development of brush block copolymers as photonic crystals that can reflect visible to near-infrared wavelengths of light. Fabrication of these materials relies on polymer self-assembly processes to achieve nanoscale ordering, which allows for the rapid preparation of photonic crystals from common organic chemical feedstocks. The characteristic physical properties of brush block copolymers are discussed, along with methods for their preparation. Strategies to induce self-assembly at ambient temperatures and the use of blending techniques to tune photonic properties are emphasized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. (Electro)Mechanical Properties of Olefinic Block Copolymers

    Science.gov (United States)

    Spontak, Richard

    2014-03-01

    Conventional styrenic triblock copolymers (SBCs) swollen with a midblock-selective oil have been previously shown to exhibit excellent electromechanical properties as dielectric elastomers. In this class of electroactive polymers, compliant electrodes applied as active areas to opposing surfaces of an elastomer attract each other, and thus compress the elastomer due to the onset of a Maxwell stress, upon application of an external electric field. This isochoric process is accompanied by an increase in lateral area, which yields the electroactuation strain (measuring beyond 300% in SBC systems). Performance parameters such as the Maxwell stress, transverse strain, dielectric breakdown, energy density and electromechanical efficiency are determined directly from the applied electric field and resulting electroactuation strain. In this study, the same principle used to evaluate SBC systems is extended to olefinic block copolymers (OBCs), which can be described as randomly-coupled multiblock copolymers that consist of crystallizable polyethylene hard segments and rubbery poly(ethylene-co-octene) soft segments. Considerations governing the development of a methodology to fabricate electroresponsive OBC systems are first discussed for several OBCs differing in composition and bulk properties. Evidence of electroactuation in selectively-solvated OBC systems is presented and performance metrics measured therefrom are quantitatively compared with dielectric elastomers derived from SBC and related materials.

  1. Acrylic Triblock Copolymers Incorporating Isosorbide for Pressure Sensitive Adhesives

    Energy Technology Data Exchange (ETDEWEB)

    Gallagher, James J.; Hillmyer, Marc A.; Reineke, Theresa M. (UMM)

    2016-05-10

    A new monomer acetylated acrylic isosorbide (AAI) was prepared in two steps using common reagents without the need for column chromatography. Free radical polymerization of AAI afforded poly(acetylated acrylic isosorbide) (PAAI), which exhibited a glass transition temperature (Tg) = 95 °C and good thermal stability (Td, 5% weight loss; N2 = 331 °C, air = 291 °C). A series of ABA triblock copolymers with either poly(n-butyl acrylate) (PnBA) or poly(2-ethylhexyl acrylate) (PEHA) as the low Tg midblocks and PAAI as the high Tg end blocks were prepared using Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization. The triblock copolymers ranging from 8–24 wt % PAAI were evaluated as pressure sensitive adhesives by 180° peel, loop tack, and static shear testing. While the PAAI-PEHA-PAAI series exhibited poor adhesive qualities, the PAAI-PnBA-PAAI series of triblock copolymers demonstrated peel forces up to 2.9 N cm–1, tack forces up to 3.2 N cm–1, and no shear failure up to 10000 min. Dynamic mechanical analysis indicated that PAAI-PEHA-PAAI lacked the dissipative qualities needed to form an adhesive bond with the substrate, while the PAAI-PnBA-PAAI series exhibited a dynamic mechanical response consistent with related high performing PSAs.

  2. Ductile electroactive biodegradable hyperbranched polylactide copolymers enhancing myoblast differentiation.

    Science.gov (United States)

    Xie, Meihua; Wang, Ling; Guo, Baolin; Wang, Zhong; Chen, Y Eugene; Ma, Peter X

    2015-12-01

    Myotube formation is crucial to restoring muscular functions, and biomaterials that enhance the myoblast differentiation into myotubes are highly desirable for muscular repair. Here, we report the synthesis of electroactive, ductile, and degradable copolymers and their application in enhancing the differentiation of myoblasts to myotubes. A hyperbranched ductile polylactide (HPLA) was synthesized and then copolymerized with aniline tetramer (AT) to produce a series of electroactive, ductile and degradable copolymers (HPLAAT). The HPLA and HPLAAT showed excellent ductility with strain to failure from 158.9% to 42.7% and modulus from 265.2 to 758.2 MPa. The high electroactivity of the HPLAAT was confirmed by UV spectrometer and cyclic voltammogram measurements. These HPLAAT polymers also showed improved thermal stability and controlled biodegradation rate compared to HPLA. Importantly, when applying these polymers for myotube formation, the HPLAAT significantly improved the proliferation of C2C12 myoblasts in vitro compared to HPLA. Furthermore, these polymers greatly promoted myogenic differentiation of C2C12 cells as measured by quantitative analysis of myotube number, length, diameter, maturation index, and gene expression of MyoD and TNNT. Together, our study shows that these electroactive, ductile and degradable HPLAAT copolymers represent significantly improved biomaterials for muscle tissue engineering compared to HPLA. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Functionalized and graft copolymers of chitosan and its pharmaceutical applications.

    Science.gov (United States)

    Bhavsar, Chintan; Momin, Munira; Gharat, Sankalp; Omri, Abdelwahab

    2017-10-01

    Chitosan is the second most abundant natural polysaccharide. It belongs a family of polycationic polymers comprised of repetitive units of glucosamine and N-acetylglucosamine. Its biodegradability, nontoxicity, non-immunogenicity and biocompatibility along with properties like mucoadhesion, fungistatic and bacteriogenic have made chitosan an appreciated polymer with numerous applications in the pharmaceutical, comestics and food industry. However, the limited solubility of chitosan at alkaline and neutral pH limits its widespread commercial use. This can be circumvented by fabrication of chitosan by graft copolymerization with acyl, alkyl, monomeric and polymeric moieties. Areas covered: Modifications like quarterization, thiolation, acylation and grafting result in copolymers with higher mucoadhesion strength, increased hydrophobic interactions (advantageous in hydrophobic drug entrapment), and increased solubility in alkaline pH, the ability for adsorption of metal ions, protein and peptide delivery and nutrient delivery. Insights on methods of polymerization, including atomic transfer radical polymerization and click chemistry are discussed. Applications of such modified chitosan copolymers in medical and surgical, and drug delivery, including nasal, oral and buccal delivery have also been covered. Expert opinion: Despite a number of successful investigations, commercialization of chitosan copolymers still remains a challenge. Further advancements in polymerization techniques may address the unmet needs of the healthcare industry.

  4. Short-chain grafting of tetrahydrofuran and 1,4-dioxane cycles on vinylchloride-maleic anhydride copolymer

    Directory of Open Access Journals (Sweden)

    2009-01-01

    Full Text Available Mass increase of vinylchloride-maleic anhydride (VC-MA copolymer samples aged in tetrahydrofuran (THF or in 1,4-dioxane results from chemical interaction of VC-MA macromolecules with 1,4-dioxane or THF. Microstructure of the products of such modification was proved by infrared spectroscopy (IR- and nuclear magnetic resonance spectroscopy (13C NMR and 1H NMR. Mechanism of modification has been proposed. The results of microstructure research of VC-MA samples aged in THF and in 1,4-dioxane coincide with already known data on the reactions of opening of these and other oxygen-containing cycles under mild conditions.

  5. Atomic layer deposition assisted pattern transfer technology for ultra-thin block copolymer films

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wenhui; Luo, Jun; Meng, Lingkuan; Li, Junjie; Xiang, Jinjuan; Li, Junfeng; Wang, Wenwu; Chen, Dapeng; Ye, Tianchun; Zhao, Chao

    2016-08-31

    As an emerging developing technique for next-generation lithography, directed self-assembly (DSA) of block copolymer (BCP) has attracted numerous attention and has been a potential alternative to supplement the intrinsic limitations of conventional photolithography. In this work, the self-assembling properties of a lamellar diblock copolymer poly(styrene-b-methylmethacrylate) (PS-b-PMMA, 22k-b-22k, L{sub 0} = 25 nm) on Si substrate and an atomic layer deposition (ALD)-assisted pattern transfer technology for the application of DSA beyond 16/14 nm complementary metal oxide semiconductor (CMOS) technology nodes, were investigated. Firstly, two key processing parameters of DSA, i.e. annealing temperatures and durations of BCP films, were optimized to achieve low defect density and high productivity. After phase separation of BCP films, self-assembling patterns of low defect density should be transferred to the substrate. However, due to the nano-scale thickness and the weak resistance of BCP films to dry etching, it is nearly impossible to transfer the BCP patterns directly to the substrate. Therefore, an ALD-based technology was explored in this work, in which deposited Al{sub 2}O{sub 3} selectively reacts with PMMA blocks thus hardening the PMMA patterns. After removing PS blocks by plasma etching, hardened PMMA patterns were left and transferred to underneath SiO{sub 2} hard mask layer. Using this patterned hard mask, nanowire array of 25 nm pitch were realized on Si substrate. From this work, a high-throughput DSA baseline flow and related ALD-assisted pattern transfer technique were developed and proved to have good capability with the mainstream CMOS technology. - Highlights: • Optimization on self-assembly process for high productivity and low defectivity • Enhancement of etching ratio and resistance by atomic layer deposition (ALD) • A hard mask was used for pattern quality improvement and contamination control.

  6. Study of the interface solid/solutions containing PEO-PPO block copolymers and asphaltenes by FTIR/ATR; Estudo de solucoes de copolimeros em bloco de PEO-PPO contendo asfaltenos por FTIR/DTA

    Energy Technology Data Exchange (ETDEWEB)

    Aguiar, Janaina I.S.; Neto, Jessica S.G.; Mansur, Claudia R.E. [Universidade Federal do Rio de Janeiro, Instituto de Macromoleculas, Laboratorio de Macromoleculas e Coloides na Industria de Petroleo, Rio de Janeiro, RJ (Brazil)], E-mails: janaina_333@hotmail.com, kinha_dac_dm@hotmail.com; celias@ima.ufrj.br

    2011-07-01

    The formation of water/oil emulsions can cause problems in various stages of production, processing and refining of petroleum. In this study, the technique of Fourier transform infrared spectroscopy (FTIR) using the method of attenuated total reflectance (ATR) was applied to study the solid-solutions of block copolymers based on poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) interface and its interaction in this interface with asphaltenic fractions of petroleum. The solid is the crystal of the ATR. Initially, we determined the critical micelle concentration values of the copolymers, which were consistent those obtained by a tensiometer. Bottle Test was also performed to correlate the efficiency of PEO-PPO copolymers in the breaking of water/oil emulsions with its adsorption at the interfaces solutions. (author)

  7. Morphology evolution of PS-b-PDMS block copolymer and its hierarchical directed self-assembly on block copolymer templates

    DEFF Research Database (Denmark)

    Rasappa, Sozaraj; Schulte, Lars; Borah, Dipu

    2018-01-01

    Cylinder-forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS, 27.2k-b-11.7k, SD39) block copolymer having a total molecular weight of 39 kg mol−1 was exploited to achieve in-plane morphologies of lines, dots and antidots. Brush-free self-assembly of the SD39 on silicon substrates was invest...... substrates provides a simplified method for surface nanopatterning, templated growth of nanomaterials and nanofabrication....... the pattern into the underlying substrate. Directed self-assembly and hierarchical directed self-assembly on block copolymer templates for confinement of dots was successfully demonstrated. The strategy for achieving multiple morphologies using one BCP by mere choice of the annealing solvents on unmodified...

  8. Coarse-grained modeling of hybrid block copolymer system

    Science.gov (United States)

    Su, Yongrui

    This thesis is comprised of three major projects of my research. In the first project, I proposed a nanoparticle model and combined it with the Theoretically Informed Coarse Grained (TICG) model for pure polymer systems and the grand canonical slip springs model developed in our group to build a new model for entangled nanocomposites. With Molecule Dynamics(MD) simulation, I studied the mechanic properties of the nanocomposites, for example the influence of nanoparticles size and volume fraction on entanglements, the diffusion of polymers and nanoparticles, and the influence of nanoparticles size and volume fraction on viscosity et al.. We found that the addition of small-size nanoparticles reduces the viscosity of the nanocomposites, which is in contrary to what Einstein predicted a century ago. However, when particle increases its size to micrometers the Einstein predictions is recovered. From our simulation, we believe that small-size nanoparticles can more effectively decrease the entanglements of nanocomposites than larger particles. The free volume effect introduced by small-size nanoparticles also helps decrease the viscosity of the whole system. In the second project, I combined the Ohta-Kawasaki (OK) model [3] and the Covariance Matrix Adaptation Evolutionary Strategy(CMA-ES) to optimize the block copolymer blends self-assembly in the hole-shrink process. The aim is to predict the optimal composition and the optimal surface energy to direct the block copolymer blends self-assembly process in the confined hole. After optimization in the OK model, we calibrated the optimal results by the more reliable TICG model and got the same morphology. By comparing different optimization process, we found that the homopolymers which are comprised of the same monomers as either block of the block copolymer can form a perfect perforated hole and might have better performance than the pure block copolymer. While homopolymers which are comprised of a third-party monomers

  9. Self-Assembled Structures of PMAA-PMMA Block Copolymers : Synthesis, Characterization, and Self-Consistent Field Computations

    NARCIS (Netherlands)

    Li, Feng; Schellekens, Mike; de Bont, Jens; Peters, Ron; Overbeek, Ad; Leermakers, Frans A. M.; Tuinier, Remco

    2015-01-01

    Block copolymers composed of methacrylic acid (MAA) and methyl methacrylate (MMA) blocks are interesting candidates for replacing surfactants in emulsion polymerization methods. Here the synthesis and experimental characterization of well-defined PMAA-PMMA block copolymers made via RAFT

  10. Self-assembled structures of PMAA-PMMA block copolymers: Synthesis, characterization, and self-consistent field computations

    NARCIS (Netherlands)

    Li, F.; Schellekens, J.; Bont, de J.A.M.; Peters, R.; Overbeek, A.; Leermakers, F.A.M.; Tuinier, R.

    2015-01-01

    Block copolymers composed of methacrylic acid (MAA) and methyl methacrylate (MMA) blocks are interesting candidates for replacing surfactants in emulsion polymerization methods. Here the synthesis and experimental characterization of well-defined PMAA–PMMA block copolymers made via RAFT

  11. Microspheres for protein delivery prepared from amphiphilic multiblock copolymers. 1. influence of preparation techniques on particle characteristics and protein delivery

    NARCIS (Netherlands)

    Bezemer, J.M.; Radersma, R.; Grijpma, Dirk W.; Dijkstra, Pieter J.; van Blitterswijk, Clemens; Feijen, Jan

    2000-01-01

    The entrapment of lysozyme in amphiphilic multiblock copolymer microspheres by emulsification and subsequent solvent removal processes was studied. The copolymers are composed of hydrophilic poly(ethylene glycol) (PEG) blocks and hydrophobic poly(butylene terephthalate) (PBT) blocks. Direct solvent

  12. Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

    Energy Technology Data Exchange (ETDEWEB)

    Determan, Michael Duane [Iowa State Univ., Ames, IA (United States)

    2005-12-17

    The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated. This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi

  13. Valorization of industrial waste and by-product streams via fermentation for the production of chemicals and biopolymers.

    Science.gov (United States)

    Koutinas, Apostolis A; Vlysidis, Anestis; Pleissner, Daniel; Kopsahelis, Nikolaos; Lopez Garcia, Isabel; Kookos, Ioannis K; Papanikolaou, Seraphim; Kwan, Tsz Him; Lin, Carol Sze Ki

    2014-04-21

    The transition from a fossil fuel-based economy to a bio-based economy necessitates the exploitation of synergies, scientific innovations and breakthroughs, and step changes in the infrastructure of chemical industry. Sustainable production of chemicals and biopolymers should be dependent entirely on renewable carbon. White biotechnology could provide the necessary tools for the evolution of microbial bioconversion into a key unit operation in future biorefineries. Waste and by-product streams from existing industrial sectors (e.g., food industry, pulp and paper industry, biodiesel and bioethanol production) could be used as renewable resources for both biorefinery development and production of nutrient-complete fermentation feedstocks. This review focuses on the potential of utilizing waste and by-product streams from current industrial activities for the production of chemicals and biopolymers via microbial bioconversion. The first part of this review presents the current status and prospects on fermentative production of important platform chemicals (i.e., selected C2-C6 metabolic products and single cell oil) and biopolymers (i.e., polyhydroxyalkanoates and bacterial cellulose). In the second part, the qualitative and quantitative characteristics of waste and by-product streams from existing industrial sectors are presented. In the third part, the techno-economic aspects of bioconversion processes are critically reviewed. Four case studies showing the potential of case-specific waste and by-product streams for the production of succinic acid and polyhydroxyalkanoates are presented. It is evident that fermentative production of chemicals and biopolymers via refining of waste and by-product streams is a highly important research area with significant prospects for industrial applications.

  14. Fabrication of Hyperbranched Block-Statistical Copolymer-Based Prodrug with Dual Sensitivities for Controlled Release.

    Science.gov (United States)

    Zheng, Luping; Wang, Yunfei; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Ji, Xiangling; Wei, Hua

    2018-01-17

    Dendrimer with hyperbranched structure and multivalent surface is regarded as one of the most promising candidates close to the ideal drug delivery systems, but the clinical translation and scale-up production of dendrimer has been hampered significantly by the synthetic difficulties. Therefore, there is considerable scope for the development of novel hyperbranched polymer that can not only address the drawbacks of dendrimer but maintain its advantages. The reversible addition-fragmentation chain transfer self-condensing vinyl polymerization (RAFT-SCVP) technique has enabled facile preparation of segmented hyperbranched polymer (SHP) by using chain transfer monomer (CTM)-based double-head agent during the past decade. Meanwhile, the design and development of block-statistical copolymers has been proven in our recent studies to be a simple yet effective way to address the extracellular stability vs intracellular high delivery efficacy dilemma. To integrate the advantages of both hyperbranched and block-statistical structures, we herein reported the fabrication of hyperbranched block-statistical copolymer-based prodrug with pH and reduction dual sensitivities using RAFT-SCVP and post-polymerization click coupling. The external homo oligo(ethylene glycol methyl ether methacrylate) (OEGMA) block provides sufficient extracellularly colloidal stability for the nanocarriers by steric hindrance, and the interior OEGMA units incorporated by the statistical copolymerization promote intracellular drug release by facilitating the permeation of GSH and H + for the cleavage of the reduction-responsive disulfide bond and pH-liable carbonate link as well as weakening the hydrophobic encapsulation of drug molecules. The delivery efficacy of the target hyperbranched block-statistical copolymer-based prodrug was evaluated in terms of in vitro drug release and cytotoxicity studies, which confirms both acidic pH and reduction-triggered drug release for inhibiting proliferation of He

  15. Study of the molecular mobility of methyl-methacrylate and methacrylic acid copolymers by solid state NMR

    International Nuclear Information System (INIS)

    Tavares, Maria Ines B.; Mansur, Claudia R.E.; Monteiro, Elisabeth E.C.

    1997-01-01

    Several methyl-methacrylate/methacrylic acid copolymers were prepared in the presence of concentrated nitric acid. The obtained copolymers were characterized by molecular weigh determination and hydrolization degree. The molecular mobility of these copolymers was studied by solid state nuclear magnetic resonance. Results are presented

  16. Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Hvilsted, Søren

    2005-01-01

    Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either I phenylethylbromide or 1,4-...

  17. Pressure jump kinetics of disorder to BCC ordering in diblock copolymer micelles in a selective solvent

    Czech Academy of Sciences Publication Activity Database

    Liu, Y.; Spring, J. D.; Steinhart, Miloš; Bansil, R.

    2012-01-01

    Roč. 45, č. 22 (2012), s. 9147-9154 ISSN 0024-9297 Institutional support: RVO:61389013 Keywords : X-ray-scattering * block-copolymer * triblock copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 5.521, year: 2012

  18. Gas-permeation properties of poly(ethylene oxide) poly(butylene terephthalate block copolymers

    NARCIS (Netherlands)

    Metz, S.J.; Mulder, M.H.V.; Wessling, Matthias

    2004-01-01

    This paper reports the gas-permeation properties of poly(ethylene oxide) (PEO) poly(butylene terephthalate) (PBT) segmented multiblock copolymers. These block copolymers allow a precise structural modification by the amount of PBT and the PEO segment length, enabling a systematic study of the

  19. Light scattering from block copolymer melts near the order-disorder transition

    Czech Academy of Sciences Publication Activity Database

    Štěpánek, Petr; Lodge, T. P.; Bates, F. S.

    1994-01-01

    Roč. 2, - (1994), s. 110 ISSN 0009-2347. [Symposium Block Copolymer Dynamics, Chain Dynamics of Block Copolymers: Dynamics near the Ordering Transition. San Diego, 13.03.1994-18.03.1994] R&D Projects: GA AV ČR IA45023 Impact factor: 0.331, year: 1994

  20. About morphology in ethylene-propylene(-diene) copolymers-based latexes

    NARCIS (Netherlands)

    Tillier, D.L.; Meuldijk, J.; Hoehne, G.W.H.; Frederik, P.M.; Regev, O.; Koning, C.E.

    2005-01-01

    Coatings and engineering plastics often require high impact strength. This property can be achieved with tougheners. For the present paper, core-shell impact modifiers were synthesized using ethylene–propylene copolymers (EPM), ethylene–propylene-diene copolymers (EPDM) or a mixture of both types