Engineering a horseradish peroxidase C stable to radical attacks by mutating multiple radical coupling sites.

PubMed

Kim, Su Jin; Joo, Jeong Chan; Song, Bong Keun; Yoo, Young Je; Kim, Yong Hwan

2015-04-01

Peroxidases have great potential as industrial biocatalysts. In particular, the oxidative polymerization of phenolic compounds catalyzed by peroxidases has been extensively examined because of the advantage of this method over other conventional chemical methods. However, the industrial application of peroxidases is often limited because of their rapid inactivation by phenoxyl radicals during oxidative polymerization. In this work, we report a novel protein engineering approach to improve the radical stability of horseradish peroxidase isozyme C (HRPC). Phenylalanine residues that are vulnerable to modification by the phenoxyl radicals were identified using mass spectrometry analysis. UV-Vis and CD spectra showed that radical coupling did not change the secondary structure or the active site of HRPC. Four phenylalanine (Phe) residues (F68, F142, F143, and F179) were each mutated to alanine residues to generate single mutants to examine the role of these sites in radical coupling. Despite marginal improvement of radical stability, each single mutant still exhibited rapid radical inactivation. To further reduce inactivation by radical coupling, the four substitution mutations were combined in F68A/F142A/F143A/F179A. This mutant demonstrated dramatic enhancement of radical stability by retaining 41% of its initial activity compared to the wild-type, which was completely inactivated. Structure and sequence alignment revealed that radical-vulnerable Phe residues of HPRC are conserved in homologous peroxidases, which showed the same rapid inactivation tendency as HRPC. Based on our site-directed mutagenesis and biochemical characterization, we have shown that engineering radical-vulnerable residues to eliminate multiple radical coupling can be a good strategy to improve the stability of peroxidases against radical attack. © 2014 Wiley Periodicals, Inc.

Potential coupling effects of ammonia-oxidizing and anaerobic ammonium-oxidizing bacteria on completely autotrophic nitrogen removal over nitrite biofilm formation induced by the second messenger cyclic diguanylate.

PubMed

Wang, Chao; Liu, Sitong; Xu, Xiaochen; Zhao, Chuanqi; Yang, Fenglin; Wang, Dong

2017-05-01

The objective of this study was to investigate the influence of extracellular polymeric substance (EPS) on the coupling effects between ammonia-oxidizing bacteria (AOB) and anaerobic ammonium-oxidizing (anammox) bacteria for the completely autotrophic nitrogen removal over nitrite (CANON) biofilm formation in a moving bed biofilm reactor (MBBR). Analysis of the quantity of EPS and cyclic diguanylate (c-di-GMP) confirmed that the contents of polysaccharides and c-di-GMP were correlated in the AOB sludge, anammox sludge, and CANON biofilm. The anammox sludge secreted more EPS (especially polysaccharides) than AOB with a markedly higher c-di-GMP content, which could be used by the bacteria to regulate the synthesis of exopolysaccharides that are ultimately used as a fixation matrix, for the adhesion of biomass. Indeed, increased intracellular c-di-GMP concentrations in the anammox sludge enhanced the regulation of polysaccharides to promote the adhesion of AOB and formation of the CANON biofilm. Overall, the results of this study provide new comprehensive information regarding the coupling effects of AOB and anammox bacteria for the nitrogen removal process.

Mesoporous poly(ionic liquid) supported palladium(II) catalyst for oxidative coupling of benzene under atmospheric oxygen

NASA Astrophysics Data System (ADS)

Liu, Yangqing; Wang, Kai; Hou, Wei; Shan, Wanjian; Li, Jing; Zhou, Yu; Wang, Jun

2018-01-01

Multi-functional mesoporous poly(ionic liquid) (MPIL) containing pyridine-based ionic liquid (IL) moieties and adjacent double sbnd COOH groups was synthesized through the free radical copolymerization of IL monomer N-propane sulfonate-4-vinylpyridine, maleic anhydride and divinylbenzene. Palladium(II) species were anchored on this MPIL support, affording the first efficient heterogeneous catalyst for the oxidative coupling of benzene to biphenyl under atmospheric oxygen at low temperature. The biphenyl yield of 15.0% (selectivity: 98.5%, turnover number: 62) was even higher than the one over the homogeneous counterpart palladium acetate. The catalyst can be facilely separated and reused. The IL moiety in the polymeric framework endowed the formation of immobilized palladium(II) species with high electrophilicity, which responds to the high performance.

Recyclable magnetic nanocluster crosslinked with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) copolymer for adsorption with antibody.

PubMed

Prai-In, Yingrak; Boonthip, Chatchai; Rutnakornpituk, Boonjira; Wichai, Uthai; Montembault, Véronique; Pascual, Sagrario; Fontaine, Laurent; Rutnakornpituk, Metha

2016-10-01

Surface modification of magnetic nanoparticle (MNP) with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) (PEO-b-PVDM) diblock copolymers and its application as recyclable magnetic nano-support for adsorption with antibody were reported herein. PEO-b-PVDM copolymers were first synthesized via a reversible addition-fragmentation chain-transfer (RAFT) polymerization using poly(ethylene oxide) chain-transfer agent as a macromolecular chain transfer agent to mediate the RAFT polymerization of VDM. They were then grafted on amino-functionalized MNP by coupling with some azlactone rings of the PVDM block to form magnetic nanoclusters with tunable cluster size. The nanocluster size could be tuned by adjusting the chain length of the PVDM block. The nanoclusters were successfully used as efficient and recyclable nano-supports for adsorption with anti-rabbit IgG antibody. They retained higher than 95% adsorption of the antibody during eight adsorption-separation-desorption cycles, indicating the potential feasibility in using this novel hybrid nanocluster as recyclable support in cell separation applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Modeling Fungal Melanin Buildup: Biomimetic Polymerization of 1,8-Dihydroxynaphthalene Mapped by Mass Spectrometry.

PubMed

Cecchini, Martina Maya; Reale, Samantha; Manini, Paola; d'Ischia, Marco; De Angelis, Francesco

2017-06-12

Due to the emerging biomedical relevance and technological potential of fungal melanins, and prompted by the virtual lack of information about their structural arrangement, an optimized synthetic protocol has been devised for a potential structural model of Ascomyces allomelanin through enzyme-catalyzed oxidative polymerization of 1,8-dihydroxynaphthalene (1,8-DHN). Electrospray ionization mass spectrometry (ESI-MS) measurements of freshly synthesized DHN-polymer recorded in the negative ion mode allowed detection of oligomers up to m/z 4000, separated by 158 Da, corresponding to the in-chain DHN-unit. The dominant peaks were assigned to singly-charged distribution, up to 23 repeating units, whereas a doubly charged polymer distribution was also detectable. Chemical derivatization, ultra-performance liquid chromatography (UPLC)-ESI MS, and MS/MS data confirmed that oxidative polymerization of 1,8-DHN proceeds through C-C coupling of the naphthalene rings. The new insights reported here into synthetic 1,8-DHN oligomers/polymers as a mimic of fungal melanins may guide novel interesting advances and applications in the field of biomimetic functional materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heat resistant polymers of oxidized styrylphosphine

NASA Technical Reports Server (NTRS)

Paciorek, K. J. L. (Inventor)

1978-01-01

Homopolymers, copolymers and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer or by polymerizing p-diphenylphosphinestyrene and then oxidizing the polymerized monomer with an organoazide. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer. Flame resistant vinyl based polymers whose degradation products are non toxic and non corrosive are obtained.

Processable Electronically Conducting Polymers

DTIC Science & Technology

1991-01-01

polyheterocycles and will be discussed in detail later. The Grignard coupling reaction of alkyl substituted 1,4- dibromobenzenes was initially employed, as...R 2 ,R 3 ) along with alkyl , aryl, benzyl, and -CH 2 CN substituents on the nitrogen (R I ). Since aniline preferentially oxidatively polymerizes at...but, in the case of N-aryl substituted anilines , an alternative mecha- nism has been proposed [171], which is outlined in Scheme 9. Both poly(N

The oxidative dissolution of arsenopyrite (FeAsS) and enargite (Cu 3AsS 4) by Leptospirillum ferrooxidans

NASA Astrophysics Data System (ADS)

Corkhill, C. L.; Wincott, P. L.; Lloyd, J. R.; Vaughan, D. J.

2008-12-01

Arsenopyrite (FeAsS) and enargite (Cu 3AsS 4) fractured in a nitrogen atmosphere were characterised after acidic (pH 1.8), oxidative dissolution in both the presence and absence of the acidophilic microorganism Leptospirillum ferrooxidans. Dissolution was monitored through analysis of the coexisting aqueous solution using inductively coupled plasma atomic emission spectroscopy and coupled ion chromatography-inductively coupled plasma mass spectrometry, and chemical changes at the mineral surface observed using X-ray photoelectron spectroscopy and environmental scanning electron microscopy (ESEM). Biologically mediated oxidation of arsenopyrite and enargite (2.5 g in 25 ml) was seen to proceed to a greater extent than abiotic oxidation, although arsenopyrite oxidation was significantly greater than enargite oxidation. These dissolution reactions were associated with the release of ˜917 and ˜180 ppm of arsenic into solution. The formation of Fe(III)-oxyhydroxides, ferric sulphate and arsenate was observed for arsenopyrite, thiosulphate and an unknown arsenic oxide for enargite. ESEM revealed an extensive coating of an extracellular polymeric substance associated with the L. ferrooxidans cells on the arsenopyrite surface and bacterial leach pits suggest a direct biological oxidation mechanism, although a combination of indirect and direct bioleaching cannot be ruled out. Although the relative oxidation rates of enargite were greater in the presence of L. ferrooxidans, cells were not in contact with the surface suggesting an indirect biological oxidation mechanism. Cells of L. ferrooxidans appear able to withstand several hundreds of ppm of As(III) and As(V).

Polymerization method for formation of thermally exfoliated graphite oxide containing polymer

NASA Technical Reports Server (NTRS)

Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Adamson, Douglas (Inventor)

2010-01-01

A process for polymerization of at least one monomer including polymerizing the at least one monomer in the presence of a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 m(esp 2)/g to 2600 m(esp 2/g.

Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis.

PubMed

Szymański, Jan K; Temprano-Coleto, Fernando; Pérez-Mercader, Juan

2015-03-14

The cerium(IV)-alcohol couple in an acidic medium is an example of a redox system capable of initiating free radical polymerization. When the alcohol has a polymeric nature, the outcome of such a process is a block copolymer, a member of a class of compounds possessing many useful properties. The most common polymer with a terminal -OH group is poly(ethylene glycol) (PEG); however, the detailed mechanism of its reaction with cerium(IV) remains underexplored. In this paper, we report our findings for this reaction based on spectrophotometric measurements and kinetic modeling. We find that both the reaction order and the net rate constant for the oxidation process depend strongly on the nature of the acidic medium used. In order to account for the experimental observations, we postulate that protonation of PEG decreases its affinity for some of the cerium(IV)-sulfate complexes formed in the system.

Polymeric Systems for Amorphous Δ9-Tetrahydrocannabinol Produced by a Hot-Melt Method. Part II: Effect of Oxidation Mechanisms and Chemical Interactions on Stability

PubMed Central

MUNJAL, MANISH; ELSOHLY, MAHMOUD A.; REPKA, MICHAEL A.

2010-01-01

The objectives of the present research investigations were to (i) elucidate the mechanism for the oxidative degradation of Δ9-tetrahydrocannabinol (THC) in polymer matrix systems prepared by a hot-melt fabrication procedure, and (ii) study the potential for controlling these mechanisms to reduce the degradation of THC in solid dosage formulations. Various factors considered and applied included drug-excipient compatibility, use of antioxidants, cross-linking in polymeric matrices, microenvironment pH, and moisture effect. Instability of THC in polyethylene oxide (PEO)-vitamin E succinate (VES) patches was determined to be due to chemical interaction between the drug and the vitamin as well as with the atmospheric oxygen. Of the different classes and mechanisms of antioxidants studied, quenching of oxygen by reducing agents, namely, ascorbic acid was the most effective in stabilizing THC in PEO-VES matrices. Only 5.8% of the drug degraded in the ascorbic acid-containing patch as compared to the control (31.6%) after 2 months of storage at 40°C. This coupled with the cross-linking extent and adjustment of the pH microenvironment, which seemed to have an impact on the THC degradation, might be effectively utilized towards stabilization of the drug in these polymeric matrices and other pharmaceutical dosage forms. These studies are relevant to the development of a stable transmucosal matrix system for the therapeutic delivery of amorphous THC. PMID:16886199

Graphene oxide reinforced polymeric ionic liquid monolith solid-phase microextraction sorbent for high-performance liquid chromatography analysis of phenolic compounds in aqueous environmental samples.

PubMed

Sun, Min; Bu, Yanan; Feng, Juanjuan; Luo, Chuannan

2016-01-01

A graphene oxide reinforced polymeric ionic liquids monolith was obtained by copolymerization of graphene oxide doped 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate monomer and 1,6-di-(3-vinylimidazolium) hexane bihexafluorophosphate cross-linking agent. Coupled to high-performance liquid chromatography, the monolith was used as a solid-phase microextraction sorbent to analyze several phenolic compounds in aqueous samples. Under the optimized extraction and desorption conditions, linear ranges were 5-400 μg/L for 3-nitrophenol, 2-nitrophenol, and 2,5-dichlorophenol and 2-400 μg/L for 4-chlorophenol, 2-methylphenol, and 2,4,6-trichlorophenol (R(2) = 0.9973-0.9988). The limits of detection were 0.5 μg/L for 3-nitrophenol and 2-nitrophenol and 0.2 μg/L for the rest of the analytes. The proposed method was used to determine target analytes in groundwater from an industrial park and river water. None of the analytes was detected. Relative recoveries were in the range of 75.5-113%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inorganic-organic hybrid coatings on stainless steel by layer-by-layer deposition and surface-initiated atom-transfer-radical polymerization for combating biocorrosion.

PubMed

Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

2009-03-01

To improve the biocorrosion resistance of stainless steel (SS) and to confer the bactericidal function on its surface for inhibiting bacterial adhesion and biofilm formation, well-defined inorganic-organic hybrid coatings, consisting of the inner compact titanium oxide multilayers and outer dense poly(vinyl-N-hexylpyridinium) brushes, were successfully developed. Nanostructured titanium oxide multilayer coatings were first built up on the SS substrates via the layer-by-layer sol-gel deposition process. The trichlorosilane coupling agent, containing the alkyl halide atom-transfer-radical polymerization (ATRP) initiator, was subsequently immobilized on the titanium oxide coatings for surface-initiated ATRP of 4-vinylpyridine (4VP). The pyridium nitrogen moieties of the covalently immobilized 4VP polymer, or P(4VP), brushes were quaternized with hexyl bromide to produce a high concentration of quaternary ammonium salt on the SS surfaces. The excellent antibacterial efficiency of the grafted polycations, poly(vinyl-N-pyridinium bromide), was revealed by viable cell counts and atomic force microscopy images of the surface. The effectiveness of the hybrid coatings in corrosion protection was verified by the Tafel plot and electrochemical impedance spectroscopy measurements.

Use of Cu+1 dopant and it's doping effects on polyaniline conducting system in water and tetrahydrofuran

NASA Astrophysics Data System (ADS)

Ali, Vazid; Kaur, Raminder; Kamal, Neel; Singh, Sukhmehar; Jain, S. C.; Kang, H. P. S.; Zulfequar, M.; Husain, M.

2006-04-01

The structural modification and properties of polymeric materials are of utmost importance in deciding their applications. In the present study, the synthesis of polyaniline (PANI) has been carried out via chemical oxidation in acidic medium by potassium-dichromate and the yield of synthesized polyaniline was found to be 75 80%. The copper per chlorate tetrabenzonitrile salt (CuClO4·4BN) used for chemical doping in synthesized polyaniline is stable in organic solvent like acetonitrile (AN) and benzonitrile (BN). The effect of Cu+1 oxidation state (dopant) in polyaniline has been characterized by FTIR. Electrical and dielectric measurements show the decrease in the intensity of the Cu+1 salt signal and the appearance of a radical signal due to the formation of oxidative coupled in polymeric species. Electrical and dielectric properties of doped polyaniline samples show significant changes due to the effect of dopant (CuClO4·4BN). It is observed that the conductivity is contributing both by formation of ionic complex and particularly dominated by electronic due to the mobility of charge carriers along the polyaniline chain.

Improved performance of protected catecholic polysiloxanes for bio-inspired wet adhesion to surface oxides

PubMed Central

Heo, Jinhwa; Kang, Taegon; Jang, Se Gyu; Hwang, Dong Soo; Spruell, Jason M.; Killops, Kato L.; Waite, J. Herbert; Hawker, Craig J.

2012-01-01

A facile synthetic strategy for introducing catecholic moieties into polymeric materials based on a readily available precursor – eugenol – and efficient chemistries – tris(pentafluorophenyl)borane catalyzed silation and thiol-ene coupling is reported. Silyl-protection is shown to be critical for the oxidative stability of catecholic moieties during synthesis and processing which allows functionalized polysiloxane derivatives to be fabricated into 3-D microstructures as well as 2-D patterned surfaces. Deprotection gives stable catechol surfaces with adhesion to a variety of oxide surfaces being precisely tuned by the level of catechol incorporation. The advantage of silyl-protection for catechol functionalized polysiloxanes is demonstrated and represents a promising and versatile new platform for underwater surface treatments. PMID:23181614

Enzyme Histochemistry for Functional Histology in Invertebrates.

PubMed

Cima, Francesca

2017-01-01

In invertebrates, enzyme histochemistry has recently found a renaissance regarding its applications in morphology and ecology. Many enzyme activities are useful for the morphofunctional characterization of cells, as biomarkers of biological and pathologic processes, and as markers of the response to environmental stressors. Here, the adjustments to classic techniques, including the most common enzymes used for digestion, absorption, transport, and oxidation, as well as techniques for azo-coupling, metal salt substitution and oxidative coupling polymerization, are presented in detail for various terrestrial and aquatic invertebrates. This chapter also provides strategies to solve the problems regarding anesthesia, small body size, the presence of an exo- or endoskeleton and the search for the best fixative in relation to the internal fluid osmolarity. These techniques have the aim of obtaining good results for both the pre- and post-embedding labeling of specimens, tissue blocks, sections, and hemolymph smears using both light and transmission electron microscopy.

Accessing conjugated polymers with precisely controlled heterobisfunctional chain ends via post-polymerization modification of the OTf group and controlled Pd(0)/t-Bu 3P-catalyzed Suzuki cross-coupling polymerization

DOE PAGES

Hu, Qiao -Sheng; Hong, Kunlun; Zhang, Hong -Hai

2015-08-12

In this study, a general strategy toward the synthesis of well-defined conjugated polymers with controlled heterobisfunctional chain ends via combination of controlled Pd(0)/t-Bu 3P Suzuki cross-coupling polymerization with the post-polymerization modification of the triflate (OTf) group was disclosed.

Accessing conjugated polymers with precisely controlled heterobisfunctional chain ends via post-polymerization modification of the OTf group and controlled Pd(0)/t-Bu 3P-catalyzed Suzuki cross-coupling polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Qiao -Sheng; Hong, Kunlun; Zhang, Hong -Hai

In this study, a general strategy toward the synthesis of well-defined conjugated polymers with controlled heterobisfunctional chain ends via combination of controlled Pd(0)/t-Bu 3P Suzuki cross-coupling polymerization with the post-polymerization modification of the triflate (OTf) group was disclosed.

Studies on silicon NMR characterization and kinetic modeling of the structural evolution of siloxane-based materials and their applications in drug delivery and adsorption

NASA Astrophysics Data System (ADS)

Ambati, Jyothirmai

This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane-materials can be engineered for drug delivery and adsorption. The phase behavior of polymerizing mixtures is first investigated to identify the solutions that favor kinetic characterization. Microphase separation is found to cause gradual loss of NMR signal for certain initial compositions. Distortionless Enhancement by Polarization Transfer 29Si NMR is employed to identify the products of polymerization of some short-bridged silanes under no signal loss conditions. This technique requires knowing indirect 29Si-1H scalar coupling constants which sometimes cannot be measured due to second-order effects. However, the B3LYP density functional method with 6-31G basis set is found to predict accurate 29Si- 1H coupling constants of organoalkoxysilanes and siloxanes. The scalar coupling constants thus estimated are employed to resolve non-trivial coupled NMR spectra and quantitative kinetic modeling is performed using the DEPT Si NMR transients. In order to investigate the role of the organic bridging group, the structural evolution of bridged and non-bridged silanes are compared using Monte Carlo simulations. Kinetic and simulation models suggest that cyclization plays a key role right from the onset of polymerization for bridged silanes even more than in non-bridged silanes. The simulations indicate that the carbosiloxane rings formed from short-bridged precursors slow down but do not prevent gelation. The tuning of siloxane-based materials for adsorption technologies are also discussed here. In the first example, antioxidant enzyme loading is investigated as a means to reduce oxidative stress generated by silica nanoparticle drug carriers. Materials are engineered for promising enzyme loading and protection from proteolysis. Second, the potential of copper sulfate impregnation to enhance adsorption of ammonia by silica is explored by molecular simulation. KEYWORDS: Sol-gel Polymerization, Kinetic Investigation, Si NMR, Bridged Silanes, DFT Calculations.

Phosphine polymerization by nitric oxide: experimental characterization and theoretical predictions of mechanism.

PubMed

Zhao, Yi-Lei; Flora, Jason W; Thweatt, William David; Garrison, Stephen L; Gonzalez, Carlos; Houk, K N; Marquez, Manuel

2009-02-02

A yellow solid material [P(x)H(y)] has been obtained in the reaction of phosphine (PH(3)) and nitric oxide (NO) at room temperature and characterized by thermogravimetric analysis mass spectrometry (TGA-MS) and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. In this work using complete basis set (CBS-QB3) methods a plausible mechanism has been investigated for phosphine polymerization in the presence of nitric oxide (NO). Theoretical explorations with the ab initio method suggest (a) instead of the monomer the nitric oxide dimer acts as an initial oxidant, (b) the resulting phosphine oxides (H(3)P=O <--> H(3)P(+)O(-)) in the gas phase draw each other via strong dipolar interactions between the P-O groups, and (c) consequently an autocatalyzed polymerization occurs among the phosphine oxides, forming P-P chemical bonds and losing water. The possible structures of polyhydride phosphorus polymer were discussed. In the calculations a series of cluster models was computed to simulate polymerization.

Cellulose biogenesis: Polymerization and crystallization are coupled processes in Acetobacter xylinum.

PubMed

Benziman, M; Haigler, C H; Brown, R M; White, A R; Cooper, K M

1980-11-01

Calcofluor White ST, stilbene derivative used commerically as an optical brightener for cellulose, increased the rate of glucose polymerization into cellulose by resting cells of the gram-negative bacterium Acetobacter xylinum. This bacterium normally produces a ribbon of cellulose that is a composite of crystalline microfibrils. In concentrations above 0.1 mM, Calcofluor disrupts the assembly of crystalline cellulose I microfibrils and their integration into a composite ribbon by stoichiometric binding to glucose residues of newly polymerized glucan chains. Under these conditions, the rate of glucose polymerization increases up to 4 times the control rate, whereas oxygen uptake increases only 10-15%. These observed effects are readily reversible. If free Calcofluor is washed away or depleted below the threshold value by binding to cellulose as polymerization continues, ribbon production and the normal rate of polymerization resume. It is concluded that polymerization and crystallization are cell-directed, coupled processes and that the rate of crystallization determines the rate of polymerization. It is suggested that coupling must be maintained for biogenesis of crystalline cellulose I.

Surface functionalization of copper via oxidative graft polymerization of 2,2'-bithiophene and immobilization of silver nanoparticles for combating biocorrosion.

PubMed

Wan, Dong; Yuan, Shaojun; Neoh, K G; Kang, E T

2010-06-01

An environmentally benign approach to surface modification was developed to impart copper surface with enhanced resistance to corrosion, bacterial adhesion and biocorrosion. Oxidative graft polymerization of 2,2'-bithiophene from the copper surface with self-assembled 2,2'-bithiophene monolayer, and subsequent reduction of silver ions to silver nanoparticles (Ag NPs) on the surface, give rise to a homogeneous bithiophene polymer (PBT) film with densely coupled Ag NPs on the copper surface (Cu-g-PBT-Ag NP surface). The immobilized Ag NPs were found to significantly inhibit bacterial adhesion and enhance the antibacterial properties of the PBT modified copper surface. The corrosion inhibition performance of the functionalized copper substrates was evaluated by Tafel polarization curves and electrochemical impedance spectroscopy. Arising from the chemical affinity of thiols for the noble and coinage metals, the copper surface functionalized with both PBT brushes and Ag NPs also exhibits long-term stability, and is thus potentially useful for combating the combined problems of corrosion and biocorrosion in harsh marine and aquatic environments.

Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers

PubMed Central

Iacomino, Mariagrazia; Mancebo-Aracil, Juan; Guardingo, Mireia; Martín, Raquel; Perfetti, Marco; Manini, Paola; Crescenzi, Orlando; Busqué, Félix; Sedó, Josep; Ruiz-Molina, Daniel

2017-01-01

The oxidative polymerization of 5,6-dihydroxybenzothiophene (DHBT), the sulfur analog of the key eumelanin building block 5,6-dihydroxyindole (DHI), was investigated to probe the role of nitrogen in eumelanin build-up and properties. Unlike DHI, which gives a typical black insoluble eumelanin polymer on oxidation, DHBT is converted to a grayish amorphous solid (referred to as thiomelanin) with visible absorption and electron paramagnetic resonance properties different from those of DHI melanin. Mass spectrometry experiments revealed gradational mixtures of oligomers up to the decamer level. Quite unexpectedly, nuclear magnetic resonance (NMR) analysis of the early oligomer fractions indicated linear, 4-, and 7-linked structures in marked contrast with DHI, which gives highly complex mixtures of partially degraded oligomers. Density functional theory (DFT) calculations supported the tendency of DHBT to couple via the 4- and 7-positions. These results uncover the role of nitrogen as a major determinant of the structural diversity generated by the polymerization of DHI, and point to replacement by sulfur as a viable entry to regioregular eumelanin-type materials for potential applications for surface functionalization by dip coating. PMID:29039817

Method of making controlled morphology metal-oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ozcan, Soydan; Lu, Yuan

2016-05-17

A method of making metal oxides having a preselected morphology includes preparing a suspension that includes a solvent, polymeric nanostructures having multiplicities of hydroxyl surface groups and/or carboxyl surface groups, and a metal oxide precursor. The suspension has a preselected ratio of the polymeric nanostructures to the metal oxide precursor of at least 1:3, the preselected ratio corresponding to a preselected morphology. Subsequent steps include depositing the suspension onto a substrate, removing the solvent to form a film, removing the film from the substrate, and annealing the film to volatilize the polymeric nanostructures and convert the metal oxide precursor tomore » metal oxide nanoparticles having the preselected morphology or to a metal oxide nanosheet including conjoined nanoparticles having the preselected morphology.« less

Effect of Profilin on Actin Critical Concentration: A Theoretical Analysis

PubMed Central

Yarmola, Elena G.; Dranishnikov, Dmitri A.; Bubb, Michael R.

2008-01-01

To explain the effect of profilin on actin critical concentration in a manner consistent with thermodynamic constraints and available experimental data, we built a thermodynamically rigorous model of actin steady-state dynamics in the presence of profilin. We analyzed previously published mechanisms theoretically and experimentally and, based on our analysis, suggest a new explanation for the effect of profilin. It is based on a general principle of indirect energy coupling. The fluctuation-based process of exchange diffusion indirectly couples the energy of ATP hydrolysis to actin polymerization. Profilin modulates this coupling, producing two basic effects. The first is based on the acceleration of exchange diffusion by profilin, which indicates, paradoxically, that a faster rate of actin depolymerization promotes net polymerization. The second is an affinity-based mechanism similar to the one suggested in 1993 by Pantaloni and Carlier although based on indirect rather than direct energy coupling. In the model by Pantaloni and Carlier, transformation of chemical energy of ATP hydrolysis into polymerization energy is regulated by direct association of each step in the hydrolysis reaction with a corresponding step in polymerization. Thus, hydrolysis becomes a time-limiting step in actin polymerization. In contrast, indirect coupling allows ATP hydrolysis to lag behind actin polymerization, consistent with experimental results. PMID:18835900

Electrochemical and ab initio investigations to design a new phenothiazine based organic redox polymeric material for metal-ion battery cathodes.

PubMed

Godet-Bar, T; Leprêtre, J-C; Le Bacq, O; Sanchez, J-Y; Deronzier, A; Pasturel, A

2015-10-14

Different N-substituted phenothiazines have been synthesized and their electrochemical behavior has been investigated in CH3CN in order to design the best polyphenothiazine based cathodic material candidate for lithium batteries. These compounds exhibit two successive reversible one-electron oxidation processes. Ab initio calculations demonstrate that the potential of the first process is a result of both the hybridization effects between the substituent and the phenothiazine unit as well as the change of conformation of the phenothiazine heterocycle during the oxidation process. More specifically, we show that an asymmetric molecular orbital spreading throughout an external cycle of the phenothiazine unit and the alkyl fragment is formed only if the alkyl fragment is long enough (from the methyl moiety onwards) and is at the origin of the bent conformation for N-substituted phenothiazines during oxidation. Electrochemical investigations supported by ab initio calculations allow the selection of a phenothiazinyl unit which is then polymerized by a Suzuki coupling strategy to avoid the common solubilization issue in carbonate-based liquid electrolytes of lithium cells. The first electrochemical measurements performed show that phenothiazine derivatives pave the way for a promising family of redox polymers intended to be used as organic positives for lithium batteries.

In situ chemical oxidative polymerization preparation of poly(3,4-ethylenedioxythiophene)/graphene nanocomposites with enhanced thermoelectric performance.

PubMed

Xu, Kongli; Chen, Guangming; Qiu, Dong

2015-05-01

Three different in situ chemical oxidative polymerization routes, that is, (A) spin-coating and subsequent liquid layer polymerization, (B) spin-coating followed by vapor phase polymerization, and (C) in situ polymerization and then post-treatment by immersion in ethylene glycol (EG), have been developed to achieve poly(3,4-ethylenedioxythiophene)/reduced graphene oxide (PEDOT/rGO) nanocomposites. As demonstrated by scanning electron microscopic and energy-dispersive X-ray spectroscopic techniques, PEDOT has been successfully coated on the surface of the rGO nanosheets by each of the three preparation routes. Importantly, all of the nanocomposites display a greatly enhanced thermoelectric performance (power factors) relative to those of the corresponding neat PEDOT. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of polymeric Janus particles by directional UV-induced reactions.

PubMed

Liu, Lianying; Ren, Mingwei; Yang, Wantai

2009-09-15

Polymeric Janus particles are obtained by UV-induced selective surface grafting polymerizations and coupling reactions, in virtue of the light-absorption of photoreactive materials such as the immobilized photoinitiator and spread photoinitiator solution on the surfaces exposed to UV light and the sheltering of densely arrayed immovable particles from light. Varying the monomers or macromolecules applied in photografting polymerization or coupling reaction, and choosing diverse polymeric particles of various size, bicolor and amphiphilic Janus particles could be successfully achieved. Observations by fluorescence microscope, scanning electron microscope ,and transmission electron microscope confirmed the asymmetrical morphology of the resultant Janus particles.

Electrochemical energy storage by polyaniline nanofibers: high gravity assisted oxidative polymerization vs. rapid mixing chemical oxidative polymerization.

PubMed

Zhao, Yibo; Wei, Huige; Arowo, Moses; Yan, Xingru; Wu, Wei; Chen, Jianfeng; Wang, Yiran; Guo, Zhanhu

2015-01-14

Polyaniline (PANI) nanofibers prepared by high gravity chemical oxidative polymerization in a rotating packed bed (RPB) have demonstrated a much higher specific capacitance of 667.6 F g(-1) than 375.9 F g(-1) of the nanofibers produced by a stirred tank reactor (STR) at a gravimetric current of 10 A g(-1). Meanwhile, the cycling stability of the electrode is 62.2 and 65.9% for the nanofibers from RPB and STR after 500 cycles, respectively.

Gum and deposit formation in diesel fuels. Final report, 1984-1988

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayo, F.R.; Mill, T.

1988-05-15

The authors examined two aspects of the stability of diesel fuels in storage: the formation of sediments in suspension, which subsequently clog filters, and the formation of soluble gum, which passes the filters but then forms hard deposits on hot engine parts. Research on fuel stability at SRI during the last 6 years has shown that soluble gum appears first on storage, and then part of it grows into sediment. If the oxidation mixture is agitated gently, the precipitating gum grows on the surface gum, and no loose sediment is formed. Three mechanisms of gum formation were distinguished: (1) amore » process intimately associated with chain propagation and termination during oxidation, (2) a coupling of fuel molecules by decomposing peroxides in the absence of oxygen, and (3) a condensation of naphthols and aldehydes from the oxidation of alkylnaphthalenes. The polymeric oxidation products from a JP-8 fuel are shown to be largely responsible for deposits in the Jet Fuel Thermal Oxidation Tester (JFTOT).« less

Photoinduced Cross-Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling.

PubMed

Feillée, Noémi; Chemtob, Abraham; Ley, Christian; Croutxé-Barghorn, Céline; Allonas, Xavier; Ponche, Arnaud; Le Nouen, Didier; Majjad, Hicham; Jacomine, Léandro

2016-01-01

Initially developed as an elastomer with an excellent record of barrier and chemical resistance properties, poly(disulfide) has experienced a revival linked to the dynamic nature of the S-S covalent bond. A novel photobase-catalyzed oxidative polymerization of multifunctional thiols to poly(disulfide) network is reported. Based solely on air oxidation, the single-step process is triggered by the photodecarboxylation of a xanthone acetic acid liberating a strong bicyclic guanidine base. Starting with a 1 μm thick film based on trithiol poly(ethylene oxide) oligomer, the UV-mediated oxidation of thiols to disulfides occurs in a matter of minutes both selectively, i.e., without overoxidation, and quantitatively as assessed by a range of spectroscopic techniques. Thiolate formation and film thickness determine the reaction rates and yield. Spatial control of the photopolymerization serves to generate robust micropatterns, while the reductive cleavage of S-S bridges allows the recycling of 40% of the initial thiol groups. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

PubMed

Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

2015-03-06

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of molar ratio of oxidizer/3-hexylthiophene monomer in chemical oxidative polymerization of poly(3-hexylthiophene)

NASA Astrophysics Data System (ADS)

Hai, Thien An Phung; Sugimoto, Ryuichi

2017-10-01

Poly(3-hexylthiophene) (P3HT) was successfully prepared by oxidative polymerization of 3-hexylthiophene (3HT) using FeCl3 in various solvents, including hexane, nitrobenzene, and acetonitrile. The range of molar ratios between the oxidant and monomer used in the reactions was 1:1-1:10. A similar result was obtained when the polymerization was conducted in ethanol-free chloroform, which indicated that the Lewis acidity of anhydrous FeCl3 was significantly affected by even a small amount of ethanol. The yield of P3HT obtained in the above solvents was proportional to the monomer/FeCl3 molar ratio, and the yield in hexane was the highest among all solvents. Analysis of the methanol extract of P3HT using Surface-Assisted Laser Desorption/Ionization Time-Of-Light Mass Spectrometry (SALDI TOF MS) showed that the 3HT dimer was formed at the initial stage of polymerization. The structure of the oligomer was also analyzed using SALDI TOF MS and 1H NMR. These results provide detailed insights into the polymerization mechanism of 3HT with FeCl3 as oxidant.

Oxidative polymerization of lignins by laccase in water-acetone mixture.

PubMed

Fiţigău, Ionița Firuța; Peter, Francisc; Boeriu, Carmen Gabriela

2013-01-01

The enzymatic oxidative polymerization of five technical lignins with different molecular properties, i.e. Soda Grass/Wheat straw Lignin, Organosolv Hardwood Lignin, Soda Wheat straw Lignin, Alkali pretreated Wheat straw Lignin, and Kraft Softwood was studied. All lignins were previously fractionated by acetone/water 50:50 (v/v) and the laccase-catalyzed polymerization of the low molecular weight fractions (Mw < 4000 g/mol) was carried out in the same solvent system. Reactivity of lignin substrates in laccase-catalyzed reactions was determined by monitoring the oxygen consumption. The oxidation reactions in 50% acetone in water mixture proceed with high rate for all tested lignins. Polymerization products were analyzed by size exclusion chromatography, FT-IR, and (31)P-NMR and evidence of important lignin modifications after incubation with laccase. Lignin polymers with higher molecular weight (Mw up to 17500 g/mol) were obtained. The obtained polymers have potential for applications in bioplastics, adhesives and as polymeric dispersants.

Synergistic effect of graphene oxide on the methanol oxidation for fuel cell application

NASA Astrophysics Data System (ADS)

Siwal, Samarjeet; Ghosh, Sarit; Nandi, Debkumar; Devi, Nishu; Perla, Venkata K.; Barik, Rasmita; Mallick, Kaushik

2017-09-01

Aromatic polypyrene was synthesized by the oxidative polymerization of pyrene with potassium tetrachloropalladate (II), as oxidant. During the polymerization process the palladium salt was reduced to metallic palladium and forms the metal-polymer composite material. Polypyrene stabilized palladium nanoparticles showed electrocatalytic activity toward the oxidation of methanol. The performance of the electrocatalytic activity was substantially improved with the incorporation of graphene oxide to the palladium-polypyrene composite and the synergistic performance was attributed to the electronic and structural properties of the system.

Fabrication of multicolor fluorescent polyvinyl alcohol through surface modification with conjugated polymers by oxidative polymerization

NASA Astrophysics Data System (ADS)

Hai, Thien An Phung; Sugimoto, Ryuichi

2018-06-01

A simple method for the preparation of multicolor polyvinyl alcohol (PVA) by chemical oxidative polymerization is introduced. The PVA surface was successfully modified with conjugated polymers composed of 3-hexylthiophene (3HT) and fluorene (F). The incorporation of the 3HT/F copolymer onto the PVA surface was confirmed by Fourier-transform infrared (FT-IR), ultraviolet-visible (UV-vis), and fluorescence spectroscopies, X-ray diffraction (XRD), as well as thermogravimetric analysis (TGA), contact angle, and field-emission scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray (EDX) analysis. Different 3HT/F ratios on the PVA surface result in optical properties that include multicolor-emission and absorption behavior. The color of the resultant (3HT/F)-g-PVA shifted from red to blue, and the quantum yield increased with increasing F content. The surface hydrophobicity of the modified PVA increased significantly through grafting with the conjugated polymers, with the water contact angle increasing by 30° compared to pristine PVA. The PVA XRD peaks were less intense following surface modification. Thermogravimetric analyses reveal that the thermal stability of the PVA decreases as a result of grafting with the 3HT/F copolymers.

Tyrosinase-catalyzed oxidation of fluorophenols.

PubMed

Battaini, Giuseppe; Monzani, Enrico; Casella, Luigi; Lonardi, Emanuela; Tepper, Armand W J W; Canters, Gerard W; Bubacco, Luigi

2002-11-22

The activity of the type 3 copper enzyme tyrosinase toward 2-, 3-, and 4-fluorophenol was studied by kinetic methods and (1)H and (19)F NMR spectroscopy. Whereas 3- and 4-fluorophenol react with tyrosinase to give products that undergo a rapid polymerization process, 2-fluorophenol is not reactive and actually acts as a competitive inhibitor in the enzymatic oxidation of 3,4-dihydroxyphenylalanine (L-dopa). The tyrosinase-mediated polymerization of 3- and 4-fluorophenols has been studied in detail. It proceeds through a phenolic coupling pathway in which the common reactive fluoroquinone, produced stereospecifically by tyrosinase, eliminates an inorganic fluorine ion. The enzymatic reaction studied as a function of substrate concentration shows a prominent lag that is completely depleted in the presence of L-dopa. The kinetic parameters of the reactions can be correlated to the electronic and steric effects of the fluorine substituent position. Whereas the fluorine electron withdrawing effect appears to control the binding of the substrates (K(m) for 3- and 4-fluorophenols and K(I) for 2-fluorophenol), the k(cat) parameters do not follow the expected trend, indicating that in the transition state some additional steric effect rules the reactivity.

Lignin oxidation and pulp delignification by laccase and mediators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bourbonnais, R.; Paice, M.G.; Reid, I.D.

1996-10-01

The phenol oxidizing enzyme laccase is produced abundantly by the lignin-degrading fungus Trametes versicolor. We found previously that laccase can oxidize veratryl alcohol and other non-phenolic lignin model compounds when a mediator such as 2,2{prime}-azinobis(3-ethylbenzthiazoline-5-sulphonate) (ABTS) was present. The laccase/mediator couple was also shown to be effective for delignification of kraft pulps. Two different isozymes of laccase produced by this fungus were purified and their reactivities towards lignins and kraft pulps were studied. The mediator ABTS was shown to be essential for pulp delignification and to reverse the polymerization of kraft lignin by either laccase. Pulp delignification with laccase andmore » ABTS was also optimized. resulting in up to 55% lignin removal from kraft pulp following sequential enzyme treatments and alkaline extractions. Several variables were surveyed including enzyme and mediator dosage, oxygen pressure, temperature, reaction time, and pH.« less

Two Dimensional Polymer That Generates Nitric Oxide.

DOEpatents

McDonald, William F.; Koren, Amy B.

2005-10-04

A polymeric composition that generates nitric oxide and a process for rendering the surface of a substrate nonthrombogenic by applying a coating of the polymeric composition to the substrate are disclosed. The composition comprises: (1) a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, and (ii) a crosslinking agent containing functional groups capable of reacting with the amino groups; and (2) a plurality of nitric oxide generating functional groups associated with the crosslinked chemical combination. Once exposed to a physiological environment, the coating generates nitric oxide thereby inhibiting platelet aggregation. In one embodiment, the nitric oxide generating functional groups are provided by a nitrated compound (e.g., nitrocellulose) imbedded in the polymeric composition. In another embodiment, the nitric oxide generating functional groups comprise N2O2- groups covalently bonded to amino groups on the polymer.

[Chemical studies on plant polyphenols and formation of black tea polyphenols].

PubMed

Tanaka, Takashi

2008-08-01

Recent biological and pharmacological studies strongly suggested that plant polyphenols in foods, beverages and crude drugs have various health benefits. However, still there are chemically uncharacterized polyphenols, especially those with large molecular weights. The typical example is black tea polyphenols. Four tea catechins of fresh tea leaves are enzymatically oxidized in tea fermentation process of black tea manufacture to give a complex mixture of the oxidation products. Despite many efforts since 1950's, major part of the black tea polyphenols has not been clarified yet. We have investigated the oxidation mechanism of each catechin by employing a newly developed in vitro model fermentation system. The oxidation was initiated by enzymatic dehydrogenation of catechins, and subsequent intermolecular quinone-phenol coupling reactions followed by cascade-type degradation of the unstable products resulted in the formation of complex black tea polyphenols. Besides black tea polyphenols, this review introduces the chemistry of insolubilization of persimmon proanthocyanidins, wood polyphenols in connection with whisky polyphenols, and co-polymerization of cinnamaldehyde and proanthocyanidins in cinnamon bark.

Towards a mechanistic understanding of carbon stabilization in manganese oxides

PubMed Central

Johnson, Karen; Purvis, Graham; Lopez-Capel, Elisa; Peacock, Caroline; Gray, Neil; Wagner, Thomas; März, Christian; Bowen, Leon; Ojeda, Jesus; Finlay, Nina; Robertson, Steve; Worrall, Fred; Greenwell, Chris

2015-01-01

Minerals stabilize organic carbon (OC) in sediments, thereby directly affecting global climate at multiple scales, but how they do it is far from understood. Here we show that manganese oxide (Mn oxide) in a water treatment works filter bed traps dissolved OC as coatings build up in layers around clean sand grains at 3%w/wC. Using spectroscopic and thermogravimetric methods, we identify two main OC fractions. One is thermally refractory (>550 °C) and the other is thermally more labile (<550 °C). We postulate that the thermal stability of the trapped OC is due to carboxylate groups within it bonding to Mn oxide surfaces coupled with physical entrapment within the layers. We identify a significant difference in the nature of the surface-bound OC and bulk OC . We speculate that polymerization reactions may be occurring at depth within the layers. We also propose that these processes must be considered in future studies of OC in natural systems. PMID:26194625

Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation.

PubMed

Planes, G A; Rodríguez, J L; Miras, M C; García, G; Pastor, E; Barbero, C A

2010-09-21

Spectroscopic methods are used to investigate the formation of low molecular mass intermediates during aniline (ANI) oxidation and polyaniline (PANI) degradation. Studying ANI anodic oxidation by in situ Fourier transform infrared spectroscopy (FTIRS) it is possible to obtain, for the first time, spectroscopic evidence for ANI dimers produced by head-to-tail (4-aminodiphenylamine, 4ADA) and tail-to-tail (benzidine, BZ) coupling of ANI cation radicals. The 4ADA dimer is adsorbed on the electrode surface during polymerization, as proved by cyclic voltammetry of thin PANI films and its infrared spectrum. This method also allows, with the help of computational simulations, to assign characteristic vibration frequencies for the different oxidation states of PANI. The presence of 4ADA retained inside thin polymer layers is established too. On the other hand, FTIRS demonstrates that the electrochemically promoted degradation of PANI renders p-benzoquinone as its main product. This compound, retained inside the film, is apparent in the cyclic voltammogram in the same potential region previously observed for 4ADA dimer. Therefore, applying in situ FTIRS is possible to distinguish between different chemical species (4ADA or p-benzoquinone) which give rise to voltammetric peaks in the same potential region. Indophenol and CO(2) are also detected by FTIRS during ANI oxidation and polymer degradation. The formation of CO(2) during degradation is confirmed by differential electrochemical mass spectroscopy. To the best of our knowledge, this is the first evidence of the oxidation of a conducting polymer to CO(2) by electrochemical means. The relevance of the production of different intermediate species towards PANI fabrication and applications is discussed.

A Review of the Environmental Degradation, Ecotoxicity, and Bioaccumulation Potential of the Low Molecular Weight Polyether Polyol Substances.

PubMed

Schupp, Thomas; Austin, Tom; Eadsforth, Charles V; Bossuyt, Bart; Shen, Summer M; West, Robert J

"Polyalkylene glycol" is the name given to a broad class of synthetic organic chemicals which are produced by polymerization of one or more alkylene oxide (epoxide) monomers, such as ethylene oxide (EO) and propylene oxide (PO), with various initiator substances which possess amine or alcohol groups. A generalization of this polymerization reaction is illustrated in Fig. 1.

Oxidative Reactions with Nonaqueous Enzymes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jonathan S. Dordick; Douglas Clark; Brian H Davison

2001-12-30

The objective of this work is to demonstrate a proof-of-concept of enzymatic oxidative processing in nonaqueous media using alkene epoxidation and phenolic polymerization as relevant targets. This project will provide both the fundamental and applied investigations necessary to initiate the implementation of oxidative biocatalysts as commercially relevant alternatives to chemical processing in general, and to phenolic polymerizations and alkene epoxidation specifically. Thus, this work will address the Bioprocessing Solicitation Area to: (1) makes major improvements to phenolic polymerization and alkene epoxidation technologies; (2) is expected to be cost competitive with competing conventional processes; and (3) produces higher yields with lessmore » waste.« less

Durable metallized polymer mirror

DOEpatents

Schissel, Paul O.; Kennedy, Cheryl E.; Jorgensen, Gary J.; Shinton, Yvonne D.; Goggin, Rita M.

1994-01-01

A metallized polymer mirror construction having improved durability against delamination and tunneling, comprising: an outer layer of polymeric material; a metal oxide layer underlying the outer layer of polymeric material; a silver reflective layer underneath the metal oxide layer; and a layer of adhesive attaching the silver layer to a substrate.

Integrated optical components in thin films of polymers

NASA Technical Reports Server (NTRS)

Sarkisov, Sergey; Abdeldayem, Hossin; Venkateswarlu, Putcha; Teague, Zedric

1995-01-01

The results will be reported on the study of integrated optical components based on nonlinear optical polymeric films. Polymers poly(methyl methacrylate) (PMMA) and polyimide (PI) doped with organic laser dyes 4-dicyanomethylene-2-methyl-6-p dimethylaminostyryl-4H pyran (DCM) and 1, 3, 5, 7, 8 - pentamethyl-2,6 -diethyl-pyrromethene -BF2-complex (Pyrommethene 567, PM-567) were selected as materials for light guiding films. Additionally, UV polymerized polydiacetylene (PDA) on glass substrate was used as a waveguide material. Optical waveguides were fabricated using spin coating of preoxidized silicon wafers (1.5 micrometer silicon oxide layer) with organic dye/polymer solution followed by soft baking. the modes in slab waveguides were studied using prism coupling techniques. Measured values of mode coupling angles in multimode waveguides were used to calculate film thickness and refractive index for different polarizations. Refractive index anisotropy was found in PDA waveguide. The optimal conditions of spin coating for single mode waveguide fabrication were estimated. Propagation losses were measured by collecting the light scattered from the trace of a propagating mode either by scanning photo detector or by CCD camera. Different types of light coupling techniques were used including end-dire coupling, prism and grating coupling. Mechanical printing technique was developed for coupling grating fabrication resulting in gratings with 4% diffraction efficiency. The gratings demonstrated good stability with diffraction efficiency relaxation rate 2.4 dB/hour at a temperature approximately 15-20 C below glass transition point. Dye doped waveguides were transversally pumped with frequency doubled Nd:YAG Q-switched laser producing intensive light emission with apparent 6 kW/sq cm pump threshold and spectrum narrowing near 617 nm peak in the case of DCM doped waveguide. PM-567 doped waveguide pumped with CW Ar(+) laser (514 nm wavelength) far below threshold (0.1 W/sq.cm pump power) demonstrated emission spectrum narrowing near 616 nm peak with 18% power conversion slope efficiency. In this case emission spectrum modification was caused by the enhanced light absorption along the direction of propagating waveguide modes. Changing length, thickness, and other morphlogical waveguide parameters one can modify emission spectrum in predictable direction. The results show that polymeric waveguides, especially based on high temperature polymers such as Pl, can be used to produce a varietiy of active and passive silicon compatible integrated optical components for aerospace applications.

Photo-triggered solvent-free metamorphosis of polymeric materials.

PubMed

Honda, Satoshi; Toyota, Taro

2017-09-11

Liquefaction and solidification of materials are the most fundamental changes observed during thermal phase transitions, yet the design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion remains challenging. Here, we demonstrate that solvent-free repeatable molecular architectural transformation between liquid-star and nonliquid-network polymers that relies on cleavage and reformation of a covalent bond in hexaarylbiimidazole. Liquid four-armed star-shaped poly(n-butyl acrylate) and poly(dimethyl siloxane) with 2,4,5-triphenylimidazole end groups were first synthesized. Subsequent oxidation of the 2,4,5-triphenylimidazoles into 2,4,5-triphenylimidazoryl radicals and their coupling with these liquid star polymers to form hexaarylbiimidazoles afforded the corresponding nonliquid network polymers. The resulting nonliquid network polymers liquefied upon UV irradiation and produced liquid star-shaped polymers with 2,4,5-triphenylimidazoryl radical end groups that reverted to nonliquid network polymers again by recoupling of the generated 2,4,5-triphenylimidazoryl radicals immediately after terminating UV irradiation.The design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion is challenging. Here, the authors show solvent-free repeatable molecular architectural transformation between liquid-star and non-liquid-network polymers by the cleavage and reformation of covalent bonds in the polymer chain.

Flexible fluoropolymer filled protective coatings

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Mirtich, Michael J.; Sovey, James S.; Nahra, Henry; Rutledge, Sharon K.

1991-01-01

Metal oxide films such as SiO2 are known to provide an effective barrier to the transport of moisture as well as gaseous species through polymeric films. Such thin film coatings have a tendency to crack upon flexure of the polymeric substrate. Sputter co-deposition of SiO2 with 4 to 15 percent fluoropolymers was demonstrated to produce thin films with glass-like barrier properties that have significant increases in strain to failure over pure glass films which improves their tolerance to flexure on polymeric substrates. Deposition techniques capable of producing these films on polymeric substrates are suitable for durable food packaging and oxidation/corrosion protection applications.

Rapid Temperature Swing Adsorption using Polymeric/Supported Amine Hollow Fibers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chance, Ronald; Chen, Grace; Dai, Ying

This project is a bench-scale, post-combustion capture project carried out at Georgia Tech (GT) with support and collaboration with GE, Algenol Biofuels, Southern Company and subcontract to Trimeric Corporation. The focus of the project is to develop a process based on composite amine-functionalized oxide / polymer hollow fibers for use as contactors in a rapid temperature swing adsorption post-combustion carbon dioxide capture process. The hollow fiber morphology allows coupling of efficient heat transfer with effective gas contacting, potentially giving lower parasitic loads on the power plant compared to traditional contacting strategies using solid sorbents.

In situ functionalization and PEO coating of iron oxide nanocrystals using seeded emulsion polymerization.

PubMed

Kloust, Hauke; Schmidtke, Christian; Feld, Artur; Schotten, Theo; Eggers, Robin; Fittschen, Ursula E A; Schulz, Florian; Pöselt, Elmar; Ostermann, Johannes; Bastús, Neus G; Weller, Horst

2013-04-16

Herein we demonstrate that seeded emulsion polymerization is a powerful tool to produce multiply functionalized PEO coated iron oxide nanocrystals. Advantageously, by simple addition of functional surfactants, functional monomers, or functional polymerizable linkers-solely or in combinations thereof-during the seeded emulsion polymerization process, a broad range of in situ functionalized polymer-coated iron oxide nanocrystals were obtained. This was demonstrated by purposeful modulation of the zeta potential of encapsulated iron oxide nanocrystals and conjugation of a dyestuff. Successful functionalization was unequivocally proven by TXRF. Furthermore, the spatial position of the functional groups can be controlled by choosing the appropriate spacers. In conclusion, this methodology is highly amenable for combinatorial strategies and will spur rapid expedited synthesis and purposeful optimization of a broad scope of nanocrystals.

Durable metallized polymer mirror

DOEpatents

Schissel, P.O.; Kennedy, C.E.; Jorgensen, G.J.; Shinton, Y.D.; Goggin, R.M.

1994-11-01

A metallized polymer mirror construction is disclosed having improved durability against delamination and tunneling, comprising: an outer layer of polymeric material; a metal oxide layer underlying the outer layer of polymeric material; a silver reflective layer underneath the metal oxide layer; and a layer of adhesive attaching the silver layer to a substrate. 6 figs.

Prebiotic Polymerization: Oxidative Polymerization of 2,3 Dimercapto-1- Propanol on the Surface of Iron(III) Hydroxide Oxide

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1995-01-01

The oxidation of 2,3-dimercapto-1-propanol by ferric ions on the surface of iron(III) hydroxide oxide (Fe(OH)O) yielded polydisulfide oligomers. This polymerization occurred readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron(III) hydroxide oxide (20 mg, 160 micromole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the FE(OH)O phase. Reactions carried out at the same ratio of dithiol to FE(OH)O but at higher dithiol concentrations gave higher yields of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis is discussed.

Prebiotic polymerization: Oxidative polymerization of 2, 3-dimercapto-1-propanol on the surface of iron(III) hydroxide oxide

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1995-01-01

The oxidation of 2, 3-dimercapto-1-propanol by ferric ions on the surface of iron(III) hydroxide oxide (Fe(OH)O) yielded polydisulfide oligomers. This polymerization occurred readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron(III) hydroxide oxide (20 mg, 160 micromole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the Fe(OH)O phase. Reactions carried out at the same ratio of dithiol to Fe(OH)O but at higher dithiol concentrations gave higher yields of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis is discussed.

Stabilization of enzymatically polymerized phenolic chemicals in a model soil organic matter-free geomaterial.

PubMed

Palomo, Mónica; Bhandari, Alok

2012-01-01

A variety of remediation methods, including contaminant transformation by peroxidase-mediated oxidative polymerization, have been proposed to manage soils and groundwater contaminated with chlorinated phenols. Phenol stabilization has been successfully observed during cross polymerization between phenolic polymers and soil organic matter (SOM) for soils with SOM >3%. This study evaluates peroxidase-mediated transformation and removal of 2,4-dichlorophenol (DCP) from an aqueous phase in contact with a natural geomaterial modified to contain negligible (<0.3%) SOM. The results are compared with those for soils with higher SOM. The SOM-free sorbent was generated by removing SOM using a NaOCl oxidation. When horseradish peroxidase (HRP) was used to induce polymerization of DCP, the soil-water phase distribution relationship (PDR) of DCP polymerization products (DPP) was complete within 1 d and PDRs did not significantly change over the 28 d of study. The conversion of DCP to DPP was close to 95% efficient. Extractable solute consisted entirely of DPP with 5% or less of unreacted DCP. The aqueous extractability of DPP from SOM-free geomaterial decreased at longer contact times and at smaller residual aqueous concentrations of DPP. DCP stabilization appeared to have resulted from a combination of sorption, precipitation, and ligand exchange between oligomeric products and the exposed mineral surfaces. Modification of the mineral surface through coverage with DPP enhanced the time-dependent retention of the oligomers. DPP stabilization in SOM-free geomaterial was comparable with that reported in the literature with soil containing SOM contents >1%. Results from this study suggest that the effectiveness of HRP-mediated stabilization of phenolic compounds not only depends on the cross-coupling with SOM, but also on the modification of the surface of the sorbent that can augment affinity with oligomers and enhance stabilization. Coverage of the mineral surface by phenolic oligomers may be analogous to SOM that can potentially sorb other xenobiotics. HRP- mediated reactions can be used to stabilize DCP associated with low SOM mineral soils or aquifer media, thereby restricting the transport of phenolic contaminants in the soil environment. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Reduction of graphene oxide by aniline with its concomitant oxidative polymerization.

PubMed

Xu, Li Qun; Liu, Yi Liang; Neoh, Koon-Gee; Kang, En-Tang; Fu, Guo Dong

2011-04-19

Graphene oxide (GO) nanosheets are readily reduced by aniline above room temperature in an aqueous acid medium, with the aniline simultaneously undergoing oxidative polymerization to produce the reduced graphene oxide-polyaniline nanofiber (RGO-PANi) composites. The resulting RGO-PANi composites and RGO (after dissolution of PANi) were characterized by XPS, XRD analysis, TGA, UV-visible absorption spectroscopy, and TEM. It was also found that the RGO-PANi composites exhibit good specific capacitance during galvanostatic charging-discharging when used as capacitor electrodes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ polymerization of highly dispersed polypyrrole on reduced graphite oxide for dopamine detection.

PubMed

Qian, Tao; Yu, Chenfei; Wu, Shishan; Shen, Jian

2013-12-15

A composite consisting of reduced graphite oxide and highly dispersed polypyrrole nanospheres was synthesized by a straightforward technique, by in situ chemical oxidative polymerization. The novel polypyrrole nanospheres can prevent the aggregation of reduced graphite oxide sheets by electrostatic repulsive interaction, and enhance their electrochemical properties in the nano-molar measurement of dopamine in biological systems with a linear range of 1-8000 nM and a detection limit as low as 0.3 nM. © 2013 Elsevier B.V. All rights reserved.

Ring-opening polymerization of 19-electron [2]cobaltocenophanes: a route to high-molecular-weight, water-soluble polycobaltocenium polyelectrolytes.

PubMed

Mayer, Ulrich F J; Gilroy, Joe B; O'Hare, Dermot; Manners, Ian

2009-08-05

Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic polymerization of a strained 19-electron dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium chloride resulted in the formation of oligomers with up to nine repeat units. Thermal ROP of dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium nitrate resulted in the formation of high-molecular-weight polycobaltocenium nitrate, a redox-active cobalt-containing polyelectrolyte.

Novel synthesis of cobalt/poly vinyl alcohol/gamma alumina nanocomposite for catalytic application

NASA Astrophysics Data System (ADS)

Hatamie, Shadie; Ahadian, Mohammad Mahdi; Rashidi, Alimoradeh; Karimi, Ali; Akhavan, Omid

2017-05-01

In this manuscript, synthesis of cobalt/poly vinyl alcohol (PVA)/gamma alumina nanocomposite via a simple room temperature, as well as its catalyst performance were explored. Brunauer-Emmett-Teller analysis, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy were conducted. The surface area of the polymeric composite was obtained to be 280 m2/g. The cobalt loading on the nanocomposite was measured using inductivity couple plasma. Transmission electron microscopy analysis showed that the size of cobalt crystalline encapsulate inside the polymer was confined to 5 nm. Magnetic property analysis, using vibrating sample magnetometer, confirmed ferromagnetic nature of the composite. Thermo-gravimetric analyses were employed to explain the degradation process for the polymeric base nanocomposite. Temperature-programmed reduction was used to evaluate the structural form of cobalt oxide in nanocomposite. The catalysis activity was determined by Fischer-Tropsch synthesize, which showed a high catalyst selectivity to C2-C4 hydrocarbons.

Extracellular polymeric substances mediate bioleaching/biocorrosion via interfacial processes involving iron(III) ions and acidophilic bacteria.

PubMed

Sand, Wolfgang; Gehrke, Tilman

2006-01-01

Extracellular polymeric substances seem to play a pivotal role in biocorrosion of metals and bioleaching, biocorrosion of metal sulfides for the winning of precious metals as well as acid rock drainage. For better control of both processes, the structure and function of extracellular polymeric substances of corrosion-causing or leaching bacteria are of crucial importance. Our research focused on the extremophilic bacteria Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans, because of the "simplicity" and knowledge about the interactions of these bacteria with their substrate/substratum and their environment. For this purpose, the composition of the corresponding extracellular polymeric substances and their functions were analyzed. The extracellular polymeric substances of both species consist mainly of neutral sugars and lipids. The functions of the exopolymers seem to be: (i) to mediate attachment to a (metal) sulfide surface, and (ii) to concentrate iron(III) ions by complexation through uronic acids or other residues at the mineral surface, thus, allowing an oxidative attack on the sulfide. Consequently, dissolution of the metal sulfide is enhanced, which may result in an acceleration of 20- to 100-fold of the bioleaching process over chemical leaching. Experiments were performed to elucidate the importance of the iron(III) ions complexed by extracellular polymeric substances for strain-specific differences in oxidative activity for pyrite. Strains of A. ferrooxidans with a high amount of iron(III) ions in their extracellular polymeric substances possess greater oxidation activity than those with fewer iron(III) ions. These data provide insight into the function of and consequently the advantages that extracellular polymeric substances provide to bacteria. The role of extracellular polymeric substances for attachment under the conditions of a space station and resulting effects like biofouling, biocorrosion, malodorous gases, etc. will be discussed.

Polyacid macromolecule primers

DOEpatents

Sugama, Toshifumi

1989-01-01

Hydrophylic polyacids, such as macromolecules of polyitaconic acid and polyacrylic acid, where such macromolecules have molecular weights >50,000 as primers between a polymeric top coating, such as polyurethane, and an oxidized aluminum or aluminum alloy. A near monolayer of primer is used in polymeric adhesive/oxidized aluminum adhered joint systems in 0.05% primer concentration to give superior results in standard peel tests.

Selective extraction of metal ions with polymeric extractants by ion exchange/redox

DOEpatents

Alexandratos, Spiro D.

1987-01-01

The specification discloses a method for the extraction of metal ions having a reduction potential of above about +0.3 from an aqueous solution. The method includes contacting the aqueous solution with a polymeric extractant having primary phosphinic acid groups, secondary phosphine oxide groups, or both phosphinic acid and phosphine oxide groups.

Apparatus and method for stabilization or oxidation of polymeric materials

DOEpatents

Paulauskas, Felix L [Knoxville, TN; Sherman, Daniel M [Knoxville, TN

2010-01-19

An apparatus for treating polymeric materials comprises a treatment chamber adapted to maintain a selected atmosphere at a selected temperature; a means for supporting the polymeric material within the chamber; and, a source of ozone-containing gas, which decomposes at the selected temperature yielding at least one reactive oxidative species whereby the polymer is stabilized and cross linked through exposure to the oxidative species in the chamber at the selected temperature. The ozone may be generated by a plasma discharge or by various chemical processes. The apparatus may be configured for either batch-type or continuous-type processing. The apparatus and method are especially useful for preparing polymer fibers, particularly PAN fibers, for later carbonization treatments as well as to make flame-retardant fabrics.

Physico-chemical effects of supercritical carbon dioxide post polymerization treatment on HCl-doped polyaniline prepared via oxidative chemical polymerization

NASA Astrophysics Data System (ADS)

Fernando, J. G.; Vequizo, R. M.; Odarve, M. K. G.; Sambo, B. R. B.; Alguno, A. C.; Malaluan, R. M.; Candidato, R. T., Jr.; Gambe, J. E.; Jabian, M.; Paylaga, G. J.; Bagsican, F. R. G.; Miyata, H.

2015-06-01

Polyanilinefilms doped with varying HClconcentrations (0.2 M, 0.6 M and 1.0 M) were synthesized on glass substrates via oxidative polymerization of aniline. The films were treated with supercritical carbon dioxide (SC-CO2) at 30 MPa and 40°C for 30 minutes. Their structural, optical and morphological properties were studied and compared to conventionally prepared polyanilinefilms using FTIR analysis, UVVisspectroscopy and scanning electron microscopy. It was observed that supercritical carbon dioxide (SC-CO2) could interact with PANI films that consequently altered the bandgapsand changed the film thickness. SC-CO2 treatment also increased the oxidation level of polyanilinefilms and modified the morphology of polyanilinefilm doped with 1M HCl.

Conductive cotton prepared by polyaniline in situ polymerization using laccase.

PubMed

Zhang, Ya; Dong, Aixue; Wang, Qiang; Fan, Xuerong; Cavaco-Paulo, Artur; Zhang, Ying

2014-09-01

The high-redox-potential catalyst laccase, isolated from Aspergillus, was first used as a biocatalyst in the oxidative polymerization of water-soluble conductive polyaniline, and then conductive cotton was prepared by in situ polymerization under the same conditions. The polymerization of aniline was performed in a water dispersion of sodium dodecylbenzenesulfonate (SDBS) micellar solution with atmospheric oxygen serving as the oxidizing agent. This method is ecologically clean and permits a greater degree of control over the kinetics of the reaction. The conditions for polyaniline synthesis were optimized. Characterizations of the conducting polyaniline and cotton were carried out using Fourier transform infrared spectroscopy, UV-vis spectroscopy, cyclic voltammetry, the fabric induction electrostatic tester, and the far-field EMC shielding effectiveness test fixture.

Polymeric Coatings that Mimic the Endothelium: Combining Nitric Oxide Release with Surface-Bound Active Thrombomodulin and Heparin

PubMed Central

Wu, Biyun; Gerlitz, Bruce; Grinnell, Brian W.; Meyerhoff, Mark E.

2007-01-01

Multi-functional bilayer polymeric coatings are prepared with both controlled nitric oxide (NO) release and surface-bound active thrombomodulin (TM) alone or in combination with immobilized heparin. The outer-layer is made of CarboSil, a commercially available copolymer of silicone rubber (SR) and polyurethane (PU). The CarboSil is either carboxylated or aminated via an allophanate reaction with a diisocyanate compound followed by a urea-forming reaction between the generated isocyanate group of the polymer and the amine group of an amino acid (glycine), an oligopeptide (triglycine) or a diamine. The carboxylated CarboSil can then be used to immobilize TM through the formation of an amide bond between the surface carboxylic acid groups and the lysine residues of TM. Aminated CarboSil can also be employed to initially couple heparin to the surface, and then the carboxylic acid groups on heparin can be further used to anchor TM. Both surface-bound TM and heparin’s activity are evaluated by chromogenic assays and found to be at clinically significant levels. The underlying NO release layer is made with another commercial SR-PU copolymer (PurSil) mixed with a lipophilic NO donor (N-diazeniumdiolated dibutylhexanediamine (DBHD/N2O2)). The NO release rate can be tuned by changing the thickness of top coatings, and the duration of NO release at physiologically relevant levels can be as long as 2 weeks. The combination of controlled NO release as well as immobilized active TM and heparin from/on the same polymeric surface mimics the highly thromboresistant endothelium layer. Hence, such multifunctional polymer coatings should provide more blood-compatible surfaces for biomedical devices. PMID:17597201

Application of controlled radical polymerization (CRP) in the design of functional biomedical architectures

NASA Astrophysics Data System (ADS)

Siegwart, Daniel John

In this thesis, atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization were utilized in the design of synthetic polymers to create tissue engineering scaffolds and drug delivery systems with improved control over structure and functionality. Thermo-sensitive injectable hydrogels based on poly(NIPAAm) with degradable ester units within the polymer backbone and at the cross-linking sites were prepared using ATRP and RAFT. Solvent induced morphologies of poly(methyl methacrylate-b-ethylene oxide-b-methyl methacrylate) triblock copolymers synthesized by ATRP were described. A micellar structure, composed of a hydrophobic PMMA core and a PEO shell was constructed for delivery of hydrophobic drugs. ATRP was carried out in inverse miniemulsion to prepare well defined functional nanogels that were capable of entrapping and releasing various molecules (Doxorubicin, carbohydrate-based drugs, fluorophores, and gold nanoparticles). The results demonstrated that nanogels prepared by ATRP in inverse miniemulsion could be internalized into cells via clathrin-mediated endocytosis. Nanogels functionalized with integrin-binding peptides increased cellular uptake. A process called Atom Transfer Radical Coupling (ATRC) was also described, which illustrated the power of functionality in ATRP. Finally, linear polymers and cross-linked nanogels were synthesized by ATRP and functionalized with biotin, pyrene, and peptide sequences, tying together the overall themes of structural control and functionality.

Conjugated Polymers Via Direct Arylation Polymerization in Continuous Flow: Minimizing the Cost and Batch-to-Batch Variations for High-Throughput Energy Conversion.

PubMed

Gobalasingham, Nemal S; Carlé, Jon E; Krebs, Frederik C; Thompson, Barry C; Bundgaard, Eva; Helgesen, Martin

2017-11-01

Continuous flow methods are utilized in conjunction with direct arylation polymerization (DArP) for the scaled synthesis of the roll-to-roll compatible polymer, poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(4,7-di(thiophen-2-yl)-benzo[c][1,2,5]thiadiazole)] (PPDTBT). PPDTBT is based on simple, inexpensive, and scalable monomers using thienyl-flanked benzothiadiazole as the acceptor, which is the first β-unprotected substrate to be used in continuous flow via DArP, enabling critical evaluation of the suitability of this emerging synthetic method for minimizing defects and for the scaled synthesis of high-performance materials. To demonstrate the usefulness of the method, DArP-prepared PPDTBT via continuous flow synthesis is employed for the preparation of indium tin oxide (ITO)-free and flexible roll-coated solar cells to achieve a power conversion efficiency of 3.5% for 1 cm 2 devices, which is comparable to the performance of PPDTBT polymerized through Stille cross coupling. These efforts demonstrate the distinct advantages of the continuous flow protocol with DArP avoiding use of toxic tin chemicals, reducing the associated costs of polymer upscaling, and minimizing batch-to-batch variations for high-quality material. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pseudocapacitive Electrodes Produced by Oxidant-Free Polymerization of Pyrrole between the Layers of 2D Titanium Carbide (MXene)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boota, Muhammad; Anasori, Babak; Voigt, Cooper

Heterocyclic pyrrole molecules are in situ aligned and polymerized in the ­absence of an oxidant between layers of the 2D Ti3C2Tx (MXene), resulting in high volumetric and gravimetric capacitances with capacitance retention of 92% after 25 000 cycles at a 100 mV s-1 scan rate.

Polyacid macromolecule primers

DOEpatents

Sugama, Toshifumi.

1989-12-26

Hydrophilic polyacids are described, such as macromolecules of polyitaconic acid and polyacrylic acid, where such macromolecules have molecular weights >50,000 as primers between a polymeric top coating, such as polyurethane, and an oxidized aluminum or aluminum alloy. A near monolayer of primer is used in polymeric adhesive/oxidized aluminum adhered joint systems in 0.05% primer concentration to give superior results in standard peel tests. 2 figs.

A label-free amplified fluorescence DNA detection based on isothermal circular strand-displacement polymerization reaction and graphene oxide.

PubMed

Li, Zhen; Zhu, Wenping; Zhang, Jinwen; Jiang, Jianhui; Shen, Guoli; Yu, Ruqin

2013-07-07

A label-free fluorescent DNA biosensor has been presented based on isothermal circular strand-displacement polymerization reaction (ICSDPR) combined with graphene oxide (GO) binding. The proposed method is simple and cost-effective with a low detection limit of 4 pM, which compares favorably with other GO-based homogenous DNA detection methods.

Comparative study on polyvinyl chloride film as flexible substrate for preparing free-standing polyaniline-based composite electrodes for supercapacitors.

PubMed

Wang, Hongxing; Liu, Dong; Du, Pengcheng; Wei, Wenli; Wang, Qi; Liu, Peng

2017-11-15

The free-standing polyaniline (PANI)-based composite film electrodes were prepared with polyvinyl chloride (PVC) and the aniline modified PVC (PVC-An) films as flexible substrates for supercapacitors, via facile in-situ chemical oxidative polymerization of aniline, with conventional chemical oxidative polymerization or rapid-mixing chemical oxidative polymerization technique. Owing to the grafting of PANI from the PVC-An film as substrate and the suppression of the secondary growth of the primary PANI particles in the rapid-mixing chemical oxidative polymerization, the PVC-g-PANI-2 composite film with loose surface possessed better comprehensive performance, accompanying the high specific capacitance (645.3F/g at a current density of 1A/g), good rate capacitance (retaining 63.2% of original value at a current density of 10A/g and 52.0% at a scan rate of 100mV/s), good cycle stability (retaining 83.1% after 1000 cycles) and the improved internal resistance. Besides its excellent flexibility, it could retain 61.2% of its original specific capacitance under the stress of 8.66MPa for 1h, demonstrating a good tensile-resistance. Copyright © 2017 Elsevier Inc. All rights reserved.

Apparatus and method for oxidation and stabilization of polymeric materials

DOEpatents

Paulauskas, Felix L [Knoxville, TN; White, Terry L [Knoxville, TN; Sherman, Daniel M [Knoxville, TN

2009-05-19

An apparatus for treating polymeric materials comprises a treatment chamber adapted to maintain a selected atmosphere; a means for supporting the polymeric material within the chamber; and, a source of plasma-derived gas containing at least one reactive oxidative species whereby the polymer is stabilized and cross linked through exposure to the oxidative species in the chamber at a selected temperature. The polymer may be directly exposed to the plasma, or alternatively, the plasma may be established in a separate volume from which the reactive species may be extracted and introduced into the vicinity of the polymer. The apparatus may be configured for either batch-type or continuous-type processing. The apparatus and method are especially useful for preparing polymer fibers, particularly PAN fibers, for later carbonization treatments.

Apparatus and method for oxidation and stabilization of polymeric materials

DOEpatents

Paulauskas, Felix L [Knoxville, TN; White, Terry L [Knoxville, TN; Sherman, Daniel M [Knoxville, TN

2010-08-31

An apparatus for treating polymeric materials comprises a treatment chamber adapted to maintain a selected atmosphere; a means for supporting the polymeric material within the chamber; and, a source of plasma-derived gas containing at least one reactive oxidative species whereby the polymer is stabilized and cross linked through exposure to the oxidative species in the chamber at a selected temperature. The polymer may be directly exposed to the plasma, or alternatively, the plasma may be established in a separate volume from which the reactive species may be extracted and introduced into the vicinity of the polymer. The apparatus may be configured for either batch-type or continuous-type processing. The apparatus and method are especially useful for preparing polymer fibers, particularly PAN fibers, for later carbonization treatments.

Ionic liquids as an electrolyte for the electro synthesis of organic compounds.

PubMed

Kathiresan, Murugavel; Velayutham, David

2015-12-25

The use of ionic liquids (ILs) as a solvent and an electrolyte for electro organic synthesis has been reviewed. To date several ILs exist, however the ILs based on tetraalkylammonium, pyrrolidinium, piperidinium and imidazolium cations with BF4(-), PF6(-), and TFSI anions have been widely used and explored the most. Electro organic synthesis in ionic liquid media leading to the synthesis of a wide range of organic compounds has been discussed. Anodic oxidation or cathodic reduction will generate radical cation or anion intermediates, respectively. These radicals can undergo self coupling or coupling with other molecules yielding organic compounds of interest. The cation of the IL is known to stabilize the radical anion extensively. This stabilization effect has a specific impact on the electrochemical CO2 reduction and coupling to various organics. The relative stability of the intermediates in IL leads to the formation of specific products in higher yields. Electrochemical reduction of imidazolium or thiazolium based ILs generates N-heterocyclic carbenes that have been shown to catalyze a wide range of base or nucleophile catalyzed organic reactions in IL media, an aspect that falls into the category of organocatalysis. Electrochemical fluorination or selective electrochemical fluorination is another fascinating area that delivers selectively fluorinated organic products in Et3N·nHF or Et4NF·nHF adducts (IL) via anodic oxidation. Oxidative polymerization in ILs has been explored the most; although morphological changes were observed compared to the conventional methods, polymers were obtained in good yields and in some cases ILs were used as dopants to improve the desired properties.

Polymeric peptide pigments with sequence-encoded properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lampel, Ayala; McPhee, Scott A.; Park, Hang-Ah

Melanins are a family of heterogeneous polymeric pigments that provide ultraviolet (UV) light protection, structural support, coloration, and free radical scavenging. Formed by oxidative oligomerization of catecholic small molecules, the physical properties of melanins are influenced by covalent and noncovalent disorder. We report the use of tyrosine-containing tripeptides as tunable precursors for polymeric pigments. In these structures, phenols are presented in a (supra-)molecular context dictated by the positions of the amino acids in the peptide sequence. Oxidative polymerization can be tuned in a sequence-dependent manner, resulting in peptide sequence–encoded properties such as UV absorbance, morphology, coloration, and electrochemical properties overmore » a considerable range. Short peptides have low barriers to application and can be easily scaled, suggesting near-term applications in cosmetics and biomedicine.« less

Positron Annihilation Spectroscopy as a Novel Interfacial Probe for Thin Polymeric Films and Nano-Composites

NASA Astrophysics Data System (ADS)

Awad, Somia; Chen, Hongmin; Maina, Grace; Lee, L. James; Gu, Xiaohong; Jean, Y. C.

2010-03-01

Positron annihilation spectroscopy (PAS) has been developed as a novel probe to characterize the sub-nanometer defect, free volume, profile from the surface, interfaces, and to the bulk in polymeric materials when a variable mono-energy slow positron beam is used. Free-volume hole sizes, fractions, and distributions are measurable as a function of depth at the high precision. PAS has been successfully used to study the interfacial properties of polymeric nanocomposites at different chemical bonding. In nano-scale thin polymeric films, such as in PS/SiO2, and PU/ZnO, significant variations of Tg as a function of depth and of wt% oxide are observed. Variations of Tg are dependent on strong or weak interactions between polymers and nano-scale oxides surfaces.

Free-radical solution-polymerization of trifluoronitrosomethane with tetrafluoroethylene

NASA Technical Reports Server (NTRS)

Gdickman, S. A.

1972-01-01

Heavy-walled glass reactor, equipped with aerosol-compatible couplings and needle valve and charged with solvent and initiator, is utilized for polymerization. Polymer conversions and reactor/vessel operation are discussed.

Molecular dynamics simulation of the polymer electrolyte poly(ethylene oxide)/LiClO(4). II. Dynamical properties.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2006-12-07

The dynamical properties of the polymer electrolyte poly(ethylene oxide) (PEO)LiClO(4) have been investigated by molecular dynamics simulations. The effect of changing salt concentration and temperature was evaluated on several time correlation functions. Ionic displacements projected on different directions reveal anisotropy in short-time (rattling) and long-time (diffusive) dynamics of Li(+) cations. It is shown that ionic mobility is coupled to the segmental motion of the polymeric chain. Structural relaxation is probed by the intermediate scattering function F(k,t) at several wave vectors. Good agreement was found between calculated and experimental F(k,t) for pure PEO. A remarkable slowing down of polymer relaxation is observed upon addition of the salt. The ionic conductivity estimated by the Nernst-Einstein equation is approximately ten times higher than the actual conductivity calculated by the time correlation function of charge current.

Effect of modified graphene on thermal, mechanical and tribological performance of polyimide based composites

NASA Astrophysics Data System (ADS)

Li, Duxin; Yang, Wenyan; Chen, Yue; Xiao, Chunguang; Wei, Mengling

2018-06-01

The graphene oxide sheets (GO) were modified by silane coupling before incorporation into the aromatic polyimide (PI) matrix via in situ polymerization. The successful grafting of silane coupling onto the surface of the graphene was confirmed by FTIR, x-ray diffraction, and Raman spectroscopy. The incorporation of modified graphene oxide(K-GO) sheets significantly enhanced the thermal stability and tensile properties of PI. It was found that the tensile stress and the Young’s modulus of 0.5 wt%K-GO/PI were increased by 27.2% and 28.0% from pure PI, respectively. The T5% values of 0.5%K-GO/PI (507 °C) were obviously higher than that of pure PI (491 °C). Compared to pure PI, the PI composites with the K-GO addition of 0.5 wt% exhibits much lower friction coefficient (0.361) and wear rate (1.247 × 10‑5 mm3 N‑1m‑1). This can be attributed to the enhanced effect of K-GO addition on the properties of the composites. This study aims to expand the range of applications of graphene and to solve wear-related mechanical failures for polymer parts.

Morphological control of conductive polymers utilized electrolysis polymerization technique: trial of fabricating biocircuit.

PubMed

Onoda, Mitsuyoshi

2014-10-01

Conductive polymers are a strong contender for making electronic circuits. The growth pattern in conductive polymer synthesis by the electrolysis polymerization method was examined. The growth pattern is deeply related to the coupling reaction of the radical cation and the deprotonation reaction following it and changes suddenly depending on the kind and concentration of the supporting electrolyte and the solvent used. That is, when the electrophilic substitution coupling reaction becomes predominant, the three-dimensional growth form is observed, and when the radical coupling reaction becomes predominant, the two-dimensional growth morphology is observed. In addition, the growth pattern can be comparatively easily controlled by changing the value of the polymerization constant current, and it is considered that the indicator and development for biocircuit research with neuron-type devices made of conjugated polymers was obtained.

Substrate-Mediated C-C and C-H Coupling after Dehalogenation.

PubMed

Kong, Huihui; Yang, Sha; Gao, Hongying; Timmer, Alexander; Hill, Jonathan P; Díaz Arado, Oscar; Mönig, Harry; Huang, Xinyan; Tang, Qin; Ji, Qingmin; Liu, Wei; Fuchs, Harald

2017-03-15

Intermolecular C-C coupling after cleavage of C-X (mostly, X = Br or I) bonds has been extensively studied for facilitating the synthesis of polymeric nanostructures. However, the accidental appearance of C-H coupling at the terminal carbon atoms would limit the successive extension of covalent polymers. To our knowledge, the selective C-H coupling after dehalogenation has not so far been reported, which may illuminate another interesting field of chemical synthesis on surfaces besides in situ fabrication of polymers, i.e., synthesis of novel organic molecules. By combining STM imaging, XPS analysis, and DFT calculations, we have achieved predominant C-C coupling on Au(111) and more interestingly selective C-H coupling on Ag(111), which in turn leads to selective synthesis of polymeric chains or new organic molecules.

Surface chemical immobilization of bioactive peptides on synthetic polymers for cardiac tissue engineering.

PubMed

Rosellini, Elisabetta; Cristallini, Caterina; Guerra, Giulio D; Barbani, Niccoletta

2015-01-01

The aim of this work was the development of new synthetic polymeric systems, functionalized by surface chemical modification with bioactive peptides, for myocardial tissue engineering. Polycaprolactone and a poly(ester-ether-ester) block copolymer synthesized in our lab, polycaprolactone-poly(ethylene oxide)-polycaprolactone (PCL-PEO-PCL), were used as the substrates to be modified. Two pentapeptides, H-Gly-Arg-Gly-Asp-Ser-OH (GRGDS) from fibronectin and H-Tyr-Ile-Gly-Ser-Arg-OH (YIGSR) from laminin, were used for the functionalization. Polymeric membranes were obtained by casting from solutions and then functionalized by means of alkaline hydrolysis and subsequent coupling of the bioactive molecules through 1-(3-dimethylaminopropyl)-3-ethylcarbodimide hydrochloride/N-hydroxysuccinimide chemistry. The hydrolysis conditions, in terms of hydrolysis time, temperature, and sodium hydroxide concentration, were optimized for the two materials. The occurrence of the coupling reaction was demonstrated by infrared spectroscopy, as the presence on the functionalized materials of the absorption peaks typical of the two peptides. The peptide surface density was determined by chromatographic analysis and the distribution was studied by infrared chemical imaging. The results showed a nearly homogeneous peptide distribution, with a density above the minimum value necessary to promote cell adhesion. Preliminary in vitro cell culture studies demonstrated that the introduction of the bioactive molecules had a positive effect on improving C2C12 myoblasts growth on the synthetic materials.

Chemistry of Secondary Polyphenols Produced during Processing of Tea and Selected Foods

PubMed Central

Tanaka, Takashi; Matsuo, Yosuke; Kouno, Isao

2010-01-01

This review will discuss recent progress in the chemistry of secondary polyphenols produced during food processing. The production mechanism of the secondary polyphenols in black tea, whisky, cinnamon, and persimmon fruits will be introduced. In the process of black tea production, tea leaf catechins are enzymatically oxidized to yield a complex mixture of oxidation products, including theaflavins and thearubigins. Despite the importance of the beverage, most of the chemical constituents have not yet been confirmed due to the complexity of the mixture. However, the reaction mechanisms at the initial stages of catechin oxidation are explained by simple quinone–phenol coupling reactions. In vitro model experiments indicated the presence of interesting regio- and stereoselective reactions. Recent results on the reaction mechanisms will be introduced. During the aging of whisky in oak wood barrels, ellagitannins originating from oak wood are oxidized and react with ethanol to give characteristic secondary ellagitannins. The major part of the cinnamon procyanidins is polymerized by copolymerization with cinnamaldehyde. In addition, anthocyanidin structural units are generated in the polymer molecules by oxidation which accounts for the reddish coloration of the cinnamon extract. This reaction is related to the insolubilization of proanthocyanidins in persimmon fruits by condensation with acetaldehyde. In addition to oxidation, the reaction of polyphenols with aldehydes may be important in food processing. PMID:20161999

Method of Cross-Linking Aerogels Using a One-Pot Reaction Scheme

NASA Technical Reports Server (NTRS)

Meador, Ann B.; Capadona, Lynn A.

2008-01-01

A document discusses a new, simplified method for cross-linking silica and other oxide aerogels, with a polymeric material to increase strength of such materials without adversely affecting porosity or low density. This innovation introduces the polymer precursor into the sol before gelation either as an agent, which co-reacts with the oxide gel, or as soluble polymer precursors, which do not interact with the oxide gel in any way. Subsequent exposure to heat, light, catalyst or other method of promoting polymerization causes cross-linking without any additional infiltration steps.

Occurrence and Speciation of Polymeric Chromium(III), Monomeric Chromium(III) and Chromium(VI) in Environmental Samples

PubMed Central

HU, LIGANG; CAI, YONG; JIANG, GUIBIN

2016-01-01

Laboratory experiments suggest that polymeric Cr(III) could exist in aqueous solution for a relative long period of time. However, the occurrence of polymeric Cr(III) has not been reported in environmental media due partially to the lack of method for speciating polymeric Cr. We observed an unknown Cr species during the course of study on speciation of Cr in the leachates of chromated-copper-arsenate (CCA)-treated wood. Efforts were made to identify structure of the unknown Cr species. Considering the forms of Cr existed in the CCA-treated woods, we mainly focused our efforts to determine if the unknown species were polymeric Cr(III), complex of Cr/As or complex of Cr with dissolved organic matter (DOM). In order to evaluate whether polymeric Cr(III) largely exist in wood leachates, high performance liquid chromatography coupled with inductively coupled mass spectrometry (HPLC-ICPMS was used) for simultaneous speciation of monomeric Cr(III), polymeric Cr(III), and Cr(VI). In addition to wood leachates where polymeric Cr (III) ranged from 39.1 to 67.4 %, occurrence of the unknown Cr species in other environmental matrices, including surface waters, tap and waste waters, was also investigated. It was found that polymeric Cr(III) could exist in environmental samples containing μg/L level of Cr, at a level up to 60% of total Cr, suggesting that polymeric Cr(III) could significantly exist in natural environments. Failure in quantifying polymeric Cr(III) would lead to the underestimation of total Cr and bias in Cr speciation. The environmental implication of the presence of polymeric Cr(III) species in the environment deserves further study. PMID:27156211

Control of lipid oxidation by nonmigratory active packaging films prepared by photoinitiated graft polymerization.

PubMed

Tian, Fang; Decker, Eric A; Goddard, Julie M

2012-08-08

Transition metal-promoted oxidation impacts the quality, shelf life, and nutrition of many packaged foods. Metal-chelating active packaging therefore offers a means to protect foods against oxidation. Herein, we report the development and characterization of nonmigratory metal-chelating active packaging. To prepare the films, carboxylic acids were grafted onto the surfaces of polypropylene films by photoinitiated graft polymerization of acrylic acid. Attenuated total reflectance/Fourier transform infrared spectroscopy, contact angle, scanning electron microscopy, and iron-chelating assay were used to characterize film properties. Graft polymerization yielded a carboxylic acid density of 68.67 ± 9.99 nmol per cm(2) film, with ferrous iron-chelating activity of 71.07 ± 12.95 nmol per cm(2). The functionalized films extended the lag phase of lipid oxidation in a soybean oil-in-water emulsion system from 2 to 9 days. The application of such nonmigratory active packaging films represents a promising approach to reduce additive use while maintaining food quality.

Synthesis and characterization of polymeric V2O5/AlO(OH) with nanopores on alumina support.

PubMed

Ahmad, A L; Abd Shukor, S R; Leo, C P

2006-12-01

Polymeric vanadium pentoxide gel was formed via the reaction of V2O5 powder with hydrogen peroxide. The polymeric vanadium pentoxide gel was then dispersed in alumina gel. Different vanadium loading composites were coated on alumina support and calcined at 500 degrees C for 1 hr. These composite layers were characterized using TGA, FT-IR, XRD, SEM, and Autosorb. It was found that the lamellar structure of polymerized vanadium pentoxide was retained in the inorganic matrix. Crystalline alumina in gamma phase was formed after calcinations. However, the vanadium-alumina mixed oxides are lack of the well defined PXRD peaks for polycrystalline V2O5. This is possibly because the vanadia species are highly dispersed in the alumina matrix or the vanadia species are dispersed as crystalline which is smaller than 4 nm. In addition, the imbedded polymeric vanadium oxide improved the specific area and average pore diameter of the composite layer.

Polymeric carbon nitride nanomesh as an efficient and durable metal-free catalyst for oxidative desulfurization.

PubMed

Shen, Lijuan; Lei, Ganchang; Fang, Yuanxing; Cao, Yanning; Wang, Xinchen; Jiang, Lilong

2018-03-06

We report the first use of polymeric carbon nitride (CN) for the catalytic selective oxidation of H 2 S. The as-prepared CN with unique ultrathin "nanomeshes" structure exhibits excellent H 2 S conversion and high S selectivity. In particular, the CN nanomesh also displays better durability in the desulfurization reaction than traditional catalysts, such as carbon- and iron-based materials.

Interactions between manganese oxides and multiple-ringed aromatic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whelan, G.; Sims, R.C.

1992-08-01

Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ''humic-like'' material precipitated,more » indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.« less

Interactions between manganese oxides and multiple-ringed aromatic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whelan, G.; Sims, R.C.

1992-08-01

Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment? Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ``humic-like`` material precipitated,more » indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.« less

Controllable fabrication of porous free-standing polypyrrole films via a gas phase polymerization.

PubMed

Lei, Junyu; Li, Zhicheng; Lu, Xiaofeng; Wang, Wei; Bian, Xiujie; Zheng, Tian; Xue, Yanpeng; Wang, Ce

2011-12-15

A facile gas phase polymerization method has been proposed in this work to fabricate porous free-standing polypyrrole (PPy) films. In the presence of pyrrole vapor, the films are obtained in the gas/water interface spontaneously through the interface polymerization with the oxidant of FeCl(3) in the water. Both the thickness of the film and the size of the pores could be controlled by adjusting the concentrations of the oxidant and the reaction time. The as-prepared PPy films exhibited a superhydrophilic behavior due to its composition and porous structures. We have demonstrated a possible formation mechanism for the porous free-standing PPy films. This gas phase polymerization is shown to be readily scalable to prepare large area of PPy films. Copyright © 2011 Elsevier Inc. All rights reserved.

Ferrocene adsorbed into the porous octakis(hydridodimethylsiloxy)silsesquioxane after thermolysis in tetrahydrofuran media: An applied surface for ascorbic acid determination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ribeiro do Carmo, Devaney, E-mail: docarmo@dfq.feis.unesp.br; Lataro Paim, Leonardo; Ramos Stradiotto, Nelson

Highlights: Black-Right-Pointing-Pointer Octakis(hydridodimethylsiloxi)silsesquioxane was synthesized and Ferrocene was adsorbed. Black-Right-Pointing-Pointer Polymeric net through electrostatic interactions was observed. Black-Right-Pointing-Pointer The novel materials presents electroacatalytic activity for Ascorbic acid. -- Abstract: Octakis(hydridodimethylsiloxi)silsesquioxane (Q{sub 8}M{sub 8}{sup H}) was synthesized and Ferrocene was adsorbed in a polymeric net through electrostatic interactions, with anion forming after the cleavage of any siloxy groups (ESFc). The nanostructured materials (Q{sub 8}M{sub 8}{sup H} and EsFc) were characterized by Fourier transform infrared spectra (FT-IR), nuclear magnetic resonance (NMR), X-ray diffraction (XRD), Thermogravimetric analyses and Voltammetric technique The cyclic voltammograms of the graphite paste electrode modified with ESFc showed onemore » redox couple with E{sup 0} Prime = 0.320 V (1.0 mol L{sup -1} NaCl, v = 50 mV s{sup -1}), with a diffusion-controlled process and the redox process shows electrocatalytic activity for the oxidation of ascorbic acid.« less

Thermal plasma process for recovering monomers and high value carbons from polymeric materials

DOEpatents

Knight, Richard; Grossmann, Elihu D.; Guddeti, Ravikishan R.

2002-01-01

The present invention relates to a method of recycling polymeric waste products into monomers and high value forms of carbon by pyrolytic conversion using an induction coupled RF plasma heated reactor.

Solvent free chemical oxidative polymerization as a universal method for the synthesis of ultra high molecular weight conjugated polymers based on 3,4-propylenedioxythiophenes.

PubMed

Kumar, Anshu; Singh, Rekha; Gopinathan, Sreelekha P; Kumar, Anil

2012-05-18

In this communication, we report on a solvent free chemical oxidative polymerization route for the monomers based on 3,4-propylenedioxythiophenes wherein the process is applicable to both solid as well as liquid monomers and results in the bulk synthesis of ultra high molecular weight polymers. This journal is © The Royal Society of Chemistry 2012

Boron/Carbon/Silicon/Nitrogen Ceramics And Precursors

NASA Technical Reports Server (NTRS)

Riccitiello, Salvatore; Hsu, Ming TA; Chen, Timothy S.

1996-01-01

Ceramics containing various amounts of boron, carbon, silicon, and nitrogen made from variety of polymeric precursors. Synthesized in high yield from readily available and relatively inexpensive starting materials. Stable at room temperature; when polymerized, converted to ceramics in high yield. Ceramics resist oxidation and other forms of degradation at high temperatures; used in bulk to form objects or to infiltrate other ceramics to obtain composites having greater resistance to oxidation and high temperatures.

Oxidation Kinetics of Bromophenols by Nonradical Activation of Peroxydisulfate in the Presence of Carbon Nanotube and Formation of Brominated Polymeric Products.

PubMed

Guan, Chaoting; Jiang, Jin; Pang, Suyan; Luo, Congwei; Ma, Jun; Zhou, Yang; Yang, Yi

2017-09-19

This work demonstrated that bromophenols (BrPs) could be readily oxidized by peroxydisulfate (PDS) activated by a commercial carbon nanotube (CNT), while furfuryl alcohol (a chemical probe for singlet oxygen ( 1 O 2 )) was quite refractory. Results obtained by radical quenching experiments, electron paramagnetic resonance spectroscopy, and Fourier transform infrared spectroscopy further confirmed the involvement of nonradical PDS-CNT complexes rather than 1 O 2 . Bicarbonate and chloride ion exhibited negligible impacts on BrPs degradation by the PDS/CNT system, while a significant inhibitory effect was observed for natural organic matter. The oxidation of BrPs was influenced by solution pH with maximum rates occurring at neutral pH. Linear free energy relationships (LFERs) were established between the observed pseudo-first-order oxidation rates of various substituted phenols and the classical descriptor variables (i.e., Hammett constant σ + , and half-wave oxidation potential E 1/2 ). Products analyses by liquid chromatography tandem mass spectrometry clearly showed the formation of hydroxylated polybrominated diphenyl ethers and hydroxylated polybrominated biphenyls on CNT surface. Their formation pathway possibly involved the generation of bromophenoxyl radicals from BrPs one-electron oxidation and their subsequent coupling reactions. These results suggest that the novel nonradical PDS/CNT oxidation technology is a good alternative for selectively eliminating BrPs with alleviating toxic byproducts in treated water effluent.

Near-Infrared Free-Radical and Free-Radical-Promoted Cationic Photopolymerizations by In-Source Lighting Using Upconverting Glass.

PubMed

Kocaarslan, Azra; Tabanli, Sevcan; Eryurek, Gonul; Yagci, Yusuf

2017-11-13

A method is presented for the initiation of free-radical and free-radical-promoted cationic photopolymerizations by in-source lighting in the near-infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron-transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free-radical-promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N-vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrasonic application to boost hydroxyl radical formation during Fenton oxidation and release organic matter from sludge

PubMed Central

Gong, Changxiu; Jiang, Jianguo; Li, De’an; Tian, Sicong

2015-01-01

We examined the effects of ultrasound and Fenton reagent on ultrasonic coupling Fenton oxidation (U+F) pre-treatment processes for the disintegration of wastewater treatment plant sludge. The results demonstrated that U+F treatment could significantly increase soluble chemical oxygen demand (SCOD), total organic carbon (TOC), and extracellular polymeric substances (EPS) concentrations in sludge supernatant. This method was more effective than ultrasonic (U) or Fenton oxidation (F) treatment alone. U+F treatment increased the release of SCOD by 2.1- and 1.4-fold compared with U and F alone, respectively. U+F treatment increased the release of EPS by 1.2-fold compared with U alone. After U+F treatment, sludge showed a considerably finer particle size and looser microstructure based on fluorescence microscopy, and the concentration of hydroxyl radicals (OH•) increased from 0.26 mM by F treatment to 0.43 mM by U+F treatment based on fluorescence spectrophotometer. This demonstrated that U+F treatment improves the release of organic matter from sludge. PMID:26066562

Interaction of Metal Oxides with Biomolecules: Implication in Astrobiology

NASA Astrophysics Data System (ADS)

Kamaluddin; Iqubal, Md. Asif

2014-08-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Polymerization of biomonomers could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

Surface functionalization of polyamide fiber via dopamine polymerization

NASA Astrophysics Data System (ADS)

Kuang, Xiao-Hui; Guan, Jin-Ping; Tang, Ren-Cheng; Chen, Guo-Qiang

2017-09-01

The oxidative polymerization of dopamine for the functional surface modification of textile fibers has drawn great attention. In this work, the functionalization of polyamide fiber via dopamine polymerization was studied with the aim of the fabrication of hydrophilic and antistatic surface. The conditions of dopamine application were first discussed in the absence of specific oxidants in terms of the apparent color depth of polyamide fiber. Dopamine concentration, pH and time were found to exert great impact on color depth. The highest color depth was achieved at pH 8.5. In the process of modification, polydopamine was deposited onto the surface of polyamide fiber. The modified polyamide fiber displayed a yellowish brown color with excellent wash and light color fastness, and exhibited good hydrophilic, UV protection and antistatic effects. A disadvantage of the present approach was the slow rate of dopamine polymerization and functionalization.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Mingyi; Xu, Xiaoyang, E-mail: xiaoyangxu2012@163.com; Wu, Tao

Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-raymore » photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.« less

Psidium guajava L. leaves as source of proanthocyanidins: Optimization of the extraction method by RSM and study of the degree of polymerization by NP-HPLC-FLD-ESI-MS.

PubMed

Díaz-de-Cerio, Elixabet; Pasini, Federica; Verardo, Vito; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio; Caboni, Maria Fiorenza

2017-01-30

Due to the importance of the proanthocyanidins (PAs) bioactivity and its relationship with the PAs degree of polymerization (DP), an experimental design was carried out to establish the best extraction conditions in order to evaluate the proanthocyanidins content and their degree of polymerization in Psidium guajava leaves at different oxidation state. Optimal conditions achieved by response surface methodology were 50% acetone/water (v/v), 48°C, 30min, and 0% acetic acid (v/v). The highest DP has been found in the low oxidized state (DP 13 plus the polymers). Medium and high oxidized state leaves reported a DP 11 plus the polymers. The total amounts of proanthocyanidins (sum of PAs by HPLC-FLD-ESI-MS) decreased when oxidation state of leaves increased (15.8±0.4, 12.6±0.4, and 10.5±0.3mg/g leaf dry weight (d.w.) in low, medium and high oxidized state leaves, respectively). Guava leaves present an interesting source of low DP-PAs. Copyright © 2016 Elsevier B.V. All rights reserved.

Board-to-board optical interconnection using novel optical plug and slot

NASA Astrophysics Data System (ADS)

Cho, In K.; Yoon, Keun Byoung; Ahn, Seong H.; Kim, Jin Tae; Lee, Woo Jin; Shin, Kyoung Up; Heo, Young Un; Park, Hyo Hoon

2004-10-01

A novel optical PCB with transmitter/receiver system boards and optical bakcplane was prepared, which is board-to-board interconnection by optical plug and slot. We report an 8Gb/s PRBS NRZ data transmission between transmitter system board and optical backplane embedded multimode polymeric waveguide arrays. The basic concept of ETRI's optical PCB is as follows; 1) Metal optical bench is integrated with optoelectronic devices, driver and receiver circuits, polymeric waveguide and access line PCB module. 2) Multimode polymeric waveguide inside an optical backplane, which is embedded into PCB. 3) Optical slot and plug for high-density(channel pitch : 500um) board-to-board interconnection. The polymeric waveguide technology can be used for transmission of data on transmitter/ receiver system boards and for backplane interconnections. The main components are low-loss tapered polymeric waveguides and a novel optical plug and slot for board-to-board interconnections, respectively. The optical PCB is characteristic of low coupling loss, easy insertion/extraction of the boards and, especially, reliable optical coupling unaffected from external environment after board insertion.

Compound oxidized styrylphosphine. [flame resistant vinyl polymers

NASA Technical Reports Server (NTRS)

Paciorek, K. J. L. (Inventor)

1979-01-01

A process is described for preparing flame resistant, nontoxic vinyl polymers which contain phosphazene groups and which do not emit any toxic or corrosive products when they are oxidatively degraded. Homopolymers, copolymers, and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer from a group of organic azides, or by polymerizing p-diphenylphosphinestyrene and then oxidizing that monomer with an organoazide from the group of (C6H5)2P(O)N3, (C6H5O)2P(O)N3, (C6H5)2C3N3(N3), and C6H5C3N3(N3)2. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer.

Contribution of galloylation and polymerization to the antioxidant activity of polyphenols in fish lipid systems.

PubMed

Iglesias, Jacobo; Pazos, Manuel; Lois, Salomé; Medina, Isabel

2010-06-23

Polyphenolic fractions extracted from pine (Pinus pinaster) bark, grape (Vitis vinifera) pomace, and witch hazel (Hamamelis virginiana) bark were selected for investigating the influence of the number of phenolic units, polymerization, and the content of esterified galloyl residues (galloylation) on their efficacy for inhibiting lipid oxidation in fish lipid enriched foodstuffs. Experiments carried out with nongalloylated pine bark fractions with different polymerization degrees demonstrated that the number of catechin residues per molecule modulates their reducing and chelating properties in solution. In real food systems such as bulk fish oil and fish oil-in-water emulsions, the efficacy against lipid oxidation was highly dependent on the physical location of the antioxidant at the oxidative sensitive sites. The lowest polymerized fractions were the most efficient in bulk fish oil samples, whereas proanthocyanidins with an intermediate polymerization degree showed the highest activity in fish oil-in-water emulsions. Galloylation did not influence the antioxidant effectiveness of proanthocyanidins in bulk fish oils. The presence of galloyl groups favored the antioxidant activity of the polyphenols in emulsions, although results indicated that a high degree of galloylation did not improve significantly the activity found with medium galloylated proanthocyanidins. The results obtained in this research provide useful information about the relationship between structure and antioxidant activity in order to design antioxidant additives with application in fish oil-enriched functional foods.

Fiber-coupled THz spectroscopy for monitoring polymeric compounding processes

NASA Astrophysics Data System (ADS)

Vieweg, N.; Krumbholz, N.; Hasek, T.; Wilk, R.; Bartels, V.; Keseberg, C.; Pethukhov, V.; Mikulics, M.; Wetenkamp, L.; Koch, M.

2007-06-01

We present a compact, robust, and transportable fiber-coupled THz system for inline monitoring of polymeric compounding processes in an industrial environment. The system is built on a 90cm x 90cm large shock absorbing optical bench. A sealed metal box protects the system against dust and mechanical disturbances. A closed loop controller unit is used to ensure optimum coupling of the laser beam into the fiber. In order to build efficient and stable fiber-coupled antennas we glue the fibers directly onto photoconductive switches. Thus, the antenna performance is very stable and it is secured from dust or misalignment by vibrations. We discuss fabrication details and antenna performance. First spectroscopic data obtained with this system is presented.

Structural studies of novel glycoconjugates from polymerized allergens (allergoids) and mannans as allergy vaccines.

PubMed

Manzano, Ana I; Javier Cañada, F; Cases, Bárbara; Sirvent, Sofia; Soria, Irene; Palomares, Oscar; Fernández-Caldas, Enrique; Casanovas, Miguel; Jiménez-Barbero, Jesús; Subiza, José L

2016-02-01

Immunotherapy for treating IgE-mediated allergies requires high doses of the corresponding allergen. This may result in undesired side effects and, to avoid them, hypoallergenic allergens (allergoids) polymerized with glutaraldehyde are commonly used. Targeting allergoids to dendritic cells to enhance cell uptake may result in a more effective immunotherapy. Allergoids coupled to yeast mannan, as source of polymannoses, would be suitable for this purpose, since mannose-binding receptors are expressed on these cells. Conventional conjugation procedures of mannan to proteins use oxidized mannan to release reactive aldehydes able to bind to free amino groups in the protein; yet, allergoids lack these latter because their previous treatment with glutaraldehyde. The aim of this study was to obtain allergoids conjugated to mannan by an alternative approach based on just glutaraldehyde treatment, taking advantage of the mannoprotein bound to the polymannose backbone. Allergoid-mannan glycoconjugates were produced in a single step by treating with glutaraldehyde a defined mixture of allergens derived from Phleum pratense grass pollen and native mannan (non-oxidized) from Saccharomyces cerevisae. Analytical and structural studies, including 2D-DOSY and (1)H-(13)C HSQC nuclear magnetic resonance spectra, demonstrated the feasibility of such an approach. The glycoconjugates obtained were polymers of high molecular weight showing a higher stability than the native allergen or the conventional allergoid without mannan. The allergoid-mannan glycoconjugates were hypoallergenic as detected by the IgE reactivity with sera from grass allergic patients, even with lower reactivity than conventional allergoid without mannan. Thus, stable hypoallergenic allergoids conjugated to mannan suitable for using in immunotherapy can be achieved using glutaraldehyde. In contrast to mannan oxidation, the glutaraldehyde approach allows to preserve mannoses with their native geometry, which may be functionally important for its receptor-mediated recognition.

Polymeric ionic liquid modified graphene oxide-grafted silica for solid-phase extraction to analyze the excretion-dynamics of flavonoids in urine by Box-Behnken statistical design.

PubMed

Hou, Xiudan; Liu, Shujuan; Zhou, Panpan; Li, Jin; Liu, Xia; Wang, Licheng; Guo, Yong

2016-07-22

A solid-phase extraction method for the efficient analysis of the excretion-dynamics of flavonoids in urine was established and described. In this work, in situ surface radical chain-transfer polymerization and in situ anion exchange were utilized to tune the extraction performance of poly(1-vinyl-3-hexylimidazolium bromide)-graphene oxide-grafted silica (poly(VHIm(+)Br(-))@GO@Sil). Graphene oxide (GO) was first coated onto the silica using a layer-by-layer fabrication method, and then the anion of poly(VHIm(+)Br(-))@GO@Sil was changed into hexafluorophosphate (PF6(-)) by in situ anion exchange. The interaction energies between two PILs and four flavonoids were calculated with the Gaussian09 suite of programs. A Box-Behnken design was used for the optimization of four greatly influential parameters after single-factor experiments to obtain more accurate and precise results. Coupled to high performance liquid chromatography, the poly(VHIm(+)PF6(-))@GO@Sil method showed acceptable extraction recoveries for the four flavonoids, with limits of detection in the range of 0.1-0.5μgL(-1), and wide linear ranges with correlation coefficients (R) ranging from 0.9935 to 0.9987. Under the optimum conditions, the proposed method was applied to analyze the urines collected from a healthy volunteer. The excretion amount-time profiles revealed that 4-15h was the main excretion time for the detected flavonoids. The results indicated that the newly developed method offered the advantages of being feasible, green and cost-effective, and could be successfully applied to the extraction and enrichment of flavonoids in human body systems allowing the study of the metabolic kinetics. Copyright © 2016. Published by Elsevier B.V.

Novel vaccines targeting dendritic cells by coupling allergoids to nonoxidized mannan enhance allergen uptake and induce functional regulatory T cells through programmed death ligand 1.

PubMed

Sirvent, Sofía; Soria, Irene; Cirauqui, Cristina; Cases, Bárbara; Manzano, Ana I; Diez-Rivero, Carmen M; Reche, Pedro A; López-Relaño, Juan; Martínez-Naves, Eduardo; Cañada, F Javier; Jiménez-Barbero, Jesús; Subiza, Javier; Casanovas, Miguel; Fernández-Caldas, Enrique; Subiza, José Luis; Palomares, Oscar

2016-08-01

Allergen immunotherapy (AIT) is the only curative treatment for allergy. AIT faces pitfalls related to efficacy, security, duration, and patient compliance. Novel vaccines overcoming such inconveniences are in demand. We sought to study the immunologic mechanisms of action for novel vaccines targeting dendritic cells (DCs) generated by coupling glutaraldehyde-polymerized grass pollen allergoids to nonoxidized mannan (PM) compared with glutaraldehyde-polymerized allergoids (P) or native grass pollen extracts (N). Skin prick tests and basophil activation tests with N, P, or PM were performed in patients with grass pollen allergy. IgE-blocking experiments, flow cytometry, confocal microscopy, cocultures, suppression assays, real-time quantitative PCR, ELISAs, and ELISpot assays were performed to assess allergen capture by human DCs and T-cell responses. BALB/c mice were immunized with PM, N, or P. Antibody levels, cytokine production by splenocytes, and splenic forkhead box P3 (FOXP3)(+) regulatory T (Treg) cells were quantified. Experiments with oxidized PM were also performed. PM displays in vivo hypoallergenicity, induces potent blocking antibodies, and is captured by human DCs much more efficiently than N or P by mechanisms depending on mannose receptor- and dendritic cell-specific intercellular adhesion molecule 3-grabbing nonintegrin-mediated internalization. PM endorses human DCs to generate functional FOXP3(+) Treg cells through programmed death ligand 1. Immunization of mice with PM induces a shift to nonallergic responses and increases the frequency of splenic FOXP3(+) Treg cells. Mild oxidation impairs these effects in human subjects and mice, demonstrating the essential role of preserving the carbohydrate structure of mannan. Allergoids conjugated to nonoxidized mannan represent suitable vaccines for AIT. Our findings might also be of the utmost relevance to development of therapeutic interventions in other immune tolerance-related diseases. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Effect of various visible light photoinitiators on the polymerization and color of light-activated resins.

PubMed

Arikawa, Hiroyuki; Takahashi, Hideo; Kanie, Takahito; Ban, Seiji

2009-07-01

The purpose of this study was to investigate effects of various visible light photoinitiators on the polymerization efficiency and color of the light-activated resins. Four photoinitiators, including camphorquinone, phenylpropanedione, monoacrylphosphine oxide (TPO), and bisacrylphosphine oxide (Ir819), were used. Each photoinitiator was dissolved in a Bis-GMA and TEGDMA monomer mixture. Materials were polymerized using dental quartz-tungsten halogen lamp (QTH), plasma-ark lamp and blue LED light-curing units, and a custom-made violet LED light unit. The degree of monomer conversion and CIE L*a*b* color values of the resins were measured using a FTIR and spectral transmittance meter. The degree of monomer conversions of TPO- and Ir819-containing resins polymerized with the violet-LED unit were higher than camphorquinone-containing resin polymerized with the QTH light-curing unit. The lowest color values were observed for the TPO-containing resin. Our results indicate that the TPO photoinitiator and the violet-LED light unit may provide a useful and improved photopolymerization system for dental light-activated resins.

Pathogenic Roles for Fungal Melanins

PubMed Central

Jacobson, Eric S.

2000-01-01

Melanins represent virulence factors for several pathogenic fungi; the number of examples is growing. Thus, albino mutants of several genera (in one case, mutated precisely in the melanizing enzyme) exhibit decreased virulence in mice. We consider the phenomenon in relation to known chemical properties of melanin, beginning with biosynthesis from ortho-hydroquinone precursors which, when oxidized enzymatically to quinones, polymerize spontaneously to melanin. It follows that melanizing intermediates are cross-linking reagents; melanization stabilizes the external cell wall against hydrolysis and is thought to determine semipermeability in the osmotic ram (the appressorium) of certain plant pathogens. Polymeric melanins undergo reversible oxidation-reduction reactions between cell wall-penetrating quinone and hydroquinone oxidation states and thus represent polymeric redox buffers; using strong oxidants, it is possible to titrate the melanin on living cells and thereby demonstrate protection conferred by melanin in several species. The amount of buffering per cell approximately neutralizes the amount of oxidant generated by a single macrophage. Moreover, the intermediate oxidation state, the semiquinone, is a very stable free radical and is thought to trap unpaired electrons. We have suggested that the oxidation state of external melanin may be regulated by external Fe(II). An independent hypothesis holds that in Cryptococcus neoformans, an important function of the melanizing enzyme (apart from melanization) is the oxidation of Fe(II) to Fe(III), thereby forestalling generation of the harmful hydroxyl radical from H2O2. Thus, problems in fungal pathogenesis have led to evolving hypotheses regarding melanin functioning. PMID:11023965

Preparation Characterization and Electrical Study of New Polymeric Mixture (Consist of Three Polymers) Nanocomposites

NASA Astrophysics Data System (ADS)

AL-Abodi, Entisar E.; Farouk, Azhar

2018-05-01

By using hummers’ method, graphene oxide (GO) was synthesized and by reducing it gave reduced graphene oxide (RGO). The polymeric blend contain three polymers; Poly Aniline (PANI), Poly Vinyl Acetate( PVAc),and Pecten(Pc) wich have been prepared at studied amount. The composites for above polymers with various concentrations of, graphene oxide (GO) and with reduced graphene oxide (RGO)were prepared, and than pour into films(chips). The dielectric constant properties of chips were measured, which its point the electrical conductivity values for the prepared chips increase with increasing of frequency. As well, the electrical conductivity is research in terms of the Arrhenius plot, it is plotted against the reverse temperature for the prepared films at different applied frequencies.

Method for production of ceramic oxide and carbide bodies by polymer inclusion and decomposition

DOEpatents

Quinby, Thomas C.

1985-01-01

A method for the preparation of thin, free-standing metal oxide films which are useful as nuclear accelerator target materials. Cations of any metal except those of Group IA and precious metals, such as, U, Zr, Nd, Ce, Th, pr or Cr, are absorbed on a thin film of polymeric material, such as, carboxymethylcellulose, viscose rayon or cellophane. The cation impregnated polymeric material is dried. Then the impregnated film is heated in an inert atmosphere to form a carbonized membrane. The carbonized membrane is oxidized to yield a thin, self-supporting, metal oxide membrane. Or, the membrane can be heated in an inert atmosphere to yield a thin, self-supporting, metal carbide-containing membrane.

Method for production of ceramic oxide and carbide bodies by polymer inclusion and decomposition

DOEpatents

Quinby, T.C.

1984-08-30

A method for the preparation of thin, free-standing metal oxide films which are useful as nuclear accelerator target materials is described. Cations of any metal except those of Group IA and precious metals, such as, U, Zr, Nd, Ce, Th, Pr or Cr, are absorbed on a thin film of polymeric material, such as carboxymethylcellulose, viscose rayon or cellophane. The cation impregnated polymeric material is dried. Then the impregnated film is heated in an inert atmosphere to form a carbonized membrane. The carbonized membrane is oxidized to yield a thin, self-supporting, metal oxide membrane. Or, the membrane can be heated in an inert atmosphere to yield a thin, self-supporting, metal carbide-containing membrane.

The Effect of Polymeric Nanoparticles on Biocompatibility of Carrier Red Blood Cells

PubMed Central

Pan, Daniel; Vargas-Morales, Omayra; Zern, Blaine; Anselmo, Aaron C.; Gupta, Vivek; Zakrewsky, Michael; Mitragotri, Samir; Muzykantov, Vladimir

2016-01-01

Red blood cells (RBCs) can be used for vascular delivery of encapsulated or surface-bound drugs and carriers. Coupling to RBC prolongs circulation of nanoparticles (NP, 200 nm spheres, a conventional model of polymeric drug delivery carrier) enabling their transfer to the pulmonary vasculature without provoking overt RBC elimination. However, little is known about more subtle and potentially harmful effects of drugs and drug carriers on RBCs. Here we devised high-throughput in vitro assays to determine the sensitivity of loaded RBCs to osmotic stress and other damaging insults that they may encounter in vivo (e.g. mechanical, oxidative and complement insults). Sensitivity of these tests is inversely proportional to RBC concentration in suspension and our results suggest that mouse RBCs are more sensitive to damaging factors than human RBCs. Loading RBCs by NP at 1:50 ratio did not affect RBCs, while 10–50 fold higher NP load accentuated RBC damage by mechanical, osmotic and oxidative stress. This extensive loading of RBC by NP also leads to RBCs agglutination in buffer; however, addition of albumin diminished this effect. These results provide a template for analyses of the effects of diverse cargoes loaded on carrier RBCs and indicate that: i) RBCs can tolerate carriage of NP at doses providing loading of millions of nanoparticles per microliter of blood; ii) tests using protein-free buffers and mouse RBCs may overestimate adversity that may be encountered in humans. PMID:27003833

A polymer of caffeyl alcohol in plant seeds

PubMed Central

Chen, Fang; Tobimatsu, Yuki; Havkin-Frenkel, Daphna; Dixon, Richard A.; Ralph, John

2012-01-01

Lignins are complex phenylpropanoid polymers mostly associated with plant secondary cell walls. Lignins arise primarily via oxidative polymerization of the three monolignols, p-coumaryl, coniferyl, and sinapyl alcohols. Of the two hydroxycinnamyl alcohols that represent incompletely methylated biosynthetic products (and are not usually considered to be monolignols), 5-hydroxyconiferyl alcohol is now well established as incorporating into angiosperm lignins, but incorporation of caffeyl alcohol has not been shown. We report here the presence of a homopolymer of caffeyl alcohol in the seed coats of both monocot and dicot plants. This polymer (C-lignin) is deposited to high concentrations in the seed coat during the early stages of seed development in the vanilla orchid (Vanilla planifolia), and in several members of the Cactaceae. The lignin in other parts of the Vanilla plant is conventionally biosynthesized from coniferyl and sinapyl alcohols. Some species of cacti contain only C-lignin in their seeds, whereas others contain only classical guaiacyl/syringyl lignin (derived from coniferyl and sinapyl alcohols). NMR spectroscopic analysis revealed that the Vanilla seed-coat polymer was massively comprised of benzodioxane units and was structurally similar to the polymer synthesized in vitro by peroxidase-catalyzed polymerization of caffeyl alcohol. CD spectroscopy did not detect any optical activity in the seed polymer. These data support the contention that the C-lignin polymer is produced in vivo via combinatorial oxidative radical coupling that is under simple chemical control, a mechanism analogous to that theorized for classical lignin biosynthesis. PMID:22307645

Redox-Controlled Olefin (Co)Polymerization Catalyzed by Ferrocene-Bridged Phosphine-Sulfonate Palladium Complexes.

PubMed

Chen, Min; Yang, Bangpei; Chen, Changle

2015-12-14

The facile and reversible interconversion between neutral and oxidized forms of palladium complexes containing ferrocene-bridged phosphine sulfonate ligands was demonstrated. The activity of these palladium complexes could be controlled using redox reagents during ethylene homopolymerization, ethylene/methyl acrylate copolymerization, and norbornene oligomerization. Specifically in norbornene oligomerization, the neutral complexes were not active at all whereas the oxidized counterparts showed appreciable activity. In situ switching between the neutral and oxidized forms resulted in an interesting "off" and "on" behavior in norbornene oligomerization. This work provides a new strategy to control the olefin polymerization process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coupling of 3,8-Dibromo-1,10-Phenanthroline With 3,5-Diethynylheptyloxybenzene: A Suzuki/Miyaura Versus a Sonogashira Perspective

NASA Technical Reports Server (NTRS)

Yang, Jinhua; Oh, Woon Su; Elder, Ian A.; Leventis, Nicholas; Sotiriou-Leventis, Chariklia

2003-01-01

We report a new application of the Suzuki-Miyaura reaction whereas two bifunctional reactants, 3,8-dibromo-1,10-phenanthroline and 3,5-diethynylheptyloxylbenzene (9), yield 3,8-bis (3-ethynyl-5-heptyloxyphenylethynyl)-1,10-phenanthroline (2) efficiently (74% yield) without polymerization. This was achieved by reacting a stoichiometric amount of 9 and (Me3Si)2NLi to obtain quantitatively the monoacetylide anion of 9 (10). The latter was activated with B-methoxy-9-BBN and reacted in analogy to the alkynyl copper complex of a Sonogashira route. However, in the Sonogashira reaction, the alkynyl copper complex is present in small equilibrium concentrations and polymerization takes place even when reagents are mixed slowly. Actually the Sonogashira route gave no desired product 2, as the latter polymerizes easily via homo-coupling in the presence of air and Cu(I). Sonogashira coupling involves the palladium(0) catalyzed reaction of terminal alkynes.

Prebiotic Oxidative Polymerization of 2,3 Dimercaptopropanol on the Surface of Iron(III) Hydroxide Oxide

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1994-01-01

The oxidation of 2,3-Dimercapto-1-propanol by ferric ions on the surface of iron (III) hydroxide oxide yielded polydisulfide polymers. This polymerization occured readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron (III) hydroxide oxide (20 mg, 160 micro mole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the mineral phase. Reactions at higher dithiol concentrations with the same ratio of dithiol to mineral gave a higher yield of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis will be discussed.

Nitroxyl-mediated oxidation of lignin and polycarboxylated products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stahl, Shannon S.; Rafiee, Mohammad

Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on .beta.-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric .beta.-hydroxy acid. The polymeric .beta.-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The .beta.-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers ormore » oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.« less

Polymerization in the gas phase, in clusters, and on nanoparticle surfaces.

PubMed

El-Shall, M Samy

2008-07-01

Gas phase and cluster experiments provide unique opportunities to quantitatively study the effects of initiators, solvents, chain transfer agents, and inhibitors on the mechanisms of polymerization. Furthermore, a number of important phenomena, unique structures, and novel properties may exist during gas-phase and cluster polymerization. In this regime, the structure of the growing polymer may change dramatically and the rate coefficient may vary significantly upon the addition of a single molecule of the monomer. These changes would be reflected in the properties of the oligomers deposited from the gas phase. At low pressures, cationic and radical cationic polymerizations may proceed in the gas phase through elimination reactions. In the same systems at high pressure, however, the ionic intermediates may be stabilized, and addition without elimination may occur. In isolated van der Waals clusters of monomer molecules, sequential polymerization with several condensation steps can occur on a time scale of a few microseconds following the ionization of the gas-phase cluster. The cluster reactions, which bridge gas-phase and condensed-phase chemistry, allow examination of the effects of controlled states of aggregation. This Account describes several examples of gas-phase and cluster polymerization studies where the most significant results can be summarized as follows: (1) The carbocation polymerization of isobutene shows slower rates with increasing polymerization steps resulting from entropy barriers, which could explain the need for low temperatures for the efficient propagation of high molecular weight polymers. (2) Radical cation polymerization of propene can be initiated by partial charge transfer from an ionized aromatic molecule such as benzene coupled with covalent condensation of the associated propene molecules. This novel mechanism leads exclusively to the formation of propene oligomer ions and avoids other competitive products. (3) Structural information on the oligomers formed by gas-phase polymerization can be obtained using the mass-selected ion mobility technique where the measured collision cross-sections of the selected oligomer ions and collision-induced dissociation can provide fairly accurate structural identifications. The identification of the structures of the dimers and trimers formed in the gas-phase thermal polymerization of styrene confirms that the polymerization proceeds according to the Mayo mechanism. Similarly, the ion mobility technique has been utilized to confirm the formation of benzene cations by intracluster polymerization following the ionization of acetylene clusters. Finally, it has been shown that polymerization of styrene vapor on the surface of activated nanoparticles can lead to the incorporation of a variety of metal and metal oxide nanoparticles within polystyrene films. The ability to probe the reactivity and structure of the small growing oligomers in the gas phase can provide fundamental insight into mechanisms of polymerization that are difficult to obtain from condensed-phase studies. These experiments are also important for understanding the growth mechanisms of complex organics in flames, combustion processes, interstellar clouds, and solar nebula where gas-phase reactions, cluster polymerization, and surface catalysis on dust nanoparticles represent the major synthetic pathways. This research can lead to the discovery of novel initiation mechanisms and reaction pathways with applications in the synthesis of oligomers and nanocomposites with unique and improved properties.

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers

PubMed Central

Kim, Moon Suk; Lee, Sang Bong

2014-01-01

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO >> GME >>> GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively. PMID:28788147

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers.

PubMed

Kim, Moon Suk; Lee, Sang Bong

2014-07-31

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF₆). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO > GME > GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively.

Synthesis of Novel μ-Star Copolymers with Poly(N-Octyl Benzamide) and Poly(ε-Caprolactone) Miktoarms through Chain-Growth Condensation Polymerization, Styrenics-Assisted Atom Transfer Radical Coupling, and Ring-Opening Polymerization.

PubMed

Huang, Chih-Feng; Aimi, Junko; Lai, Kuan-Yu

2017-02-01

Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(ε-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ring-opening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and 1 H NMR spectroscopy reveal the successful synthesis of a well-defined (PBA 11 ) 2 -(PCL 15 ) 4 μ-star copolymer (M n ,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA 2 PCL 4 μ-star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The use of Trametes versicolor laccase for the polymerization of aniline in the presence of vesicles as templates.

PubMed

Junker, Katja; Kissner, Reinhard; Rakvin, Boris; Guo, Zengwei; Willeke, Martin; Busato, Stephan; Weber, Thomas; Walde, Peter

2014-02-05

The enzymatic polymerization of aniline to polyaniline (PANI) with Trametes versicolor laccase (TvL) as catalyst and dioxygen (O₂) as oxidant was investigated in an aqueous medium containing unilamellar vesicles with an average diameter of about 80 nm formed from AOT (=sodium bis(2-ethylhexyl) sulfosuccinate). Compared to the same reaction carried out with horseradish peroxidase isoenzyme C (HRPC) as catalyst and hydrogen peroxide (H₂O₂) as oxidant, notable differences were found in the kinetics of the reaction, as well as in the characteristics of the PANI obtained. Under comparable optimal conditions, which are pH 3.5 for TvL/O₂ and pH 4.3 for HRPC/H₂O₂, the reaction with TvL/O₂ was much slower than with HRPC/H₂O₂, i.e. ≈27 days vs. 1 day reaction time to reach equilibrium with >90% yield at 25 °C. Although in both cases, aniline monomer coupling occurred mainly via the carbon atom in para position of aniline, UV-vis-NIR absorption and EPR measurements indicate that the reaction with TvL/O₂ yielded mainly overoxidized products (with λ(max)=730 nm). These products had a lower amount of unpaired electrons if compared with the products obtained with HRPC/H₂O₂ (with λ(max)≈1000 nm, which is characteristic for the polaron state of PANI-ES, the emeraldine salt form of PANI). Similarly to previous findings with HRPC/H₂O₂, enzyme inactivation occurred during the polymerization also in the case of TvL/O₂. Since the aqueous PANI-vesicle suspensions obtained are of high colloidal stability, they can be used directly as ink in a conventional thermal inkjet printer for printing on paper or on surface treated polyimide films. Printed PANI-ES patterns on paper changed colour from green (emeraldine salt) to blue (emeraldine base) upon exposure to ammonia gas, demonstrating the expected ammonia sensing properties. Copyright © 2013 Elsevier Inc. All rights reserved.

Improving the Thermoelectric Properties of Polyaniline by Introducing Poly(3,4-ethylenedioxythiophene)

NASA Astrophysics Data System (ADS)

Wang, Xiao Yang; Liu, Cheng Yan; Miao, Lei; Gao, Jie; Chen, Yu

2016-03-01

By using the parent monomers, 3,4-ethylenedioxythiophene and aniline, a series of nanocomposites consisting of different mass ratios of polyaniline (PANI) to poly(3,4-ethylenedioxythiophene) (PEDOT) have been successfully prepared in hydrochloric acid solution through oxidative polymerization, then redoped with p-toluenesulfonic acid ( p-TSA). Firstly, PEDOT nanoparticles were fabricated via chemical oxidation polymerization in reverse (water-in-oil) microemulsions. Then, PANI-doped PEDOT nanoparticles were formed by oxidative polymerization of aniline to form PANI/PEDOT nanofibers. The resulting nanostructured components were characterized by scanning electron microscopy (SEM) and a series of spectroscopic methods. The presence of PEDOT increased the room-temperature electrical conductivity of the PANI/PEDOT nanocomposites by more than two orders of magnitude in comparison with the parent PANI. Moreover, the PANI/PEDOT nanocomposites showed better thermoelectric properties than PANI. Different concentrations of p-TSA also affected the electrical conductivity and Seebeck coefficient of the nanocomposites. With increasing temperature, both the electrical conductivity and Seebeck coefficient increased.

End-group-functionalized poly(N,N-diethylacrylamide) via free-radical chain transfer polymerization: Influence of sulfur oxidation and cyclodextrin on self-organization and cloud points in water

PubMed Central

Reinelt, Sebastian; Steinke, Daniel

2014-01-01

Summary In this work we report the synthesis of thermo-, oxidation- and cyclodextrin- (CD) responsive end-group-functionalized polymers, based on N,N-diethylacrylamide (DEAAm). In a classical free-radical chain transfer polymerization, using thiol-functionalized 4-alkylphenols, namely 3-(4-(1,1-dimethylethan-1-yl)phenoxy)propane-1-thiol and 3-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)propane-1-thiol, poly(N,N-diethylacrylamide) (PDEAAm) with well-defined hydrophobic end-groups is obtained. These end-group-functionalized polymers show different cloud point values, depending on the degree of polymerization and the presence of randomly methylated β-cyclodextrin (RAMEB-CD). Additionally, the influence of the oxidation of the incorporated thioether linkages on the cloud point is investigated. The resulting hydrophilic sulfoxides show higher cloud point values for the lower critical solution temperature (LCST). A high degree of functionalization is supported by 1H NMR-, SEC-, FTIR- and MALDI–TOF measurements. PMID:24778720

Characterization of procyanidin B2 oxidation products in an apple juice model solution and confirmation of their presence in apple juice by high-performance liquid chromatography coupled to electrospray ion trap mass spectrometry.

PubMed

Poupard, Pascal; Sanoner, Philippe; Baron, Alain; Renard, Catherine M G C; Guyot, Sylvain

2011-11-01

Procyanidins (i.e. condensed tannins) are polyphenols commonly found in fruits. During juice and cider making, apple polyphenol oxidase catalyzes the oxidation of caffeoylquinic acid (CQA) into its corresponding o-quinone which further reacts with procyanidins and other polyphenols, leading to the formation of numerous oxidation products. However, the structure and the reaction pathways of these neoformed phenolic compounds are still largely unknown. Experiments were carried out on a model system to gain insights into the chemical processes occurring during the initial steps of fruit processing. Procyanidin B2 was oxidized by caffeoylquinic acid o-quinone (CQAoq) in an apple juice model solution. The reaction products were monitored using high performance liquid chromatography (HPLC) coupled to ultraviolet (UV)-visible and electrospray tandem mass spectrometry (ESI-MS/MS) in the negative mode. Oxidative conversion of procyanidin B2 ([M-H](-) at m/z 577) into procyanidin A2 at m/z 575 was unambiguously confirmed. In addition, several classes of products were characterized by their deprotonated molecules ([M-H](-)) and their MS/MS fragmentation patterns: hetero-dimers (m/z 929) and homo-dimers (m/z 1153 and 705) resulting from dimerization involving procyanidin and CQA molecules; intramolecular addition products at m/z 575, 573, 927, 1151 and 703. Interestingly, no extensive polymerization was observed. Analysis of a cider apple juice enabled comparison with the results obtained on a biosynthetic model solution. However, procyanidin A2 did not accumulate but seemed to be an intermediate in the formation of an end-product at m/z 573 for which two structural hypotheses are given. These structural modifications of native polyphenols as a consequence of oxidation probably have an impact on the organoleptic and nutritional properties of apple juices and other apple-derived foods. Copyright © 2011 John Wiley & Sons, Ltd.

Electron beam-induced graft polymerization of acrylic acid and immobilization of arginine-glycine-aspartic acid-containing peptide onto nanopatterned polycaprolactone.

PubMed

Sun, Hui; Wirsén, Anders; Albertsson, Ann-Christine

2004-01-01

Electron beam- (EB-) induced graft polymerization of acrylic acid and the subsequent immobilization of arginine-glycine-aspartic acid (RGD) peptide onto nanopatterned polycaprolactone with parallel grooves is reported. A high concentration of carboxylic groups was introduced onto the polymer substrate by EB-induced polymerization of acrylic acid. In the coupling of the RGD peptide to the carboxylated polymer surface, a three-step peptide immobilization process was used. This process included the activation of surface carboxylic acid into an active ester intermediate by use of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), the introduction of disulfide groups by use of 2-(2-pyridinyldithio)ethanamine hydrochloride (PDEA), and final immobilization of the peptide via a thiol-disulfide exchange reaction. The extent of coupling was measured by UV spectroscopy. A preliminary study of the in vitro behavior of keratinocytes (NCTC 2544) cultured on the acrylic acid-grafted and RGD peptide-coupled surface showed that most cells grown on the coupled samples had a spread-rounded appearance, while the majority of cells tended to be elongated along the grooves on uncoupled substrates.

Effect of wet oxidation on the fingerprints of polymeric substances from an activated sludge.

PubMed

Urrea, José Luis; Collado, Sergio; Oulego, Paula; Díaz, Mario

2016-11-15

Thermal pre-treatments of activated sludge involve the release of a high amount of polymeric substances into the bulk medium. The molecular size of these polymers will largely define the subsequent biological treatment of the liquid effluent generated. In this work, the effects of wet oxidation treatment (WO) on the fingerprints of the polymeric substances which compose the activated sludge, were analysed. For a better understanding of these transformations, the sludge was separated into its main fractions: soluble microbial products (SMP), loosely bound extracellular polymeric substances (LB-EPS), tightly bound extracellular polymeric substances (TB-EPS) and naked cells, and then each one was subjected to WO separately (190 °C and 65 bar), determining the fingerprints evolution by size exclusion technique. Results revealed a fast degradation of larger molecules (over 500 kDa) during the first minutes of treatment (40 min). WO also increases the absorptive properties of proteins (especially for 30 kDa), which is possibly due to the hydroxylation of phenylalanine amino acids in their structure. WO of naked cells involved the formation of molecules between 23 and 190 kDa, which are related to the release of cytoplasmic polymers, and more hydrophobic polymers, probably from the cell membrane. The results allowed to establish a relationship between the location of polymeric material and its facility to become oxidised; thus, the more internal the polymeric material in the cell, the easier its oxidation. When working directly with the raw sludge, hydrolysis mechanisms played a key role during the starting period. Once a high degree of solubilisation was reached, the molecules were rapidly oxidised into other compounds with refractory characteristics. The final effluent after WO showed almost 90% of low molecular weight solubilised substances (0-35 kDa). Copyright © 2016 Elsevier Ltd. All rights reserved.

Adhesive F-actin Waves: A Novel Integrin-Mediated Adhesion Complex Coupled to Ventral Actin Polymerization

PubMed Central

Case, Lindsay B.; Waterman, Clare M.

2011-01-01

At the leading lamellipodium of migrating cells, protrusion of an Arp2/3-nucleated actin network is coupled to formation of integrin-based adhesions, suggesting that Arp2/3-mediated actin polymerization and integrin-dependent adhesion may be mechanistically linked. Arp2/3 also mediates actin polymerization in structures distinct from the lamellipodium, in “ventral F-actin waves” that propagate as spots and wavefronts along the ventral plasma membrane. Here we show that integrins engage the extracellular matrix downstream of ventral F-actin waves in several mammalian cell lines as well as in primary mouse embryonic fibroblasts. These “adhesive F-actin waves” require a cycle of integrin engagement and disengagement to the extracellular matrix for their formation and propagation, and exhibit morphometry and a hierarchical assembly and disassembly mechanism distinct from other integrin-containing structures. After Arp2/3-mediated actin polymerization, zyxin and VASP are co-recruited to adhesive F-actin waves, followed by paxillin and vinculin, and finally talin and integrin. Adhesive F-actin waves thus represent a previously uncharacterized integrin-based adhesion complex associated with Arp2/3-mediated actin polymerization. PMID:22069459

NMR spectroscopy for assessment of lipid oxidation during frying

USDA-ARS?s Scientific Manuscript database

Except for total polar compounds (TPC), polymerized triacylglycerols (PTAG) and fatty acid composition, most other current standard methods for lipid oxidation detect very small amounts of oxidation products such as hydroperoxides, conjugated dienes, aldehydes, and epoxides. Therefore, amounts of th...

A Hydrogel of Ultrathin Pure Polyaniline Nanofibers: Oxidant-Templating Preparation and Supercapacitor Application.

PubMed

Zhou, Kun; He, Yuan; Xu, Qingchi; Zhang, Qin'e; Zhou, An'an; Lu, Zihao; Yang, Li-Kun; Jiang, Yuan; Ge, Dongtao; Liu, Xiang Yang; Bai, Hua

2018-05-15

Although challenging, fabrication of porous conducting polymeric materials with excellent electronic properties is crucial for many applications. We developed a fast in situ polymerization approach to pure polyaniline (PANI) hydrogels, with vanadium pentoxide hydrate nanowires as both the oxidant and sacrifice template. A network comprised of ultrathin PANI nanofibers was generated during the in situ polymerization, and the large aspect ratio of these PANI nanofibers allowed the formation of hydrogels at a low solid content of 1.03 wt %. Owing to the ultrathin fibril structure, PANI hydrogels functioning as a supercapacitor electrode display a high specific capacitance of 636 F g -1 , a rate capability, and good cycling stability (∼83% capacitance retention after 10,000 cycles). This method was also extended to the preparation of polypyrrole and poly(3,4-ethylenedioxythiophene) hydrogels. This template polymerization method represents a rational strategy for design of conducing polymer networks, which can be readily integrated in high-performance devices or a further platform for functional composites.

Modular in situ-Functionalization Strategy: Multicomponent Polymerization via Palladium/Norbornene Cooperative Catalysis.

PubMed

Yoon, Ki-Young; Dong, Guangbin

2018-05-23

Herein, we report the palladium/norbornene cooperatively catalyzed polymerization, which simplifies synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2B2C-type multicomponent polymerization is developed using ortho-amination/ipso-alkynylation reaction for preparing various amine-functionalized arylacetylene-containing polymers. Within a single catalytic cycle, the amine side-chains are site-selectively installed in situ via C-H activation during the polymerization process, which represents a major difference from conventional cross-coupling polymerizations. This in situ-functionalization strategy enables modular incorporation of functional side-chains from simple monomers, thereby conveniently affording a diverse range of functional polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective in vitro anticancer effect of superparamagnetic iron oxide nanoparticles loaded in hyaluronan polymeric micelles.

PubMed

Smejkalová, Daniela; Nešporová, Kristina; Huerta-Angeles, Gloria; Syrovátka, Jakub; Jirák, Daniel; Gálisová, Andrea; Velebný, Vladimír

2014-11-10

Due to its native origin, excellent biocompatibility and biodegradability, hyaluronan (HA) represents an attractive polymer for superparamagnetic iron oxide nanoparticles (SPION) coating. Herein, we report HA polymeric micelles encapsulating oleic acid coated SPIONs, having a hydrodynamic size of about 100 nm and SPION loading capacity of 1-2 wt %. The HA-SPION polymeric micelles were found to be selectively cytotoxic toward a number of human cancer cell lines, mainly those of colon adenocarcinoma (HT-29). The selective inhibition of cell growth was even observed when the SPION loaded HA polymeric micelles were incubated with a mixture of control and cancer cells. The selective in vitro inhibition could not be connected with an enhanced CD44 uptake or radical oxygen species formation and was rather connected with a different way of SPION intracellular release. While aggregated iron particles were visualized in control cells, nonaggregated solubilized iron oxide particles were detected in cancer cells. In vivo SPION accumulation in intramuscular tumor following an intravenous micelle administration was confirmed by magnetic resonance (MR) imaging and histological analysis. Having a suitable hydrodynamic size, high magnetic relaxivity, and being cancer specific and able to accumulate in vivo in tumors, SPION-loaded HA micelles represent a promising platform for theranostic applications.

Molecularly uniform poly(ethylene glycol) certified reference material

NASA Astrophysics Data System (ADS)

Takahashi, Kayori; Matsuyama, Shigetomo; Kinugasa, Shinichi; Ehara, Kensei; Sakurai, Hiromu; Horikawa, Yoshiteru; Kitazawa, Hideaki; Bounoshita, Masao

2015-02-01

A certified reference material (CRM) for poly(ethylene glycol) with no distribution in the degree of polymerization was developed. The degree of polymerization of the CRM was accurately determined to be 23. Supercritical fluid chromatography (SFC) was used to separate the molecularly uniform polymer from a standard commercial sample with wide polydispersity in its degree of polymerization. Through the use of a specific fractionation system coupled with SFC, we are able to obtain samples of poly(ethylene glycol) oligomer with exact degrees of polymerization, as required for a CRM produced by the National Metrology Institute of Japan.

Size matters: smart copolymeric nanohydrogels: synthesis and applications.

PubMed

Katime, Issa; Guerrero, Luis Guillermo; Mendizabal, Eduardo

2012-01-01

In this work the synthesis of smart nanoparticles capable of respond to external stimulus (pH and temperature variations) is reported. To avoid post-polymerization modification, functionalized monomers able to respond to pH and temperature changes were and then polymerized. The synthesized monomers have the capability for coupling with folic acid which is the target molecule. For this reason their polymers can be used as targeted drug delivery systems. Smart polymeric nanoparticles were prepared by direct and inverse microemulsion polymerization of the synthesized monomers. The nanoparticles were charged with drugs and their release kinetic was studied.

Organometallic Polymeric Conductors

NASA Technical Reports Server (NTRS)

1997-01-01

For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. The highest conductivities reported (approximately 4/Scm) were achieved with polythiophene in a polystyrene host polymer. The best films using a polyamide as base polymer were four orders of magnitude less conductive than the polystyrene films. The authors suggested that this was because polyimides were unable to swell sufficiently for infiltration of monomer as in the polystyrene. It was not clear, however, if the different conductivities obtained were merely the result of differing oxidation conditions. Oxidation time, temperature and oxidant concentration varied widely among the studies.

Bulk synthesis of polypyrrole nanofibers by a seeding approach.

PubMed

Zhang, Xinyu; Manohar, Sanjeev K

2004-10-13

The morphology of doped polypyrrole.Cl powder changes dramatically from granular to nanofibrillar when a very small amount (1-4 mg) of V2O5 nanofibers are added to a chemical oxidative polymerization of pyrrole in aq 1.0 M HCl using (NH4)2S2O8 as the oxidant. Unlike the polyaniline system, a key synthetic requirement in the polypyrrole system is for the seed template to be "active", i.e., to be capable of independently oxidizing the pyrrole monomer. Thin, strongly adherent films can be obtained on inert surfaces such as glass, plastics, etc., directly from the polymerization mixture without any bulk product isolation steps, significantly simplifying the processing of these nanofibers.

Fabrication of polymeric nano-batteries array using anodic aluminum oxide templates.

PubMed

Zhao, Qiang; Cui, Xiaoli; Chen, Ling; Liu, Ling; Sun, Zhenkun; Jiang, Zhiyu

2009-02-01

Rechargeable nano-batteries were fabricated in the array pores of anodic aluminum oxide (AAO) template, combining template method and electrochemical method. The battery consisted of electropolymerized PPy electrode, porous TiO2 separator, and chemically polymerized PAn electrode was fabricated in the array pores of two-step anodizing aluminum oxide (AAO) membrane, based on three-step assembling method. It performs typical electrochemical battery behavior with good charge-discharge ability, and presents a capacity of 25 nAs. AFM results show the hexagonal array of nano-batteries' top side. The nano-battery may be a promising device for the development of Micro-Electro-Mechanical Systems (MEMS), and Nano-Electro-Mechanical Systems (NEMS).

Mass Transfer Study of Chlorine Dioxide Gas Through Polymeric Packaging Materials

USDA-ARS?s Scientific Manuscript database

A continuous system for measuring the mass transfer of gaseous chlorine dioxide (ClO2), a strong oxidizing agent and used in food and pharmaceutical packaging, through 10 different types of polymeric packaging material was developed utilizing electrochemical sensor as a detector. Permeability, diff...

A polymeric-semiconductor-metal-complex hybrid photocatalyst for visible-light CO(2) reduction.

PubMed

Maeda, Kazuhiko; Sekizawa, Keita; Ishitani, Osamu

2013-10-03

A polymeric carbon nitride semiconductor is demonstrated to photocatalyse CO2 reduction to formic acid under visible light (λ > 400 nm) with a high turnover number (>200 for 20 hours) and selectivity (>80%), when coupled with a molecular ruthenium complex as a catalyst.

Simultaneous measurement of polymerization stress and curing kinetics for photo-polymerized composites with high filler contents.

PubMed

Wang, Zhengzhi; Landis, Forrest A; Giuseppetti, Anthony A M; Lin-Gibson, Sheng; Chiang, Martin Y M

2014-12-01

Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈80% (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites. Published by Elsevier Ltd.

Simultaneous Measurement of Polymerization Stress and Curing Kinetics for Photo-polymerized Composites with High Filler Contents

PubMed Central

Wang, Zhengzhi; Landis, Forrest A.; Giuseppetti, Anthony A.M.; Lin-Gibson, Sheng; Chiang, Martin Y.M.

2015-01-01

Objectives Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Methods Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. Results Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈ 80 % (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. Significance The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites. PMID:25443160

Micro-array versus nano-array platforms: a comparative study for ODN detection based on SPR enhanced ellipsometry

NASA Astrophysics Data System (ADS)

Celen, Burcu; Demirel, Gökhan; Piskin, Erhan

2011-04-01

The rapid and sensitive detection of DNA has recently attracted worldwide attention for a variety of disease diagnoses and detection of harmful bacteria in food and drink. In this paper, we carried out a comparative study based on surface plasmon resonance enhanced ellipsometry (SPREE) for the detection of oligodeoxynucleotides (ODNs) using micro- and nano-array platforms. The micro-arrayed surfaces were fabricated by a photolithography approach using different types of mask having varying size and shape. Well-ordered arrays of high aspect ratio polymeric nanotubes were also obtained using high molecular weight polystyrene (PS) and anodic aluminum oxide (AAO) membranes having 200 nm pore diameters. The SPREE sensors were then prepared by direct coupling of thiolated probe-ODNs, which contain suitable spacer arms, on gold-coated micro- and nano-arrayed surfaces. We experimentally demonstrated that, for the first time, gold-coated free standing polymeric nano-arrayed platforms can easily be produced and lead to a significant sensor sensitivity gain compared to that of the conventional SPREE surfaces of about four times. We believe that such an enhancement in sensor response could be useful for next generation sensor systems.

Role of metal oxides in chemical evolution

NASA Astrophysics Data System (ADS)

Kamaluddin

2013-06-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Formation of small molecules like amino acids, organic bases, sugar etc. could have occurred in the reducing atmosphere of the primitive Earth. Polymerization of these small molecules could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

Synthesis of nanostructured materials in inverse miniemulsions and their applications.

PubMed

Cao, Zhihai; Ziener, Ulrich

2013-11-07

Polymeric nanogels, inorganic nanoparticles, and organic-inorganic hybrid nanoparticles can be prepared via the inverse miniemulsion technique. Hydrophilic functional cargos, such as proteins, DNA, and macromolecular fluoresceins, may be conveniently encapsulated in these nanostructured materials. In this review, the progress of inverse miniemulsions since 2000 is summarized on the basis of the types of reactions carried out in inverse miniemulsions, including conventional free radical polymerization, controlled/living radical polymerization, polycondensation, polyaddition, anionic polymerization, catalytic oxidation reaction, sol-gel process, and precipitation reaction of inorganic precursors. In addition, the applications of the nanostructured materials synthesized in inverse miniemulsions are also reviewed.

Performance and properties of atomic oxygen protective coatings for polymeric materials

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Lamoreaux, Cynthia

1992-01-01

Such large LEO spacecraft as the Space Station Freedom will encounter high atomic oxygen fluences which entail the use of protective coatings for their polymeric structural materials. Such coatings have demonstrated polymer mass losses due to oxidation that are much smaller than those of unprotected materials. Attention is here given to protective and/or electrically conductive coatings of SiO(x), Ge, and indium-tin oxide which have been exposed to atomic oxygen in order to ascertain mass loss, electrical conductivity, and optical property dependence on atomic oxygen exposure.

Uncondensed Graphitic Carbon Nitride on Reduced Graphene Oxide for Oxygen Sensing via a Photoredox Mechanism

DOE PAGES

Ellis, James E.; Sorescu, Dan C.; Burkert, Seth C.; ...

2017-07-24

Melon, a polymeric, uncondensed graphitic carbon nitride with a two-dimensional structure, has been coupled with reduced graphene oxide (rGO) to create an oxygen chemiresistor sensor that is active under UV photoactivation. Oxygen gas is an important sensor target in a variety of areas including industrial safety, combustion process monitoring, as well as environmental and biomedical fields. Because of the intimate electrical interface formed between melon and rGO, charge transfer of photoexcited electrons occurs between the two materials when under UV (λ = 365 nm) irradiation. A photoredox mechanism wherein oxygen is reduced on the rGO surface provides the basis formore » sensing oxygen gas in the concentration range 300–100 000 ppm. The sensor response was found to be logarithmically proportional to oxygen gas concentration. DFT calculations of a melon-oxidized graphene composite found that slight protonation of melon leads to charge accumulation on the rGO layer and a corresponding charge depletion on the melon layer. As a result, this work provides an example of a metal-free system for solid–gas interface sensing via a photoredox mechanism.« less

Uncondensed Graphitic Carbon Nitride on Reduced Graphene Oxide for Oxygen Sensing via a Photoredox Mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ellis, James E.; Sorescu, Dan C.; Burkert, Seth C.

Melon, a polymeric, uncondensed graphitic carbon nitride with a two-dimensional structure, has been coupled with reduced graphene oxide (rGO) to create an oxygen chemiresistor sensor that is active under UV photoactivation. Oxygen gas is an important sensor target in a variety of areas including industrial safety, combustion process monitoring, as well as environmental and biomedical fields. Because of the intimate electrical interface formed between melon and rGO, charge transfer of photoexcited electrons occurs between the two materials when under UV (λ = 365 nm) irradiation. A photoredox mechanism wherein oxygen is reduced on the rGO surface provides the basis formore » sensing oxygen gas in the concentration range 300–100 000 ppm. The sensor response was found to be logarithmically proportional to oxygen gas concentration. DFT calculations of a melon-oxidized graphene composite found that slight protonation of melon leads to charge accumulation on the rGO layer and a corresponding charge depletion on the melon layer. As a result, this work provides an example of a metal-free system for solid–gas interface sensing via a photoredox mechanism.« less

Convective instabilities in traveling fronts of addition polymerization

NASA Technical Reports Server (NTRS)

Pojman, John A.; Jones, Chris E.; Khan, Akhtar M.

1993-01-01

An autocatalytic reaction in an unstirred vessel can support a constant velocity wavefront resulting from the coupling of diffusion to the chemical reaction. A flare front is a common example in which heat is the autocatalytic species that diffuses into unreacted regions stimulating a reaction that produces more heat. Traveling fronts were studied in synthetic polymerization reactions under high pressure by workers in the former USSR. More recently, propagating fronts of methacrylic acid polymerization were studied under ambient conditions, both with video techniques and by NMR.

Thiolated alkyl-modified carbomers: Novel excipients for mucoadhesive emulsions.

PubMed

Bonengel, Sonja; Hauptstein, Sabine; Leonaviciute, Gintare; Griessinger, Julia; Bernkop-Schnürch, Andreas

2015-07-30

The aim of this study was the design and evaluation of mucoadhesive emulsifying polymeric excipients. Three thiol bearing ligands with increasing pKa values of their sulfhydryl group, namely 4-aminothiophenol (pKa=6.86), l-cysteine (pKa=8.4) and d/l-homocysteine (pKa=10.0) were coupled to the polymeric backbone of alkyl-modified carbomer (PA1030). Resulting conjugates displayed 818.5μmol 4-aminothiophenol, 698.5μmol cysteine and 651.5μmol homocysteine per gram polymer and were evaluated regarding the reactivity of thiol groups, emulsifying and mucoadhesive properties. In general, the synthesized conjugates showed a pH dependent reactivity, whereby the fastest oxidation occurred in PA1030-cysteine, as almost no free thiol groups could be detected after 120min. Emulsification of medium chain triglycerides was feasible with all synthesized conjugates leading to oil-in-water-emulsions. Emulsions with PA1030-cysteine displayed the highest stability and the smallest droplet size among the tested formulations. Oxidation and consequently cross-linking of the thiomers prior to the emulsification process led to an overall decreased emulsion stability. Evaluating mucosal residence time of thiomer emulsions on porcine buccal mucosa, a 9.2-fold higher amount of formulation based on PA1030-cysteine remained on the mucosal tissue within 3h compared to the unmodified polymer. According to these results, the highest reactive ligand l-cysteine seems to be most promising in order to obtain thiolated polymers for the preparation of mucoadhesive o/w-emulsions. Copyright © 2015 Elsevier B.V. All rights reserved.

Cellobiose Dehydrogenase Inhibition of Polymerization of Phenolic Compounds and Enhancing Lignin Degradation by Lignina.

PubMed

Fang, Jing; Liu, Wen; Gao, Pei-Ji

1999-01-01

The kinetic behavior of cellobiose dehydrogenase (CDH) was investigated by steady-state initial velocity studies. Variation in the concentration of one substrate led to changes in K(m) and V(max) of the other substrate. The results were consistent with a ping-pong mechanism. In the presence of cellobiose, CDH could reduce many oxidized products catalyzed by soybean hull peroxidase (SHP). The oxidation product of 1-hydroxybenzotriazole (HBT) catalyzed by SHP inactivated the enzyme itself however, CDH could prevent SHP from inactivation by reducing the oxidation product of HBT. CDH could also inhibit the polymerization of phenolic compounds catalyzed by SHP. It was found that the addition of CDH could enhance kraft pulp lignin degradation by ligninases.

Polymeric nanocomposites loaded with fluoridated hydroxyapatite Ln3+ (Ln = Eu or Tb)/iron oxide for magnetic targeted cellular imaging

PubMed Central

Pan, Jie; Liu, Wei-Jiao; Hua, Chao; Wang, Li-Li; Wan, Dong; Gong, Jun-Bo

2015-01-01

Objective To fabricate polymeric nanocomposites with excellent photoluminescence, magnetic properties, and stability in aqueous solutions, in order to improve specificity and sensitivity of cellular imaging under a magnetic field. Methods Fluoridated Ln3+-doped HAP (Ln3+-HAP) NPs and iron oxides (IOs) can be encapsulated with biocompatible polymers via a modified solvent exaction/evaporation technique to prepare polymeric nanocomposites with fluoridated Ln3+-HAP/iron oxide. The nanocomposites were characterized for surface morphology, fluorescence spectra, magnetic properties and in vitro cytotoxicity. Magnetic targeted cellular imaging of such nanocomposites was also evaluated with confocal laser scanning microscope using A549 cells with or without magnetic field. Results The fabricated nanocomposites showed good stability and excellent luminescent properties, as well as low in vitro cytotoxicity, indicating that the nanocomposites are suitable for biological applications. Nanocomposites under magnetic field achieved much higher cellular uptake via an energy-dependent pathway than those without magnetic field. Conclusion The nanocomposites fabricated in this study will be a promising tool for magnetic targeted cellular imaging with improved specificity and enhanced selection. PMID:26487962

Fabrication of polyimide-based nanocomposites containing functionalized graphene oxide nanosheets by in-situ polymerization and their properties

NASA Astrophysics Data System (ADS)

Qian, Yong; Lan, Yanfei; Xu, Jianping; Ye, Fucheng; Dai, Shizhen

2014-09-01

In this study, a facile and effective strategy is proposed to fabricate polyimide (PI)-based nanocomposites containing functionalized graphene oxide (FGO) nanosheets by in-situ polymerization and thermal imidization. Highly dispersed CIGO which was firstly obtained by graphene oxide (GO) functionalized with cyclohexyl isocyanate (CI) exhibited excellent dispersibility and compatibility in polyamic acid (PAA, precursor of PI) matrix via in-situ polymerization. Then the CIGO sheets were partially thermally reduced efficiently to FGO during the thermal imidization process of PAA. The incorporation of FGO sheets significantly affected the macroscopic properties of the PI-based composites. A 56.5% increase in the tensile strength and a 43.8% improvement in the Young's modulus were achieved for 2.0 wt% FGO loading. Furthermore, the thermal stability and glass transition temperature (Tg) were improved by adding FGO. In addition, the hydrophobic behavior of the PI-FGO composite clearly improved because of the excellent hydrophobic properties of FGO. The success of this approach provides a good rational for developing high-performance polymer-based composite materials.

Crosslinked Carbon Nanotubes/Polyaniline Composites as a Pseudocapacitive Material with High Cycling Stability

PubMed Central

Liu, Dong; Wang, Xue; Deng, Jinxing; Zhou, Chenglong; Guo, Jinshan; Liu, Peng

2015-01-01

The poor cycling stability of polyaniline (PANI) limits its practical application as a pseudocapacitive material due to the volume change during the charge-discharge procedure. Herein, crosslinked carbon nanotubes/polyaniline (C-CNTs/PANI) composites had been designed by the in situ chemical oxidative polymerization of aniline in the presence of crosslinked carbon nanotubes (C-CNTs), which were obtained by coupling of the functionalized carbon nanotubes with 1,4-benzoquinone. The composite showed a specific capacitance of 294 F/g at the scan rate of 10 mV/s, and could retain 95% of its initial specific capacitance after 1000 CV cycles. Such high electrochemical cycling stability resulting from the crosslinked skeleton of the C-CNTs makes them potential electrode materials for a supercapacitor. PMID:28347050

Studies on High Energy Density Reactions for Development of Nanostructured Hybrid Supercapacitors

DTIC Science & Technology

2015-09-25

deposited on the graphene sheets to form graphene-silver nanoparticles composite. To this 0.45 gm of pyrrole monomer is added and polymerization is...by in situ oxidative polymerization of pyrrole in the presence of GNS and AgNPs. The different mass concentrations of AgNPs were utilized to improve

Synthesis of selenium nano-composite (t-Se@PS) by surface initiated atom transfer radical polymerization.

PubMed

Wang, Michael C P; Gates, Byron D

2012-09-04

Selenium nanostructures, which are otherwise susceptible to oxidative damage, were encapsulated with a thin layer of polystyrene. The thin layer of polystyrene was grafted onto the surfaces of selenium by a surface initiated atom transfer radical polymerization reaction. These encapsulated nanostructures demonstrate an enhanced resistance towards corrosion.

Impregnated metal-polymeric functional beads

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Volksen, Willi (Inventor)

1980-01-01

Amine containing polymeric microspheres such as polyvinyl pyridine are complexed with metal salts or acids containing metals such as gold, platinum or iron. After reduction with sodium borohydride, the salt is reduced to finely divided free metal or metal oxides, useful as catalysts. Microspheres containing covalent bonding sites can be used for labeling or separating proteins.

Impregnated metal-polymeric functional beads

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Volksen, Willi (Inventor)

1978-01-01

Amine containing polymeric microspheres such as polyvinyl pyridine are complexed with metal salts or acids containing metals such as gold, platinum or iron. After reduction with sodium borohydride, the salt is reduced to finely divided free metal or metal oxides, useful as catalysts. Microspheres containing covalent bonding sites can be used for labeling or separating proteins.

Microfluidic-Assisted Production of Size-Controlled Superparamagnetic Iron Oxide Nanoparticles-Loaded Poly(methyl methacrylate) Nanohybrids.

PubMed

Ding, Shukai; Attia, Mohamed F; Wallyn, Justine; Taddei, Chiara; Serra, Christophe A; Anton, Nicolas; Kassem, Mohamad; Schmutz, Marc; Er-Rafik, Meriem; Messaddeq, Nadia; Collard, Alexandre; Yu, Wei; Giordano, Michele; Vandamme, Thierry F

2018-02-06

In this paper, superparamagnetic iron oxide nanoparticles (SPIONs, around 6 nm) encapsulated in poly(methyl methacrylate) nanoparticles (PMMA NPs) with controlled sizes ranging from 100 to 200 nm have been successfully produced. The hybrid polymeric NPs were prepared following two different methods: (1) nanoprecipitation and (2) nanoemulsification-evaporation. These two methods were implemented in two different microprocesses based on the use of an impact jet micromixer and an elongational-flow microemulsifier. SPIONs-loaded PMMA NPs synthesized by the two methods presented completely different physicochemical properties. The polymeric NPs prepared with the micromixer-assisted nanoprecipitation method showed a heterogeneous dispersion of SPIONs inside the polymer matrix, an encapsulation efficiency close to 100 wt %, and an irregular shape. In contrast, the polymeric NPs prepared with the microfluidic-assisted nanoemulsification-evaporation method showed a homogeneous dispersion, an almost complete encapsulation, and a spherical shape. The properties of the polymeric NPs have been characterized by dynamic light scattering, thermogravimetric analysis, and transmission electron microscope. In vitro cytotoxicity assays were also performed on the nanohybrids and pure PMMA NPs.

Testing of Candidate Polymeric Materials for Compatibility with Pure Alternate Pretreat as Part of the Universal Waste Management System (UWMS)

NASA Technical Reports Server (NTRS)

Wingard, C. D.

2018-01-01

The Universal Waste Management System (UWMS) is an improved Waste Collection System for astronauts living and working in low Earth orbit spacecraft. Polymeric materials used in water recovery on International Space Station are regularly exposed to phosphoric acid-treated 'pretreated' urine. Polymeric materials used in UWMS are not only exposed to pretreated urine, but also to concentrated phosphoric acid with oxidizer before dilution known as 'pure pretreat.' Samples of five different polymeric materials immersed in pure pretreat for 1 year were tested for liquid compatibility by measuring changes in storage modulus with a dynamic mechanical analyzer.

Antimicrobial activity of silver nanoparticles encapsulated in poly-N-isopropylacrylamide-based polymeric nanoparticles.

PubMed

Qasim, Muhammad; Udomluck, Nopphadol; Chang, Jihyun; Park, Hansoo; Kim, Kyobum

2018-01-01

In this study, we analyzed the antimicrobial activities of poly- N -isopropylacrylamide (pNIPAM)-based polymeric nanoparticles encapsulating silver nanoparticles (AgNPs). Three sizes of AgNP-encapsulating pNIPAM- and pNIPAM-NH 2 -based polymeric nanoparticles were fabricated. Highly stable and uniformly distributed AgNPs were encapsulated within polymeric nanoparticles via in situ reduction of AgNO 3 using NaBH 4 as the reducing agent. The formation and distribution of AgNPs was confirmed by UV-visible spectroscopy, transmission electron microscopy, and inductively coupled plasma optical emission spectrometry, respectively. Both polymeric nanoparticles showed significant bacteriostatic activities against Gram-negative ( Escherichia coli ) and Gram-positive ( Staphylococcus aureus ) bacteria depending on the nanoparticle size and amount of AgNO 3 used during fabrication.

Antimicrobial activity of silver nanoparticles encapsulated in poly-N-isopropylacrylamide-based polymeric nanoparticles

PubMed Central

Qasim, Muhammad; Udomluck, Nopphadol; Chang, Jihyun; Park, Hansoo; Kim, Kyobum

2018-01-01

In this study, we analyzed the antimicrobial activities of poly-N-isopropylacrylamide (pNIPAM)-based polymeric nanoparticles encapsulating silver nanoparticles (AgNPs). Three sizes of AgNP-encapsulating pNIPAM- and pNIPAM-NH2-based polymeric nanoparticles were fabricated. Highly stable and uniformly distributed AgNPs were encapsulated within polymeric nanoparticles via in situ reduction of AgNO3 using NaBH4 as the reducing agent. The formation and distribution of AgNPs was confirmed by UV-visible spectroscopy, transmission electron microscopy, and inductively coupled plasma optical emission spectrometry, respectively. Both polymeric nanoparticles showed significant bacteriostatic activities against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria depending on the nanoparticle size and amount of AgNO3 used during fabrication. PMID:29379284

Collaborative Research: Polymeric Multiferroics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ren, Shenqiang

2017-04-20

The goal of this project is to investigate room temperature magnetism and magnetoelectric coupling of polymeric multiferroics. A new family of molecular charge-transfer crystals has been emerged as a fascinating opportunity for the development of all-organic electrics and spintronics due to its weak hyperfine interaction and low spin-orbit coupling; nevertheless, direct observations of room temperature magnetic spin ordering have yet to be accomplished in organic charge-transfer solids. Furthermore, room temperature magnetoelectric coupling effect hitherto known multiferroics, is anticipated in organic donor-acceptor complexes because of magnetic field effects on charge-transfer dipoles, yet this is also unexplored. The PI seeks to fundamentalmore » understanding of the control of organic crystals to demonstrate and explore room temperature multiferroicity. The experimental results have been verified through the theoretical modeling.« less

Non-fouling surfaces produced by gas phase pulsed plasma polymerization of an ultra low molecular weight ethylene oxide containing monomer.

PubMed

Wu; Timmons; Jen; Molock

2000-10-01

The pulsed plasma polymerization of low molecular weight molecules containing only one (ethylene oxide vinyl ether) and two (diethylene oxide vinyl ether) ethylene oxide units were investigated. The surface density of EO units retained in the polymer films increases sharply with decreasing average power input during deposition, particularly at very low plasma duty cycles. The protein adsorption properties of these plasma synthesized polymer were investigated using 125I-labeled albumin and fibrinogen. Surprisingly effective, non-fouling surfaces were observed with films synthesized from the monomer containing two ethylene oxide units; however, the monomer containing only one EO unit gave surfaces that were not particularly effective in preventing protein adsorptions. The results obtained show that ultra short chain length PEO modified surfaces can be biologically non-fouling. This, in turn, has interesting consequences in terms of trying to identify the basic reason for the effectiveness of EO units in preventing biomolecule adsorptions on surfaces.

NiTi shape memory alloys treated by plasma-polymerized tetrafluoroethylene. A physicochemical and electrochemical characterization.

PubMed

Yahia, L H; Lombardi, S; Piron, D; Klemberg-Sapieha, J E; Wertheimer, M R

NiTi alloy specimens were plasma cleaned and then coated with a thin film of plasma-polymerized tetrafluoroethylene (TFE) in a Radio-Frequency reactor. The corrosion protection provided by these films was studied by potentiodynamic tests performed in Hank's physiological solution. Surface properties which determine biocompatibility were characterized by X-ray photoelectron spectroscopy (XPS). The results showed that the surface of untreated NiTi was mostly composed by oxygen, carbon, titanium oxide (TiO2) with traces of nickel oxides (NiO and Ni2O3) and metallic Ni. The passivity of untreated NiTi was found to be unstable in the simulated human body media. After plasma treatment, the NiTi surface contained only carbon and fluor. The plasma-polymerized thin film was found to stabilize the NiTi passivity and to increase its pitting potential. This treatment provides a good protection against dissolution of nickel from NiTi alloys.

A redox beginning: Which came first phosphoryl, acyl, or electron transfer ?. [Abstract only

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1994-01-01

Thermodynamic and kinetic information available on the synthesis of prebiotic monomers and polymers will be examined in order to illuminate the prebiotic plausibility of polymer syntheses based on (a) phosphoryl transfer that yields phosphodiester polymers, (b) acyl transfer that gives polyamides, and (c) electron transfer that produces polydisulfide or poly(thio)ester polymers. New experimental results on the oxidative polymerization of 2,3-dimercaptopropanol by ferric ions on the surface of ferric hydroxide oxide will be discussed as a chemical model of polymerization by electron transfer. This redox polymerization that yields polymers with a polydisulfide backbone was found to give oligomers up to the 15-mer from 1 mM of 2,3-dimercaptopropanol after one day at 25 C. High pressure liquid chromatography (HPLC) analysis of the oligomers was carried out on an Alltech OH-100 column eluted with acetonitrile-water.

Polymer grafted magnetic nanoparticles for delivery of anticancer drug at lower pH and elevated temperature.

PubMed

Dutta, Sujan; Parida, Sheetal; Maiti, Chiranjit; Banerjee, Rakesh; Mandal, Mahitosh; Dhara, Dibakar

2016-04-01

Efficient and controlled delivery of therapeutics to tumor cells is one of the important issues in cancer therapy. In the present work, a series of pH- and temperature-responsive polymer grafted iron oxide nanoparticles were prepared by simple coupling of aminated iron oxide nanoparticle with poly(N-isopropylacrylamide-ran-poly(ethylene glycol) methyl ether acrylate)-block-poly(acrylic acid) (P(NIPA-r-PEGMEA)-b-PAA). For this, three water soluble block polymers were prepared via reversible addition fragmentation transfer (RAFT) polymerization technique. At first, three different block copolymers were prepared by polymerizing mixture of NIPA and PEGMEA (with varying mole ratio) in presence of poly(tert-butyl acrylate) (PtBA) macro chain transfer agent. Subsequently, P(NIPA-r-PEGMEA)-b-PAA copolymers were synthesized by hydrolyzing tert-butyl acrylate groups of the P(NIPA-r-PEGMEA)-b-PtBA copolymers. The resulting polymers were then grafted to iron oxide nanoparticles, and these functionalized nanoparticles were thoroughly characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), zeta potential measurements, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), vibrating sample magnetometer (VSM) and Fourier transform infrared spectroscopy (FTIR). Doxorubicin (DOX), an anti-cancer drug, was loaded into the polymer coated nanoparticles and its release behavior was subsequently studied at different pH and temperatures. The drug release pattern revealed a sustained release of DOX preferentially at the desired lysosomal pH of cancer cells (pH 5.0) and slightly above the physiological temperature depending upon the composition of the copolymers. The potential anticancer activity of the polymer grafted DOX loaded nanoparticles were established by MTT assay and apoptosis study of cervical cancer ME 180cells in presence of the nanoparticles. Thus, these particles can be utilized for controlled delivery of anticancer drugs at the desired lysosomal pH and/or by slightly heating the cells using magnetic hyperthermia. Copyright © 2016 Elsevier Inc. All rights reserved.

Recent advances and developments in composite dental restorative materials.

PubMed

Cramer, N B; Stansbury, J W; Bowman, C N

2011-04-01

Composite dental restorations represent a unique class of biomaterials with severe restrictions on biocompatibility, curing behavior, esthetics, and ultimate material properties. These materials are presently limited by shrinkage and polymerization-induced shrinkage stress, limited toughness, the presence of unreacted monomer that remains following the polymerization, and several other factors. Fortunately, these materials have been the focus of a great deal of research in recent years with the goal of improving restoration performance by changing the initiation system, monomers, and fillers and their coupling agents, and by developing novel polymerization strategies. Here, we review the general characteristics of the polymerization reaction and recent approaches that have been taken to improve composite restorative performance.

Recent Advances and Developments in Composite Dental Restorative Materials

PubMed Central

Cramer, N.B.; Stansbury, J.W.; Bowman, C.N.

2011-01-01

Composite dental restorations represent a unique class of biomaterials with severe restrictions on biocompatibility, curing behavior, esthetics, and ultimate material properties. These materials are presently limited by shrinkage and polymerization-induced shrinkage stress, limited toughness, the presence of unreacted monomer that remains following the polymerization, and several other factors. Fortunately, these materials have been the focus of a great deal of research in recent years with the goal of improving restoration performance by changing the initiation system, monomers, and fillers and their coupling agents, and by developing novel polymerization strategies. Here, we review the general characteristics of the polymerization reaction and recent approaches that have been taken to improve composite restorative performance. PMID:20924063

Influence of ethylene oxide exposure on the extraction of indomethacin from dimethicone polymeric rods.

PubMed

Hurst, P R; Peplow, P V; von Dadelszen, P

1982-05-01

Dimethicone polymeric rods were made to contain 0.3, 2.0, or 3.3% by weight of indomethacin. For each different loading of indomethacin, some of the rods were treated with ethylene oxide at 55 degrees for 1 hr, while others were not exposed to the gas. Treated and untreated rods were sliced, placed in ethanol to extract the indomethacin, and the concentrations of indomethacin in the extracts determined by fluorometry and high-performance liquid chromatography (HPLC). After ethylene oxide treatment, the quantity of indomethacin in the extracts was significantly reduced in rods containing 0.3 and 2.0% indomethacin. For the rods containing 3.3% indomethacin, the recovery of the drug from treated rods was not significantly different from those not exposed.

Enhanced performance of biodegradable poly(butylene succinate)/graphene oxide nanocomposites via in situ polymerization.

PubMed

Wang, X W; Zhang, C-A; Wang, P L; Zhao, J; Zhang, W; Ji, J H; Hua, K; Zhou, J; Yang, X B; Li, X P

2012-05-08

Poly(butylene succinate) (PBS)/graphene oxide (GO) nanocomposites were facilely prepared via in situ polymerization. The properties of the nanocomposites were studied using FTIR, XRD, and (1)H NMR, and the state of dispersion of GO in the PBS matrix was examined by SEM. The crystallization and melting behavior of the PBS matrix in the presence of dispersed GO nanosheets have been studied by DSC and polarized optical microscopy. Through the mechnical testing machine and DMA, PBS/GO nanocomposites with 3% GO have shown a 43% increase in tensile strength and a 45% improvement in storage modulus. This high performance of the nanocomposites is mainly attributed to the high strength of graphene oxide combined with the strong interfacial interactions in the uniformly dispersed PBS/GO nanocomposites.

Efficient simultaneous adsorption-biodegradation of high-concentrated N,N-dimethylformamide from water by Paracoccus denitrificans-graphene oxide microcomposites

NASA Astrophysics Data System (ADS)

Zheng, Yuan; Chen, Dongyun; Li, Najun; Xu, Qingfeng; Li, Hua; He, Jinghui; Lu, Jianmei

2016-02-01

Water contamination becomes one of the most pervasive environmental issues all over the world in recent years. In this paper, the functionalization of graphene oxide (GO) with copolymers containing methacrylic acid (MAA) and butyl methacrylate (BMA) was investigated to prepare a new microcomposite material (PGO) via free radical solution polymerization. PGO was used for the adsorption of N,N-dimethylformamide (DMF) from aqueous solution by utilizing the characteristics of ultralarge surface and the Van der Waals force between DMF molecules and polymers on the surface of PGO. Besides, PGO was used not only a high-capable adsorbent but also a carrier for the immobilization of Paracoccus denitrificans cells in the treatment of high-concentrated DMF. Bacterial cells could immobilized on the PGO (PGO@P. denitrificans) stably by covalent coupling process after acclimatization and high-concentrated DMF (2000 mg/L) could be removed completely and relatively rapidly from aqueous solutions by the simultaneous adsorption-biodegradation (SAB) process of PGO@P. denitrificans. Furthermore, the excellent recycle performance of PGO@P. denitrificans made the whole process more economical and practical.

Sustained magnetization oscillations in polyaniline-Fe{sub 3}O{sub 4} nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Araújo, A. C. V. de; Rodrigues, A. R., E-mail: ricalde@df.ufpe.br; Machado, F. L. A.

2015-09-28

We report experiments with polyaniline-Fe{sub 3}O{sub 4} (PANI-Fe{sub 3}O{sub 4}) nanocomposites synthesized under several different conditions. With a reaction carried out at room temperature and assisted by intense ultra-violet (UV) irradiation, we observe sustained oscillations in the magnetization with a period of about 25 min. The oscillations are interpreted as the result of an oscillatory chemical reaction in which part of the Fe{sup +2} ions of magnetite, Fe{sub 3}O{sub 4}, are oxidized by the UV irradiation to form Fe{sup +3} so that a fraction of the magnetite content transforms into maghemite, γ-Fe{sub 2}O{sub 3}. Then, Fe{sup +3} ions at themore » nanoparticle surfaces are reduced and transformed back into Fe{sup +2}, when acting as an oxidizing agent for polyaniline in the polymerization process. Since maghemite has smaller magnetization than magnetite, the oscillating chemical reaction results in the oscillatory magnetization. The observations are interpreted with the Lotka-Volterra nonlinear coupled equations with parameters that can be adjusted to fit very well the experimental data.« less

Amperometric urea biosensors based on sulfonated graphene/polyaniline nanocomposite

PubMed Central

Das, Gautam; Yoon, Hyon Hee

2015-01-01

An electrochemical biosensor based on sulfonated graphene/polyaniline nanocomposite was developed for urea analysis. Oxidative polymerization of aniline in the presence of sulfonated graphene oxide was carried out by electrochemical methods in an aqueous environment. The structural properties of the nanocomposite were characterized by Fourier-transform infrared, Raman spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy techniques. The urease enzyme-immobilized sulfonated graphene/polyaniline nanocomposite film showed impressive performance in the electroanalytical detection of urea with a detection limit of 0.050 mM and a sensitivity of 0.85 (μA · cm−2·mM−1. The biosensor achieved a broad linear range of detection (0.12–12.3 mM) with a notable response time of approximately 5 seconds. Moreover, the fabricated biosensor retained 81% of its initial activity (based on sensitivity) after 15 days of storage at 4°C. The ease of fabrication coupled with the low cost and good electrochemical performance of this system holds potential for the development of solid-state biosensors for urea detection. PMID:26346240

High-concentration graphene dispersion stabilized by block copolymers in ethanol.

PubMed

Perumal, Suguna; Lee, Hyang Moo; Cheong, In Woo

2017-07-01

This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion. Copyright © 2017 Elsevier Inc. All rights reserved.

Recent aspects of self-oscillating polymeric materials: designing self-oscillating polymers coupled with supramolecular chemistry and ionic liquid science.

PubMed

Ueki, Takeshi; Yoshida, Ryo

2014-06-14

Herein, we summarise the recent developments in self-oscillating polymeric materials based on the concepts of supramolecular chemistry, where aggregates of molecular building blocks with non-covalent bonds evolve the temporal or spatiotemporal structure. By utilising the rhythmic oscillation of the association/dissociation of molecular aggregates coupled with the redox oscillation by the BZ reaction, novel soft materials that express similar functions as those of living matter will be achieved. Further, from the viewpoint of materials science, our recent approach to prepare self-oscillating materials that operate long-term under mild conditions will be introduced.

Chemical sensors

DOEpatents

Lowell, Jr., James R.; Edlund, David J.; Friesen, Dwayne T.; Rayfield, George W.

1992-01-01

Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising a mechanicochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, either operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical or optical response, or adhered to a second inert polymeric strip, or doped with a conductive material.

Magnetism in (Semi)Conducting Macrocycles of pi conjugated Polymers

DTIC Science & Technology

2016-12-09

wise and avoiding a break in the continuity of the macrocycle. As a first criterion we tested the continuity of the electron orbitals over the...magnesium chloride) and post polymerization functionalization by a Sonogashira coupling reaction is required (scheme 2). Scheme 2: Synthetic...Sonogashira post - polymerization chain end functionalization and B isotopic model of the different population present in the final batch

Evaluation of antibacterial activity of nitric oxide-releasing polymeric particles against Staphylococcus aureus and Escherichia coli from bovine mastitis.

PubMed

Cardozo, Viviane F; Lancheros, Cesar A C; Narciso, Adélia M; Valereto, Elaine C S; Kobayashi, Renata K T; Seabra, Amedea B; Nakazato, Gerson

2014-10-01

Bovine mastitis is a serious veterinary disease that causes great loss to the dairy industry worldwide. It is a major infectious disease and is difficult to manage and control. Furthermore, emerging multidrug resistant bacteria that cause mastitis have complicated such management. The free radical nitric oxide (NO) is a potent antimicrobial agent. Thus, the aims of this study were to prepare and evaluate the antibacterial activity of nitric oxide-releasing polymeric particles against Staphylococcus aureus (MBSA) and Escherichia coli (MBEC), which were isolated from bovine mastitis. Fifteen MBSA isolates and fifteen MBEC were collected from subclinical and clinical bovine mastitis. Biocompatible polymeric particles composed of alginate/chitosan or chitosan/sodium tripolyphosphate (TPP) were prepared and used to encapsulate mercaptosuccinic acid (MSA), which is a thiol-containing molecule. Nitrosation of thiol groups of MSA-containing particles formed S-nitroso-MSA particles, which are NO donors. The NO release kinetics from the S-nitroso-MSA particles showed sustained and controlled NO release over several hours. The antibacterial activity of NO-releasing particles was evaluated by incubating the particles with an MBSA multi-resistant strain, which is responsible for bovine mastitis. The minimum inhibitory concentration for S-nitroso-MSA-alginate/chitosan particles against MBSA ranged from 125 μg/mL to 250 μg/mL. The results indicate that NO-releasing polymeric particles are an interesting approach to combating bacteria resistance in bovine mastitis treatment and prevention. Copyright © 2014. Published by Elsevier B.V.

Effects of nitric oxide and its congeners on sickle red blood cell deformability.

PubMed

Belanger, Andrea M; Keggi, Christian; Kanias, Tamir; Gladwin, Mark T; Kim-Shapiro, Daniel B

2015-10-01

Sickle cell disease (SCD) is characterized by hemoglobin polymerization upon deoxygenation. Polymerization causes the sickle cells to become rigid and misshapen (sickling). Red blood cell (RBC) dehydration greatly increases polymerization. Cycles of sickling and unsickling cause an influx of calcium that leads to loss of potassium via the calcium-activated Gardos channel, which dehydrates the cells leading to increased polymerization. In this study the effects of nitric oxide (NO) and its congeners on RBC deformability were examined, focusing on sickle RBCs (sRBCs). RBCs from patients with SCD and from nonpatients were exposed to various compounds that release NO or its congeners. Intracellular calcium was increased using a calcium ionophore or cycling of oxygen tension for sRBCs. Deformability was measured by laser-assisted osmotic gradient ektacytometry. Consistent with a previous report, sodium nitroprusside (SNP) was found to protect against calcium-induced loss of deformability in normal RBCs, but (contrary to some previous reports) no effect of any NO donors was observed when calcium influx was not induced. Importantly, in studies of deoxygenation-induced dehydration of sRBCs, SNP resulted in substantial improvements in deformability (p = 0.036) and hydration (p = 0.024). Sodium nitrite showed similar trends. SNP was shown to have no effect on calcium influx, but reduced potassium efflux. These data suggest that SNP and perhaps certain nitrogen oxides (like nitrite) inhibit the Gardos channel and may be able to protect sickle cells from dehydration and thereby improve outcome in the disease. © 2015 AABB.

Large enhanced dielectric permittivity in polyaniline passivated core-shell nano magnetic iron oxide by plasma polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joy, Lija K.; Sooraj, V.; Sethulakshmi, N.

2014-03-24

Commercial samples of Magnetite with size ranging from 25–30 nm were coated with polyaniline by using radio frequency plasma polymerization to achieve a core shell structure of magnetic nanoparticle (core)–Polyaniline (shell). High resolution transmission electron microscopy images confirm the core shell architecture of polyaniline coated iron oxide. The dielectric properties of the material were studied before and after plasma treatment. The polymer coated magnetite particles exhibited a large dielectric permittivity with respect to uncoated samples. The dielectric behavior was modeled using a Maxwell–Wagner capacitor model. A plausible mechanism for the enhancement of dielectric permittivity is proposed.

Advancement in conductive cotton fabrics through in situ polymerization of polypyrrole-nanocellulose composites.

PubMed

Hebeish, A; Farag, S; Sharaf, S; Shaheen, Th I

2016-10-20

Current research was undertaking with a view to innovate a new approach for development of conductive - coated textile materials through coating cotton fabrics with nanocellulose/polypyrrole composites. The study was designed in order to have a clear understanding of the role of nanocellulose as well as modified composite thereof under investigation. It is anticipated that incorporation of nanocellulose in the pyrrole/cotton fabrics/FeCl3/H2O system would form an integral part of the composites with mechanical, electrical or both properties. Three different nanocellulosic substrates are involved in the oxidation polymerization reaction of polypyrrole (Ppy) in presence of cotton fabrics. Polymerization was subsequently carried out by admixing at various ratios of FeCl3 and pyrrole viz. Ppy1, Ppy2 and pp3. The conductive, mechanical and thermal properties of cotton fabrics coated independently with different nanocellulose/polypyrrole were investigated. FTIR, TGA, XRD, SEM and EDX were also used for further characterization. Results signify that, the conductivity of cotton fabrics increases exponentially with increasing the dose of pyrrole and oxidant irrespective of nanocellulose substrate used. While, the mechanical properties of cotton fabrics are not significantly affected by the oxidant treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

An amplified graphene oxide-based fluorescence aptasensor based on target-triggered aptamer hairpin switch and strand-displacement polymerization recycling for bioassays.

PubMed

Hu, Kun; Liu, Jinwen; Chen, Jia; Huang, Yong; Zhao, Shulin; Tian, Jianniao; Zhang, Guohai

2013-04-15

An amplified graphene oxide (GO) based fluorescence aptasensor based on target-triggered aptamer hairpin switch and strand-displacement polymerization recycling is developed for bioassays. The dye-labeled single-strand DNA (aptamer hairpin) was adsorbed on the surface of GO, which result in the fluorescence quenching of dye, and exhibiting minimal background fluorescence. Upon the target, primer and polymerase, the stem of the aptamer hairpin was opened, and binds with the primer to triggers the circular target strand-displacement polymerization reaction, which produces huge amounts of duplex helixes DNA and lead to strong fluorescence emission due to shielding of nucelobases within its double-helix structure. During the polymerization reaction, the primer was extended, and target was displaced. And the displaced target recognizes and hybridizes with another hairpin probe, triggering the next round of polymerization reaction, and the circle process induces fluorescence signal amplification for the detection of analyte. To test the feasibility of the aptasensor systems, interferon-gamma (IFN-γ) was employed as a model analyte. A detection limit as low as 1.5 fM is obtained based on the GO aptasensor with a linear range of three orders of magnitude. The present method was successfully applied for the detection of IFN-γ in human plasma. Copyright © 2012 Elsevier B.V. All rights reserved.

Interfacial chemical oxidative synthesis of multifunctional polyfluoranthene† †Electronic supplementary information (ESI) available: The optimization of polymerization conditions, size distribution and morphology of the PFA particles, and solubility and DMSO solution in sunlight and in 365 nm UV of FA and PFA synthesized. See DOI: 10.1039/c4sc03890h Click here for additional data file.

PubMed Central

Liao, Yaozu

2015-01-01

A novel polyfluoranthene (PFA) exhibiting strong visual fluorescence emission, a highly amplified quenching effect, and widely controllable electrical conductivity is synthesized by the direct cationic oxidative polymerization of fluoranthene in a dynamic interface between n-hexane and nitromethane containing fluoranthene and FeCl3, respectively. A full characterization of the molecular structure signifies that the PFAs have a degree of polymerization from 22–50 depending on the polymerization conditions. A polymerization mechanism at the interface of the hexane/nitromethane biphasic system is proposed. The conductivity of the PFA is tunable from 6.4 × 10–6 to 0.074 S cm–1 by doping with HCl or iodine. The conductivity can be significantly enhanced to 150 S cm–1 by heat treatment at 1100 °C in argon. A PFA-based chemosensor shows a highly selective sensitivity for Fe3+ detection which is unaffected by other common metal ions. The detection of Fe3+ likely involves the synergistic effect of well-distributed π-conjugated electrons throughout the PFA helical chains that function as both the fluorophore and the receptor units. PMID:29142676

Recent Advances in the Synthesis and Biomedical Applications of Nanocomposite Hydrogels

PubMed Central

Spizzirri, Umile Gianfranco; Curcio, Manuela; Cirillo, Giuseppe; Spataro, Tania; Vittorio, Orazio; Picci, Nevio; Hampel, Silke; Iemma, Francesca; Nicoletta, Fiore Pasquale

2015-01-01

Hydrogels sensitive to electric current are usually made of polyelectrolytes and undergo erosion, swelling, de-swelling or bending in the presence of an applied electric field. The electrical conductivity of many polymeric materials used for the fabrication of biomedical devices is not high enough to achieve an effective modulation of the functional properties, and thus, the incorporation of conducting materials (e.g., carbon nanotubes and nanographene oxide) was proposed as a valuable approach to overcome this limitation. By coupling the biological and chemical features of both natural and synthetic polymers with the favourable properties of carbon nanostructures (e.g., cellular uptake, electromagnetic and magnetic behaviour), it is possible to produce highly versatile and effective nanocomposite materials. In the present review, the recent advances in the synthesis and biomedical applications of electro-responsive nanocomposite hydrogels are discussed. PMID:26473915

3D-Printable Photochromic Molecular Materials for Reversible Information Storage.

PubMed

Wales, Dominic J; Cao, Qun; Kastner, Katharina; Karjalainen, Erno; Newton, Graham N; Sans, Victor

2018-06-01

The formulation of advanced molecular materials with bespoke polymeric ionic-liquid matrices that stabilize and solubilize hybrid organic-inorganic polyoxometalates and allow their processing by additive manufacturing, is effectively demonstrated. The unique photo and redox properties of nanostructured polyoxometalates are translated across the scales (from molecular design to functional materials) to yield macroscopic functional devices with reversible photochromism. These properties open a range of potential applications including reversible information storage based on controlled topological and temporal reduction/oxidation of pre-formed printed devices. This approach pushes the boundaries of 3D printing to the molecular limits, allowing the freedom of design enabled by 3D printing to be coupled with the molecular tuneability of polymerizable ionic liquids and the photoactivity and orbital engineering possible with hybrid polyoxometalates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Advances in the Synthesis and Biomedical Applications of Nanocomposite Hydrogels.

PubMed

Spizzirri, Umile Gianfranco; Curcio, Manuela; Cirillo, Giuseppe; Spataro, Tania; Vittorio, Orazio; Picci, Nevio; Hampel, Silke; Iemma, Francesca; Nicoletta, Fiore Pasquale

2015-10-13

Hydrogels sensitive to electric current are usually made of polyelectrolytes and undergo erosion, swelling, de-swelling or bending in the presence of an applied electric field. The electrical conductivity of many polymeric materials used for the fabrication of biomedical devices is not high enough to achieve an effective modulation of the functional properties, and thus, the incorporation of conducting materials (e.g., carbon nanotubes and nanographene oxide) was proposed as a valuable approach to overcome this limitation. By coupling the biological and chemical features of both natural and synthetic polymers with the favourable properties of carbon nanostructures (e.g., cellular uptake, electromagnetic and magnetic behaviour), it is possible to produce highly versatile and effective nanocomposite materials. In the present review, the recent advances in the synthesis and biomedical applications of electro-responsive nanocomposite hydrogels are discussed.

Sol processing of conjugated carbon nitride powders for thin-film fabrication.

PubMed

Zhang, Jinshui; Zhang, Mingwen; Lin, Lihua; Wang, Xinchen

2015-05-18

The chemical protonation of graphitic carbon nitride (CN) solids with strong oxidizing acids, for example HNO3, is demonstrated as an efficient pathway for the sol processing of a stable CN colloidal suspension, which can be translated into thin films by dip/disperse-coating techniques. The unique features of CN colloids, such as the polymeric matrix and the reversible hydrogen bonding, result in the thin-film electrodes derived from the sol solution exhibiting a high mechanical stability with improved conductivity for charge transport, and thus show a remarkably enhanced photo-electrochemical performance. The polymer system can in principle be broadly tuned by hybridization with desired functionalities, thus paving the way for the application of CN for specific tasks, as exemplified here by coupling with carbon nanotubes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorination Induced the Surface Segregation of High Voltage Spinel on Lithium-Rich Layered Cathodes for Enhanced Rate Capability in Lithium Ion Batteries.

PubMed

Jin, Yi-Chun; Duh, Jenq-Gong

2016-02-17

This study is aimed to explore the effect of fluoride doping and the associated structural transformation on lithium-rich layered cathode materials. The polymeric fluoride source is first adopted for synthesizing lithium intercalated oxide through a newly developed organic precipitation process. A heterostructured spinel/layered composite cathode material is obtained after appreciable fluorination and a superior rate capability is successfully achieved. The fluoride dopant amount and the surface spinel phase are evidenced and systematically examined by various structural spectroscopy and electrochemical analysis. It appears the reversible Ni(2+/4+) redox couple at high voltage regime around 4.8 V because of the formation of spinel LiNi1/2Mn3/2O4 phase. The mechanism of "layer to spinel" phase transformation is discussed in detail.

Bimetallic complexes and polymerization catalysts therefrom

DOEpatents

Patton, Jasson T.; Marks, Tobin J.; Li, Liting

2000-11-28

Group 3-6 or Lanthanide metal complexes possessing two metal centers, catalysts derived therefrom by combining the same with strong Lewis acids, Bronsted acid salts, salts containing a cationic oxidizing agent or subjected to bulk electrolysis in the presence of compatible, inert non-coordinating anions and the use of such catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers are disclosed.

Transition-metal-ion-mediated polymerization of dopamine: mussel-inspired approach for the facile synthesis of robust transition-metal nanoparticle-graphene hybrids.

PubMed

Yang, Liping; Kong, Junhua; Zhou, Dan; Ang, Jia Ming; Phua, Si Lei; Yee, Wu Aik; Liu, Hai; Huang, Yizhong; Lu, Xuehong

2014-06-16

Inspired by the high transition-metal-ion content in mussel glues, and the cross-linking and mechanical reinforcement effects of some transition-metal ions in mussel threads, high concentrations of nickel(II), cobalt(II), and manganese(II) ions have been purposely introduced into the reaction system for dopamine polymerization. Kinetics studies were conducted for the Ni(2+)-dopamine system to investigate the polymerization mechanism. The results show that the Ni(2+) ions could accelerate the assembly of dopamine oligomers in the polymerization process. Spectroscopic and electron microscopic studies reveal that the Ni(2+) ions are chelated with polydopamine (PDA) units, forming homogeneous Ni(2+)-PDA complexes. This facile one-pot approach is utilized to construct transition-metal-ion-PDA complex thin coatings on graphene oxide, which can be carbonized to produce robust hybrid nanosheets with well-dispersed metallic nickel/metallic cobalt/manganese(II) oxide nanoparticles embedded in PDA-derived thin graphitic carbon layers. The nickel-graphene hybrid prepared by using this approach shows good catalytic properties and recyclability for the reduction of p-nitrophenol. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mite allergoids coupled to nonoxidized mannan from Saccharomyces cerevisae efficiently target canine dendritic cells for novel allergy immunotherapy in veterinary medicine.

PubMed

Soria, Irene; Alvarez, Javier; Manzano, Ana I; López-Relaño, Juan; Cases, Bárbara; Mas-Fontao, Ana; Cañada, F Javier; Fernández-Caldas, Enrique; Casanovas, Miguel; Jiménez-Barbero, Jesús; Palomares, Oscar; Viñals-Flórez, Luis M; Subiza, José L

2017-08-01

We have recently reported that grass pollen allergoids conjugated with nonoxidized mannan of Saccharomyces cerevisae using glutaraldehyde results in a novel hypoallergenic mannan-allergen complex with improved properties for allergen vaccination. Using this approach, human dendritic cells show a better allergen uptake and cytokine profile production (higher IL-10/IL-4 ratio) for therapeutic purposes. Here we aim to address whether a similar approach can be extended to dogs using canine dendritic cells. Six healthy Spanish Greyhound dogs were used as blood donors to obtain canine dendritic cells (DC) derived from peripheral blood monocytes. Allergens from Dermatophagoides farinae mite were polymerized and conjugated with nonoxidized mannan. Nuclear magnetic resonance (NMR), gel electrophoresis (SDS-PAGE), immunoblotting and IgE-ELISA inhibition studies were conducted to evaluate the main characteristics of the allergoid obtained. Mannan-allergen conjugate and controls were assayed in vitro for canine DC uptake and production of IL-4 and IL-10. The results indicate that the conjugation of D. farinae allergens with nonoxidized mannan was feasible using glutaraldehyde. The resulting product was a polymerized structure showing a high molecular weight as detected by NMR and SDS-PAGE analysis. The mannan-allergen conjugate was hypoallergenic with a reduced reactivity with specific dog IgE. An increase in both allergen uptake and IL-10/IL-4 ratio was obtained when canine DCs were incubated with the mannan-allergen conjugate, as compared with the control allergen preparations (unmodified D. farinae allergens and oxidized mannan-allergen conjugate). We conclude that hypoallergenic D. farinae allergens coupled to nonoxidized mannan is a novel allergen preparation suitable for canine allergy immunotherapy targeting dendritic cells. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

New Development of Polymer-Based Cotton for Breathable Material

USDA-ARS?s Scientific Manuscript database

Recently, we converted the poly (ethylene oxide) dibromide to poly (ethylene oxide) diazides and reacted to study cycloaddition polymerization with bisphenol-A dipropargyl ether to produce elastomers compatible with cotton (Polymer Preprints, 2005, 46(1), 737-738). The reactants were characterized w...

The initiating radical yields and the efficiency of polymerization for various dental photoinitiators excited by different light curing units.

PubMed

Neumann, Miguel G; Schmitt, Carla C; Ferreira, Giovana C; Corrêa, Ivo C

2006-06-01

To evaluate the efficiency of the photopolymerization of dental resins it is necessary to know to what extent the light emitted by the light curing units is absorbed by the photoinitiators. On the other hand, the efficiency of the absorbed photons to produce species that launch the polymerization process is also of paramount importance. Therefore, the previously determined PAE (photon absorption efficiency) is used in conjunction with the polymerization quantum yields for the photoinitiators, in order to be able to compare the total process on an equivalent basis. This parameter can be used to identify the best performance for the photochemical process with specific photoinitiators. The efficiency of LED (Ultrablue IS) and QTH (Optilux 401) lamps were tested comparing their performances with the photoinitiators camphorquinone (CQ); phenylpropanedione (PPD); monoacylphosphine oxide (Lucirin TPO); and bisacylphosphine oxide (Irgacure 819). The extent of photopolymerization per absorbed photon was determined from the polymerization quantum yields obtained by using the photoinitiators to polymerize methyl methacrylate, and afterwards combined with the previously determined PAEs. Although CQ presents a rather low polymerization quantum yield, its photopolymerization efficiency is practically the highest when irradiated with the Ultrablue LED. On the other hand, Lucirin is much more efficient than the other photoinitiators when irradiated with a QTH lamp, due to its high quantum yield and the overlap between its absorption spectrum and the output of the visible lamp light. Difference in photopolymerization efficiencies arise when combinations of photoinitiators are used, and when LED sources are used in preference to QTH. Mechanistic understanding is essential to optimal initiator formulation.

Glycine Polymerization on Oxide Minerals.

PubMed

Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

2017-06-01

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

Amino Acid Bound Surfactants: A New Synthetic Family of Polymeric Monoliths Open Up Possibilities for Chiral Separations in Capillary Electrochromatography

PubMed Central

He, Jun; Wang, Xiaochun; Morrill, Mike; Shamsi, Shahab A.

2012-01-01

By combining a novel chiral amino-acid surfactant containing acryloyl amide tail, carbamate linker and leucine head group of different chain lengths with a conventional cross linker and a polymerization technique, a new “one-pot”, synthesis for the generation of amino-acid based polymeric monolith is realized. The method promises to open up the discovery of amino-acid based polymeric monolith for chiral separations in capillary electrochromatography (CEC). Possibility of enhanced chemoselectivity for simultaneous separation of ephedrine and pseudoephedrine containing multiple chiral centers, and the potential use of this amino-acid surfactant bound column for CEC and CEC coupled to mass spectrometric detection is demonstrated. PMID:22607448

Bis(trifluoromethanesulfonyl)imide-based ionic liquids grafted on graphene oxide-coated solid-phase microextraction fiber for extraction and enrichment of polycyclic aromatic hydrocarbons in potatoes and phthalate esters in food-wrap.

PubMed

Hou, Xiudan; Guo, Yong; Liang, Xiaojing; Wang, Xusheng; Wang, Lei; Wang, Licheng; Liu, Xia

2016-06-01

A class of novel, environmental friendly ionic liquids (ILs) were synthesized by on-fiber preparation strategy and modified on graphene oxide (GO)-coated stainless steel wire, which was used as a solid-phase microextraction (SPME) fiber for efficient enrichment of polycyclic aromatic hydrocarbons (PAHs) and phthalate esters (PAEs). Surface characteristic of the ILs and polymeric-ILs (PILs) fibers with the wave-structure were inspected by scanning electron microscope. The successfully synthesis of bis(trifluoromethanesulfonyl)imide (NTf2(-))-based ILs were also characterized by energy dispersive spectrometer analysis. Through the chromatograms of the proposed two ILs (1-aminoethyl-3-methylimidazolium bromide (C2NH2MIm(+)Br(-)), C2NH2MIm(+)NTf2(-)) and two PILs (polymeric 1-vinyl-3-hexylimidazolium bromide (poly(VHIm(+)Br(-))), poly(VHIm(+)NTf2(-)))-GO-coated fibers for the extraction of analytes, NTf2(-)-based PIL demonstrated higher extraction capacity for hydrophobic compounds than other as-prepared ILs. Analytical performances of the proposed fibers were investigated under the optimized extraction and desorption conditions coupled with gas chromatography (GC). Compared with the poly(VHIm(+)Br(-))-GO fiber, the poly(VHIm(+)NTf2(-))-GO SPME fiber brought wider linear ranges for analytes with correlation coefficient in the range of 0.9852-0.9989 and lower limits of detection ranging from 0.015-0.025μgL(-1). The obtained results indicated that the newly prepared PILs-GO coating was a feasible, selective and green microextraction medium, which could be suitable for extraction and determination of PAHs and PAEs in potatoes and food-wrap sample, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

Enzymatic synthesis of polymers containing nicotinamide mononucleotide

NASA Technical Reports Server (NTRS)

Liu, Rihe

1995-01-01

Nicotinamide mononucleoside 5'-diphosphate in its reduced form is an excellent substrate for polynucleotide phosphorylase from Micrococcus luteus both in de novo polymerization reactions and in primer extension reactions. The oxidized form of the diphosphate is a much less efficient substrate; it can be used to extend primers but does not oligomerize in the absence of a primer. The cyanide adduct of the oxidized substrate, like the reduced substrate, polymerizes efficiently. Loss of cyanide yields high molecular weight polymers of the oxidized form. Terminal transferase from calf thymus accepts nicotinamide mononucleoside 5'-triphosphate as a substrate and efficiently adds one residue to the 3'-end of an oligodeoxynucleotide. T4 polynucleotide kinase accepts oligomers of nicotinamide mononucleotide as substrates. However, RNA polymerases do not incorporate nicotinamide mononucleoside 5'-triphosphate into products on any of the templates that we used.

Enzymatic Synthesis of Polymers Containing Nicotinamide Mononucleotide

NASA Technical Reports Server (NTRS)

Liu, Rihe; Orgel, Leslie E.

1995-01-01

Nicotinamide mononucleoside 5'-diphosphate in its reduced form is an excellent substrate for polynucleotide phosphorylase from Micrococcus luteus both in de novo polymerization reactions and in primer extension reactions. The oxidized form of the diphosphate is a much less efficient substrate; it can be used to extend primers but does not oligomerize in the absence of a primer. The cyanide adduct of the oxidized substrate, like the reduced substrate, polymerizes efficiently. Loss of cyanide yields high molecular weight polymers of the oxidized form. Terminal transferase from calf thymus accepts nicotinamide mononucleoside 5'-triphosphate as a substrate and efficiently adds one residue to the 3'-end of an oligodeoxynucleotide. T4 polynucleotide kinase accepts oligomers of nicotinamide mononucleotide as substrates. However, RNA polymerases do not incorporate nicotinamide mononucleoside 5'-triphosphate into products on any of the templates that we used.

Chemical sensors

DOEpatents

Lowell, J.R. Jr.; Edlund, D.J.; Friesen, D.T.; Rayfield, G.W.

1992-06-09

Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising a mechanicochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, either operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical or optical response, or adhered to a second inert polymeric strip, or doped with a conductive material. 12 figs.

Hybrid polymer networks as ultra low `k` dielectric layers

DOEpatents

Lewicki, James; Worsley, Marcus A.

2016-02-16

According to one embodiment, a polymeric material includes at least one polydimethylsiloxane (PDMS) polymer, and at least one polyhedral oligomericsilsequioxane (POSS) molecule. According to another embodiment, a method includes providing at least one polydimethylsiloxane (PDMS) polymer, providing at least one polyhedral oligomericsilsequioxane (POSS) molecule, and coupling the at least one PDSM polymer to the at least one POSS molecule to form a hybrid polymeric material.

Mechanistic Investigation of Catalyst-Transfer Suzuki-Miyaura Condensation Polymerization of Thiophene-Pyridine Biaryl Monomers with the Aid of Model Reactions.

PubMed

Tokita, Yu; Katoh, Masaru; Ohta, Yoshihiro; Yokozawa, Tsutomu

2016-11-21

We have investigated the requirements for efficient Pd-catalyzed Suzuki-Miyaura catalyst-transfer condensation polymerization (Pd-CTCP) reactions of 2-alkoxypropyl-6-(5-bromothiophen-2-yl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (12) as a donor-acceptor (D-A) biaryl monomer. As model reactions, we first carried out the Suzuki-Miyaura coupling reaction of X-Py-Th-X' (Th=thiophene, Py=pyridine, X, X'=Br or I) 1 with phenylboronic acid ester 2 by using tBu 3 PPd 0 as the catalyst. Monosubstitution with a phenyl group at Th-I mainly took place in the reaction of Br-Py-Th-I (1 b) with 2, whereas disubstitution selectively occurred in the reaction of I-Py-Th-Br (1 c) with 2, indicating that the Pd catalyst is intramolecularly transferred from acceptor Py to donor Th. Therefore, we synthesized monomer 12 by introduction of a boronate moiety and bromine into Py and Th, respectively. However, examination of the relationship between monomer conversion and the M n of the obtained polymer, as well as the matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectra, indicated that Suzuki-Miyaura coupling polymerization of 12 with (o-tolyl)tBu 3 PPdBr initiator 13 proceeded in a step-growth polymerization manner through intermolecular transfer of the Pd catalyst. To understand the discrepancy between the model reactions and polymerization reaction, Suzuki-Miyaura coupling reactions of 1 c with thiopheneboronic acid ester instead of 2 were carried out. This resulted in a decrease of the disubstitution product. Therefore, step-growth polymerization appears to be due to intermolecular transfer of the Pd catalyst from Th after reductive elimination of the Th-Pd-Py complex formed by transmetalation of polymer Th-Br with (Pin)B-Py-Th-Br monomer 12 (Pin=pinacol). Catalysts with similar stabilization energies of metal-arene η 2 -coordination for D and A monomers may be needed for CTCP reactions of biaryl D-A monomers. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

2DCOS and PCMW2D analysis of FT-IR/ATR spectra measured at variable temperatures on-line to a polyurethane polymerization

NASA Astrophysics Data System (ADS)

Schuchardt, Patrick; Unger, Miriam; Siesler, Heinz W.

2018-01-01

In the present communication the potential of 2DCOS analysis and the spin-off technique perturbation-correlation moving window 2D (PCMW2D) analysis is illustrated with reference to spectroscopic changes observed in a data set recorded by in-line fiber-coupled FT-IR spectroscopy in the attenuated total reflection (ATR) mode during a polyurethane solution polymerization at different temperatures. In view of the chemical functionalities involved, hydrogen bonding plays an important role in this polymerization reaction. Based on the 2DCOS and PCMW2D analysis, the sequence of hydrogen bonding changes accompanying the progress of polymerization and precipitation of solid polymer can be determined. Complementary to the kinetic data derived from the original variable-temperature spectra in a previous publication the results provide a more detailed picture of the investigated solution polymerization.

(1-Adamantyl)methyl glycidyl ether: a versatile building block for living polymerization.

PubMed

Moers, Christian; Wrazidlo, Robert; Natalello, Adrian; Netz, Isabelle; Mondeshki, Mihail; Frey, Holger

2014-06-01

(1-Adamantyl)methyl glycidyl ether (AdaGE) is introduced as a versatile monomer for oxyanionic polymerization, enabling controlled incorporation of adamantyl moieties in aliphatic polyethers. Via copolymerization with ethoxyethyl glycidyl ether (EEGE) and subsequent cleavage of the acetal protection groups of EEGE, hydrophilic linear polyglycerols with an adjustable amount of pendant adamantyl moieties are obtained. The adamantyl unit permits control over thermal properties and solubility profile of these polymers (LCST). Additionally, AdaGE is utilized as a termination agent in carbanionic polymerization, affording adamantyl-terminated polymers. Using these structures as macroinitiators for the polymerization of ethylene oxide affords amphiphilic, in-chain adamantyl-functionalized block copolymers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of Bottlebrush Polymers via a One-Pot Ring-Opening Polymerization (ROP) and Ring-Opening Metathesis Polymerization (ROMP) Grafting-Through Strategy.

PubMed

Radzinski, Scott C; Foster, Jeffrey C; Matson, John B

2016-04-01

Bottlebrush polymers are synthesized using a tandem ring-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) strategy. For the first time, ROP and ROMP are conducted sequentially in the same pot to yield well-defined bottlebrush polymers with molecular weights in excess of 10(6) Da. The first step of this process involves the synthesis of a polylactide macromonomer (MM) via ROP of d,l-lactide initiated by an alcohol-functionalized norbornene. ROMP grafting-through is then carried out in the same pot to produce the bottlebrush polymer. The applicability of this methodology is evaluated for different MM molecular weights and bottlebrush backbone degrees of polymerization. Size-exclusion chromatographic and (1)H NMR spectroscopic analyses confirm excellent control over both polymerization steps. In addition, bottlebrush polymers are imaged using atomic force microscopy and stain-free transmission electron microscopy on graphene oxide. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Better End-Cap Processing for Oxidation-Resistant Polyimides

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Frimer, Aryeh A.

2004-01-01

A class of end-cap compounds that increase the thermo-oxidative stab ility of polyimides of the polymerization of monomeric reactants (PM R) type has been extended. In addition, an improved processing proto col for this class of end-cap compounds has been invented.

The Chemistry Involved in the Preparation of a Paint Pigment: An Experiment for the Freshman Laboratory

ERIC Educational Resources Information Center

Daines, Terri L.; Morse, Karen W.

1976-01-01

Describes an experiment that demonstrates the following principles and reactions: amphoterism, oxidation-reduction, equilibrium dependence on pH, solubility, and polymerization. The experiment involves the oxidation of chromium and the precipitation of a chromate salt. (MLH)

Pro-stimulatory role of methemoglobin in inflammation through hemin oxidation and polymerization.

PubMed

Deshmukh, Rohitas; Trivedi, Vishal

2013-02-01

Inflammation or vascular occlusion by parasitized red blood cell contributes to the pathogenesis of cerebral malaria. The current study aimed to characterize the role of major pro-oxidant factor methemoglobin present in the malaria culture supernatant contributing in inflammation during malaria. Heme and heme polymer stimulate macrophage to secrete large amount of reactive oxygen species into the external micro-environment. The addition of methemoglobin along with heme or heme polymer amplifies production of ROS from macrophages several folds. Methemoglobin mediated stimulatory effect is not due to release of iron, enhanced production of H2O2 or mutual interaction of reaction components. Spectroscopic studies show that methemoglobin accepts heme as a substrate and oxidizes it through a single electron transfer mechanism. Heme oxidation product is a heme polymer with similar chemical and structural properties to synthetic β-hematin. Phenyl N-t-butylnitrone inhibits heme polymerization (IC50=30 nM) and indicates the absolute necessity of heme oxidation and heme free radical generation for heme polymerization. Methemoglobin produced heme polymer is a potent pro-inflammatory factor to release ROS into external microenvironment. Interestingly, methemoglobin not only produces pro-inflammatory heme polymer, but it also amplifies the potential of heme or preformed heme polymer (haemozoin or β-hematin) to produce several folds high ROS production from macrophages. This study illustrates the pro-inflammatory effect of methemoglobin, the underlying novel mechanism by which this occurs and a possible clinical intervention. Based on the results, we recommend methemoglobin directed peroxidase inhibitors as an adjuvant therapy during malaria.

Cell for making secondary batteries

DOEpatents

Visco, Steven J.; Liu, Meilin; DeJonghe, Lutgard C.

1992-01-01

The present invention provides all solid-state lithium and sodium batteries operating in the approximate temperature range of ambient to 145.degree. C. (limited by melting points of electrodes/electrolyte), with demonstrated energy and power densities far in excess of state-of-the-art high-temperature battery systems. The preferred battery comprises a solid lithium or sodium electrode, a polymeric electrolyte such as polyethylene oxide doped with lithium triflate (PEO.sub.8 LiCF.sub.3 SO.sub.3), and a solid-state composite positive electrode containing a polymeric organosulfur electrode, (SRS).sub.n, and carbon black, dispersed in a polymeric electrolyte.

Cell for making secondary batteries

DOEpatents

Visco, S.J.; Liu, M.; DeJonghe, L.C.

1992-11-10

The present invention provides all solid-state lithium and sodium batteries operating in the approximate temperature range of ambient to 145 C (limited by melting points of electrodes/electrolyte), with demonstrated energy and power densities far in excess of state-of-the-art high-temperature battery systems. The preferred battery comprises a solid lithium or sodium electrode, a polymeric electrolyte such as polyethylene oxide doped with lithium trifluorate (PEO[sub 8]LiCF[sub 3]SO[sub 3]), and a solid-state composite positive electrode containing a polymeric organosulfur electrode, (SRS)[sub n], and carbon black, dispersed in a polymeric electrolyte. 2 figs.

Electrophilic Cleavage and Functionalization of Polyisobutylenes Bearing Unsaturations in the Backbone and Synthesis of Polymers for this Process

NASA Astrophysics Data System (ADS)

Campbell, Christopher Garrett

Polyisobutylene is a polymer of high commercial and academic interest due to its low cost of synthesis, high gas barrier properties, and high chemical and oxidative stability. Polyisobutylene (PIB) can only be synthesized by the cationic polymerization of isobutylene (IB). Commercial processes are currently only capable of producing monofunctional PIB or copolymers thereof. The living cationic polymerization of isobutylene is capable of producing difunctional telechelic PIB, but at the expense of difficultly or expensively synthesized initiators. Thus there exists a need for new synthetic routes for multifunctional PIBs, which can be adopted on a commercial scale. In the first project, we demonstrated a new reaction, which is a subset of the Friedel Crafts alkylation reaction, in which the alkylating carbocation undergoes a cleavage reaction prior to reaction with the aromatic substrate. This reaction was discovered by the observation that when a PIB containing a large amount of coupled fraction was subjected to a mixture of protic and Lewis acids (HCl/TiCl4) in the presence of an alkoxybenzene compound, the coupled fraction was quantitatively converted to its constituent monofunctional chains, which became functionalized by the alkoxybenzene. In the second project, a commercial polymer, poly(isobutylene- co-isoprene) (butyl rubber) was used as a substrate upon which the aforementioned electrophilic cleavage and functionalization reaction was performed. The goal of this project was to degrade a high molecular weight, main-chain olefin-containing copolymer of isobutylene into low molecular weight difunctional telechelic polyisobutylenes. This general process, though not necessarily proceeding by the aforementioned novel chemical reaction, has been described in the literature as "constructive degradation." Though we were unable to synthesize truly telechelic polyisobutylenes by this method, we were able to demonstrate this method as a viable route to low molecular weight multifunctional PIBs. In the third project, we attempted to synthesize a random copolymer, previously reported by Kennedy et al., of isobutylene and 2,4-dimethyl-1,3-pentadiene (DMPD). The interest in this copolymer was based on its structural similarity to the coupled PIB mentioned in the first project. However, we found that these two monomers are not well suited to the creation of random copolymers due to a large difference in reactivity ratios. The project presented in this chapter was then redirected toward the structural characterization of the products of attempted copolymerization and of the homo-polymerization of DMPD. In the fourth project, we investigated the copolymer of isobutylene and beta-pinene as a substrate for the aforementioned cleavage/functionalization reaction. We were able to synthesize high molecular weight copolymers of these two monomers via slurry polymerization catalyzed by either TiCl4 or ethylaluminum dichloride (EADC), and though the degradation and functionalization kinetics were much slower than for butyl rubber, we did observe a drastic decrease in molecular weight accompanied by functionalization of the polymer, thus proving this chemistry is applicable to copolymers of isobutylene other than butyl rubber.

Consequence of oxidant to monomer ratio on optical and structural properties of Polypyrrole thin film deposited by oxidation polymerization technique

NASA Astrophysics Data System (ADS)

Jatratkar, Aviraj A.; Yadav, Jyotiprakash B.; Kamat, Sandip V.; Patil, Vaishali S.; Mahadik, D. B.; Barshilia, Harish C.; Puri, Vijaya; Puri, R. K.

2015-05-01

This paper reports the effect of oxidant to monomer (O/M) ratio on optical and structural properties of Polypyrrole (PPy) thin film deposited by chemical oxidation polymerization technique. Noticeable changes have observed in the properties of PPy thin films with O/M ratio. Cauliflower structure have been observed in FE-SEM images, wherein grain size is observed to decrease with increase in O/M ratio. AFM results are in good agreement with FE-SEM results. From FTIR spectra it is found that, PPy is in highly oxidized form at low O/M ratio but oxidation decreased with increase in O/M ratio. Also C-C stretching vibrations of PPy ring is decreased whereas C=C stretching is increased with ratio. Absorption peak around 450 nm corresponds to π-π* transition and around 800 nm for polarons and bipolarons. The intensity of such peaks confirms the conductivity of PPy, which is observed maximum at low O/M ratio and found to decrease with increase in ratio. Optical band gap (BG) is found to increase from 2.07 eV to 2.11 eV with increase in the O/M ratio.

Self-Assembled Polymeric Micelles Based on Hyaluronic Acid-g-Poly(d,l-lactide-co-glycolide) Copolymer for Tumor Targeting

PubMed Central

Son, Gyung Mo; Kim, Hyun Yul; Ryu, Je Ho; Chu, Chong Woo; Kang, Dae Hwan; Park, Su Bum; Jeong, Young-IL

2014-01-01

Graft copolymer composed hyaluronic acid (HA) and poly(d,l-lactide-co-glycolide) (PLGA) (HAgLG) was synthesized for antitumor targeting via CD44 receptor of tumor cells. The carboxylic end of PLGA was conjugated with hexamethylenediamine (HMDA) to have amine end group in the end of chain (PLGA-amine). PLGA-amine was coupled with carboxylic acid of HA. Self-assembled polymeric micelles of HAgLG have spherical morphologies and their sizes were around 50–200 nm. Doxorubicin (DOX)-incorporated polymeric micelles were prepared by dialysis procedure. DOX was released over 4 days and its release rate was accelerated by the tumoric enzyme hyaluronidase. To assess targetability of polymeric micelles, CD44-positive HepG2 cells were employed treated with fluorescein isothiocyanate (FITC)-labeled polymeric micelles. HepG2 cells strongly expressed green fluorescence at the cell membrane and cytosol. However, internalization of polymeric micelles were significantly decreased when free HA was pretreated to block the CD44 receptor. Furthermore, the CD44-specific anticancer activity of HAgLG polymeric micelles was confirmed using CD44-negative CT26 cells and CD44-positive HepG2 cells. These results indicated that polymeric micelles of HaLG polymeric micelles have targetability against CD44 receptor of tumor cells. We suggest HAgLG polymeric micelles as a promising candidate for specific drug targeting. PMID:25216338

Polyethylene Oxide Films Polymerized by Radio Frequency Plasma-Enhanced Chemical Vapour Phase Deposition and Its Adsorption Behaviour of Platelet-Rich Plasma

NASA Astrophysics Data System (ADS)

Hu, Wen-Juan; Xie, Fen-Yan; Chen, Qiang; Weng, Jing

2008-10-01

We present polyethylene oxide (PEO) functional films polymerized by rf plasma-enhanced vapour chemical deposition (rf-PECVD) on p-Si (100) surface with precursor ethylene glycol dimethyl ether (EGDME) and diluted Ar in pulsed plasma mode. The influences of discharge parameters on the film properties and compounds are investigated. The film structure is analysed by Fourier transform infrared (FTIR) spectroscopy. The water contact angle measurement and atomic force microscope (AFM) are employed to examine the surface polarity and to detect surface morphology, respectively. It is concluded that the smaller duty cycle in pulsed plasma mode contributes to the rich C-O-C (EO) group on the surfaces. As an application, the adsorption behaviour of platelet-rich plasma on plasma polymerization films performed in-vitro is explored. The shapes of attached cells are studied in detail by an optic invert microscope, which clarifies that high-density C-O-C groups on surfaces are responsible for non-fouling adsorption behaviour of the PEO films.

A theory for fracture of polymeric gels

NASA Astrophysics Data System (ADS)

Mao, Yunwei; Anand, Lallit

2018-06-01

A polymeric gel is a cross-linked polymer network swollen with a solvent. If the concentration of the solvent or the deformation is increased to substantial levels, especially in the presence of flaws, then the gel may rupture. Although various theoretical aspects of coupling of fluid permeation with large deformation of polymeric gels are reasonably well-understood and modeled in the literature, the understanding and modeling of the effects of fluid diffusion on the damage and fracture of polymeric gels is still in its infancy. In this paper we formulate a thermodynamically-consistent theory for fracture of polymeric gels - a theory which accounts for the coupled effects of fluid diffusion, large deformations, damage, and also the gradient effects of damage. The particular constitutive equations for fracture of a gel proposed in our paper, contain two essential new ingredients: (i) Our constitutive equation for the change in free energy of a polymer network accounts for not only changes in the entropy, but also changes in the internal energy due the stretching of the Kuhn segments of the polymer chains in the network. (ii) The damage and failure of the polymer network is taken to occur by chain-scission, a process which is driven by the changes in the internal energy of the stretched polymer chains in the network, and not directly by changes in the configurational entropy of the polymer chains. The theory developed in this paper is numerically implemented in an open-source finite element code MOOSE, by writing our own application. Using this simulation capability we report on our study of the fracture of a polymeric gel, and some interesting phenomena which show the importance of the diffusion of the fluid on fracture response of the gel are highlighted.

Polyimide resin composites via in situ polymerization of monomeric reactants

NASA Technical Reports Server (NTRS)

Cavano, P. J.

1974-01-01

Thermo-oxidatively stable polyimide/graphite-fiber composites were prepared using a unique in situ polymerization of monomeric reactants directly on reinforcing fibers. This was accomplished by using an aromatic diamine and two ester-acids in a methyl alcohol solvent, rather than a previously synthesized prepolymer varnish, as with other A-type polyimides. A die molding procedure was developed and a composite property characterization conducted with high modulus graphite fiber tow. Flexure, tensile, compressive, and shear tests were conducted at temperatures from 72 to 650 F on laminates before and after exposures at the given temperatures in an air environment for times up to 1000 hours. The composite material was determined to be oxidatively, thermally, and hydrolytically stable.

Synthesis and Processing of Ultra-High Temperature Metal Carbide and Metal Diboride Nanocomposite Materials

DTIC Science & Technology

2008-04-15

cellulose acetate polymers, and diols. Common sol- uble metal/metal oxide-bearing materials are metal alkoxides, metal diketonates, and metal ... carboxylates . Metal-organic compounds are usually subjected to hydrolysis and condensa- tion reactions to produce polymeric or colloidal metal-oxide

Iron-oxide minerals affect extracellular electron-transfer paths of Geobacter spp.

PubMed

Kato, Souichiro; Hashimoto, Kazuhito; Watanabe, Kazuya

2013-01-01

Some bacteria utilize (semi)conductive iron-oxide minerals as conduits for extracellular electron transfer (EET) to distant, insoluble electron acceptors. A previous study demonstrated that microbe/mineral conductive networks are constructed in soil ecosystems, in which Geobacter spp. share dominant populations. In order to examine how (semi)conductive iron-oxide minerals affect EET paths of Geobacter spp., the present study grew five representative Geobacter strains on electrodes as the sole electron acceptors in the absence or presence of (semi)conductive iron oxides. It was found that iron-oxide minerals enhanced current generation by three Geobacter strains, while no effect was observed in another strain. Geobacter sulfurreducens was the only strain that generated substantial amounts of currents both in the presence and absence of the iron oxides. Microscopic, electrochemical and transcriptomic analyses of G. sulfurreducens disclosed that this strain constructed two distinct types of EET path; in the absence of iron-oxide minerals, bacterial biofilms rich in extracellular polymeric substances were constructed, while composite networks made of mineral particles and microbial cells (without polymeric substances) were developed in the presence of iron oxides. It was also found that uncharacterized c-type cytochromes were up-regulated in the presence of iron oxides that were different from those found in conductive biofilms. These results suggest the possibility that natural (semi)conductive minerals confer energetic and ecological advantages on Geobacter, facilitating their growth and survival in the natural environment.

Covalently bonded networks through surface-confined polymerization

NASA Astrophysics Data System (ADS)

El Garah, Mohamed; MacLeod, Jennifer M.; Rosei, Federico

2013-07-01

The prospect of synthesizing ordered, covalently bonded structures directly on a surface has recently attracted considerable attention due to its fundamental interest and for potential applications in electronics and photonics. This prospective article focuses on efforts to synthesize and characterize epitaxial one- and two-dimensional (1D and 2D, respectively) polymeric networks on single crystal surfaces. Recent studies, mostly performed using scanning tunneling microscopy (STM), demonstrate the ability to induce polymerization based on Ullmann coupling, thermal dehalogenation and dehydration reactions. The 2D polymer networks synthesized to date have exhibited structural limitations and have been shown to form only small domains on the surface. We discuss different approaches to control 1D and 2D polymerization, with particular emphasis on the surface phenomena that are critical to the formation of larger ordered domains.

Novel synthesis and characterization of a collagen-based biopolymer initiated by hydroxyapatite nanoparticles.

PubMed

Bhuiyan, D; Jablonsky, M J; Kolesov, I; Middleton, J; Wick, T M; Tannenbaum, R

2015-03-01

In this study, we developed a novel synthesis method to create a complex collagen-based biopolymer that promises to possess the necessary material properties for a bone graft substitute. The synthesis was carried out in several steps. In the first step, a ring-opening polymerization reaction initiated by hydroxyapatite nanoparticles was used to polymerize d,l-lactide and glycolide monomers to form poly(lactide-co-glycolide) co-polymer. In the second step, the polymerization product was coupled with succinic anhydride, and subsequently was reacted with N-hydroxysuccinimide in the presence of dicyclohexylcarbodiimide as the cross-linking agent, in order to activate the co-polymer for collagen attachment. In the third and final step, the activated co-polymer was attached to calf skin collagen type I, in hydrochloric acid/phosphate buffer solution and the precipitated co-polymer with attached collagen was isolated. The synthesis was monitored by proton nuclear magnetic resonance, infrared and Raman spectroscopies, and the products after each step were characterized by thermal and mechanical analysis. Calculations of the relative amounts of the various components, coupled with initial dynamic mechanical analysis testing of the resulting biopolymer, afforded a preliminary assessment of the structure of the complex biomaterial formed by this novel polymerization process. Copyright © 2015. Published by Elsevier Ltd.

Modeling the chemistry of plasma polymerization using mass spectrometry.

PubMed

Ihrig, D F; Stockhaus, J; Scheide, F; Winkelhake, Oliver; Streuber, Oliver

2003-04-01

The goal of the project is a solvent free painting shop. The environmental technologies laboratory is developing processes of plasma etching and polymerization. Polymerized thin films are first-order corrosion protection and primer for painting. Using pure acetylene we get very nice thin films which were not bonded very well. By using air as bulk gas it is possible to polymerize, in an acetylene plasma, well bonded thin films which are stable first-order corrosion protections and good primers. UV/Vis spectroscopy shows nitrogen oxide radicals in the emission spectra of pure nitrogen and air. But nitrogen oxide is fully suppressed in the presence of acetylene. IR spectroscopy shows only C=O, CH(2) and CH(3) groups but no nitrogen species. With the aid of UV/Vis spectra and the chemistry of ozone formation it is possible to define reactive traps and steps, molecule depletion and processes of proton scavenging and proton loss. Using a numerical model it is possible to evaluate these processes and to calculate theoretical mass spectra. Adjustment of theoretical mass spectra to real measurements leads to specific channels of polymerization which are driven by radicals especially the acetyl radical. The estimated theoretical mass spectra show the specific channels of these chemical processes. It is possible to quantify these channels. This quantification represents the mass flow through this chemical system. With respect to these chemical processes it is possible to have an idea of pollutant production processes.

Biquadratic coupling through nano-oxide layers in pinned layers of IrMn-based spin valves

NASA Astrophysics Data System (ADS)

Lai, Chih-Huang; Lu, K. H.

2003-05-01

We have investigated the coupling between top and bottom pinned layers through various nano-oxide layers (NOLs) in IrMn-based spin valves. The NOLs were formed by using oxygen-plasma oxidation or natural oxidation on 1 nm metallic layers. By inserting naturally oxidized Co-NOLs in the pinned layer, strong ferromagnetic coupling through NOLs and high specularity at the NOL interface were achieved. In contrast, when the plasma-oxidized Co-NOLs were inserted, ferromagnetic coupling through NOLs disappeared, plausibly due to the formation of nonferromagnetic oxides, which led to a low magnetoresistance (MR). Insertion of naturally oxidized Ni80Fe20-NOLs showed the same results as that of naturally oxidized Co-NOLs. On the other hand, biquadratic coupling between top and bottom pinned-Co90Fe10 layers was observed by inserting plasma-oxidized Ni80Fe20-NOLs. The highest MR was obtained when the field was applied along the direction perpendicular to the field-annealing direction. Similar biquadratic coupling was also found with naturally oxidized or plasma-oxidized Fe-NOLs. We suggest that the biquadratic coupling between pinned Co90Fe10 layers through NOLs results from the coupling between Fe (or Co90Fe10) and Fe+3 oxides

System to continuously produce carbon fiber via microwave assisted plasma processing

DOEpatents

White, Terry L [Knoxville, TN; Paulauskas, Felix L [Knoxville, TN; Bigelow, Timothy S [Knoxville, TN

2010-11-02

A system to continuously produce fully carbonized or graphitized carbon fibers using microwave-assisted plasma (MAP) processing comprises an elongated chamber in which a microwave plasma is excited in a selected gas atmosphere. Fiber is drawn continuously through the chamber, entering and exiting through openings designed to minimize in-leakage of air. There is a gradient of microwave power within the chamber with generally higher power near where the fiber exits and lower power near where the fiber enters. Polyacrylonitrile (PAN), pitch, or any other suitable organic/polymeric precursor fibers can be used as a feedstock for the inventive system. Oxidized or partially oxidized PAN or pitch or other polymeric fiber precursors are run continuously through a MAP reactor in an inert, non-oxidizing atmosphere to heat the fibers, drive off the unwanted elements such as oxygen, nitrogen, and hydrogen, and produce carbon or graphite fibers faster than conventionally produced carbon fibers.

Effect of interface reaction and diffusion on stress-oxidation coupling at high temperature

NASA Astrophysics Data System (ADS)

Yue, Mengkun; Dong, Xuelin; Fang, Xufei; Feng, Xue

2018-04-01

High-temperature structural materials undergo oxidation during the service, and stress would generate in the oxide film. Understanding the coupling effect between stress and oxidation contributes to the understanding of material degradation and failure during the oxidation process. Here, we propose a model to investigative the coupling effect of stress and oxidation at high temperature by considering the three-stage oxidation process, where both the interface reaction and the diffusion process are present. The governing equations including the oxidation kinetics and stress equilibrium for isothermal oxidation under stress-oxidation coupling effect have been derived. The theory is validated by comparing with the experimental results of SiO2 grown on Si substrate. Results show that the coupling of stress and oxidation influences the growth of the oxide film by affecting all three stages of the oxidation process.

Hydrolase stabilization via entanglement in poly(propylene sulfide) nanoparticles: stability towards reactive oxygen species.

PubMed

Allen, Brett L; Johnson, Jermaine D; Walker, Jeremy P

2012-07-27

In the advancement of green syntheses and sustainable reactions, enzymatic biocatalysis offers extremely high reaction rates and selectivity that goes far beyond the reach of chemical catalysts; however, these enzymes suffer from typical environmental constraints, e.g. operational temperature, pH and tolerance to oxidative environments. A common hydrolase enzyme, diisopropylfluorophosphatase (DFPase, EC 3.1.8.2), has demonstrated a pronounced efficacy for the hydrolysis of a variety of substrates for potential toxin remediation, but suffers from the aforementioned limitations. As a means to enhance DFPase's stability in oxidative environments, enzymatic covalent immobilization within the polymeric matrix of poly(propylene sulfide) (PPS) nanoparticles was performed. By modifying the enzyme's exposed lysine residues via thiolation, DFPase is utilized as a comonomer/crosslinker in a mild emulsion polymerization. The resultant polymeric polysulfide shell acts as a 'sacrificial barrier' by first oxidizing to polysulfoxides and polysulfones, rendering DFPase in an active state. DFPase-PPS nanoparticles thus retain activity upon exposure to as high as 50 parts per million (ppm) of hypochlorous acid (HOCl), while native DFPase is observed as inactive at 500 parts per billion (ppb). This trend is also confirmed by enzyme-generated (chloroperoxidase (CPO), EC 1.11.1.10) reactive oxygen species (ROS) including both HOCl (3 ppm) and ClO(2) (100 ppm).

A Visible Light Initiating System for Free Radical Promoted Cationic Polymerization

DTIC Science & Technology

1994-02-02

identify the end groups in the polymer of cyclohexene oxide. N,N-Dimethylnaphthyl amine (DNA), a compound with high fluorescence quantum yield, was used...candidates to be polymerized via a cationic mechanism include cyclic ethers, cyclic formals and acetals, vinyl ethers, and epoxy compounds . Of these...reported sensitizer, bears two dimethylamino groups, is direct evidence that an aromatic amine can be present in a cationically photopolymerizable system

Synthesis and Characterization of High Molecular Weight Peptide Polymers and Copolymers Containing L-Dopa Residues

DTIC Science & Technology

1988-07-01

polymerize E- aminocaproic acid with DPPA for the S same period of time. Portions of each sample were then mixed together and the polymerization was...copolymers between GLUE polypeptides and poly(?c.-amino caproic acid ). Concurrent enzymatic oxidation studies with GLUE peptidesihas given some...insight into the crosslinking mechanisms which control relative reactivities of specific amino acid residues towards intramolecular or intermolecular bond

Biologically Active Polymeric Coating Materials

DTIC Science & Technology

1975-04-01

unsaturated alkyds , or through a condensation reaction of an organometallic oxide and a resin containing carboxylic acid groups as side chains. The...extend the service life of antifouling coatings by means of polymerization of toxicant into paint resins . The coating binder is so constructed that the...from styrene (s6) and polyester (P54, figure 5) organometallic resins . To date, the antifouling performance of epoxy (WS 52B, figure 6) and

In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

PubMed

Chen, Daqun; Hu, Weihua

2017-04-18

Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

Arabidopsis peroxidase-catalyzed copolymerization of coniferyl and sinapyl alcohols: kinetics of an endwise process.

PubMed

Demont-Caulet, Nathalie; Lapierre, Catherine; Jouanin, Lise; Baumberger, Stéphanie; Méchin, Valérie

2010-10-01

In order to determine the mechanism of the earlier copolymerization steps of two main lignin precursors, sinapyl (S) alcohol and coniferyl (G) alcohol, microscale in vitro oxidations were carried out with a PRX34 Arabidopsis thaliana peroxidase in the presence of H(2)O(2). This plant peroxidase was found to have an in vitro polymerization activity similar to the commonly used horseradish peroxidase. The selected polymerization conditions lead to a bulk polymerization mechanism when G alcohol was the only phenolic substrate available. In the same conditions, the presence of S alcohol at a 50/50 S/G molar ratio turned this bulk mechanism into an endwise one. A kinetics monitoring (size-exclusion chromatography and liquid chromatography-mass spectrometry) of the different species formed during the first 24h oxidation of the S/G mixture allowed sequencing the bondings responsible for oligomerization. Whereas G homodimers and GS heterodimers exhibit low reactivity, the SS pinoresinol structure act as a nucleating site of the polymerization through an endwise process. This study is particularly relevant to understand the impact of S units on lignin structure in plants and to identify the key step at which this structure is programmed. Copyright © 2010 Elsevier Ltd. All rights reserved.

Study of aniline polymerization reactions through the particle size formation in acidic and neutral medium

NASA Astrophysics Data System (ADS)

Aribowo, Slamet; Hafizah, Mas Ayu Elita; Manaf, Azwar; Andreas

2018-04-01

In the present paper, we reported particle size kinetic studies on the conducting polyaniline (PANI) which synthesized through a chemical oxidative polymerization technique from aniline monomer. PANI was prepared using ammonium persulfate (APS) as oxidizing agent which carried out in acidic and neutral medium at various batch temperatures of respectively 20, 30 and 50 °C. From the studies, it was noticed that the complete polymerization reaction progressed within 480 minutes duration time. The pH of the solution during reaction kinetic reached values 0.8 - to 1.2 in acidic media, while in the neutral media the pH value reached values 3.8 - 4.9. The batch temperature controlled the polymerization reaction in which the reaction progressing, which followed by the temperature rise of solution above the batch temperature before settled down to the initial temperature. An increment in the batch temperature gave highest rise in the solution temperature for the two media which cannot be more than 50 °C. The final product of polymerization reaction was PANI confirmed by Fourier Transform Infra-Red (FTIR) spectrophotometer for molecule structure identification. The averages particle size of PANI which carried out in the two different media is evidently similar in the range 30 - 40 μm and insensitive to the batch temperature. However, the particle size of PANI which obtained from the polymerization reaction at a batch temperature of 50 °C under acidic condition reached ˜53.1 μm at the tip of the propagation stage which started in the first 5 minutes. The size is obviously being the largest among the batch temperatures. Whereas, under neutral condition the particle size is much larger which reached the size 135 μm at the batch temperature of 20 °C. It is concluded that the particle size formation during the polymerization reaction being one of the important parameter to determine particle growing of polymer which indicated the reaction kinetics mechanism of synthesize polyaniline.

Air-coupled ultrasound: a novel technique for monitoring the curing of thermosetting matrices.

PubMed

Lionetto, Francesca; Tarzia, Antonella; Maffezzoli, Alfonso

2007-07-01

A custom-made, air-coupled ultrasonic device was applied to cure monitoring of thick samples (7-10 mm) of unsaturated polyester resin at room temperature. A key point was the optimization of the experimental setup in order to propagate compression waves during the overall curing reaction by suitable placement of the noncontact transducers, placed on the same side of the test material, in the so-called pitch-catch configuration. The progress of polymerization was monitored through the variation of the time of flight of the propagating longitudinal waves. The exothermic character of the polymerization was taken into account by correcting the measured value of time of flight with that one in air, obtained by sampling the air velocity during the experiment. The air-coupled ultrasonic results were compared with those obtained from conventional contact ultrasonic measurements. The good agreement between the air-coupled ultrasonic results and those obtained by the rheological analysis demonstrated the reliability of air-coupled ultrasound in monitoring the changes of viscoelastic properties at gelation and vitrification. The position of the transducers on the same side of the sample makes this technique suitable for on-line cure monitoring during several composite manufacturing technologies.

A simple method for determining polymeric IgA-containing immune complexes.

PubMed

Sancho, J; Egido, J; González, E

1983-06-10

A simplified assay to measure polymeric IgA-immune complexes in biological fluids is described. The assay is based upon the specific binding of a secretory component for polymeric IgA. In the first step, multimeric IgA (monomeric and polymeric) immune complexes are determined by the standard Raji cell assay. Secondly, labeled secretory component added to the assay is bound to polymeric IgA-immune complexes previously fixed to Raji cells, but not to monomeric IgA immune complexes. To avoid false positives due to possible complement-fixing IgM immune complexes, prior IgM immunoadsorption is performed. Using anti-IgM antiserum coupled to CNBr-activated Sepharose 4B this step is not time-consuming. Polymeric IgA has a low affinity constant and binds weakly to Raji cells, as Scatchard analysis of the data shows. Thus, polymeric IgA immune complexes do not bind to Raji cells directly through Fc receptors, but through complement breakdown products, as with IgG-immune complexes. Using this method, we have been successful in detecting specific polymeric-IgA immune complexes in patients with IgA nephropathy (Berger's disease) and alcoholic liver disease, as well as in normal subjects after meals of high protein content. This new, simple, rapid and reproducible assay might help to study the physiopathological role of polymeric IgA immune complexes in humans and animals.

Actin Polymerization: An Event Regulated by Tyrosine Phosphorylation During Buffalo Sperm Capacitation.

PubMed

Naresh, S; Atreja, S K

2015-12-01

In the female reproductive tract, the spermatozoa undergo a series of physiological and biochemical changes, prior to gaining the ability to fertilize, that result to capacitation. However, the actin polymerization and protein tyrosine phosphorylation are the two necessary steps for capacitation. In this study, we have demonstrated the actin polymerization and established the correlation between protein tyrosine phosphorylation and actin reorganization during in vitro capacitation in buffalo (Bubalus bubalis) spermatozoa. Indirect immunofluorescence and Western blot techniques were used to detect actin polymerization and tyrosine phosphorylation. The time-dependent fluorimetric studies revealed that the actin polymerization starts from the tail region and progressed towards the head region of spermatozoa during capacitation. The lysophosphatidyl choline (LPC)-induced acrosome reaction (AR) stimulated quick actin depolymerization. The inhibitor cytochalasin D (CD) blocked the in vitro capacitation by inhibiting the actin polymerization. In addition, we also performed different inhibitor (Genistein, H-89, PD9809 and GF-109) and enhancer (dbcAMP, H(2)O(2) and vanadate) studies on actin tyrosine phosphorylation and actin polymerization. The inhibitors of tyrosine phosphorylation inhibit actin tyrosine phosphorylation and polymerization, whereas enhancers of tyrosine phosphorylation stimulate F-actin formation and tyrosine phosphorylation. These observations suggest that the tyrosine phosphorylation regulates the actin polymerization, and both are coupled processes during capacitation of buffalo spermatozoa. © 2015 Blackwell Verlag GmbH.

Covalently coupled hybrid of graphitic carbon nitride with reduced graphene oxide as a superior performance lithium-ion battery anode

NASA Astrophysics Data System (ADS)

Fu, Yongsheng; Zhu, Junwu; Hu, Chong; Wu, Xiaodong; Wang, Xin

2014-10-01

An in situ chemical synthetic approach has been designed for the fabrication of a covalently coupled hybrid consisting of graphitic carbon nitride (g-C3N4) with reduced graphene oxide (rGO) with differing g-C3N4/rGO ratio. The epoxy groups of graphene oxide (GO) undergo a nucleophilic substitution reaction with dicyandiamide (C2H4N4) to form the C2H4N4-GO composite via a covalent C-N bond, and then both the in situ polymerization of C2H4N4 and the thermal reduction of GO can be achieved at higher temperatures, forming the covalently coupled g-C3N4-rGO. FT-IR, CP-MAS NMR and XPS analyses, clearly revealed a covalent interaction between the g-C3N4 and rGO sheets. The g-C3N4-rGO exhibits an unprecedented high, stable and reversible capacity of 1525 mA h g-1 at a current density of 100 mA g-1 after 50 cycles. Even at a large current density of 1000 mA g-1, a reversible capacity of 943 mA h g-1 can still be retained. The superior electrochemical performance of g-C3N4-rGO is attributed to the specific characteristics of the unique nanostructure of g-C3N4-rGO and the concerted effects of g-C3N4 and rGO, including covalent interactions between the two moieties, the good conductivity and high special surface area of the nanocomposite, as well as the template effect of the planar amino group of g-C3N4 for the dispersed decoration of Li+ ions.An in situ chemical synthetic approach has been designed for the fabrication of a covalently coupled hybrid consisting of graphitic carbon nitride (g-C3N4) with reduced graphene oxide (rGO) with differing g-C3N4/rGO ratio. The epoxy groups of graphene oxide (GO) undergo a nucleophilic substitution reaction with dicyandiamide (C2H4N4) to form the C2H4N4-GO composite via a covalent C-N bond, and then both the in situ polymerization of C2H4N4 and the thermal reduction of GO can be achieved at higher temperatures, forming the covalently coupled g-C3N4-rGO. FT-IR, CP-MAS NMR and XPS analyses, clearly revealed a covalent interaction between the g-C3N4 and rGO sheets. The g-C3N4-rGO exhibits an unprecedented high, stable and reversible capacity of 1525 mA h g-1 at a current density of 100 mA g-1 after 50 cycles. Even at a large current density of 1000 mA g-1, a reversible capacity of 943 mA h g-1 can still be retained. The superior electrochemical performance of g-C3N4-rGO is attributed to the specific characteristics of the unique nanostructure of g-C3N4-rGO and the concerted effects of g-C3N4 and rGO, including covalent interactions between the two moieties, the good conductivity and high special surface area of the nanocomposite, as well as the template effect of the planar amino group of g-C3N4 for the dispersed decoration of Li+ ions. Electronic supplementary information (ESI) available: N species content (at%) of g-C3N4-rGO-1 based on XPS analysis; the first cycle discharge capacity, charge capacity and coulombic efficiency for the g-C3N4, rGO, and g-C3N4-rGO-n (n = 0.25, 0.5, 1, 2, 3) electrodes; nitrogen adsorption/desorption isotherm of g-C3N4; cycle performance of the g-C3N4-rGO-n (n = 0.25, 0.5, 3) electrodes at a current rate of 100 mA g-1 between 3.0 and 0.01 V versus Li+/Li. See DOI: 10.1039/c4nr03145h

Large-scale filament formation inhibits the activity of CTP synthetase

PubMed Central

Barry, Rachael M; Bitbol, Anne-Florence; Lorestani, Alexander; Charles, Emeric J; Habrian, Chris H; Hansen, Jesse M; Li, Hsin-Jung; Baldwin, Enoch P; Wingreen, Ned S; Kollman, Justin M; Gitai, Zemer

2014-01-01

CTP Synthetase (CtpS) is a universally conserved and essential metabolic enzyme. While many enzymes form small oligomers, CtpS forms large-scale filamentous structures of unknown function in prokaryotes and eukaryotes. By simultaneously monitoring CtpS polymerization and enzymatic activity, we show that polymerization inhibits activity, and CtpS's product, CTP, induces assembly. To understand how assembly inhibits activity, we used electron microscopy to define the structure of CtpS polymers. This structure suggests that polymerization sterically hinders a conformational change necessary for CtpS activity. Structure-guided mutagenesis and mathematical modeling further indicate that coupling activity to polymerization promotes cooperative catalytic regulation. This previously uncharacterized regulatory mechanism is important for cellular function since a mutant that disrupts CtpS polymerization disrupts E. coli growth and metabolic regulation without reducing CTP levels. We propose that regulation by large-scale polymerization enables ultrasensitive control of enzymatic activity while storing an enzyme subpopulation in a conformationally restricted form that is readily activatable. DOI: http://dx.doi.org/10.7554/eLife.03638.001 PMID:25030911

A novel headspace gas chromatographic method for in situ monitoring of monomer conversion during polymerization in an emulsion environment.

PubMed

Chai, Xin-Sheng; Zhong, Jin-Feng; Hu, Hui-Chao

2012-05-18

This paper describes a novel multiple-headspace extraction/gas chromatographic (MHE-GC) technique for monitoring monomer conversion during a polymerization reaction in a water-based emulsion environment. The polymerization reaction of methyl methacrylate (MMA) in an aqueous emulsion is used as an example. The reaction was performed in a closed headspace sample vial (as a mini-reactor), with pentane as a tracer. In situ monitoring of the vapor concentration of the tracer, employing a multiple headspace extraction (sampling) scheme, coupled to a GC, makes it possible to quantitatively follow the conversion of MMA during the early stages of polymerization. Data on the integrated amount of the tracer vapor released from the monomer droplet phase during the polymerization is described by a mathematic equation from which the monomer conversion can be calculated. The present method is simple, automated and economical, and provides an efficient tool in the investigation of the reaction kinetics and effects of the reaction conditions on the early stage of polymerization. Copyright © 2012 Elsevier B.V. All rights reserved.

A supported liquid membrane system for the selective recovery of rare earth elements from neodymium-based permanent magnets

DOE PAGES

Kim, Daejin; Powell, Lawrence; Delmau, Lætitia H.; ...

2016-04-04

We present that the rare earth elements (REEs) play a vital role in the development of green energy and high-tech industries. In order to meet the fast-growing demand and to ensure sufficient supply of the REEs, it is essential to develop an efficient REE recovery process from post-consumer REE-containing products. In this research effort, we have developed a supported liquid membrane system utilizing polymeric hollow fiber modules to extract REEs from neodymium-based magnets with neutral extractants such as tetraoctyl digylcol amide (TODGA). The effect of process variables such as REE concentration, molar concentration of acid, and membrane area on REEmore » recovery was investigated. We have demonstrated the selective extraction and recovery of REEs such as Nd, Pr, and Dy without co-extraction of non-REEs from permanent NdFeB magnets through the supported liquid membrane system. The extracted REEs were then recovered by precipitation followed by the annealing step to obtain crystalline REE powders in nearly pure form. Finally, the recovered REE oxides were characterized by X-ray diffraction, scanning electron microscope coupled with energy-dispersive X-ray spectroscopy, and inductively coupled plasma–optical emission spectroscopy.« less

Enhanced treatment of Fischer-Tropsch wastewater using up-flow anaerobic sludge blanket system coupled with micro-electrolysis cell: A pilot scale study.

PubMed

Wang, Dexin; Han, Yuxing; Han, Hongjun; Li, Kun; Xu, Chunyan

2017-08-01

The coupling of micro-electrolysis cell (MEC) with an up-flow anaerobic sludge blanket (UASB) system in pilot scale was established for enhanced treatment of Fischer-Tropsch (F-T) wastewater. The lowest influent pH (4.99±0.10) and reduced alkali addition were accomplished under the assistance of anaerobic effluent recycling of 200% (stage 5). Simultaneously, the optimum COD removal efficiency (93.5±1.6%) and methane production (2.01±0.13m 3 /m 3 ·d) at the lower hydraulic retention time (HRT) were achieved in this stage. In addition, the dissolved iron from MEC could significantly increase the protein content of tightly bound extracellular polymeric substances (TB-EPS), which was beneficial to formation of stable granules. Furthermore, the high-throughput 16S rRNA gene pyrosequencing in this study further confirmed that Geobacter species could utilize iron oxides particles as electron conduit to perform the direct interspecies electron transfer (DIET) with Methanothrix, finally facilitating the syntrophic degradation of propionic acid and butyric acid and contributing completely methane production. Copyright © 2017 Elsevier Ltd. All rights reserved.

Separation and identification of various carotenoids by C30 reversed-phase high-performance liquid chromatography coupled to UV and atmospheric pressure chemical ionization mass spectrometric detection.

PubMed

Lacker, T; Strohschein, S; Albert, K

1999-08-27

In this paper the application of on-line HPLC-UV-APCI (atmospheric pressure chemical ionization) mass spectrometry (MS) coupling for the separation and determination of different carotenoids as well as cis/trans isomers of beta-carotene is reported. All HPLC separations were carried out under RP conditions on self-synthesized polymeric C30 phases. The analysis of a carotenoid mixture containing astaxanthin, canthaxanthin, zeaxanthin, echinenone and beta-carotene by HPLC-APCI-MS was achieved by scanning the mass range from m/z 200 to 700. For the characterization of a sample containing cis/trans isomers of beta-carotene as well as their oxidation products, a photodiode-array UV-visible absorbance detector was used in addition between the column and the mass spectrometer for structural elucidation of the geometrical isomers. The detection limit for beta-carotene in positive-ion APCI-MS was determined to be 1 pmol. In addition, an extract of non-polar substances in vegetable juice has been analyzed by HPLC-APCI-MS. The included carotenoids could be identified by their masses and their retention times.

Effect of overcharge on Li(Ni 0.5Mn 0.3Co 0.2)O 2 cathodes: NMP-soluble binder. II — Chemical changes in the anode

DOE PAGES

Bloom, Ira; Bareno, Javier; Dietz Rago, Nancy; ...

2018-02-13

For this study, cells based on nickel manganese cobalt oxide (NMC)/graphite electrodes, which contained polyvinylidene difluoride (PVDF) binders in the electrodes, were systematically charged to 100, 120, 140, 160, 180, and 250% state of charge (SOC). Characterization of the anodes by inductively-coupled-plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), and high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) showed several extent-of-overcharge-dependent trends. The concentrations (by wt) of nickel, manganese, and cobalt in the negative electrode increased with SOC, but the metals remained in the same ratio as that of the positive. Electrolyte reaction products, such as LiF:LiPO 3,more » increased with overcharge, as expected. Three organic products were found by HPLC-ESI-MS. From an analysis of the mass spectra, two of these compounds seem to be organophosphates, which were formed by the reaction of polymerized electrolyte decomposition products and PF 3 or O=PF 3. Their concentration tended to reach a constant ratio. The third was seen at 250% SOC only.« less

Effect of overcharge on Li(Ni 0.5Mn 0.3Co 0.2)O 2 cathodes: NMP-soluble binder. II — Chemical changes in the anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bloom, Ira; Bareno, Javier; Dietz Rago, Nancy

For this study, cells based on nickel manganese cobalt oxide (NMC)/graphite electrodes, which contained polyvinylidene difluoride (PVDF) binders in the electrodes, were systematically charged to 100, 120, 140, 160, 180, and 250% state of charge (SOC). Characterization of the anodes by inductively-coupled-plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), and high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) showed several extent-of-overcharge-dependent trends. The concentrations (by wt) of nickel, manganese, and cobalt in the negative electrode increased with SOC, but the metals remained in the same ratio as that of the positive. Electrolyte reaction products, such as LiF:LiPO 3,more » increased with overcharge, as expected. Three organic products were found by HPLC-ESI-MS. From an analysis of the mass spectra, two of these compounds seem to be organophosphates, which were formed by the reaction of polymerized electrolyte decomposition products and PF 3 or O=PF 3. Their concentration tended to reach a constant ratio. The third was seen at 250% SOC only.« less

Effect of overcharge on Li(Ni0.5Mn0.3Co0.2)O2 cathodes: NMP-soluble binder. II - Chemical changes in the anode

NASA Astrophysics Data System (ADS)

Bloom, Ira; Bareño, Javier; Dietz Rago, Nancy; Dogan, Fulya; Graczyk, Donald G.; Tsai, Yifen; Naik, Seema R.; Han, Sang-Don; Lee, Eungje; Du, Zhijia; Sheng, Yangping; Li, Jianlin; Wood, David L.; Steele, Leigh Anna; Lamb, Joshua; Spangler, Scott; Grosso, Christopher; Fenton, Kyle

2018-05-01

Cells based on nickel manganese cobalt oxide (NMC)/graphite electrodes, which contained polyvinylidene difluoride (PVDF) binders in the electrodes, were systematically charged to 100, 120, 140, 160, 180, and 250% state of charge (SOC). Characterization of the anodes by inductively-coupled-plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), and high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) showed several extent-of-overcharge-dependent trends. The concentrations (by wt) of nickel, manganese, and cobalt in the negative electrode increased with SOC, but the metals remained in the same ratio as that of the positive. Electrolyte reaction products, such as LiF:LiPO3, increased with overcharge, as expected. Three organic products were found by HPLC-ESI-MS. From an analysis of the mass spectra, two of these compounds seem to be organophosphates, which were formed by the reaction of polymerized electrolyte decomposition products and PF3 or O=PF3. Their concentration tended to reach a constant ratio. The third was seen at 250% SOC only.

Fabrication of Nanoscaled Systems

DTIC Science & Technology

2007-05-01

corresponds to an effective dose as low as a few ýC/cm2 for sputtering of a 50 rum resist film. Comparison to observed sputtering rates in other polymeric ...materials (e.g. polystyrene and AZ and SU8 resists), coupled with time of flight SIMS measurements indicate that the relevant mechanism is indeed ion...approximately unity between GMR substrate and resist (for both electron and ion exposed HSQ), which we would not expect to be attainable using polymeric

Construction of three-dimensional graphene interfaces into carbon fiber textiles for increasing deposition of nickel nanoparticles: flexible hierarchical magnetic textile composites for strong electromagnetic shielding

NASA Astrophysics Data System (ADS)

Bian, Xing-Ming; Liu, Lin; Li, Hai-Bing; Wang, Chan-Yuan; Xie, Qing; Zhao, Quan-Liang; Bi, Song; Hou, Zhi-Ling

2017-01-01

Since manipulating electromagnetic waves with electromagnetic active materials for environmental and electric engineering is a significant task, here a novel prototype is reported by introducing reduced graphene oxide (RGO) interfaces in carbon fiber (CF) networks for a hierarchical carbon fiber/reduced graphene oxide/nickel (CF-RGO-Ni) composite textile. Upon charaterizations of the microscopic morphologies, electrical and magnetic properties, the presence of three-dimensional RGO interfaces and bifunctional nickel nanoparticles substantially influences the related physical properties in the resulting hierarchical composite textiles. Eletromagnetic interference (EMI) shielding performance suggests that the hierarchical composite textiles hold a strong shielding effectiveness greater than 61 dB, showing greater advantages than conventional polymeric and foamy shielding composites. As a polymer-free lightweight structure, flexible CF-RGO-Ni composites of all electromagnetic active components offer unique understanding of the multi-scale and multiple mechanisms in electromagnetic energy consumption. Such a novel prototype of shielding structures along with convenient technology highlight a strategy to achieve high-performance EMI shielding, coupled with a universal approach for preparing advanced lightweight composites with graphene interfaces.

Construction of three-dimensional graphene interfaces into carbon fiber textiles for increasing deposition of nickel nanoparticles: flexible hierarchical magnetic textile composites for strong electromagnetic shielding.

PubMed

Bian, Xing-Ming; Liu, Lin; Li, Hai-Bing; Wang, Chan-Yuan; Xie, Qing; Zhao, Quan-Liang; Bi, Song; Hou, Zhi-Ling

2017-01-27

Since manipulating electromagnetic waves with electromagnetic active materials for environmental and electric engineering is a significant task, here a novel prototype is reported by introducing reduced graphene oxide (RGO) interfaces in carbon fiber (CF) networks for a hierarchical carbon fiber/reduced graphene oxide/nickel (CF-RGO-Ni) composite textile. Upon charaterizations of the microscopic morphologies, electrical and magnetic properties, the presence of three-dimensional RGO interfaces and bifunctional nickel nanoparticles substantially influences the related physical properties in the resulting hierarchical composite textiles. Eletromagnetic interference (EMI) shielding performance suggests that the hierarchical composite textiles hold a strong shielding effectiveness greater than 61 dB, showing greater advantages than conventional polymeric and foamy shielding composites. As a polymer-free lightweight structure, flexible CF-RGO-Ni composites of all electromagnetic active components offer unique understanding of the multi-scale and multiple mechanisms in electromagnetic energy consumption. Such a novel prototype of shielding structures along with convenient technology highlight a strategy to achieve high-performance EMI shielding, coupled with a universal approach for preparing advanced lightweight composites with graphene interfaces.

Quinone-formaldehyde polymer as an active material in Li-ion batteries

NASA Astrophysics Data System (ADS)

Pirnat, Klemen; Mali, Gregor; Gaberscek, Miran; Dominko, Robert

2016-05-01

A benzoquinone polymer is synthesized by the polymerisation of hydrobenzoquinone and formaldehyde, followed by oxidation process using a hydrogen peroxide to convert hydroquinone to quinone. As prepared materials are characterized with FTIR, 1H-13C CPMAS NMR, pyrolysis coupled with gas chromatography (GC) and mass spectrometer (MS), TGA-MS analysis, EDX, elemental analysis, XRD, SEM and TEM microscopies and BET nitrogen adsorption. The benzoquinone polymer shows an excellent electrochemical performance when used as a positive electrode material in Li-ion secondary batteries. Using an electrolyte consisting 1 M bis(trifluoromethane)-sulfonimide lithium salt dissolved in 1,3-dioxolane and dimethoxyethane in a vol. ratio 1:1 (1 M LiTFSI/DOL + DME = 1:1) a stable capacity close to 150 mAh/g can be obtained. Compared to other electroactive materials based on benzoquinones it has a supreme capacity stability and is prepared by a simple synthesis using easily accessible starting materials. Further improvements in the capacity value (up to the theoretical value of 406 mAh/g) can be foreseen by achieving a higher degree of oxidation and by modification of polymerization process to enhance the electronic and ionic conductivity.

Biochemistry of microbial polyvinyl alcohol degradation.

PubMed

Kawai, Fusako; Hu, Xiaoping

2009-08-01

Effect of minor chemical structures such as 1,2-diol content, ethylene content, tacticity, a degree of polymerization, and a degree of saponification of the main chain on biodegradability of polyvinyl alcohol (PVA) is summarized. Most PVA-degraders are Gram-negative bacteria belonging to the Pseudomonads and Sphingomonads, but Gram-positive bacteria also have PVA-degrading abilities. Several examples show symbiotic degradation of PVA by different mechanisms. Penicillium sp. is the only reported eukaryotic degrader. A vinyl alcohol oligomer-utilizing fungus, Geotrichum fermentans WF9101, has also been reported. Lignolytic fungi have displayed non-specific degradation of PVA. Extensive published studies have established a two-step process for the biodegradation of PVA. Some bacteria excrete extracellular PVA oxidase to yield oxidized PVA, which is partly under spontaneous depolymerization and is further metabolized by the second step enzyme (hydrolase). On the other hand, PVA (whole and depolymerized to some extent) must be taken up into the periplasmic space of some Gram-negative bacteria, where PVA is oxidized by PVA dehydrogenase, coupled to a respiratory chain. The complete pva operon was identified in Sphingopyxis sp. 113P3. Anaerobic biodegradability of PVA has also been suggested.

Design and synthesis of inorganic/organic hybrid electrochemical materials

NASA Astrophysics Data System (ADS)

Harreld, John H.

An ambient pressure method for drying sol-gel materials is developed to synthesize high porosity (80--90%), high surface area vanadium oxide and silica aerogel materials (150--300 and 1000 m2/g for vanadium pentoxide and silica, respectively). The synthesis approach uses liquid exchange to replace the pore fluid with a low surface tension, nonpolar solvent which reduces the capillary pressures developed during drying. The Good-Girifalco interaction parameter is used to calculate pore stresses resulting from drying silica gels from various liquids. Vanadium oxide/polypyrrole hybrid aerogels are prepared using three strategies. These approaches focus on either sequential or consecutive polymerization of the inorganic and organic networks. Microcomposite aerogels are synthesized by encapsulating a dispersion of preformed polypyrrole in a vanadium pentoxide gel. In the second approach, pyrrole is polymerized and doped within the pore volume of preformed vanadium pentoxide gel. When the inorganic and organic precursors are polymerized simultaneously, the resulting gels exhibited a nanometer scaled microstructure with homogeneous distributions of either phases. Through this route, a suitable microstructure and composition for a lithium secondary battery cathode is obtained. Lithiated aerogels of hydrated nickel, cobalt, and mixed nickel-cobalt oxides are synthesized from lithium hydroxide and transition metal acetate precursors. The XRD analyses indicate that the nickel containing gels exhibit a lithium deficiency (less than 1 Li/transition metal. By increasing the concentration of the lithium precursor the lithium content in nickel oxides is increased, and additional base solution is no longer required to catalyze gelation. A non-hydrolytic sol-gel approach is utilized to create tin oxide and tin-aluminum binary oxide aerogels with high porosity (90%) and high surface area (300 m2/g). XRD data from single phase tin oxide aerogel indicates the growth of SnO2 crystallites between 150--400°C in air, accompanied by a reduction in surface area (30 m2/g). Heated tin oxide aerogel exhibits comparable reversible specific capacity (390 mAh/g) as that of commercial SnO2 (420 mAh/g). Amorphous tin oxide aerogel is stabilized to higher temperatures when aluminum oxide is incorporated into the structure. The tin oxide phase remains electrochemically active towards lithium insertion and exhibits excellent reversibility during cycling.

Glucose biosensor from covalent immobilization of chitosan-coupled carbon nanotubes on polyaniline-modified gold electrode.

PubMed

Wan, Dong; Yuan, Shaojun; Li, G L; Neoh, K G; Kang, E T

2010-11-01

An amperometric glucose biosensor was prepared using polyaniline (PANI) and chitosan-coupled carbon nanotubes (CS-CNTs) as the signal amplifiers and glucose oxidase (GOD) as the glucose detector on a gold electrode (the Au-g-PANI-c-(CS-CNTs)-GOD biosensor). The PANI layer was prepared via oxidative graft polymerization of aniline from the gold electrode surface premodified by self-assembled monolayer of 4-aminothiophenol. CS-CNTs were covalently coupled to the PANI-modified gold substrate using glutaradehyde as a bifunctional linker. GOD was then covalently bonded to the pendant hydroxyl groups of chitosan using 1,4-carbonyldiimidazole as the bifunctional linker. The surface functionalization processes were ascertained by X-ray photoelectron spectroscopy (XPS) analyses. The field emission scanning electron microscopy (FESEM) images of the Au-g-PANI-c-(CS-CNTs) electrode revealed the formation of a three-dimensional surface network structure. The electrode could thus provide a more spatially biocompatible microenvironment to enhance the amount and biocatalytic activity of the immobilized enzyme and to better mediate the electron transfer. The resulting Au-g-PANI-c-(CS-CNTs)-GOD biosensor exhibited a linear response to glucose in the concentration range of 1-20 mM, good sensitivity (21 μA/(mM·cm(2))), good reproducibility, and retention of >80% of the initial response current after 2 months of storage.

Polymerization-based signal amplification under ambient conditions with thirty-five second reaction times.

PubMed

Kaastrup, Kaja; Sikes, Hadley D

2012-10-21

Although polymerization-based amplification (PBA) has demonstrated promise as an inexpensive technique for use in molecular diagnostics, oxygen inhibition of radical photopolymerization has hindered its implementation in point-of-care devices. The addition of 0.3-0.7 μM eosin to an aqueous acrylate monomer solution containing a tertiary amine allows an interfacial polymerization reaction to proceed in air only near regions of a test surface where additional eosin initiators coupled to proteins have been localized as a function of molecular recognition events. The dose of light required for the reaction is inversely related to eosin concentration. This system achieves sensitivities comparable to those reported for inert gas-purged systems and requires significantly shorter reaction times. We provide several comparisons of this system with other implementations of polymerization-based amplification.

Low temperature catalytic oxidative aging of LDPE films in response to heat excitation.

PubMed

Luo, Xuegang; Zhang, Sizhao; Ding, Feng; Lin, Xiaoyan

2015-09-14

The waste treatment of polymer materials is often conducted using the photocatalytic technique; however, complete decomposition is frequently inhibited owing to several shortcomings such as low quantum yield and the requirement of ultraviolet irradiation. Herein, we report a strategy to implement moderate management of polymeric films via thermocatalytic oxidative route, which is responsive to heat stimulus. Diverse LDPE-matrix films together with as-prepared thermal catalysts (TCs) or initiators were synthesized to further investigate heat-dependent-catalytic degradation effects. After artificial ageing, structural textures of the as-synthesized films could be chemically deteriorated, followed by a huge increase in surface roughness values, and appreciable loss was also found in the average molecular weights and mechanical parameters. We found an emergent phenomenon in which crystallization closely resembled two-dimensional (2D) growth, which displayed rod-like or disc-type crystal shapes. New chemical groups generated on film surfaces were monitored, and led to a higher limiting oxygen index because of strong catalytic oxidation, thus demonstrating the success of catalytic oxidative ageing by heat actuation. The underlying mechanism responsible for thermocatalytic oxidative pattern is also discussed. Accordingly, these findings may have important implications for better understanding the development of polymeric-matrix waste disposal.

Synthesis of nanocrystalline Ni/Ce-YSZ powder via a polymerization route

NASA Astrophysics Data System (ADS)

Abolghasemi, Z.; Tamizifar, M.; Arzani, K.; Nemati, A.; Khanfekr, A.; Bolandi, M.

2013-08-01

Pechini process was used for preparation of three kinds of nanocrystalline powders of yttria-stabilized zirconia (YSZ): doped with 1.5 mol% nickel oxide, doped with 15 mol% ceria, and doped with 1.5 mol% nickel oxide plus 15 mol% ceria. Zirconium chloride, yttrium nitrate, cerium nitrate, nickel nitrate, citric acid and ethylene glycol were polymerized at 80 °C to produce a gel. XRD, SEM and TEM analyses were used to investigate the crystalline phases and microstructures of obtained compounds. The results of XRD revealed the formation of nanocrystalline powder at 900 °C. Morphology of the powder calcined at 900 °C, examined with a scanning electron microscope, showed that the presence of nickel and cerium inhibited the grain growth in the system. The average crystallite size of the material doped with nickel oxide (9.33 nm) was bigger than the one doped with cerium oxide (9.29 nm), while the YSZ doping with the two oxides simultaneously promoted the grain growth with crystallite size of 11.37 nm. Yttria-stabilized zirconia powder with a mean crystallite size of 9.997 nm was prepared successfully by this method.

Crosslinking hydroxylated reduced graphene oxide with RAFT-CTA: A nano-initiator for preparation of well-defined amino acid-based polymer nanohybrids.

PubMed

Namvari, Mina; Biswas, Chandra S; Wang, Qiao; Liang, Wenlang; Stadler, Florian J

2017-10-15

Here, we demonstrate a novel reversible addition-fragmentation chain transfer agent (RAFT-CTA)-modified reduced graphene oxide nanosheets (CTA-rGONSs) by crosslinking rGONSs with a RAFT-CTA via esterification reaction. These nano CTA-rGONSs were used to polymerize a hydrophobic amino acid-based methacrylamide (N-acryloyl-l-phenylalanine methyl ester) monomer with different monomer/initiator ratios. Thermogravimetric analysis showed that the polymer-graphene composites were thermally more stable than GO itself. M n of the polymers increased with increasing monomer/initiator ratio, while the polydispersity index decreased, indicating controlled polymerization. The composites were stable in DMF even after two months. Copyright © 2017 Elsevier Inc. All rights reserved.

An analytical approach for the non-invasive selection of consolidants in rubber artworks.

PubMed

Manfredi, Marcello; Barberis, Elettra; Rava, Antonio; Poli, Tommaso; Chiantore, Oscar; Marengo, Emilio

2016-08-01

The effectiveness of five polymeric materials for the long-term conservation and restoration of rubber artworks was evaluated by accelerated photo-oxidative degradation studies. Two different ethylene vinyl-acetate resins, generally used in industry and uncommon in conservation field, a new water-based polyurethane, and two ethylene butyl-acrylate resins were assessed for the consolidation of rubber. By monitoring their degradation along time with LED imaging coupled to statistics and Fourier transform infrared spectroscopy (FTIR), the polymeric materials with the best properties that ensure the protection and security of the artwork were identified. The degradation was performed in solar box simulating the light exposure in a museum, under controlled temperature at no more than 35 °C in order to exclude the thermal effects that could influence the ageing of polymers. The mechanical stress of the treated samples was also investigated. The spectroscopic analyses, the chromatic changes study, and the mechanical degradation were used as indicators of the consolidant stability, allowing the evaluation of the materials selected for the consolidation and conservation of rubber. The ethylene-vinyl acetate copolymers resulted the most stable and suitable for the conservation of rubber artworks. Lastly, the conservation treatment identified in this research was employed for the restoration of the contemporary artwork "Presagi di Birnam" made with bicycle inner tubes by the artist Carol Rama.

Preparation and Characterization of WS2@SiO2 and WS2@PANI Core-Shell Nanocomposites

PubMed Central

Sade, Hagit

2018-01-01

Two tungsten disulfide (WS2)-based core-shell nanocomposites were fabricated using readily available reagents and simple procedures. The surface was pre-treated with a surfactant couple in a layer-by-layer approach, enabling good dispersion of the WS2 nanostructures in aqueous media and providing a template for the polymerization of a silica (SiO2) shell. After a Stöber-like reaction, a conformal silica coating was achieved. Inspired by the resulting nanocomposite, a second one was prepared by reacting the surfactant-modified WS2 nanostructures with aniline and an oxidizing agent in an aqueous medium. Here too, a conformal coating of polyaniline (PANI) was obtained, giving a WS2@PANI nanocomposite. Both nanocomposites were analyzed by electron microscopy, energy dispersive X-ray spectroscopy (EDS) and FTIR, verifying the core-shell structure and the character of shells. The silica shell was amorphous and mesoporous and the surface area of the composite increases with shell thickness. Polyaniline shells slightly differ in their morphologies dependent on the acid used in the polymerization process and are amorphous like the silica shell. Electron paramagnetic resonance (EPR) spectroscopy of the WS2@PANI nanocomposite showed variation between bulk PANI and the PANI shell. These two nanocomposites have great potential to expand the use of transition metals dichalcogenides (TMDCs) for new applications in different fields. PMID:29534426

Biologically produced acid precipitable polymeric lignin

DOEpatents

Crawford, Don L.; Pometto, III, Anthony L.

1984-01-01

A water soluble, acid precipitable polymeric degraded lignin (APPL), having a molecular weight of at least 12,000 daltons, and comprising, by percentage of total weight, at least three times the number of phenolic hydroxyl groups and carboxylic acid groups present in native lignin. The APPL may be modified by chemical oxidation and reduction to increase its phenolic hydroxyl content and reduce the number of its antioxidant inhibitory side chains, thereby improving antioxidant properties.

Thickness-self-controlled synthesis of porous transparent polyaniline-reduced graphene oxide composites towards advanced bifacial dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Wang, Yu-Sheng; Li, Shin-Ming; Hsiao, Sheng-Tsung; Liao, Wei-Hao; Yang, Shin-Yi; Tien, Hsi-Wen; Ma, Chen-Chi M.; Hu, Chi-Chang

2014-08-01

A powerful synthesis strategy is proposed for fabricating porous polyaniline-reduced graphene oxide (PANI-RGO) composites with transparency up to 80% and thickness from 300 to 1000 nm for the counter electrode (CE) of bifacial dye-sensitizing solar cells (DSSCs). The first step is to combine the in-situ positive charge transformation of graphene oxide (GO) through aniline (ANI) prepolymerization and the electrostatic adsorption of ANI oligomer-GO to effectively control the thickness of ultrathin PANI-GO films by adjusting pH of the polymerization media. In the second step, PANI-GO films are reduced with hydroiodic acid to simultaneously enhance the apparent redox activity for the I3-/I- couple and their electronic conductivity. Incorporating the RGO increases the transparency of PANI and facilitates the light-harvesting from the rear side. A DSSC assembled with such a transparent PANI-RGO CE exhibits an excellent efficiency of 7.84%, comparable to 8.19% for a semi-transparent Pt-based DSSC. The high light-harvesting ability of PANI-RGO enhances the efficiency retention between rear- and front-illumination modes to 76.7%, compared with 69.1% for a PANI-based DSSC. The higher retention reduces the power-to-weight ratio and the total cost of bifacial DSSCs, which is also promising in other applications, such as windows, power generators, and panel screens.

40 CFR Appendix A to Part 414 - Non-Complexed Metal-Bearing Waste Streams and Cyanide-Bearing Waste Streams

Code of Federal Regulations, 2010 CFR

2010-07-01

... Mercaptan/Ethanol + Hydrogen sulfide Methanol/H.P. Synthesis from natural gas via synthetic gas Oxo Alcohols... + Ammonia n-Propyl alcohol/Hydrogenation of propionaldehyde, Oxo process SAN resin/Suspension polymerization... methanol Acetaldehyde/Oxidation of ethylene with cupric chloride catalyst Acetic acid/Catalytic oxidation...

Amphiphilic polymeric micelles originating from 1,4-β-D-glucan-g-polyphenylene oxide as the carriers for delivery of docetaxel and the corresponding release behaviors.

PubMed

Yang, Fang; Xiao, Dan; Han, Huaxin; Chen, Yuhuan; Li, Gang

2018-07-15

A novel amphiphilic polymeric drug carrier was synthesized through grafting polymerization of water-soluble 1,4-β-D-glucan from cotton cellulose tailored and polypropylene oxide (PPO), and then use thereof to synthesize graft copolymer 1,4-β-D-glucan-PPO-docetaxel (DTX). The products were characterized by FTIR, 1 H NMR, and 13 C NMR. The physicochemical characteristics of 1,4-β-D-glucan-PPO and 1,4-β-D-glucan-PPO-DTX such as molecular weight distribution (MWD), micro-morphology, size, critical micelle concentration (CMC), aggregation number of micelle (N), in vitro stability and drug pharmacokinetic study in vivo were investigated. The results reveal that the degree of polymerization (DP) of the water-soluble 1,4-β-D-glucan from cotton cellulose tailored is equal to 7; the 1,4-β-D-glucan-PPO surfactant possesses good surface activity while the adduct number of propylene oxide reaches appropriately to 20; the DTX is completely dispersed in water medium with 1,4-β-D-glucan-PPO-DTX micelle and the drug conjugated percent is up to 40.3%; In vitro study confirms that 1,4-β-D-glucan-PPO-DTX has the capacity for sustained drug release; In plasma, 1,4-β-D-glucan-PPO-DTX exhibits a significantly enhanced C max , AUC (0-t) and T 1/2 compared with DTX. These results demonstrate that 1,4-β-D-glucan-PPO has the potential to be used as a novel biocompatible biomaterial for drug delivery. Copyright © 2018 Elsevier B.V. All rights reserved.

Magnetically stimulated ciprofloxacin release from polymeric microspheres entrapping iron oxide nanoparticles

PubMed Central

Sirivisoot, Sirinrath; Harrison, Benjamin S

2015-01-01

To extend the external control capability of drug release, iron oxide nanoparticles (NPs) encapsulated into polymeric microspheres were used as magnetic media to stimulate drug release using an alternating magnetic field. Chemically synthesized iron oxide NPs, maghemite or hematite, and the antibiotic ciprofloxacin were encapsulated together within polycaprolactone microspheres. The polycaprolactone microspheres entrapping ciprofloxacin and magnetic NPs could be triggered for immediate drug release by magnetic stimulation at a maximum value of 40%. Moreover, the microspheres were cytocompatible with fibroblasts in vitro with a cell viability percentage of more than 100% relative to a nontreated control after 24 hours of culture. Macrophage cell cultures showed no signs of increased inflammatory responses after in vitro incubation for 56 hours. Treatment of Staphylococcus aureus with the magnetic microspheres under an alternating (isolating) magnetic field increased bacterial inhibition further after 2 days and 5 days in a broth inhibition assay. The findings of the present study indicate that iron oxide NPs, maghemite and hematite, can be used as media for stimulation by an external magnetic energy to activate immediate drug release. PMID:26185446

Poly(3,4-ethylenedioxythiophene)/reduced graphene oxide composites as counter electrodes for high efficiency dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Ma, Jinfu; Yuan, Shenghua; Yang, Shaolin; Lu, Hui; Li, Yingtao

2018-05-01

A facile, low cost, easy-controllable method to prepare Poly(3,4-ethylenedioxythiophene) (PEDOT)/reduced graphene oxide (rGO) composites by electrochemical deposition onto fluorinated tin oxide (FTO) as counter electrodes (CEs) in high performance dye-sensitized solar cells (DSSCs) is reported. The electro-deposition process was accomplished by electro-polymerization of graphene oxide (GO)/PEDOT composites onto FTO substrates followed by electrochemical reduction of the GO component. Electrochemical measurements show that the I-/I3- catalytic activity of the as-prepared PEDOT/rGO CE is improved compared with that of the pure PEDOT and PEDOT/GO electrode. Through the analysis of photoelectric properties, the performance of the electrodes fabricated with different polymerization times are compared, and the optimal preparation condition is determined. The photoelectric conversion efficiency (PCE) of the DSSC assembled with PEDOT/rGO electrode reaches 7.79%, close to 8.33% of the cell with Platinum (Pt) electrode, and increases by 13.2% compared with 6.88% of the device with the PEDOT electrode.

Formyl-ended heterobifunctional poly(ethylene oxide): synthesis of poly(ethylene oxide) with a formyl group at one end and a hydroxyl group at the other end.

PubMed

Nagasaki, Y; Kutsuna, T; Iijima, M; Kato, M; Kataoka, K; Kitano, S; Kadoma, Y

1995-01-01

Well-defined poly(ethylene oxide) (PEO) with a formyl group at one end and a hydroxyl group at the other terminus was synthesized by the anionic ring opening polymerization of ethylene oxide (EO) with a new organometallic initiator possessing an acetal moiety, potassium 3,3-diethoxypropyl alkoxide. Hydrolysis of the acetal moiety produced a formyl group-terminated heterobifunctional PEO with a hydroxyl group at the other end.

Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver

NASA Astrophysics Data System (ADS)

Gutzler, Rico; Cardenas, Luis; Lipton-Duffin, Josh; El Garah, Mohamed; Dinca, Laurentiu E.; Szakacs, Csaba E.; Fu, Chaoying; Gallagher, Mark; Vondráček, Martin; Rybachuk, Maksym; Perepichka, Dmitrii F.; Rosei, Federico

2014-02-01

We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C. On Cu(111) only organometallic structures are formed, while on Ag(111) both organometallic and covalent polymeric networks were found to coexist. The ratio between organometallic and covalent bonds could be controlled by means of the annealing temperature. The thiophene moieties start degrading at 200 °C on the copper surface, whereas on silver the degradation process becomes significant only at 400 °C. Our work reveals how the interplay of a specific surface type and temperature steers the formation of organometallic and polymeric networks and describes how these factors influence the structural integrity of two-dimensional organic networks.We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C. On Cu(111) only organometallic structures are formed, while on Ag(111) both organometallic and covalent polymeric networks were found to coexist. The ratio between organometallic and covalent bonds could be controlled by means of the annealing temperature. The thiophene moieties start degrading at 200 °C on the copper surface, whereas on silver the degradation process becomes significant only at 400 °C. Our work reveals how the interplay of a specific surface type and temperature steers the formation of organometallic and polymeric networks and describes how these factors influence the structural integrity of two-dimensional organic networks. Electronic supplementary information (ESI) available: Additional STM data and DFT results. See DOI: 10.1039/c3nr05710k

Self-Healing of biocompatible polymeric nanocomposities

NASA Astrophysics Data System (ADS)

Espino, Omar; Chipara, Dorina

2014-03-01

Polymers are vulnerable to damage in form of cracks deep within the structure, where detection is difficult and repair is near to impossible. These cracks lead to mechanical degradation of the polymer. A method has been created to solve this problem named polymeric self healing. Self healing capabilities implies the dispersion within the polymeric matrix of microcapsules filled with a monomer and of catalyst. Poly urea-formaldehyde microcapsules used in this method are filled with dicyclopentadiene that is liberated after being ruptured by the crack propagation in the material. Polymerization is assisted by a catalyst FGGC that ignites the self healing process. Nanocomposites, such as titanium oxide, will be used as an integration of these polymers that will be tested by rupturing mechanically slowly. In order to prove the self healing process, Raman spectroscopy, FTIR, and SEM are used.

Conductivity enhancement of surface-polymerized polyaniline films via control of processing conditions

NASA Astrophysics Data System (ADS)

Park, Chung Hyoi; Jang, Sung Kyu; Kim, Felix Sunjoo

2018-01-01

We investigate a fast and facile approach for the simultaneous synthesis and coating of conducting polyaniline (PANI) onto a substrate and the effects of processing conditions on the electrical properties of the fabricated films. Simultaneous polymerizing and depositing on the substrate forms a thin film with the average thickness of 300 nm and sheet resistance of 304 Ω/sq. Deposition conditions such as polymerization time (3-240 min), temperature (-10 to 40 °C), concentrations of monomer and oxidant (0.1-0.9 M), and type of washing solvents (acetone, water, and/or HCl solution) affect the film thickness, doping state, absorption characteristics, and solid-state nanoscale morphology, therefore affecting the electrical conductivity. Among the conditions, the surface-polymerized PANI film deposited at room temperature with acetone washing showed the highest conductivity of 22.2 S/cm.

Dielectric loss property of strong acids doped polyaniline (PANi)

NASA Astrophysics Data System (ADS)

Amalia, Rianti; Hafizah, Mas Ayu Elita; Andreas, Manaf, Azwar

2018-04-01

In this study, strong acid doped polyaniline (PANi) has been successfully fabricated through the chemical oxidative polymerization process with various polymerization times. Nonconducting PANi resulting from the polymerization process at various polymerization times were then doped by a strong acid HClO4 to generate dielectric properties. Ammonium Persulfate (APS) as an initiator was used during Polymerization process to develop dark green precipitates which then called Emeraldine Base Polyaniline (PANi-EB). The PANi-EB was successively doped by strong acid HClO4 with dopant and PANi ratio 10:1 to enhance the electrical conductivity. The conductivity of doped PANi was evaluated by Four Point Probe. Results of evaluation showed that the conductivity values of HClO4 doped PANi were in the range 337-363 mS/cm. The dielectric properties of doped PANi were evaluated by Vector Network Analyzer (VNA) which suggested that an increase in the permittivity value in the conducting PANi. It is concluded that PANi could be a potential candidate for electromagnetic waves absorbing materials.

Polymerization model for hydrogen peroxide initiated synthesis of polypyrrole nanoparticles.

PubMed

Leonavicius, Karolis; Ramanaviciene, Almira; Ramanavicius, Arunas

2011-09-06

A very simple, environmentally friendly, one-step oxidative polymerization route to fabricate polypyrrole (Ppy) nanoparticles of fixed size and morphology was developed and investigated. The herein proposed method is based on the application of sodium dodecyl sulfate and hydrogen peroxide, both easily degradable and cheap materials. The polymerization reaction is performed on 24 h time scale under standard conditions. We monitored a polaronic peak at 465 nm and estimated nanoparticle concentration during various stages of the reaction. Using this data we proposed a mechanism for Ppy nanoparticle formation in accordance with earlier emulsion polymerization mechanisms. Rates of various steps in the polymerization mechanism were accounted for and the resulting particles identified using atomic force microscopy. Application of Ppy nanoparticles prepared by the route presented here seems very promising for biomedical applications where biocompatibility is paramount. In addition, this kind of synthesis could be suitable for the development of solar cells, where very pure and low-cost conducting polymers are required. © 2011 American Chemical Society

Advanced Synthesis of Conductive Polyaniline Using Laccase as Biocatalyst.

PubMed

de Salas, Felipe; Pardo, Isabel; Salavagione, Horacio J; Aza, Pablo; Amougi, Eleni; Vind, Jesper; Martínez, Angel T; Camarero, Susana

2016-01-01

Polyaniline is a conductive polymer with distinctive optical and electrical properties. Its enzymatic synthesis is an environmentally friendly alternative to the use of harsh oxidants and extremely acidic conditions. 7D5L, a high-redox potential laccase developed in our lab, is the biocatalyst of choice for the synthesis of green polyaniline (emeraldine salt) due to its superior ability to oxidize aniline and kinetic stability at the required polymerization conditions (pH 3 and presence of anionic surfactants) as compared with other fungal laccases. Doses as low as 7.6 nM of 7D5L catalyze the polymerization of 15 mM aniline (in 24 h, room temperature, 7% yield) in the presence of different anionic surfactants used as doping templates to provide linear and water-soluble polymers. Aniline polymerization was monitored by the increase of the polaron absorption band at 800 nm (typical for emeraldine salt). Best polymerization results were obtained with 5 mM sodium dodecylbenzenesulfonate (SDBS) as template. At fixed conditions (15 mM aniline and 5mM SDBS), polymerization rates obtained with 7D5L were 2.5-fold the rates obtained with commercial Trametes villosa laccase. Moreover, polyaniline yield was notably boosted to 75% by rising 7D5L amount to 0.15 μM, obtaining 1g of green polyaniline in 1L-reaction volume. The green polymer obtained with the selected system (7D5L/SDBS) holds excellent electrochemical and electro-conductive properties displayed in water-dispersible nanofibers, which is advantageous for the nanomaterial to be readily cast into uniform films for different applications.

Advanced Synthesis of Conductive Polyaniline Using Laccase as Biocatalyst

PubMed Central

de Salas, Felipe; Pardo, Isabel; Salavagione, Horacio J.; Aza, Pablo; Amougi, Eleni; Vind, Jesper; Martínez, Angel T.; Camarero, Susana

2016-01-01

Polyaniline is a conductive polymer with distinctive optical and electrical properties. Its enzymatic synthesis is an environmentally friendly alternative to the use of harsh oxidants and extremely acidic conditions. 7D5L, a high-redox potential laccase developed in our lab, is the biocatalyst of choice for the synthesis of green polyaniline (emeraldine salt) due to its superior ability to oxidize aniline and kinetic stability at the required polymerization conditions (pH 3 and presence of anionic surfactants) as compared with other fungal laccases. Doses as low as 7.6 nM of 7D5L catalyze the polymerization of 15 mM aniline (in 24 h, room temperature, 7% yield) in the presence of different anionic surfactants used as doping templates to provide linear and water-soluble polymers. Aniline polymerization was monitored by the increase of the polaron absorption band at 800 nm (typical for emeraldine salt). Best polymerization results were obtained with 5 mM sodium dodecylbenzenesulfonate (SDBS) as template. At fixed conditions (15 mM aniline and 5mM SDBS), polymerization rates obtained with 7D5L were 2.5-fold the rates obtained with commercial Trametes villosa laccase. Moreover, polyaniline yield was notably boosted to 75% by rising 7D5L amount to 0.15 μM, obtaining 1g of green polyaniline in 1L-reaction volume. The green polymer obtained with the selected system (7D5L/SDBS) holds excellent electrochemical and electro-conductive properties displayed in water-dispersible nanofibers, which is advantageous for the nanomaterial to be readily cast into uniform films for different applications. PMID:27741301

Thiol surface functionalization via continuous phase plasma polymerization of allyl mercaptan, with subsequent maleimide-linked conjugation of collagen.

PubMed

Stynes, Gil D; Gengenbach, Thomas R; Kiroff, George K; Morrison, Wayne A; Kirkland, Mark A

2017-07-01

Thiol groups can undergo a large variety of chemical reactions and are used in solution phase to conjugate many bioactive molecules. Previous research on solid substrates with continuous phase glow discharge polymerization of thiol-containing monomers may have been compromised by oxidation. Thiol surface functionalization via glow discharge polymerization has been reported as requiring pulsing. Herein, continuous phase glow discharge polymerization of allyl mercaptan (2-propene-1-thiol) was used to generate significant densities of thiol groups on a mixed macrodiol polyurethane and tantalum. Three general classes of chemistry are used to conjugate proteins to thiol groups, with maleimide linkers being used most commonly. Here the pH specificity of maleimide reactions was used effectively to conjugate surface-bound thiol groups to amine groups in collagen. XPS demonstrated surface-bound thiol groups without evidence of oxidation, along with the subsequent presence of maleimide and collagen. Glow discharge reactor parameters were optimized by testing the resistance of bound collagen to degradation by 8 M urea. The nature of the chemical bonding of collagen to surface thiol groups was effectively assessed by colorimetric assay (ELISA) of residual collagen after incubation in 8 M urea over 8 days and after incubation with keratinocytes over 15 days. The facile creation of useable solid-supported thiol groups via continuous phase glow discharge polymerization of allyl mercaptan opens a route for attaching a vast array of bioactive molecules. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1940-1948, 2017. © 2017 Wiley Periodicals, Inc.

Environmentally friendly, one-pot synthesis of folic acid-decorated graphene oxide-based drug delivery system

NASA Astrophysics Data System (ADS)

Lin, Quankui; Huang, Xiaojie; Tang, Junmei; Han, Yuemei; Chen, Hao

2013-12-01

A targeted drug delivery system based on graphene oxide (GO) was produced via one-pot synthesis method, taking advantages of the self-polymerization of the dopamine (DA). The polymerization of dopamine resulted in polydopamine capped GO nanocomposite. Meanwhile, the anti-tumor drug doxorubicin (DOX) can be loaded in the nanocomposite and the tumor cell targeting molecule folic acid (FA) can also been immobilized on the nanocomposite surface simultaneously. The size of the obtained FA-decorated GO-based drug delivery system (DA/GO(DOX)-FA) is about 600 nm. It renders a sustained drug release manner. The cell culture results reveal that the FA-decorated GO-based drug delivery system (DA/GO(DOX)-FA) via one-pot method shows property of targeted killing of cancer cells in vitro. This one-pot method just needs the pH adjusting to induce the self-polymerization of DA, but excludes the fussy chemical grafting process and the organic solvents, which make it an environmentally friendly method to synthesize FA-decorated GO-based drug delivery system.

Synthesis of HNTs@PEDOT composites via in situ chemical oxidative polymerization and their application in electrode materials

NASA Astrophysics Data System (ADS)

Wang, Fang; Zhang, Xianhong; Ma, Yuhong; Yang, Wantai

2018-01-01

The hybrid composite of poly(3,4-ethylenedioxythiophene) (PEDOT) and halloysite nanotubes (HNTs) was synthesized by a two-step process. First, poly(sodium styrene sulfonate) (PSSNa) was grafted onto HNTs via surface initiated atom transfer radical polymerization. Then with the HNTs-g-PSS as a template and the grafted PSS chains as the counterion dopant, PEDOT was precipitated onto the template via in situ oxidization polymerization of EDOT to form HNTs@PEDOT hybrid composites. The conductivity of HNTs@PEDOT can reach up to 9.35 S/cm with the content of 40% HNTs-g-PSS, which increased almost 78 times than that of pure PEDOT (about 0.12 S/cm) prepared at the similar condition. Further treated with p-toluenesulfonic acid (TsOH) as external dopant, the conductivity of HNTs@PEDOT increased to 24.3 S/cm. The electrochemical properties of the composites were investigated with cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy with three-electrode cell configuration. The results showed that the capacitance of HNTs@PEDOT composite increased 55% than that of pure PEDOT.

Biocatalytic synthesis of maltodextrin-based acrylates from starch and α-cyclodextrin.

PubMed

Kloosterman, Wouter M J; Spoelstra-van Dijk, Gerda; Loos, Katja

2014-09-01

Novel 2-(β-maltooligooxy)-ethyl (meth)acrylate monomers are successfully synthesized by CGTase from Bacillus macerans catalyzed coupling of 2-(β-glucosyloxy)-ethyl acrylate and methacrylate with α-cyclodextrin or starch. HPLC-UV analysis shows that the CGTase catalyzed reaction yields 2-(β-maltooligooxy)-ethyl acrylates with 1 to 15 glucopyranosyl units. (1) H NMR spectroscopy reveals that the β-linkage in the acceptor molecule is preserved during the CGTase catalyzed coupling reaction, whereas the newly introduced glucose units are attached by α-(1,4)-glycosidic linkages. The synthesized 2-(β-maltooligooxy)-ethyl acrylate monomers are successfully polymerized by aqueous free radical polymerization to yield the comb-shaped glycopolymer poly(2-(β-maltooligooxy)-ethyl acrylate). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phosphoniums as catalysts for metal-free polymerization: Synthesis of well-defined poly(propylene oxide)

NASA Astrophysics Data System (ADS)

Zhang, Jie; Liu, Quan; Ren, Haojun; Zhang, Nanjie; Li, Pengfei; Yang, Kang

2017-11-01

The anionic ring-opening polymerization of propylene oxide (PO) was initiated with glycerol and catalyzed by three new synthetic phosphonium salts, tetrakis (pyrrolidino) phosphonium (Py4P1+), tetrakis (piperidino) phosphonium (Pi4P1+), tetrakis (morpholino) phosphonium (Mo4P1+), and the known tetrakis [cyclohexyl (methyl) amino] phosphonium (Cy4P1+) and tetrakis [tris (dimethylamino) phosphonoamino] phosphazene (P5+). The effects of substituents on the polymerization behavior, especially the molecular weight and its distribution, degree of unsaturation, and the sequential structures of poly (propylene oxide) (PPO) were investigated. The structures of these catalysts and PPOs were characterized by FT-IR, 1H and 13C NMR, and GPC. The results indicate that Cy4P1+, Py4P1+, and Pi4P1+ have lower optimum reaction temperatures at 90, 70, and 70 °C, respectively, and are better than traditional catalysts KOH and double metal cyanide. PPO samples with high molecular weight, narrow polydispersity, and high functionality were accessible when catalyzed with Cy4P1+, Pi4P1+, and P5+ at the optimum temperature. Notably, Pi4P1+ formed unimodal distribution PPO with 9000 g/mol, 2.93 of functionality, and 0.008 mmol/g degree of unsaturation. Majority segments of PPO from five catalysts adopted the stereoregular head-to-tail structure, exhibiting excellent regularity.

Glucose Oxidase-Mediated Polymerization as a Platform for Dual-Mode Signal Amplification and Biodetection

PubMed Central

Berron, Brad J; Johnson, Leah M; Ba, Xiao; McCall, Joshua D; Alvey, Nicholas J; Anseth, Kristi S; Bowman, Christopher N

2011-01-01

We report the first use of a polymerization-based ELISA substrate solution employing enzymatically mediated radical polymerization as a dual-mode amplification strategy. Enzymes are selectively coupled to surfaces to generate radicals that subsequently lead to polymerization-based amplification (PBA) and biodetection. Sensitivity and amplification of the polymerization-based detection system were optimized in a microwell strip format using a biotinylated microwell surface with a glucose oxidase (GOx)–avidin conjugate. The immobilized GOx is used to initiate polymerization, enabling the detection of the biorecognition event visually or through the use of a plate reader. Assay response is compared to that of an enzymatic substrate utilizing nitroblue tetrazolium in a simplified assay using biotinylated wells. The polymerization substrate exhibits equivalent sensitivity (2 µg/mL of GOx-avidin) and over three times greater signal amplification than this traditional enzymatic substrate since each radical that is enzymatically generated leads to a large number of polymerization events. Enzyme-mediated polymerization proceeds in an ambient atmosphere without the need for external energy sources, which is an improvement upon previous PBA platforms. Substrate formulations are highly sensitive to both glucose and iron concentrations at the lowest enzyme concentrations. Increases in amplification time correspond to higher assay sensitivities with no increase in non-specific signal. Finally, the polymerization substrate generated a signal to noise ratio of 14 at the detection limit (156 ng/mL) in an assay of transforming growth factor-beta. Biotechnol. Bioeng. 2011; 108:1521–1528. © 2011 Wiley Periodicals, Inc. PMID:21337335

INORGANIC COORDINATION POLYMERS. IV. THE ATTEMPTED REPLACEMENT OF ACETYLACETONATE LIGANDS WITH PICOLINATE LIGANDS,

DTIC Science & Technology

HETEROCYCLIC COMPOUNDS, PHOSPHENE OXIDES, BENZENE, CHROMIUM COMPOUNDS, CHEMICAL REAC, SYNTHESIS (CHEMISTRY), CHEMICAL ANALY, SPECTRA (INFRARED), ABSORPTION, DISPLACE, POLYMERIZATION, ORGANIC NITROGEN, AROMATIC COMPOUNDS.

Fabrication of mullite-bonded porous SiC ceramics from multilayer-coated SiC particles through sol-gel and in-situ polymerization techniques

NASA Astrophysics Data System (ADS)

Ebrahimpour, Omid

In this work, mullite-bonded porous silicon carbide (SiC) ceramics were prepared via a reaction bonding technique with the assistance of a sol-gel technique or in-situ polymerization as well as a combination of these techniques. In a typical procedure, SiC particles were first coated by alumina using calcined powder and alumina sol via a sol-gel technique followed by drying and passing through a screen. Subsequently, they were coated with the desired amount of polyethylene via an in-situ polymerization technique in a slurry phase reactor using a Ziegler-Natta catalyst. Afterward, the coated powders were dried again and passed through a screen before being pressed into a rectangular mold to make a green body. During the heating process, the polyethylene was burnt out to form pores at a temperature of about 500°C. Increasing the temperature above 800°C led to the partial oxidation of SiC particles to silica. At higher temperatures (above 1400°C) derived silica reacted with alumina to form mullite, which bonds SiC particles together. The porous SiC specimens were characterized with various techniques. The first part of the project was devoted to investigating the oxidation of SiC particles using a Thermogravimetric analysis (TGA) apparatus. The effects of particle size (micro and nano) and oxidation temperature (910°C--1010°C) as well as the initial mass of SiC particles in TGA on the oxidation behaviour of SiC powders were evaluated. To illustrate the oxidation rate of SiC in the packed bed state, a new kinetic model, which takes into account all of the diffusion steps (bulk, inter and intra particle diffusion) and surface oxidation rate, was proposed. Furthermore, the oxidation of SiC particles was analyzed by the X-ray Diffraction (XRD) technique. The effect of different alumina sources (calcined Al2O 3, alumina sol or a combination of the two) on the mechanical, physical, and crystalline structure of mullite-bonded porous SiC ceramics was studied in the second part of the project. Alumina sol was synthesized by the hydrolysis of Aluminum isopropoxide using the Yoldas method. Alumina sol was homogenous and had a needle-like shape with a thickness of 2--3 nm. Crystalline changes during the heating process of alumina sol were studied using XRD. In addition, Fourier transform infrared (FTIR) spectroscopy was performed to identify the functional groups on the alumina sol surface as a function of temperature. In the third part of the project, the feasibility of the in-situ polymerization technique was investigated to fabricate porous SiC ceramics. In this part, the mixture of SiC and calcined alumina powders were coated by polyethylene via in-situ polymerizing referred to as the polymerization compounding process in a slurry phase. The polymerization was conducted under very moderate operational conditions using the Ziegler-Natta catalyst system. Differential scanning calorimetry (DSC) and TGA analysis and morphological studies (SEM and TEM) revealed the presence of a high density of polyethylene on the surface of SiC and alumina powders. The amount of polymer was controlled by the polymerization reaction time. Most parts of particles were coated by a thin layer of polyethylene and polymer. The porous SiC ceramics, which were fabricated by these treated particles showed higher mechanical and physical properties compared to the samples made without any treatment. The relative intensity of mullite was higher compared to the samples prepared by the traditional process. The effects of the sintering temperature, forming pressure and polymer content were also studied on the physical and mechanical properties of the final product. In the last phase of this research work, the focus of the investigation was to take advantage of both the sol-gel processing and in-situ polymerization method to develop a new process to manufacture mullite-bonded porous SiC ceramic with enhanced mechanical and physical properties. Therefore, first the SiC particles and alumina nano powders were mixed in alumina sol to adjust the alumina weight to 35 wt%. Then, the desired amount of catalyst, which depends on the total surface area of the particles, was grafted onto the surface of the powders under an inert atmosphere. Consequently, the polymerization started from the surface of the substrate. The treated powders were characterized by SEM, XPS and TGA. In addition, the amount of pore-former was determined by TGA analysis. Porous SiC ceramics, which were fabricated by the novel process, consist of mullite, SiC, cristobalite and a small amount of alumina and TiO 2 as a result of reaction of TiCl4 with air. Furthermore, the effect of the sintering temperatures (1500°C, 1550°C and 1600°C) on the crystalline structure of the porous samples was investigated. Furthermore, it was proposed that converting TiCl4 to TiO2 acted as the sintering additive to form mullite at a lower sintering temperature. (Abstract shortened by UMI.).

Electrical Properties and Manufacturability of ITO-MgF2 and Related Transparent Arcproof Spacecraft Coatings

NASA Technical Reports Server (NTRS)

Hambourger, Paul D.

2003-01-01

To investigate the applicability of co-deposited indium tin oxide and magnesium fluoride as a transparent arcproof coating on the exterior of PowerSphere microsatellites. This included testing coating performance after deposition on flexible polymeric substrates, determining whether ultraviolet (UV) radiation present during deposition might affect the UV-curing resin contained in the substrate, and preparation of coated polymeric samples for radiation damage studies by the PowerSphere team.

Proton conducting membranes for high temperature fuel cells with solid state water free membranes

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Yen, Shiao-Pin S. (Inventor)

2006-01-01

A water free, proton conducting membrane for use in a fuel cell is fabricated as a highly conducting sheet of converted solid state organic amine salt, such as converted acid salt of triethylenediamine with two quaternized tertiary nitrogen atoms, combined with a nanoparticulate oxide and a stable binder combined with the converted solid state organic amine salt to form a polymeric electrolyte membrane. In one embodiment the membrane is derived from triethylenediamine sulfate, hydrogen phosphate or trifiate, an oxoanion with at least one ionizable hydrogen, organic tertiary amine bisulfate, polymeric quaternized amine bisulfate or phosphate, or polymeric organic compounds with quaternizable nitrogen combined with Nafion to form an intimate network with ionic interactions.

Interaction between a recombinant prion protein and organo-mineral complexes as evidenced by CPMAS 13C-NMR

NASA Astrophysics Data System (ADS)

Russo, F.; Scotti, R.; Gianfreda, L.; Conte, P.; Rao, M. A.

2009-04-01

Prion proteins (PrP) are the main responsible for Transmissible Spongiform Encephalopathies (TSE). The TSE etiological agent is a misfolded form of the normal cellular prion protein. The amyloidal aggregates accumulated in the brain of infected animals and mainly composed of PrPSc exhibit resistance to protease attack and many conventional inactivating procedures. The prion protein diseases cause an environmental issue because the environment and in particular the soil compartment can be contaminated and then become a potential reservoir and diffuser of TSEs infectivity as a consequence of (i) accidental dispersion from storage plants of meat and bone meal, (ii) incorporation of contaminated material in fertilizers, (iii) possible natural contamination of pasture soils by grazing herds, and (v) burial of carcasses. The environmental problem can be even more relevant because very low amounts of PrPSc are able to propagate the disease. Several studies evidenced that infectious prion protein remains active in soils for years. Contaminated soils result, thus, a possible critical route of TSE transmission in wild animals. Soil can also protect prion protein toward degradation processes due to the presence of humic substances and inorganic components such as clays. Mineral and organic colloids and the more common association between clay minerals and humic substances can contribute to the adsorption/entrapment of molecules and macromolecules. The polymerization of organic monomeric humic precursors occurring in soil in the presence of oxidative enzymes or manganese and iron oxides, is considered one of the most important processes contributing to the formation of humic substances. The process is very fast and produces a population of polymeric products of different molecular structures, sizes, shapes and complexity. Other molecules and possibly biomacromolecules such as proteins may be involved. The aim of the present work was to study by CPMAS 13C-NMR the interactions between a non pathogenic ovine recombinant prion protein and a model soil system represented by a manganese oxide in the form of birnessite (δ-MnO2), coated with a polymerized catechol. To better understand the effect of the polymerization process, PrP was added to the birnessite-cathecol system either before or after the polymerization processes. The NMR spectra of the prion protein interacting directly with birnessite revealed disappearance of the signals due to the paramagnetic nature of manganese oxide or abiotic degradation. Conversely, the signal pattern of the protein re-appeared as it is mixed to the soil-like system either during or after the catechol polymerization process. Results suggested that the possible interactions of the prion protein on soil systems can be mediated by natural organic matter. However, deeper studies on more complex real soil systems are needed to definitely confirm such hypothesis.

Iron oxide nanoparticle-based magnetic resonance method to monitor release kinetics from polymeric particles with high resolution.

PubMed

Chan, Minnie; Schopf, Eric; Sankaranarayanan, Jagadis; Almutairi, Adah

2012-09-18

A new method to precisely monitor rapid release kinetics from polymeric particles using super paramagnetic iron oxide nanoparticles, specifically by measuring spin-spin relaxation time (T(2)), is reported. Previously, we have published the formulation of logic gate particles from an acid-sensitive poly-β-aminoester ketal-2 polymer. Here, a series of poly-β-aminoester ketal-2 polymers with varying hydrophobicities were synthesized and used to formulate particles. We attempted to measure fluorescence of released Nile red to determine whether the structural adjustments could finely tune the release kinetics in the range of minutes to hours; however, this standard technique did not differentiate each release rate of our series. Thus, a new method based on encapsulation of iron oxide nanoparticles was developed, which enabled us to resolve the release kinetics of our particles. Moreover, the kinetics matched the relative hydrophobicity order determined by octanol-water partition coefficients. To the best of our knowledge, this method provides the highest resolution of release kinetics to date.

In Situ Polymerization and Characterization of Highly Conducting Polypyrrole Fish Scales for High-Frequency Applications

NASA Astrophysics Data System (ADS)

Velhal, Ninad B.; Patil, Narayan D.; Puri, Vijaya R.

2015-12-01

Polypyrrole (Ppy) thin films on alumina were synthesized by an in situ chemical oxidative polymerization method at 300 K with equal monomer-to-oxidant ratio. Fourier transform infrared spectroscopy (FTIR) and FT-Raman spectroscopy confirmed the formation of Ppy. A thickness-dependent change from cauliflower to fish-scale morphology was observed. Microwave properties such as transmission, reflection, shielding effectiveness, permittivity, and microwave conductivity are reported in the frequency range from 8 GHz to 12 GHz. The direct-current (DC) conductivity varied from 9.45 × 10-3 S/cm to 17.29 × 10-3 S/cm, whereas the microwave conductivity varied from 63.07 S/cm to 349.08 S/cm. The shielding effectiveness varied between 6.18 dB and 10.39 dB.

Fabrication of Graphene Oxide/Polypropylene Nanocomposites and Their Electrical Conductivity Study

NASA Astrophysics Data System (ADS)

Dong, Jinyong

2011-03-01

Graphene oxide (GO) /polypropylene nanocomposites were fabricated via in situ polymerizing propylene monomer over a GO that had been treated with a Grignard reagent and TiCl 4 successively when GO was not only catalytically activated but also largely reduced to an almost O- free state. The polymerization led to the in situ formation of the PP matrix, which was synchronized by the nanoscale exfoliation of the reduced GO as well as its gradual dispersion. Morphological examination of the ultimate GO/PP nanocomposites by TEM and SEM techniques revealed effective dispersion in nanoscale of GO in PP matrix. High electrical conductivity was discovered with thus prepared GO/PP nanocomposites, e.g. at a GO loading of 4.9 wt%, σc was measured at 0.3 S . m -1

Nanosized cancer cell-targeted polymeric immunomicelles loaded with superparamagnetic iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Sawant, Rishikesh M.; Sawant, Rupa R.; Gultepe, Evin; Nagesha, Dattatri; Papahadjopoulos-Sternberg, Brigitte; Sridhar, Srinivas; Torchilin, Vladimir P.

2009-10-01

Stable 30-50 nm polymeric polyethylene glycol-phosphatidylethanolamine (PEG-PE)-based micelles entrapping superparamagnetic iron oxide nanoparticles (SPION) have been prepared. At similar concentrations of SPION, the SPION-micelles had significantly better magnetic resonance imaging (MRI) T2 relaxation signal compared to `plain' SPION. Freeze-fracture electron microscopy confirmed SPION entrapment in the lipid core of the PEG-PE micelles. To enhance the targeting capability of these micelles, their surface was modified with the cancer cell-specific anti-nucleosome monoclonal antibody 2C5 (mAb 2C5). Such mAb 2C5-SPION immunomicelles demonstrated specific binding with cancer cells in vitro and were able to bring more SPION to the cancer cells thus demonstrating the potential to be used as targeted MRI contrast agents for tumor imaging.

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, M.S.; Saunders, R.

1997-02-18

Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

End-functionalized ROMP polymers for Biomedical Applications

PubMed Central

Madkour, Ahmad E.; Koch, Amelie H. R.; Lienkamp, Karen; Tew, Gregory N.

2010-01-01

We present two novel allyl-based terminating agents that can be used to end-functionalize living polymer chains obtained by ring-opening metathesis polymerization (ROMP) using Grubbs’ third generation catalyst. Both terminating agents can be easily synthesized and yield ROMP polymers with stable, storable activated ester groups at the chain-end. These end-functionalized ROMP polymers are attractive building blocks for advanced polymeric materials, especially in the biomedical field. Dye-labeling and surface-coupling of antimicrobially active polymers using these end-groups were demonstrated. PMID:21499549

Antibacterial Drug Releasing Materials by Post-Polymerization Surface Modification

NASA Astrophysics Data System (ADS)

Chng, Shuyun; Moloney, Mark G.; Wu, Linda Y. L.

Functional materials are available by the post-polymerization surface modification of diverse polymers in a three-step process mediated, firstly, by carbene insertion chemistry, secondly, by diazonium coupling, and thirdly by modification with a remotely tethered spiropyran unit, and these materials may be used for the reversible binding and release of Penicillin V. Surface loading densities of up to 0.19mmol/g polymer are achievable, leading to materials with higher loading densities and release behavior relative to unmodified controls, and observable antibacterial biocidal activity.

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, Michael S.; Saunders, Randall

1997-01-01

Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

Synthesis of nanostructured bio-related materials by hybridization of synthetic polymers with polysaccharides or saccharide residues.

PubMed

Kaneko, Yoshiro; Kadokawa, Jun-Ichi

2006-01-01

In the first part of this review, we describe the synthesis of nanostructured hybrid materials composed of polysaccharides and synthetic polymers. Amylose-synthetic polymer inclusion complexes were synthesized by amylose-forming polymerization using phosphorylase enzyme in the presence of synthetic polymers such as polyethers and polyesters. Alginate-polymethacrylate hybrid materials were prepared by free-radical polymerization of cationic methacrylate in the presence of sodium alginate. These methods allow the simultaneous control of the nanostructure with polymerization, giving well-defined hybrid materials. In the second part of this review, we describe the synthesis of novel glycopolymers with rigid structures. Polyaniline-based glycopolymers were synthesized by means of oxidative polymerization of N-glycosylaniline. Polysiloxane-based glycopolymers were prepared by means of introduction of sugar-lactone to the rodlike polysiloxane. These glycopolymers had regular higher-ordered structures due to their rigid polymer backbones, resulting in control of the three-dimensional array of sugar-residues.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li Hong.

A new technique was developed and demonstrated for combining carbon fibers with aromatic thermoplastic matrices to form a high-quality towpreg. The developed technique utilizes an in-situ electrochemical process (Electrochemical polymerization - ECP) to create the entire polymer matrix surrounding the fiber array by direct polymerization of monomer. Poly-paraxylylene (PPX) and derivatives are successfully polymerized in-situ on carbon fiber surfaces through ECP. A PPX/carbon-fiber towpreg with 40 vol % of matrix is achieved in a fairly short reaction time with a high polymer-coating efficiency. Vapor deposition polymerization (VDP) was also studied. PPX and carbon-fiber towpreg were made successfully by this process.more » A comparison between ECP and VDP was conducted. A study on electrochemical oxidation (ECO) of carbon fibers was also performed. The ECO treatment may be suitable for carbon fibers incorporated in composites with high-temperature curing resins and thermoplastic matrices.« less

Advanced analysis of polymer emulsions: Particle size and particle size distribution by field-flow fractionation and dynamic light scattering.

PubMed

Makan, Ashwell C; Spallek, Markus J; du Toit, Madeleine; Klein, Thorsten; Pasch, Harald

2016-04-15

Field flow fractionation (FFF) is an advanced fractionation technique for the analyses of very sensitive particles. In this study, different FFF techniques were used for the fractionation and analysis of polymer emulsions/latexes. As model systems, a pure acrylic emulsion and emulsions containing titanium dioxide were prepared and analyzed. An acrylic emulsion polymerization was conducted, continuously sampled from the reactor and subsequently analyzed to determine the particle size, radius of gyration in specific, of the latex particles throughout the polymerization reaction. Asymmetrical flow field-flow fractionation (AF4) and sedimentation field-flow fractionation (SdFFF), coupled to a multidetector system, multi-angle laser light scattering (MALLS), ultraviolet (UV) and refractive index (RI), respectively, were used to investigate the evolution of particle sizes and particle size distributions (PSDs) as the polymerization progressed. The obtained particle sizes were compared against batch-mode dynamic light scattering (DLS). Results indicated differences between AF4 and DLS results due to DLS taking hydration layers into account, whereas both AF4 and SdFFF were coupled to MALLS detection, hence not taking the hydration layer into account for size determination. SdFFF has additional separation capabilities with a much higher resolution compared to AF4. The calculated radii values were 5 nm larger for SdFFF measurements for each analyzed sample against the corresponding AF4 values. Additionally a low particle size shoulder was observed for SdFFF indicating bimodality in the reactor very early during the polymerization reaction. Furthermore, different emulsions were mixed with inorganic species used as additives in cosmetics and coatings such as TiO2. These complex mixtures of species were analyzed to investigate the retention and particle interaction behavior under different AF4 experimental conditions, such as the mobile phase. The AF4 system was coupled online to inductively coupled plasma mass spectrometry (ICP-MS) for elemental speciation and identification of the inorganic additive. SdFFF had a larger separation power to distinguish different particle size populations whereas AF4 had the capability of separating the organic particles and inorganic TiO2 particles, with high resolution. Copyright © 2016 Elsevier B.V. All rights reserved.

Covalent coupling via dehalogenation on Ni(111) supported boron nitride and graphene.

PubMed

Morchutt, Claudius; Björk, Jonas; Krotzky, Sören; Gutzler, Rico; Kern, Klaus

2015-02-11

Polymerization of 1,3,5-tris(4-bromophenyl)benzene via dehalogenation on graphene and hexagonal boron nitride is investigated by scanning tunneling microscopy experiments and density functional theory calculations. This work reveals how the interactions between molecules and graphene or h-BN grown on Ni(111) govern the surface-confined synthesis of polymers through C-C coupling.

Electrochromic material and electro-optical device using same

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1992-01-01

An oxidatively coloring electrochromic layer of composition M.sub.y CrO.sub.2+x (0.33.ltoreq.y.ltoreq.2.0 and x.ltoreq.2) where M=Li, Na or K with improved transmittance modulation, improved thermal and environmental stability, and improved resistance to degradation in organic liquid and polymeric electrolytes. The M.sub.y CrO.sub.2+x provides complementary optical modulation to cathodically coloring materials in thin-film electrochromic glazings and electrochromic devices employing polymeric Li.sup.+ ion conductors.

Electrochromic material and electro-optical device using same

DOEpatents

Cogan, S.F.; Rauh, R.D.

1992-01-14

An oxidatively coloring electrochromic layer of composition M[sub y]CrO[sub 2+x] (0.33[le]y[le]2.0 and x[le]2) where M=Li, Na or K with improved transmittance modulation, improved thermal and environmental stability, and improved resistance to degradation in organic liquid and polymeric electrolytes. The M[sub y]CrO[sub 2+x] provides complementary optical modulation to cathodically coloring materials in thin-film electrochromic glazings and electrochromic devices employing polymeric Li[sup +] ion conductors. 12 figs.

Creation of high-refractive-index amorphous titanium oxide thin films from low-fractal-dimension polymeric precursors synthesized by a sol-gel technique with a hydrazine monohydrochloride catalyst.

PubMed

Shimizu, Wataru; Nakamura, Satoshi; Sato, Takaaki; Murakami, Yasushi

2012-08-21

Amorphous titanium dioxide (TiO(2)) thin films exhibiting high refractive indices (n ≈ 2.1) and high transparency were fabricated by spin-coating titanium oxide liquid precursors having a weakly branched polymeric structure. The precursor solution was prepared from titanium tetra-n-butoxide (TTBO) via the catalytic sol-gel process with hydrazine monohydrochloride used as a salt catalyst, which serves as a conjugate acid-base pair catalyst. Our unique catalytic sol-gel technique accelerated the overall polycondensation reaction of partially hydrolyzed alkoxides, which facilitated the formation of liner polymer-like titanium oxide aggregates having a low fractal dimension of ca. (5)/(3), known as a characteristic of the so-called "expanded polymer chain". Such linear polymeric features are essential to the production of highly dense amorphous TiO(2) thin films; mutual interpenetration of the linear polymeric aggregates avoided the creation of void space that is often generated by the densification of high-fractal-dimension (particle-like) aggregates produced in a conventional sol-gel process. The mesh size of the titanium oxide polymers can be tuned either by water concentration or the reaction time, and the smaller mesh size in the liquid precursor led to a higher n value of the solid thin film, thanks to its higher local electron density. The reaction that required no addition of organic ligand to stabilize titanium alkoxides was advantageous to overcoming issues from organic residues such as coloration. The dense amorphous film structure suppressed light scattering loss owing to its extremely smooth surface and the absence of inhomogeneous grains or particles. Furthermore, the fabrication can be accomplished at a low heating temperature of <80 °C. Indeed, we successfully obtained a transparent film with a high refractive index of n = 2.064 (at λ = 633 nm) on a low-heat-resistance plastic, poly(methyl methacrylate), at 60 °C. The result offers an efficient route to high-refractive-index amorphous TiO(2) films as well as base materials for a wider range of applications.

Compositions and methods for adoptive and active immunotherapy

DOEpatents

Fahmy, Tarek; Steenblock, Erin

2014-01-14

Modular aAPCs and methods of their manufacture and use are provided. The modular aAPCs are constructed from polymeric microparticles. The aAPCs include encapsulated cytokines and coupling agents which modularly couple functional elements including T cell receptor activators, co-stimulatory molecules and adhesion molecules to the particle. The ability of these aAPCs to release cytokines in a controlled manner, coupled with their modular nature and ease of ligand attachment, results in an ideal, tunable APC capable of stimulating and expanding primary T cells.

Modeling Lignin Polymerization. I. Simulation Model of Dehydrogenation Polymers1[OA

PubMed Central

van Parijs, Frederik R.D.; Morreel, Kris; Ralph, John; Boerjan, Wout; Merks, Roeland M.H.

2010-01-01

Lignin is a heteropolymer that is thought to form in the cell wall by combinatorial radical coupling of monolignols. Here, we present a simulation model of in vitro lignin polymerization, based on the combinatorial coupling theory, which allows us to predict the reaction conditions controlling the primary structure of lignin polymers. Our model predicts two controlling factors for the β-O-4 content of syringyl-guaiacyl lignins: the supply rate of monolignols and the relative amount of supplied sinapyl alcohol monomers. We have analyzed the in silico degradability of the resulting lignin polymers by cutting the resulting lignin polymers at β-O-4 bonds. These are cleaved in analytical methods used to study lignin composition, namely thioacidolysis and derivatization followed by reductive cleavage, under pulping conditions, and in some lignocellulosic biomass pretreatments. PMID:20472753

Preparation of inulin-type fructooligosaccharides using fast protein liquid chromatography coupled with refractive index detection.

PubMed

Li, J; Cheong, K L; Zhao, J; Hu, D J; Chen, X Q; Qiao, C F; Zhang, Q W; Chen, Y W; Li, S P

2013-09-20

A fast protein liquid chromatography coupled with refractive index detection (FPLC-RID) method was firstly developed for preparation and purification of fructooligosaccharides with different degree of polymerization from burdock, Arctium lappa. After extraction with 60% ethanol and decolorization with MCI gel CHP20P, total fructooligosaccharides were purified on Bio-Gel P-2 column eluted with water at the flow rate of 0.3 ml/min, which was the optimized conditions. The obtained fructooligosaccharides with degree of polymerization of 3-9 were identified based on their methylation analysis, MS and NMR data. This method has the advantages of high automation, good recovery and easy performance, which could be used for preparation of FOS from other sources, as well as other targeted compounds without UV absorbance. Copyright © 2013 Elsevier B.V. All rights reserved.

Controlled Pd(0)/t Bu3P Catalyzed Suzuki Cross-Coupling Polymerization of AB-Type Monomers with ArPd(t Bu3P)X or Pd2(dba)3/t Bu3P/ArX as the Initiator

DOE PAGES

Zhang, Honghai; Xing, Chun-Hui; Hu, Qiao-Sheng; ...

2015-02-05

The synthesis of well-defined and functionalized conjugated polymers, which are essential in the development of efficient organic electronics, through Suzuki cross-coupling polymerizations has been a challenging task. We developed controlled Pd(0)/t-Bu3P-catalyzed Suzuki cross-coupling polymerizations of AB-type monomers via the chain-growth mechanism with a series of in situ generated ArPd(t-Bu3P)X (X = I, Br, Cl) complexes as initiators. Among them, the combinations of Pd2(dba)3/t-Bu3P/p-BrC6H4I, Pd2(dba)3/t-Bu3P/p-BrC6H4CH2OH and Pd2(dba)3/t-Bu3P/p-PhCOC6H4Br were identified as highly robust initiator systems, resulting in polymers with predictable molecular weight and narrow polydispersity (PDI~1.13-1.20). In addition, Pd2(dba)3/t-Bu3P/p-BrC6H4CH2OH and Pd2(dba)3/t-Bu3P/p-PhCOC6H4Br initiator systems afforded functional polymers with >95% fidelity. Our results pavedmore » the road to access well-defined conjugated polymers, including conjugated polymers with complex polymer architectures such as block copolymers and branch copolymers.« less

Surface functionalization of a polymeric lipid bilayer for coupling a model biological membrane with molecules, cells, and microstructures.

PubMed

Morigaki, Kenichi; Mizutani, Kazuyuki; Saito, Makoto; Okazaki, Takashi; Nakajima, Yoshihiro; Tatsu, Yoshiro; Imaishi, Hiromasa

2013-02-26

We describe a stable and functional model biological membrane based on a polymerized lipid bilayer with a chemically modified surface. A polymerized lipid bilayer was formed from a mixture of two diacetylene-containing phospholipids, 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine (DiynePC) and 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphoethanolamine (DiynePE). DiynePC formed a stable bilayer structure, whereas the ethanolamine headgroup of DiynePE enabled functional molecules to be grafted onto the membrane surface. Copolymerization of DiynePC and DiynePE resulted in a robust bilayer. Functionalization of the polymeric bilayer provided a route to a robust and biomimetic surface that can be linked with biomolecules, cells, and three-dimensional (3D) microstructures. Biotin and peptides were grafted onto the polymeric bilayer for attaching streptavidin and cultured mammalian cells by molecular recognition, respectively. Nonspecific adsorption of proteins and cells on polymeric bilayers was minimum. DiynePE was also used to attach a microstructure made of an elastomer (polydimethylsiloxan: PDMS) onto the membrane, forming a confined aqueous solution between the two surfaces. The microcompartment enabled us to assay the activity of a membrane-bound enzyme (cyochrome P450). Natural (fluid) lipid bilayers were incorporated together with membrane-bound proteins by lithographically polymerizing DiynePC/DiynePE bilayers. The hybrid membrane of functionalized polymeric bilayers and fluid bilayers offers a novel platform for a wide range of biomedical applications including biosensor, bioassay, cell culture, and cell-based assay.

Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: coupling of primary amines and cyanation of tertiary amines.

PubMed

Liu, Lianghui; Wang, Zikuan; Fu, Xuefeng; Yan, Chun-Hua

2012-11-16

In the presence of a catalytic amount of radical initiator AIBN, primary amines are oxidatively coupled to imines and tertiary amines are cyanated to α-aminonitriles. These "metal-free" aerobic oxidative coupling reactions may find applications in a wide range of "green" oxidation chemistry.

Temperature-dependent charge transport mechanisms in carbon sphere/polyaniline composite

NASA Astrophysics Data System (ADS)

Nieves, Cesar A.; Martinez, Luis M.; Meléndez, Anamaris; Ortiz, Margarita; Ramos, Idalia; Pinto, Nicholas J.; Zimbovskaya, Natalya

2017-12-01

Charge transport in the temperature range 80 K < T < 300 K was studied in a composite of carbon spheres (CS), prepared via hydrothermal carbonization of sucrose, and the conducting polymer polyaniline (PANi). PANi was synthesized via the oxidative polymerization of aniline with ammonium peroxydisulfate (APS) in acidic media. The CS/PANi composite was prepared by coating the spheres with a thin polyaniline (PANi) film doped with hydrochloric acid (HCl) in situ during the polymerization process. Temperature dependent conductivity measurements show that three dimensional variable range hopping of electrons between polymeric chains in PANi-filled gaps between CS is the predominant transport mechanism through CS/PANi composites. The high conductivity of the CS/PANi composite makes the material attractive for the fabrication of devices and sensors.

Inorganic and organic structures as interleavers among [bis(1-methyl-3-(p-carboxylatephenyl)triazenide 1-oxide)Ni(II)] complexes to form supramolecular arrangements

NASA Astrophysics Data System (ADS)

Santos, Aline Joana Rolina Wohlmuth Alves; dos Santos Hackbart, Helen Cristina; Giacomini, Gabriela Xavier; Bersch, Patrícia; Paraginski, Gustavo Luiz; Hörner, Manfredo

2016-12-01

Alternative compounds to capture metal ions are triazenes 1-oxide since they are basic compounds O(N) with negative charge in the deprotonated form. The proximity of both coordination sites (O and N) enables these compounds to have good chelating ability and a tendency to stabilize in the formation of rings with soft and hard transition metal ions. The structure analysis by single crystal X-ray diffraction of compounds (1) and (2) demonstrate the formation of 3D supramolecular arrangements through ion-ion, ion-dipolo and dipolo-dipolo interactions. In one of them, there are [(H2O)2(CH3CH3SO)K2]2+ as linkers of polymerization and, in another complex, there are [(H2O)(CH3CH3SO)Ni(H2O)6]2+ as a linker of polymerization. These linkers act in the polymerization of the novel mononuclear complex [bis(1-methyl (p-carboxylatephenyl) triazenide 1-oxide) NiII] (3). The crystallography analysis of (1) and (2) showed distorted quadratic geometry for Ni (II), thus, there are two axial positions available in Ni (II) to be used in catalysis studies and as sensor or biosensor. In addition, this study shows the support of this novel mononuclear complex of Ni (II) (3) on protonated chitosan chains (4). The compounds (3) and (4) were characterized by spectroscopic analysis, infrared (IR) and energy dispersive X-ray detector (EDS), and by differential scanning calorimetry analysis (DSC). The specificity of ligand 1-methyl (p-carboxyphenyl) triazene 1-oxide to capture potassium and nickel ions will be tested at different pH values, as well as the capacity of the triazenide 1-oxide of Ni (II) complex, supported on chitosan polymer, or not, to act as a catalyst for organic reactions and biomimetic organic reactions.

Flexible diode of polyaniline/ITO heterojunction on PET substrate

NASA Astrophysics Data System (ADS)

Bera, A.; Deb, K.; Kathirvel, V.; Bera, T.; Thapa, R.; Saha, B.

2017-10-01

Hybrid organic-inorganic heterojunction between polyaniline and ITO film coated on flexible polyethylene terephthalate (PET) substrate has been prepared through vapor phase polymerization process. Polaron and bipolaron like defect states induced hole transport and exceptional mobility makes polyaniline a noble hole transport layer. Thus a p-n junction has been obtained between the hole transport layer of polyaniline and highly conductive n-type layer of ITO film. The synthesis process was carried out using FeCl3 as polymerizing agent in the oxidative chemical polymerization process. The prepared polyaniline has been found to be crystalline on characterization through X-ray diffraction measurement. X-ray photoelectron spectroscopic measurements were done for compositional analysis of the prepared film. The UV-vis-NIR absorbance spectra obtained for polyaniline shows the characteristics absorbance as observed for highly conductive polyaniline and confirms the occurrence of partially oxidized emeraldine form of polyaniline. The energy band gap of the polyaniline has been obtained as 2.52 eV, by analyzing the optical transmittance spectra. A rectifying behavior has been observed in the electrical J-V plot, which is of great significance in designing polymer based flexible electronic devices.

Polythioether Particles Armored with Modifiable Graphene Oxide Nanosheets.

PubMed

Rodier, Bradley J; Mosher, Eric P; Burton, Spencer T; Matthews, Rachael; Pentzer, Emily

2016-06-01

Facile and scalable fabrication methods are attractive to prepare materials for diverse applications. Herein, a method is presented to prepare cross-linked polymeric nanoparticles with graphene oxide (GO) nanosheets covalently attached to the surface. Alkene-modified GO serves as a surfactant in a miniemulsion polymerization, and the alkene functionalities of GO exposed to the oil-phase are incorporated into the polymer particle through thiol-ene reactions, leaving the unreacted alkene functional groups of the other face of GO available for further functionalization. The surface of GO-armored polymer particles is then modified with a small molecule fluorophore or carboxylic acid functional groups that bind to Fe2 O3 and TiO2 nanoparticles. This methodology provides a facile route to preparing complex hybrid composite materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multifunctional polymeric micelles loaded with doxorubicin and poly(dithienyl-diketopyrrolopyrrole) for near-infrared light-controlled chemo-phototherapy of cancer cells.

PubMed

Liu, Hui; Wang, Kai; Yang, Cangjie; Huang, Shuo; Wang, Mingfeng

2017-09-01

Polymeric micelles loaded with multiple therapeutic modalities are important to overcome challenges such as drug resistance and improve the therapeutic efficacy. Here we report a new polymer micellar drug carrier that integrates chemotherapy and photothermal therapy in a single platform. Specifically, a narrow bandgap poly(dithienyl-diketopyrrolopyrrole) (PDPP) polymer was encapsulated together with a model anticancer drug doxorubicin (DOX) in the hydrophobic cores of polymeric micelles formed by Pluronic F127, an amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer. The PDPP polymer served as an organic photothermal agent that absorbs near-infrared light (700-1000nm) and transforms into heat efficiently. The dual functional micelles co-loaded with PDPP and DOX in the hydrophobic compartment showed good colloidal stability after being stored at 4°C at least over two months, and remained visibly stable after 808-nm laser irradiation. The loaded DOX had negligible effect on the size and photothermal property of the micelles. The release of DOX from the micelles could be enhanced by the "breathing" effect of shrinking/swelling of the micelles induced by the temperature change, owing to the thermosensitive nature of the F127 polymers. Importantly, the ternary F127/PDPP/DOX micelles under 808-nm laser irradiation showed enhanced cytotoxicity against cancer cells such as HeLa cells, compared to F127 micelles containing single modality of either PDPP or DOX only. Copyright © 2017 Elsevier B.V. All rights reserved.

Injectible bodily prosthetics employing methacrylic copolymer gels

DOEpatents

Mallapragada, Surya K.; Anderson, Brian C.

2007-02-27

The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol) methyl ether polymer.

pH-sensitive methacrylic copolymer gels and the production thereof

DOEpatents

Mallapragada, Surya K [Ames, IA; Anderson, Brian C [Lake Bluff, IA

2007-05-15

The present invention provides novel gel forming methacrylic blocking copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol)methyl ether polymer. The polymers may be used for drug and gene delivery, protein separation, as structural supplements, and more.

Self-sorting of dynamic metallosupramolecular libraries (DMLs) via metal-driven selection.

PubMed

Kocsis, Istvan; Dumitrescu, Dan; Legrand, Yves-Marie; van der Lee, Arie; Grosu, Ion; Barboiu, Mihail

2014-03-11

"Metal-driven" selection between finite mononuclear and polymeric metallosupramolecular species can be quantitatively achieved in solution and in a crystalline state via coupled coordination/stacking interactional algorithms within dynamic metallosupramolecular libraries - DMLs.

Anchoring ceria nanoparticles on graphene oxide and their radical scavenge properties under gamma irradiation environment.

PubMed

Xia, Wei; Zhao, Jun; Wang, Tao; Song, Li; Gong, Hao; Guo, Hu; Gao, Bing; Fan, Xiaoli; He, Jianping

2017-06-28

Polymer networks such as those of epoxy resin, as common protection materials, possess radiolytic oxidation degradation effects under gamma irradiation environment, which have a great accelerating effect on the ageing rate and severely limit their potential applications for metal protection in the nuclear industry. To overcome this, we report a simple scheme of anchoring crystalline ceria nanoparticles onto graphene sheets (CG) and incorporate it into the epoxy resin, followed by thermal polymerization to obtain CeO 2 /graphene-epoxy nanocomposite coating (CGNS). We had proven that graphene might act as "interwalls" in the epoxy matrix, which will result in space location-obstruct effect as well as absorb the radicals induced by γ-ray irradiation. Moreover, owing to the interconversion of cerium ions between their +3 and +4 states coupled with the formation of oxygen vacancy defects, electron spin resonance (ESR) detection shows that CeO 2 /graphene (CG) could act as a preferable radical scavenger and achieve better performance in trapping radicals than single graphene based composite. Electrochemical data strongly demonstrate that CeO 2 /graphene is capable of maintaining the anti-corrosion properties under gamma irradiation environment. Therefore, the designed hybrid CeO 2 /graphene-epoxy composite can be considered as potential candidates for protective coatings in nuclear industry.

Polyacrylonitrile-Derived Sponge-Like Micro/Macroporous Carbon for Selective CO2 Separation.

PubMed

Guo, Li-Ping; Hu, Qing-Tao; Zhang, Peng; Li, Wen-Cui; Lu, An-Hui

2018-06-12

CO 2 capture under a dynamical flow situation requires adsorbents possessing balanced proportion of macropores as diffusion path and micropores as adsorption reservoir. However, the construction of interconnected micro-/macropores structure coupled with abundant nitrogen species into one carbon skeleton remains a challenge. Here, we report a new approach to prepare sponge-like carbon with a well-developed micro-/macroporous structure and enriched nitrogen species through aqueous phase polymerization of acrylonitrile in the presence of graphene oxide. The tension stress caused by the uniform thermal shrinkage of polyacrylonitrile during the pyrolysis together with the favorable flexibility of graphene oxide sheets are responsible for the formation of the sponge-like morphology. The synergistic effect of micro-/macroporous framework and rich CO 2 -philic site enables such carbon to decrease resistance to mass transfer and show high CO 2 dynamic selectivity over N 2 (454) and CH 4 (11), as well as good CO 2 capacity at 298 K under low CO 2 partial pressure (0.17 bar, a typical CO 2 partial pressure in flue gas). The above attributes make this porous carbon a promising candidate for CO 2 capture from flue gas, methane sources and other relevant applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coherent photoluminescence excitation spectroscopy of semicrystalline polymeric semiconductors

NASA Astrophysics Data System (ADS)

Silva, Carlos; Grégoire, Pascal; Thouin, Félix

In polymeric semiconductors, the competition between through-bond (intrachain) and through-space (interchain) electronic coupling determines two-dimensional spatial coherence of excitons. The balance of intra- and interchain excitonic coupling depends very sensitively on solid-state microstructure of the polymer film (polycrystalline, semicrystalline with amorphous domains, etc.). Regioregular poly(3-hexylthiophene) has emerged as a model material because its photoluminescence (PL) spectral lineshape reveals intricate information on the magnitude of excitonic coupling, the extent of energetic disorder, and on the extent to which the disordered energy landscape is correlated. I discuss implementation of coherent two-dimensional electronic spectroscopy. We identify cross peaks between 0-0 and 0-1 excitation peaks, and we measure their time evolution, which we interpret within the context of a hybrid HJ aggregate model. By measurement of the homogeneous linewidth in diverse polymer microstructures, we address the nature of optical transitions within such hynbrid aggregate model. These depend strongly on sample processing, and I discuss the relationship between microstructure, steady-state absorption and PL spectral lineshape, and 2D coherent PL excitation spectral lineshapes.

Enzymatic Browning in Sugar Beet Leaves (Beta vulgaris L.): Influence of Caffeic Acid Derivatives, Oxidative Coupling, and Coupled Oxidation.

PubMed

Vissers, Anne; Kiskini, Alexandra; Hilgers, Roelant; Marinea, Marina; Wierenga, Peter Alexander; Gruppen, Harry; Vincken, Jean-Paul

2017-06-21

Sugar beet (Beta vulgaris L.) leaves of 8 month (8 m ) plants showed more enzymatic browning than those of 3 month (3 m ). Total phenolic content increased from 4.6 to 9.4 mg/g FW in 3 m and 8 m , respectively, quantitated by reverse-phase-ultrahigh-performance liquid chromatography-ultraviolet-mass spectrometry (RP-UHPLC-UV-MS). The PPO activity was 6.7 times higher in extracts from 8 m than from 3 m leaves. Substrate content increased from 0.53 to 2.45 mg/g FW in 3 m and 8 m , respectively, of which caffeic acid glycosyl esters were most important, increasing 10-fold with age. Caffeic acid glycosides and vitexin derivatives were no substrates. In 3 m and 8 m, nonsubstrate-to-substrate ratios were 8:1 and 3:1, respectively. A model system showed browning at 3:1 ratio due to formation of products with extensive conjugated systems through oxidative coupling and coupled oxidation. The 8:1 ratio did not turn brown as oxidative coupling occurred without much coupled oxidation. We postulate that differences in nonsubstrate-to-substrate ratio and therewith extent of coupled oxidation explain browning.

Enzymatic Browning in Sugar Beet Leaves (Beta vulgaris L.): Influence of Caffeic Acid Derivatives, Oxidative Coupling, and Coupled Oxidation

PubMed Central

2017-01-01

Sugar beet (Beta vulgaris L.) leaves of 8 month (8m) plants showed more enzymatic browning than those of 3 month (3m). Total phenolic content increased from 4.6 to 9.4 mg/g FW in 3m and 8m, respectively, quantitated by reverse-phase-ultrahigh-performance liquid chromatography–ultraviolet-mass spectrometry (RP-UHPLC–UV-MS). The PPO activity was 6.7 times higher in extracts from 8m than from 3m leaves. Substrate content increased from 0.53 to 2.45 mg/g FW in 3m and 8m, respectively, of which caffeic acid glycosyl esters were most important, increasing 10-fold with age. Caffeic acid glycosides and vitexin derivatives were no substrates. In 3m and 8m, nonsubstrate-to-substrate ratios were 8:1 and 3:1, respectively. A model system showed browning at 3:1 ratio due to formation of products with extensive conjugated systems through oxidative coupling and coupled oxidation. The 8:1 ratio did not turn brown as oxidative coupling occurred without much coupled oxidation. We postulate that differences in nonsubstrate-to-substrate ratio and therewith extent of coupled oxidation explain browning. PMID:28570816

Analysis of the control structures for an integrated ethanol processor for proton exchange membrane fuel cell systems

NASA Astrophysics Data System (ADS)

Biset, S.; Nieto Deglioumini, L.; Basualdo, M.; Garcia, V. M.; Serra, M.

The aim of this work is to investigate which would be a good preliminary plantwide control structure for the process of Hydrogen production from bioethanol to be used in a proton exchange membrane (PEM) accounting only steady-state information. The objective is to keep the process under optimal operation point, that is doing energy integration to achieve the maximum efficiency. Ethanol, produced from renewable feedstocks, feeds a fuel processor investigated for steam reforming, followed by high- and low-temperature shift reactors and preferential oxidation, which are coupled to a polymeric fuel cell. Applying steady-state simulation techniques and using thermodynamic models the performance of the complete system with two different control structures have been evaluated for the most typical perturbations. A sensitivity analysis for the key process variables together with the rigorous operability requirements for the fuel cell are taking into account for defining acceptable plantwide control structure. This is the first work showing an alternative control structure applied to this kind of process.

Well-defined flake-like polypyrrole grafted graphene nanosheets composites as electrode materials for supercapacitors with enhanced cycling stability

NASA Astrophysics Data System (ADS)

Wang, Xue; Wang, Tingmei; Yang, Chao; Li, Haidong; Liu, Peng

2013-12-01

Well-defined flake-like polypyrrole grafted graphene nanosheets composites (PPy-g-GNS) were fabricated by the in-situ chemical oxidative grafting polymerization of pyrrole in the presence of the 4-aminophenyl modified graphene nanosheets (AP-GNS), which were prepared via the coupling reaction of the graphene nanosheets (GNS) with diazonium salt. The flake-like PPy-g-GNS composite showed the high conductivity at room temperature. A maximum discharge capacitance of 191.2 F/g at the scan rate of 10 mV/s could be achieved in the three-electrode cell electrochemical testing in 1.0 mol/L NaNO3 electrolyte solution. It is higher than those of the AP-GNS, pure PPy, and the GNS/PPy composite prepared with the unmodified graphene nanosheets (GNS). The flake-like PPy-g-GNS composites also exhibited the excellent electrochemical stability even after 1000 cycles. It revealed the synergistic effect between the conducting polymer and the carbon-based support.

Cellulose-coupled graphene/polypyrrole composite electrodes containing conducting networks built by carbon fibers as wearable supercapacitors with excellent foldability and tailorability

NASA Astrophysics Data System (ADS)

Lyu, Shaoyi; Chang, Huanjun; Fu, Feng; Hu, La; Huang, Jingda; Wang, Siqun

2016-09-01

A paper-based wearable supercapacitor with excellent foldability and tailorability is fabricated from a chopped carbon fiber (CCF)-reinforced cellulose paper electrode material by coating with reduced graphene oxide (RGO) and polypyrrole (PPy) via in situ polymerization. The CCFs not only form an interpenetrating conducting network that acts as highly conductive electron transfer highways for the RGO/PPy layer in the paper electrode, but also endow the resulting electrode with an excellent areal capacitance of 363 mF cm-2 and a volumetric energy density of 0.28 mW h cm-3. Further, the CCFs give the electrode remarkable mechanical robustness, guaranteeing foldability and tailorability, with only slight loss of capacitance after repeated folding 600 times. Even after being subjected to severe cut-in fracture, the capacitance retention is up to 84%, indicating outstanding damage tolerance. The present study reveals a promising candidate for flexible wearable energy storage devices that are required to function in harsh environments.

Hierarchically Structured Electrospun Fibers

DTIC Science & Technology

2013-01-07

polymeric materials such as ceramics and metals, can be fabricated into nanofibers via electrospinning . An assortment of natural polymers, such as the...are traditionally made by electrospinning of the core material, which serves as a template for the deposition of the shell layer via chemical vapor...been made from the contraction of a manganese oxide sol gel upon solvent evaporation, as well as from zinc oxide and silicon dioxide using vapor

High-Voltage Polymers for High-Power Supercapacitors. Version 1

DTIC Science & Technology

2006-05-30

affect the supercapacitor’s performance. Subsequently, our efforts focused on fabricating polymers with high oxidation potentials to increase the power...including spin activation with out significant modifications. Electroactive polymers such as polythiophene, polyacetylene, or polyaniline can be...potentials in excess of 2 V for facile polymerization. In the present case, the triaryl ammine functionality of 2 and 3 is oxidized at the low

Marine Exposure of Preservative-Treated Small Wood Panels.

DTIC Science & Technology

1984-10-01

oxide (table 5) are unattacked after 5-1/2 years. Impregnation with tributyltin ( TBT ) oxide (table 6-1), TBT -modified methacrylate polymers (table 6...1), or TBT - modified monomers (with subsequent polymerization) (tables 6-2, 6-3) has prevented borer damage for 6 to 6-112 years. Methacrylates...copper zinc 5 arsenate 3-10 Polymers Prepolymerized tributyltin Dual treatments methacrylate and Chromated copper methyl methacrylate arsenate (B

Self-assembly and graft polymerization route to Monodispersed Fe3O4@SiO2--polyaniline core-shell composite nanoparticles: physical properties.

PubMed

Reddy, Kakarla Raghava; Lee, Kwang-Pill; Kim, Ju Young; Lee, Youngil

2008-11-01

This study describes the synthesis of monodispersed core-shell composites of silica-modified magnetic nanoparticles and conducting polyaniline by self-assembly and graft polymerization. Magnetic ferrite nanoparticles (Fe3O4) were prepared by coprecipitation of Fe+2 and Fe+3 ions in alkaline solution, and then silananized. The silanation of magnetic particles (Fe3O4@SiO2) was carried out using 3-bromopropyltrichlorosilane (BPTS) as the coupling agent. FT-IR spectra indicated the presence of Fe--O--Si chemical bonds in Fe3O4@SiO2. Core-shell type nanocomposites (Fe3O4@SiO2/PANI) were prepared by grafting polyaniline (PANI) on the surface of silanized magnetic particles through surface initiated in-situ chemical oxidative graft polymerization. The nanocomposites were characterized by high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Fourier transform infrared (FTIR) spectra, UV-visible spectroscopy, photoluminescence (PL) spectra, electrical conductivity and magnetic characteristics. HRTEM images of the nanocomposites revealed that the silica-modified magnetic particles made up the core while PANI made up the shell. The XPS spectrum revealed the presence of silica in the composites, and the XRD results showed that the composites were more crystalline than pure PANI. PL spectra show that composites exhibit photoluminescent property. Conductivity of the composites (6.2 to 9.4 x 10(-2) S/cm) was higher than that of pristine PANI (3.7 x 10(-3) S/cm). The nanocomposites exhibited superparamagnetism. Formation mechanism of the core-shell structured nanocomposites and the effect of modified magnetic nanoparticles on the electro-magnetic properties of the Fe3O4@SiO2/PANI nanocomposites are also investigated. This method provides a new strategy for the generation of multi-functional nanocomposites that composed of other conducting polymers and metal nanoparticles.

Use of polyurethane foam and 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline for determination of nitrite by diffuse reflectance spectroscopy and colorimetry.

PubMed

Apyari, V V; Dmitrienko, S G; Ostrovskaya, V M; Anaev, E K; Zolotov, Y A

2008-07-01

Polyurethane foam (PUF) has been suggested as a solid polymeric reagent for determination of nitrite. The determination is based on the diazotization of end toluidine groups of PUF with nitrite in acidic medium followed by coupling of polymeric diazonium cation with 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline. The intensely colored polymeric azodye formed in this reaction can be used as a convenient analytic form for the determination of nitrite by diffuse reflectance spectroscopy (c (min) = 0.7 ng mL(-1)). The possibility of using a desktop scanner, digital camera, and computer data processing for the numerical evaluation of the color intensity of the polymeric azodye has been investigated. A scanner and digital camera can be used for determination of nitrite with the same sensitivity and reproducibility as with diffuse reflectance spectroscopy. The approach developed was applied for determination of nitrite in river water and human exhaled breath condensate.

Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

DOE PAGES

Fan, Fei; Wang, Weiyu; Holt, Adam P.; ...

2016-06-07

The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

Frontal Polymerization in Microgravity: Bubble Behavior and Convection on the KC-135 Aircraft

NASA Technical Reports Server (NTRS)

Pojman, John A.; Ainsworth, William; Chekanov, Yuri; Masere, Jonathan; Volpert, Vitaly; Dumont, Thierry; Wilke, Hermann

2001-01-01

Frontal polymerization is a mode of converting monomer into polymer via a localized exothermic reaction zone that propagates through the coupling of thermal diffusion and Arrhenius reaction kinetics. Frontal polymerization was discovered in Russia by Chechilo and Enikolopyan in 1972. The macrokinetics and dynamics of frontal polymerization have been examined in detail and applications for materials synthesis considered. Large temperature and concentration gradients that occur in the front lead to large density gradients. A schematic is presented for a liquid monomer, usually a monoacrylate, being converted to a liquid (thermoplastic) polymer. The velocity can be controlled by the initiator concentration but is on the order of a cm/min. If the liquid monomer is multifunctional, then a solid (thermoset) polymer is formed. Convection can occur with all types of monomers if the front propagates up a tube. Bowden et al. studied liquid/solid systems. McCaughey et al. studied liquid polymer systems. Descending fronts in thermoplastic systems are also susceptible to the Rayleigh-Taylor instability.

Bacterial DNA segregation dynamics mediated by the polymerizing protein ParF.

PubMed

Barillà, Daniela; Rosenberg, Mark F; Nobbmann, Ulf; Hayes, Finbarr

2005-04-06

Prokaryotic DNA segregation most commonly involves members of the Walker-type ParA superfamily. Here we show that the ParF partition protein specified by the TP228 plasmid is a ParA ATPase that assembles into extensive filaments in vitro. Polymerization is potentiated by ATP binding and does not require nucleotide hydrolysis. Analysis of mutations in conserved residues of the Walker A motif established a functional coupling between filament dynamics and DNA partitioning. The partner partition protein ParG plays two separable roles in the ParF polymerization process. ParF is unrelated to prokaryotic polymerizing proteins of the actin or tubulin families, but is a homologue of the MinD cell division protein, which also assembles into filaments. The ultrastructures of the ParF and MinD polymers are remarkably similar. This points to an evolutionary parallel between DNA segregation and cytokinesis in prokaryotic cells, and reveals a potential molecular mechanism for plasmid and chromosome segregation mediated by the ubiquitous ParA-type proteins.

Bacterial DNA segregation dynamics mediated by the polymerizing protein ParF

PubMed Central

Barillà, Daniela; Rosenberg, Mark F; Nobbmann, Ulf; Hayes, Finbarr

2005-01-01

Prokaryotic DNA segregation most commonly involves members of the Walker-type ParA superfamily. Here we show that the ParF partition protein specified by the TP228 plasmid is a ParA ATPase that assembles into extensive filaments in vitro. Polymerization is potentiated by ATP binding and does not require nucleotide hydrolysis. Analysis of mutations in conserved residues of the Walker A motif established a functional coupling between filament dynamics and DNA partitioning. The partner partition protein ParG plays two separable roles in the ParF polymerization process. ParF is unrelated to prokaryotic polymerizing proteins of the actin or tubulin families, but is a homologue of the MinD cell division protein, which also assembles into filaments. The ultrastructures of the ParF and MinD polymers are remarkably similar. This points to an evolutionary parallel between DNA segregation and cytokinesis in prokaryotic cells, and reveals a potential molecular mechanism for plasmid and chromosome segregation mediated by the ubiquitous ParA-type proteins. PMID:15775965

Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fan, Fei; Wang, Weiyu; Holt, Adam P.

The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

Light-harvesting organic photoinitiators of polymerization.

PubMed

Lalevée, Jacques; Tehfe, Mohamad-Ali; Dumur, Frédéric; Gigmes, Didier; Graff, Bernadette; Morlet-Savary, Fabrice; Fouassier, Jean-Pierre

2013-02-12

Two new photoinitiators with unprecedented light absorption properties are proposed on the basis of a suitable truxene skeleton where several UV photoinitiators PI units such as benzophenone and thioxanthone are introduced at the periphery and whose molecular orbitals MO can be coupled with those of the PI units: a red-shifted absorption and a strong increase of the molecular extinction coefficients (by a ≈ 20-1000 fold factor) are found. These compounds are highly efficient light-harvesting photoinitiators. The scope and practicality of these photoinitiators of polymerization can be dramatically expanded, that is, both radical and cationic polymerization processes are accessible upon very soft irradiation conditions (halogen lamp, LED…︁) thanks to the unique light absorption properties of the new proposed structures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Green synthesis, characterization and catalytic activity of the Pd/TiO2 nanoparticles for the ligand-free Suzuki-Miyaura coupling reaction.

PubMed

Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad

2016-03-01

A green synthesis process was developed for production of the Pd/TiO2 nanoparticles (NPs) without using toxic, hazardous and dangerous materials. Myrtus communis L. leaf extract serves as a mild, renewable and non-toxic reducing agent. The advantages of this biosynthesis method include use of cheap, clean, nontoxic and environmentally benign precursors and simple procedures without time-consuming polymerization and problems with treatment of a highly viscous polymeric resin. More importantly, the synthesized Pd/TiO2 NPs presented excellent catalytic activity for ligand-free Suzuki-Miyaura coupling which could be easily separated from the reaction mixture and reused many times with no loss of activity. Therefore, these properties indicate demonstrative benefits of the catalyst. The Pd/TiO2 NPs was characterized by FESEM, TEM, FT-IR, UV-vis spectroscopy and EDS. Copyright © 2015 Elsevier Inc. All rights reserved.

Combining Orthogonal Chain-End Deprotections and Thiol-Maleimide Michael Coupling: Engineering Discrete Oligomers by an Iterative Growth Strategy.

PubMed

Huang, Zhihao; Zhao, Junfei; Wang, Zimu; Meng, Fanying; Ding, Kunshan; Pan, Xiangqiang; Zhou, Nianchen; Li, Xiaopeng; Zhang, Zhengbiao; Zhu, Xiulin

2017-10-23

Orthogonal maleimide and thiol deprotections were combined with thiol-maleimide coupling to synthesize discrete oligomers/macromolecules on a gram scale with molecular weights up to 27.4 kDa (128mer, 7.9 g) using an iterative exponential growth strategy with a degree of polymerization (DP) of 2 n -1. Using the same chemistry, a "readable" sequence-defined oligomer and a discrete cyclic topology were also created. Furthermore, uniform dendrons were fabricated using sequential growth (DP=2 n -1) or double exponential dendrimer growth approaches (DP=22n -1) with significantly accelerated growth rates. A versatile, efficient, and metal-free method for construction of discrete oligomers with tailored structures and a high growth rate would greatly facilitate research into the structure-property relationships of sophisticated polymeric materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Viscoelastic coupling of nanoelectromechanical resonators.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simonson, Robert Joseph; Staton, Alan W.

2009-09-01

This report summarizes work to date on a new collaboration between Sandia National Laboratories and the California Institute of Technology (Caltech) to utilize nanoelectromechanical resonators designed at Caltech as platforms to measure the mechanical properties of polymeric materials at length scales on the order of 10-50 nm. Caltech has succeeded in reproducibly building cantilever resonators having major dimensions on the order of 2-5 microns. These devices are fabricated in pairs, with free ends separated by reproducible gaps having dimensions on the order of 10-50 nm. By controlled placement of materials that bridge the very small gap between resonators, the mechanicalmore » devices become coupled through the test material, and the transmission of energy between the devices can be monitored. This should allow for measurements of viscoelastic properties of polymeric materials at high frequency over short distances. Our work to date has been directed toward establishing this measurement capability at Sandia.« less

High catalytic activity of oriented 2.0.0 copper(I) oxide grown on graphene film

PubMed Central

Primo, Ana; Esteve-Adell, Ivan; Blandez, Juan F.; Dhakshinamoorthy, Amarajothi; Álvaro, Mercedes; Candu, Natalia; Coman, Simona M.; Parvulescu, Vasile I.; García, Hermenegildo

2015-01-01

Metal oxide nanoparticles supported on graphene exhibit high catalytic activity for oxidation, reduction and coupling reactions. Here we show that pyrolysis at 900 °C under inert atmosphere of copper(II) nitrate embedded in chitosan films affords 1.1.1 facet-oriented copper nanoplatelets supported on few-layered graphene. Oriented (1.1.1) copper nanoplatelets on graphene undergo spontaneous oxidation to render oriented (2.0.0) copper(I) oxide nanoplatelets on few-layered graphene. These films containing oriented copper(I) oxide exhibit as catalyst turnover numbers that can be three orders of magnitude higher for the Ullmann-type coupling, dehydrogenative coupling of dimethylphenylsilane with n-butanol and C–N cross-coupling than those of analogous unoriented graphene-supported copper(I) oxide nanoplatelets. PMID:26509224

Doping optimization of polypyrrole with toluenesulfonic acid using Box-Behnken design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Syed Draman, Sarifah Fauziah; Daik, Rusli; El-Sheikh, Said M.

A three-level Box-Behnken design was employed in doping optimization of polypyrrole with toluenesulfonic acid (TSA-doped PPy). The material was synthesized via chemical oxidative polymerization using pyrrole, toluenesulfonic acid (TSA) and ammonium persulfate (APS) as monomer, dopant and oxidant, respectively. The critical factors selected for this study were concentration of dopant, molar ratio between dopant to monomer (pyrrole) and concentration of oxidant. Obtaining adequate doping level of TSA-doped PPy is crucial because it affects the charge carriers for doped PPy and usually be responsible for electronic mobility along polymeric chain. Furthermore, the doping level also affects other properties such as electricalmore » and thermal conductivity. Doping level was calculated using elemental analysis. SEM images shows that the prepared TSA-doped PPy particles are spherical in shape with the diameters of about. The range of nanoparticles size is around 80-100 nm. The statistical analysis based on a Box–Behnken design showed that 0.01 mol of TSA, 1:1 mole ratio TSA to pyrrole and 0.25 M APS were the optimum conditions for sufficient doping level.« less

Structure-activity relationships of polyphenols to prevent lipid oxidation in pelagic fish muscle.

PubMed

Pazos, Manuel; Iglesias, Jacobo; Maestre, Rodrigo; Medina, Isabel

2010-10-27

The influence of polymerization (number of monomers) and galloylation (content of esterified gallates) of oligomeric catechins (proanthocyanidins) on their effectiveness to prevent lipid oxidation in pelagic fish muscle was evaluated. Non-galloylated oligomers of catechin with diverse mean polymerization (1.9-3.4 monomeric units) were extracted from pine (Pinus pinaster) bark. Homologous fractions with galloylation ranging from 0.25 to <1 gallate group per molecule were obtained from grape (Vitis vinifera) and witch hazel (Hamamelis virginiana). The results showed the convenience of proanthocyanidins with medium size (2-3 monomeric units) and low galloylation degree (0.15-0.25 gallate group/molecule) to inhibit lipid oxidation in pelagic fish muscle. These optimal structural characteristics of proanthocyanidins were similar to those lately reported in fish oil-in-water emulsions using phosphatidylcholine as emulsifier. This finding suggests that the antioxidant behavior of polyphenols in muscle-based foods can be mimicked in emulsions prepared with phospholipids as emulsifier agents. The present data give relevant information to achieve an optimum use of polyphenols in pelagic fish muscle.

Formation of conductive polymers using nitrosyl ion as an oxidizing agent

DOEpatents

Choi, Kyoung-Shin; Jung, Yongju; Singh, Nikhilendra

2016-06-07

A method of forming a conductive polymer deposit on a substrate is disclosed. The method may include the steps of preparing a composition comprising monomers of the conductive polymer and a nitrosyl precursor, contacting the substrate with the composition so as to allow formation of nitrosyl ion on the exterior surface of the substrate, and allowing the monomer to polymerize into the conductive polymer, wherein the polymerization is initiated by the nitrosyl ion and the conductive polymer is deposited on the exterior surface of the substrate. The conductive polymer may be polypyrrole.

Nanocomposite Prepared from In Situ Grafting of Polypyrrole to Aminobenzoyl-Functionalized Multiwalled Carbon Nanotube and Its Electrochemical Properties

DTIC Science & Technology

2011-01-01

Soxhlet extracted overnight with distilled water and methanol, and finally freeze-dried for 48 h to afford AF-MWCNT. Polymerization of PPy Pyrrole (10.0...Synthesis of PPy-g-MWCNT Composite In the same set-up for the synthesis of PPy, AF-MWCNT (1.0 g), pyrrole (9.0 g, 134 mmol), and 1 M aqueous HCl (120...sites for the covalent attachment of PPy. Thus, the PPy was grafted onto the surface of AF-MWCNT by chemical oxidation polymerization of pyrrole in

Photo-induced living radical polymerization of acrylates utilizing a discrete copper(II)-formate complex.

PubMed

Anastasaki, Athina; Nikolaou, Vasiliki; Brandford-Adams, Francesca; Nurumbetov, Gabit; Zhang, Qiang; Clarkson, Guy J; Fox, David J; Wilson, Paul; Kempe, Kristian; Haddleton, David M

2015-04-04

A photo-polymerization protocol, utilizing a pre-formed and well-characterized Cu(II) formate complex, [Cu(Me6-Tren)(O2CH)](ClO4), mediated by UV light is described. In the absence of additional reducing agents and/or photosensitizers, ppm concentrations of the oxidatively stable [Cu(Me6-Tren)(O2CH)](ClO4), furnish near-quantitative conversions within 2 h, yielding poly(acrylates) with low dispersities (∼1.10) and exceptional end-group fidelity, capable of undergoing in situ chain extension and block copolymerization.

Status review of PMR polyimides. [Polymerization of Monomer Reactants

NASA Technical Reports Server (NTRS)

Serafini, T. T.

1979-01-01

In the NASA developed PMR (polymerization of monomer reactants) the reinforcing fibers are impregnated with a solution containing a mixture of monomers dissolved in a low boiling point alkyl alcohol solvent, with the monomers reacting in situ at elevated temperatures to form a thermo-oxidatively stable polyimide matrix. The current status of first and second generation PMR polyimides is reviewed, considering synthesis and properties, processing, and applications. It is concluded that the PMR approach offers various significant advantages, especially superior high temperature properties and processing versatility, to fabricators and users of polyimide/fiber composites.

Polymeric Coatings for Combating Biocorrosion

NASA Astrophysics Data System (ADS)

Guo, Jing; Yuan, Shaojun; Jiang, Wei; Lv, Li; Liang, Bin; Pehkonen, Simo O.

2018-03-01

Biocorrosion has been considered as big trouble in many industries and marine environments due to causing great economic loss. The main disadvantages of present approaches to prevent corrosion include being limited by environmental factors, being expensive, inapplicable to field, and sometimes inefficient. Studies show that polymer coatings with anti-corrosion and anti-microbial properties have been widely accepted as a novel and effective approach to preventbiocorrosion. The main purpose of this review is to summarize up the progressive status of polymer coatings used for combating microbially-induced corrosion. Polymers used to synthesize protective coatings are generally divided into three categories: i) traditional polymers incorporated with biocides, ii) antibacterial polymers containing quaternary ammonium compounds, and iii) conductive polymers. The strategies to synthesize polymer coatings resort mainly to grafting anti-bacterial polymers from the metal substrate surface using novel surface-functionalization approaches, such as free radical polymerization, chemically oxidative polymerization and surface-initiated atom transfer radical polymerization, as opposed to the traditional approaches of dip coating or spin coating.

Alkaline battery, separator therefore

NASA Technical Reports Server (NTRS)

Schmidt, George F. (Inventor)

1980-01-01

An improved battery separator for alkaline battery cells has low resistance to electrolyte ion transfer and high resistance to electrode ion transfer. The separator is formed by applying an improved coating to an electrolyte absorber. The absorber, preferably, is a flexible, fibrous, and porous substrate that is resistant to strong alkali and oxidation. The coating composition includes an admixture of a polymeric binder, a hydrolyzable polymeric ester and inert fillers. The coating composition is substantially free of reactive fillers and plasticizers commonly employed as porosity promoting agents in separator coatings. When the separator is immersed in electrolyte, the polymeric ester of the film coating reacts with the electrolyte forming a salt and an alcohol. The alcohol goes into solution with the electrolyte while the salt imbibes electrolyte into the coating composition. When the salt is formed, it expands the polymeric chains of the binder to provide a film coating substantially permeable to electrolyte ion transfer but relatively impermeable to electrode ion transfer during use.

3D full field strain analysis of polymerization shrinkage in a dental composite.

PubMed

Martinsen, Michael; El-Hajjar, Rani F; Berzins, David W

2013-08-01

The objective of this research was to study the polymerization shrinkage in a dental composite using 3D digital image correlation (DIC). Using 2 coupled cameras, digital images were taken of bar-shaped composite (Premise Universal Composite; Kerr) specimens before light curing and after for 10 min. Three-dimensional DIC was used to assess in-plane and out-of-plane deformations associated with polymerization shrinkage. The results show the polymerization shrinkage to be highly variable with the peak values occurring 0.6-0.8mm away from the surface. Volumetric shrinkage began to significantly decrease at 3.2mm from the specimen surface and reached a minimum at 4mm within the composite. Approximately 25-30% of the strain registered at 5 min occurred after light-activation. Application of 3D DIC dental applications can be performed without the need for assumptions on the deformation field. Understanding the local deformations and strain fields from the initial polymerization shrinkage can lead to a better understanding of the composite material and interaction with surrounding tooth structure, aiding in their further development and clinical prognosis. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Cobalt-Mediated Radical Polymerization of Vinyl Acetate and Acrylonitrile in Supercritical Carbon Dioxide.

PubMed

Kermagoret, Anthony; Chau, Ngoc Do Quyen; Grignard, Bruno; Cordella, Daniela; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe

2016-03-01

Cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) is successfully achieved in supercritical carbon dioxide (scCO2). CMRP of VAc is conducted using an alkyl-cobalt(III) adduct that is soluble in scCO2. Kinetics studies coupled to visual observations of the polymerization medium highlight that the melt viscosity and PVAc molar mass (Mn) are key parameters that affect the CMRP in scCO2. It is noticed that CMRP is controlled for Mn up to 10 000 g mol(-1), but loss of control is progressively observed for higher molar masses when PVAc precipitates in the polymerization medium. Low molar mass PVAc macroinitiator, prepared by CMRP in scCO2, is then successfully used to initiate the acrylonitrile polymerization. PVAc-b-PAN block copolymer is collected as a free flowing powder at the end of the process although the dispersity of the copolymer increases with the reaction time. Although optimization is required to decrease the dispersity of the polymer formed, this CMRP process opens new perspectives for macromolecular engineering in scCO2 without the utilization of fluorinated comonomers or organic solvents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bactericidal Specificity and Resistance Profile of Poly(Quaternary Ammonium) Polymers and Protein-Poly(Quaternary Ammonium) Conjugates.

PubMed

Ji, Weihang; Koepsel, Richard R; Murata, Hironobu; Zadan, Sawyer; Campbell, Alan S; Russell, Alan J

2017-08-14

Antibacterial polymers are potentially powerful biocides that can destroy bacteria on contact. Debate in the literature has surrounded the mechanism of action of polymeric biocides and the propensity for bacteria to develop resistance to them. There has been particular interest in whether surfaces with covalently coupled polymeric biocides have the same mechanism of action and resistance profile as similar soluble polymeric biocides. We designed and synthesized a series of poly(quaternary ammonium) polymers, with tailorable molecular structures and architectures, to engineer their antibacterial specificity and their ability to delay the development of bacterial resistance. These linear poly(quaternary ammonium) homopolymers and block copolymers, generated using atom transfer radical polymerization, had structure-dependent antibacterial specificity toward Gram positive and negative bacterial species. When single block copolymers contained two polymer segments of differing antibacterial specificity, the polymer combined the specificities of its two components. Nanoparticulate human serum albumin-poly(quaternary ammonium) conjugates of these same polymers, synthesized via "grafting from" atom transfer radical polymerization, were strongly biocidal and also exhibited a marked decrease in the rate of bacterial resistance development relative to linear polymers. These protein-biocide conjugates mimicked the behavior of surface-presented polycationic biocides rather than their nonproteinaceous counterparts.

Effects of polymerization and nucleotide identity on the conformational dynamics of the bacterial actin homolog MreB

PubMed Central

Colavin, Alexandre; Hsin, Jen; Huang, Kerwyn Casey

2014-01-01

The assembly of protein filaments drives many cellular processes, from nucleoid segregation, growth, and division in single cells to muscle contraction in animals. In eukaryotes, shape and motility are regulated through cycles of polymerization and depolymerization of actin cytoskeletal networks. In bacteria, the actin homolog MreB forms filaments that coordinate the cell-wall synthesis machinery to regulate rod-shaped growth and contribute to cellular stiffness through unknown mechanisms. Like actin, MreB is an ATPase and requires ATP to polymerize, and polymerization promotes nucleotide hydrolysis. However, it is unclear whether other similarities exist between MreB and actin because the two proteins share low sequence identity and have distinct cellular roles. Here, we use all-atom molecular dynamics simulations to reveal surprising parallels between MreB and actin structural dynamics. We observe that MreB exhibits actin-like polymerization-dependent structural changes, wherein polymerization induces flattening of MreB subunits, which restructures the nucleotide-binding pocket to favor hydrolysis. MreB filaments exhibited nucleotide-dependent intersubunit bending, with hydrolyzed polymers favoring a straighter conformation. We use steered simulations to demonstrate a coupling between intersubunit bending and the degree of flattening of each subunit, suggesting cooperative bending along a filament. Taken together, our results provide molecular-scale insight into the diversity of structural states of MreB and the relationships among polymerization, hydrolysis, and filament properties, which may be applicable to other members of the broad actin family. PMID:24550504

Effects of polymerization and nucleotide identity on the conformational dynamics of the bacterial actin homolog MreB.

PubMed

Colavin, Alexandre; Hsin, Jen; Huang, Kerwyn Casey

2014-03-04

The assembly of protein filaments drives many cellular processes, from nucleoid segregation, growth, and division in single cells to muscle contraction in animals. In eukaryotes, shape and motility are regulated through cycles of polymerization and depolymerization of actin cytoskeletal networks. In bacteria, the actin homolog MreB forms filaments that coordinate the cell-wall synthesis machinery to regulate rod-shaped growth and contribute to cellular stiffness through unknown mechanisms. Like actin, MreB is an ATPase and requires ATP to polymerize, and polymerization promotes nucleotide hydrolysis. However, it is unclear whether other similarities exist between MreB and actin because the two proteins share low sequence identity and have distinct cellular roles. Here, we use all-atom molecular dynamics simulations to reveal surprising parallels between MreB and actin structural dynamics. We observe that MreB exhibits actin-like polymerization-dependent structural changes, wherein polymerization induces flattening of MreB subunits, which restructures the nucleotide-binding pocket to favor hydrolysis. MreB filaments exhibited nucleotide-dependent intersubunit bending, with hydrolyzed polymers favoring a straighter conformation. We use steered simulations to demonstrate a coupling between intersubunit bending and the degree of flattening of each subunit, suggesting cooperative bending along a filament. Taken together, our results provide molecular-scale insight into the diversity of structural states of MreB and the relationships among polymerization, hydrolysis, and filament properties, which may be applicable to other members of the broad actin family.

Mapping Polymerization and Allostery of Hemoglobin S Using Point Mutations

PubMed Central

Weinkam, Patrick; Sali, Andrej

2014-01-01

Hemoglobin is a complex system that undergoes conformational changes in response to oxygen, allosteric effectors, mutations, and environmental changes. Here, we study allostery and polymerization of hemoglobin and its variants by application of two previously described methods: (i) AllosMod for simulating allostery dynamics given two allosterically related input structures and (ii) a machine-learning method for dynamics- and structure-based prediction of the mutation impact on allostery (Weinkam et al. J. Mol. Biol. 2013), now applicable to systems with multiple coupled binding sites such as hemoglobin. First, we predict the relative stabilities of substates and microstates of hemoglobin, which are determined primarily by entropy within our model. Next, we predict the impact of 866 annotated mutations on hemoglobin’s oxygen binding equilibrium. We then discuss a subset of 30 mutations that occur in the presence of the sickle cell mutation and whose effects on polymerization have been measured. Seven of these HbS mutations occur in three predicted druggable binding pockets that might be exploited to directly inhibit polymerization; one of these binding pockets is not apparent in the crystal structure but only in structures generated by AllosMod. For the 30 mutations, we predict that mutation-induced conformational changes within a single tetramer tend not to significantly impact polymerization; instead, these mutations more likely impact polymerization by directly perturbing a polymerization interface. Finally, our analysis of allostery allows us to hypothesize why hemoglobin evolved to have multiple subunits and a persistent low frequency sickle cell mutation. PMID:23957820

Ladder polymers for use as high temperature stable resins or coatings

NASA Technical Reports Server (NTRS)

Meador, Mary Ann (Inventor)

1990-01-01

An object of the invention is to synthesize a new class of ladder and partial ladder polymers. In accordance with the invention, the new class of ladder and partial ladder polymers are synthesized by polymerizing a bis-dienophile with a bis-diene. Another object of the invention is to provide a fabricated, electrically conducting, void free composite comprising the new class of the ladder and partial ladder polymers described above. The novelty of the invention relates to a new class of ladder and partial ladder polymers and a process for synthesizing these polymers. These polymers are soluble in common organic solvents and are characterized with a unique dehydration property at temperatures of 300 to 400 C to provide thermo-oxidatively stable pentiptycene units along the polymeric backbone. These polymers are further characterized with high softening points and good thermo-oxidative stability properties. Thus these polymers have potential as processable, matrix resins for high temperature composite applications.

Metallization of electronic insulators

DOEpatents

Gottesfeld, Shimshon; Uribe, Francisco A.

1994-01-01

An electroplated element is formed to include an insulating substrate, a conducting polymer polymerized in situ on the substrate, and a metal layer deposited on the conducting polymer. In one application a circuit board is formed by polymerizing pyrrole on an epoxy-fiberglass substrate in a single step process and then electrodepositing a metal over the resulting polypyrrole polymer. No chemical deposition of the metal is required prior to electroplating and the resulting layer of substrate-polymer-metal has excellent adhesion characteristics. The metal deposition is surprisingly smooth and uniform over the relatively high resistance film of polypyrrole. A continuous manufacturing process is obtained by filtering the solution between successive substrates to remove polymer formed in the solution, by maintaining the solution oxidizing potential within selected limits, and by adding a strong oxidant, such as KMnO.sub.4 at periodic intervals to maintain a low sheet resistivity in the resulting conducting polymer film.

Phosphorylation of ubiquitin at Ser65 affects its polymerization, targets, and proteome-wide turnover

PubMed Central

Swaney, Danielle L; Rodríguez-Mias, Ricard A; Villén, Judit

2015-01-01

Ubiquitylation is an essential post-translational modification that regulates numerous cellular processes, most notably protein degradation. Ubiquitin can itself be phosphorylated at nearly every serine, threonine, and tyrosine residue. However, the effect of this modification on ubiquitin function is largely unknown. Here, we characterized the effects of phosphorylation of yeast ubiquitin at serine 65 in vivo and in vitro. We find this post-translational modification to be regulated under oxidative stress, occurring concomitantly with the restructuring of the ubiquitin landscape into a highly polymeric state. Phosphomimetic mutation of S65 recapitulates the oxidative stress phenotype, causing a dramatic accumulation of ubiquitylated proteins and a proteome-wide reduction of protein turnover rates. Importantly, this mutation impacts ubiquitin chain disassembly, chain linkage distribution, ubiquitin interactions, and substrate targeting. These results demonstrate that phosphorylation is an additional mode of ubiquitin regulation with broad implications in cellular physiology. PMID:26142280

All-polymeric sensing platform based on packaged self-assembled bottle microresonator (Conference Presentation)

NASA Astrophysics Data System (ADS)

Bernini, Romeo; Grimaldi, Immacolata A.; Persichetti, Gianluca; Testa, Genni

2017-02-01

In recent years, microbottle resonators that support non-degenerate whispering gallery modes (WGMs), propagating by successive total internal reflections close to the resonator surface and all along its axis, have been widely investigated due to their potential applications in optical sensing, microlasers and nonlinear optics. To overcome some drawbacks of the standard silica microbottle resonators, we focused our attention on polymers such as SU-8 resist and NOA resins. A drop of polymeric material is dispensed onto a fiber stem, providing a mechanical support for the bottle resonator, and is photo-polymerized by an UV lamp. The interrogation system, usually constituted by a tapered silica fiber evanescently coupled with the microresonator, is substituted by a more stable planar waveguide realized in SU-8 by means of standard photolithography technique. Moreover, for guarantying the stability to surrounding disturbance of the coupling between the microbottle resonator and the planar waveguide, the fiber stem is glued to substrate. Two drilled holes in the substrate allow the rise of the glue at the ends of the fiber stem and the fixing of sensor on PMMA substrate. In the present work, we presented an integrated full polymeric platform with self-assembled bottle microresonators packaged in a stable structure. SU-8 and NOA based microbottles are realized and morphologically characterized. The low autofluorescence emission and long term stability make the NOA based bottles suitable to be employed in a great variety of conditions. Bulk sensing measurements are performed by using water:ethanol solutions and a bulk sensitivity of 120 nm/RIU is estimated.

Deposition of functionalized polymer layers in surface plasmon resonance immunosensors by in-situ polymerization in the evanescent wave field.

PubMed

Chegel, Vladimir; Whitcombe, Michael J; Turner, Nicholas W; Piletsky, Sergey A

2009-01-01

Traditionally, the integration of sensing gel layers in surface plasmon resonance (SPR) is achieved via "bulk" methods, such as precipitation, spin-coating or in-situ polymerization onto the total surface of the sensor chip, combined with covalent attachment of the antibody or receptor to the gel surface. This is wasteful in terms of materials as the sensing only occurs at the point of resonance interrogated by the laser. By isolating the sensing materials (antibodies, enzymes, aptamers, polymers, MIPs, etc.) to this exact spot a more efficient use of these recognition elements will be achieved. Here we present a method for the in-situ formation of polymers, using the energy of the evanescent wave field on the surface of an SPR device, specifically localized at the point of interrogation. Using the photo-initiator couple of methylene blue (sensitizing dye) and sodium p-toluenesulfinate (reducing agent) we polymerized a mixture of N,N-methylene-bis-acrylamide and methacrylic acid in water at the focal point of SPR. No polymerization was seen in solution or at any other sites on the sensor surface. Varying parameters such as monomer concentration and exposure time allowed precise control over the polymer thickness (from 20-200 nm). Standard coupling with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide was used for the immobilization of protein G which was used to bind IgG in a typical biosensor format. This model system demonstrated the characteristic performance for this type of immunosensor, validating our deposition method.

Antioxidant and pro-oxidant activities of aqueous extracts and crude polyphenolic fractions of rooibos (Aspalathus linearis).

PubMed

Joubert, Elizabeth; Winterton, Paula; Britz, Trevor J; Gelderblom, Wentzel C A

2005-12-28

Unfermented rooibos tea is known to contain higher levels of total polyphenols and flavonoids than its fermented counterpart, making it the obvious choice for the preparation of flavonoid-enriched fractions. Evaluation of aqueous extracts and crude polyphenolic fractions of unfermented and fermented rooibos showed anti- and/or pro-oxidant activities, using a linoleic acid-Tween-buffer emulsion for lipid peroxidation and the deoxyribose degradation assay, based on a Fenton reaction model system containing FeCl3-EDTA and H2O2 for the generation of hydroxyl radicals. Except for the ethyl acetate fraction, with the highest total polyphenol (TP) content and offering the least protection presumably due to pro-oxidant activity, the inhibition of lipid peroxidation by the samples correlated moderately with their TP content in a linear relationship (r = 0.896, P < 0.01). Using the deoxyribose degradation assay, the pro-oxidant activity of the aqueous extracts and their crude polymeric fractions (0.1 mg/mL in the reaction mixture) was linear with respect to their dihydrochalcone (aspalathin and nothofagin) (r = 0.977, P = 0.023) and flavonoid (r = 0.971, P = 0.029) content. Pro-oxidant activity was demonstrated for pure aspalathin. Using the same assay, but with ascorbate added to regenerate Fe3+ to Fe2+, the aqueous extract and crude polymeric fraction of fermented rooibos displayed hydroxyl radical scavenging activity. Fermentation (i.e., oxidation) of rooibos decreased the pro-oxidant activity of aqueous extracts, which was contributed to a decrease in their dihydrochalcone content. The in vitro pro-oxidant activity displayed by flavonoid-enriched fractions of rooibos demonstrates that one must be aware of the potential adverse biological properties of potent antioxidant extracts utilized as dietary supplements.

CVD Polymers for Devices and Device Fabrication.

PubMed

Wang, Minghui; Wang, Xiaoxue; Moni, Priya; Liu, Andong; Kim, Do Han; Jo, Won Jun; Sojoudi, Hossein; Gleason, Karen K

2017-03-01

Chemical vapor deposition (CVD) polymerization directly synthesizes organic thin films on a substrate from vapor phase reactants. Dielectric, semiconducting, electrically conducting, and ionically conducting CVD polymers have all been readily integrated into devices. The absence of solvent in the CVD process enables the growth of high-purity layers and avoids the potential of dewetting phenomena, which lead to pinhole defects. By limiting contaminants and defects, ultrathin (<10 nm) CVD polymeric device layers have been fabricated in multiple laboratories. The CVD method is particularly suitable for synthesizing insoluble conductive polymers, layers with high densities of organic functional groups, and robust crosslinked networks. Additionally, CVD polymers are prized for the ability to conformally cover rough surfaces, like those of paper and textile substrates, as well as the complex geometries of micro- and nanostructured devices. By employing low processing temperatures, CVD polymerization avoids damaging substrates and underlying device layers. This report discusses the mechanisms of the major CVD polymerization techniques and the recent progress of their applications in devices and device fabrication, with emphasis on initiated CVD (iCVD) and oxidative CVD (oCVD) polymerization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of repair resin type and surface treatment on the repair strength of heat-polymerized denture base resin.

PubMed

Alkurt, Murat; Yeşil Duymuş, Zeynep; Gundogdu, Mustafa

2014-01-01

Acrylic resin denture fracture is common in prosthodontic practice. When fractured denture bases are repaired, recurrent fractures frequently occur at the repair surface interface or adjacent areas. The purpose of this study was to evaluate the effect of different surface treatments on the flexural strength of the acrylic resin denture base repaired with heat-polymerized acrylic resin, autopolymerizing resin, and light-polymerized acrylic resin. Ninety-six specimens of heat-polymerized acrylic resin were prepared according to the American Dental Association Specification No. 12 (65.0 × 10.0 × 2.5 mm) and sectioned into halves to create a repair gap (3.0 × 10 × 2.5 mm). The sectioned specimens were divided into 3 groups according to their repair materials. The specimens from each group were divided into 4 subgroups according to their surface treatments: a control group without any surface treatment; an experimental group treated with methyl methacrylate monomer (MMA group); an experimental group treated with airborne-particle abrasion with aluminum oxide particles of 250-μm particle size (abrasion group); and an experimental group treated with erbium:yttrium-aluminum-garnet laser (laser group). After the surface treatments, the 3 materials were placed into the repair gaps and then polymerized. After all of the specimens had been ground and polished, they were stored in distilled water at 37°C for 1 week and subjected to a 3-point bend test. Data were analyzed with a 2-way analysis of variance, and the Tukey honestly significant difference test was performed to identify significant differences (α=.05). The effects of the surface treatments and repair resins on the surface of the denture base resin were examined with scanning electron microscopy. Significant differences were found among the groups in terms of repair resin type (P<.001). All surface-treated specimens had higher flexural strength than controls, except the surface treated with the methyl methacrylate in the heat-polymerized group. A significant difference between the control and abrasion groups (P=.013) was found. The scanning electron microscopy observations showed that the application of surface treatments modified the surface of the denture base resin. The repair procedure with heat-polymerized resin exhibited significantly higher flexural strength than that of the autopolymerized and light-polymerized resins. In addition, the airborne-particle abrasion with aluminum oxide particles of 250-μm particle size improved the flexural strength of the specimens tested. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights reserved.

Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

PubMed

Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger

2016-05-01

Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A fragmentation-based approach for evaluating the intra-chain excitonic couplings in conjugated polymers

NASA Astrophysics Data System (ADS)

Wen, Jing; Ma, Haibo

2017-07-01

For computing the intra-chain excitonic couplings in polymeric systems, here we propose a new fragmentation approach. A comparison for the energetic and spatial properties of the low-lying excited states in PPV between our scheme and full quantum chemical calculations, reveals that our scheme can nicely reproduce full quantum chemical results in weakly coupled systems. Further wavefunction analysis indicate that improved description for strongly coupled system can be achieved by the inclusion of the higher excited states within each fragments. Our proposed scheme is helpful for building the bridge linking the phenomenological descriptions of excitons and microscopic modeling for realistic polymers.

Role of carbon source in the shift from oxidative to hydrolytic wood decomposition by Postia placenta.

PubMed

Zhang, Jiwei; Schilling, Jonathan S

2017-09-01

Brown rot fungi initiate wood decay using oxidative pretreatments to improve access for cellulolytic enzymes. These pretreatments are incompatible with enzymes, and we recently showed that Postia placenta overcomes this issue by delaying glycoside hydrolase (GH) gene upregulation briefly (<48h) until expression of oxidoreductases (ORs) is repressed. This implies an inducible cellulase system rather than a constitutive system, as often reported, and it remains unclear what cues this transition. To address this, we grew P. placenta along wood wafers and spatially mapped expression (via quantitative PCR) of twelve ORs and GHs targeted using functional genomics analyses. By layering expression patterns over solubilized sugar data (via HPLC) from wood, we observed solubilization of wood glucose, cellobiose, mannose, and xylose coincident with the OR-GH transition. We then tested effects of these soluble sugars, plus polymeric carbon sources (spruce powder, cellulose), on P. placenta gene expression in liquid cultures. Expression of ORs was strictly (aox1, cro5) or progressively repressed over time (qrd1, lcc1) by all soluble sugars, including cellobiose, but not by polymeric sources. Simple sugars repressed hemicellulase gene expression over time, but these sugars did not repress cellulases. Cellulase genes were upregulated, however, along with hemicellulases in the presence of soluble cellobiose and in the presence of polymeric carbon sources, relative to starvation (carbon-free). This verifies an inducible cellulase system in P. placenta that lacks carbon catabolite repression (CCR), and it suggests that brown rot fungi use soluble sugars, particularly cellobiose, to cue a critical oxidative-hydrolytic transition. Copyright © 2017 Elsevier Inc. All rights reserved.

Applicability of samarium(III) complexes for the role of luminescent molecular sensors for monitoring progress of photopolymerization processes and control of the thickness of polymer coatings

NASA Astrophysics Data System (ADS)

Topa, Monika; Ortyl, Joanna; Chachaj-Brekiesz, Anna; Kamińska-Borek, Iwona; Pilch, Maciej; Popielarz, Roman

2018-06-01

Applicability of 15 trivalent samarium complexes as novel luminescent probes for monitoring progress of photopolymerization processes or thickness of polymer coatings by the Fluorescence Probe Technique (FPT) was studied. Three groups of samarium(III) complexes were evaluated in cationic photopolymerization of triethylene glycol divinyl ether monomer (TEGDVE) and free-radical photopolymerization of trimethylolpropane triacrylate (TMPTA). The complexes were the derivatives of tris(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate)samarium(III), tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionate)samarium(III) and tris(4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate)samarium(III), which were further coordinated with auxiliary ligands, such as 1,10-phenanthroline, triphenylphosphine oxide, tributylphosphine oxide and trioctylphosphine oxide. It has been found that most of the complexes studied are sensitive enough to be used as luminescent probes for monitoring progress of cationic photopolymerization of vinyl ether monomers over entire range of monomer conversions. In the case of free-radical polymerization processes, the samarium(III) complexes are not sensitive enough to changes of microviscosity and/or micropolarity of the medium, so they cannot be used to monitor progress of the polymerization. However, high stability of luminescence intensity of some of these complexes under free-radical polymerization conditions makes them good candidates for application as thickness sensors for polymer coatings prepared by free-radical photopolymerization. A quantitative relationship between a coating thickness and the luminescence intensity of the samarium(III) probes has been derived and verified experimentally within a broad range of the thicknesses.

Using solvent-free sample preparation to promote protonation of poly(ethylene oxide)s with labile end-groups in matrix-assisted laser desorption/ionisation.

PubMed

Mazarin, Michael; Phan, Trang N T; Charles, Laurence

2008-12-01

Protonation is usually required to observe intact ions during matrix-assisted laser desorption/ionization (MALDI) of polymers containing fragile end-groups while cation adduction induces chain-end degradation. These polymers, generally obtained via living free radical polymerization techniques, are terminated with a functionality in which a bond is prone to homolytic cleavage, as required by the polymerization process. A solvent-free sample preparation method was used here to avoid salt contaminant from the solvent traditionally used in the dried-droplet MALDI procedure. Solvent-based and solvent-free sample preparations were compared for a series of three poly(ethylene oxide) polymers functionalized with a labile end-group in a nitroxide-mediated polymerization reaction, using 2,4,6-trihydroxyacetophenone (THAP) as the matrix without any added salt. Intact oligomer ions could only be produced as protonated molecules in solvent-free MALDI while sodium adducts of degraded polymers were formed from the dried-droplet samples. Although MALDI analysis was performed at the laser threshold, fragmentation of protonated macromolecules was still observed to occur. However, in contrast to sodiated molecules, dissociation of protonated oligomers does not involve the labile C--ON bond of the end-group. As the macromolecule size increased, protonation appeared to be less efficient and sodium adduction became the dominant ionization process, although no sodium salt was added in the preparation. Formation of sodiated degraded macromolecules would be dictated by increasing cation affinity as the size of the oligomers increases and would reveal the presence of salts at trace levels in the MALDI samples.

Effects of nitric oxide and its congeners on sickle red blood cell deformability

PubMed Central

Belanger, Andrea M.; Keggi, Christian; Kanias, Tamir; Gladwin, Mark T.; Kim-Shapiro, Daniel B.

2015-01-01

BACKGROUND Sickle cell disease is characterized by hemoglobin (Hb) polymerization upon deoxygenation. Polymerization causes the sickle cells to become rigid and misshapen (sickling). Red blood cell (RBC) dehydration greatly increases polymerization. Cycles of sickling and unsickling cause an influx of calcium that leads to loss of potassium via the calcium-activated Gardos channel which dehydrates the cells leading to increased polymerization. In this study effects of NO and its congeners on RBC deformability were examined, focusing on sickle red blood cells. STUDY DESIGN AND METHODS Red blood cells from patients with sickle cell disease and from non-patients were exposed to various compounds that release NO or its congeners. Intracellular calcium was increased using a calcium ionophore or cycling of oxygen tension for sickle red blood cells. Deformability was measured by laser-assisted osmotic gradient ektacytometry. RESULTS Consistent with a previous report, sodium nitroprusside (SNP) was found to protect against calcium-induced loss of deformability in normal red blood cells, but (contrary to some previous reports) no effect of any NO donors was observed when calcium influx was not induced. Importantly, in studies of deoxygenation-induced dehydration of sickle RBCs, SNP resulted in substantial improvements in deformability (p=0.036) and hydration (p=0.024). Sodium nitrite showed similar trends. SNP was shown to have no effect on calcium influx, but reduced potassium efflux. CONCLUSION These data suggest SNP and perhaps certain nitrogen oxides (like nitrite) inhibit the Gardos channel and may be able to protect sickle cells from dehydration and thereby improve outcome in the disease. PMID:25912054

Concurrent Formation of Carbon–Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction

PubMed Central

Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

2016-01-01

Oxidative C–H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C–C bond formation via C–H transformation and production of functionalized graphene. PMID:27181191

One-Pot Anchoring of Pd Nanoparticles on Nitrogen-Doped Carbon through Dopamine Self-Polymerization and Activity in the Electrocatalytic Methanol Oxidation Reaction.

PubMed

Li, Xin; Niu, Xiangheng; Zhang, Wenchi; He, Yanfang; Pan, Jianming; Yan, Yongsheng; Qiu, Fengxian

2017-03-09

Exploration of advanced electrocatalysts to promote the sluggish methanol oxidation reaction (MOR) is of vital importance for developing high efficiency and low-cost direct methanol fuel cells. Highly dispersed palladium nanoparticles (Pd NPs) anchored on a nitrogen-doped carbon support were fabricated using a facile one-pot dopamine self-polymerization mediated redox strategy, in which dopamine not only acted as a moderate reductant to induce the formation of Pd NPs during self-polymerization but was also the precursor of the nitrogen-doped carbon support for Pd. The synthesized hybrid features the following characteristics: 1) High dispersity of Pd NPs, which exposed a high abundance of active surfaces and sites for heterogeneous electrocatalysis; 2) metal-support interactions, which may affect the surface chemistry and electron distribution of active Pd NPs; 3) the Pd NPs were partially imbedded or encapsulated into the support, thus reducing the possible agglomeration of Pd NPs during cyclic measurements. The electrocatalyst with such favorable features provided higher mass activity (2.2 times that of commercial Pd/C) and better durability (reduced loss of activity during simulated frequent startup-shutdown operations) for the MOR in alkaline media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Folate-bovine serum albumin functionalized polymeric micelles loaded with superparamagnetic iron oxide nanoparticles for tumor targeting and magnetic resonance imaging.

PubMed

Li, Huan; Yan, Kai; Shang, Yalei; Shrestha, Lochan; Liao, Rufang; Liu, Fang; Li, Penghui; Xu, Haibo; Xu, Zushun; Chu, Paul K

2015-03-01

Polymeric micelles functionalized with folate conjugated bovine serum albumin (FA-BSA) and loaded with superparamagnetic iron oxide nanoparticles (SPIONs) are investigated as a specific contrast agent for tumor targeting and magnetic resonance imaging (MRI) in vitro and in vivo. The SPIONs-loaded polymeric micelles are produced by self-assembly of amphiphilic poly(HFMA-co-MOTAC)-g-PEGMA copolymers and oleic acid modified Fe3O4 nanoparticles and functionalized with FA-BSA by electrostatic interaction. The FA-BSA modified magnetic micelles have a hydrodynamic diameter of 196.1 nm, saturation magnetization of 5.5 emu/g, and transverse relaxivity of 167.0 mM(-1) S(-1). In vitro MR imaging, Prussian blue staining, and intracellular iron determination studies demonstrate that the folate-functionalized magnetic micelles have larger cellular uptake against the folate-receptor positive hepatoma cells Bel-7402 than the unmodified magnetic micelles. In vivo MR imaging conducted on nude mice bearing the Bel-7402 xenografts after bolus intravenous administration reveals excellent tumor targeting and MR imaging capabilities, especially at 24h post-injection. These findings suggest the potential of FA-BSA modified magnetic micelles as targeting MRI probe in tumor detection. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Multifunctional polymeric nanoconstructs for biomedical applications (Conference Presentation)

NASA Astrophysics Data System (ADS)

Decuzzi, Paolo

2016-09-01

Multifunctional nanoconstructs are particle-based nano-scale systems designed for the `smart' delivery of therapeutic and imaging agents. The Laboratory of Nanotechnology for Precision Medicine at the Italian Institute of Technology synthesizes polymeric nanoconstructs with different sizes, ranging from a few tens of nanometers to a few microns; shapes, including spherical, cubical and discoidal; surface properties, with positive, negative, neutral coatings; and mechanical stiffness, varying from that of cells to rigid, inorganic materials, such as iron oxide. These are the 4S parameters - size, shape, surface, stiffness - which can be precisely tuned in the synthesis process enabling disease- and patient-specific designs of multifunctional nanoconstructs. In this lecture, the application of these nanoconstructs to the detection and treatment of cancer lesions and cardiovascular diseases, such as thrombosis and atherosclerosis, is discussed. The contribution of the 4S parameters in modulating nanoconstruct sequestration by the mononuclear phagocyte system, organ specific accumulation, and blood longevity is also critically presented. These polymeric nanoconstructs can be loaded with a variety of therapeutic payloads - anti-cancer molecules (docetaxel, paclitaxel, doxorubicin), anti-inflammatory molecules (curcumin, diclofenac, celecoxib) and small biologicals (peptides, siRNAs, miRNAs); and imaging agents - optical probes; Gd and iron oxide nanoparticles for MR imaging; and radio-isotopes for Nuclear Imaging.

Self-powered heat-resistant polymeric 1D nanowires and 3D micro/nanowire assemblies in a pressure-crystallized size-distributed graphene oxide/poly (vinylidene fluoride) composite

NASA Astrophysics Data System (ADS)

Tian, Pengfei; Lyu, Jun; Huang, Rui; Zhang, Chaoliang

2017-12-01

Piezoelectric one- (1D) and three-dimensional (3D) hybrid micro/nanostructured materials have received intense research interest because of their ability in capturing trace amounts of energy and transforming it into electrical energy. In this work, a size-distributed graphene oxide (GO) was utilized for the concurrent growth of both the 1D nanowires and 3D micro/nanowire architectures of poly (vinylidene fluoride) (PVDF) with piezoelectricity. The in situ formation of the polymeric micro/nanostructures, with crystalline beta phase, was achieved by the high-pressure crystallization of a well dispersed GO/PVDF composite, fabricated by an environmentally friendly physical approach. Particularly, by controlling the crystallization conditions of the binary composite at high pressure, the melting point of the polymeric micro/nanowires, which further constructed the 3D micro/nanoarchitectures, was nearly 30°C higher than that of the original PVDF. The large scale simultaneous formation of the 1D and 3D micro/nanostructures was attributed to a size-dependent catalysis of the GOs in the pressure-treated composite system. The as-fabricated heat-resistant hybrid micro/nanoarchitectures, consisting of GOs and piezoelectric PVDF micro/nanowires, may permit niche applications in self-powered micro/nanodevices for energy scavenging from their working environments.

Cellulose based polymeric systems in drug delivery

USDA-ARS?s Scientific Manuscript database

The pharmaceutical industry requires the development of biodegradable, biocompatible, non toxic, site specific drug delivery polymers, which can be easily coupled with drugs to be delivered orally, topically, locally, or parenterally. The use of the most abundant biopolymer, cellulose along with its...

Fluorescence-tagged monolignols: Synthesis, and application to studying in vitro lignification

USDA-ARS?s Scientific Manuscript database

Coniferyl alcohol gamma-coupled by ethylenediamine spacers to dimethylaminocoumarin or nitrobenzofuran fluorophores was tested as a photoprobe to study the oxidase-mediated polymerization of monolignols. The fluorescent coniferyl alcohol derivatives readily underwent peroxidase-catalyzed in vitro co...

How actin binds and assembles onto plasma membranes from Dictyostelium discoideum

PubMed Central

1988-01-01

We have shown previously (Schwartz, M. A., and E. J. Luna. 1986. J. Cell Biol. 102: 2067-2075) that actin binds with positive cooperativity to plasma membranes from Dictyostelium discoideum. Actin is polymerized at the membrane surface even at concentrations well below the critical concentration for polymerization in solution. Low salt buffer that blocks actin polymerization in solution also prevents actin binding to membranes. To further explore the relationship between actin polymerization and binding to membranes, we prepared four chemically modified actins that appear to be incapable of polymerizing in solution. Three of these derivatives also lost their ability to bind to membranes. The fourth derivative (EF actin), in which histidine-40 is labeled with ethoxyformic anhydride, binds to membranes with reduced affinity. Binding curves exhibit positive cooperativity, and cross- linking experiments show that membrane-bound actin is multimeric. Thus, binding and polymerization are tightly coupled, and the ability of these membranes to polymerize actin is dramatically demonstrated. EF actin coassembles weakly with untreated actin in solution, but coassembles well on membranes. Binding by untreated actin and EF actin are mutually competitive, indicating that they bind to the same membrane sites. Hill plots indicate that an actin trimer is the minimum assembly state required for tight binding to membranes. The best explanation for our data is a model in which actin oligomers assemble by binding to clustered membrane sites with successive monomers on one side of the actin filament bound to the membrane. Individual binding affinities are expected to be low, but the overall actin-membrane avidity is high, due to multivalency. Our results imply that extracellular factors that cluster membrane proteins may create sites for the formation of actin nuclei and thus trigger actin polymerization in the cell. PMID:3392099

Nanoporous polymeric nanofibers based on selectively etched PS-b-PDMS block copolymers.

PubMed

Demirel, Gokcen B; Buyukserin, Fatih; Morris, Michael A; Demirel, Gokhan

2012-01-01

One-dimensional nanoporous polymeric nanofibers have been fabricated within an anodic aluminum oxide (AAO) membrane by a facile approach based on selective etching of poly(dimethylsiloxane) (PDMS) domains in polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS) block copolymers that had been formed within the AAO template. It was observed that prior to etching, the well-ordered PS-b-PDMS nanofibers are solid and do not have any porosity. The postetched PS nanofibers, on the other hand, had a highly porous structure having about 20-50 nm pore size. The nanoporous polymeric fibers were also employed as a drug carrier for the native, continuous, and pulsatile drug release using Rhodamine B (RB) as a model drug. These studies showed that enhanced drug release and tunable drug dosage can be achieved by using ultrasound irradiation. © 2011 American Chemical Society

A review of processable high temperature resistant addition-type laminating resins

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.

1973-01-01

An important finding that resulted from research that was conducted to develop improved ablative resins was the discovery of a novel approach to synthesize processable high temperature resistant polymers. Low molecular weight polyimide prepolymers end-capped with norbornene groups were polymerized into thermo-oxidatively stable modified polyimides without the evolution of void producing volatile materials. This paper reviews basic studies that were performed using model compounds to elucidate the polymerization mechanism of the so-called addition-type polyimides. The fabrication and properties of polyimide/graphite fiber composites using A-type polyimide prepolymer as the matrix are described. An alternate method for preparing processable A-type polyimides by means of in situ polymerization of monomeric reactants on the fiber reinforcement is also described. Polyimide/graphite fiber composite performance at elevated temperatures is presented for A-type polyimides.

Oxidative coupling of sp 2 and sp 3 carbon-hydrogen bonds to construct dihydrobenzofurans.

PubMed

Shi, Jiang-Ling; Wang, Ding; Zhang, Xi-Sha; Li, Xiao-Lei; Chen, Yu-Qin; Li, Yu-Xue; Shi, Zhang-Jie

2017-08-10

Metal-catalyzed cross-couplings provide powerful, concise, and accurate methods to construct carbon-carbon bonds from organohalides and organometallic reagents. Recent developments extended cross-couplings to reactions where one of the two partners connects with an aryl or alkyl carbon-hydrogen bond. From an economic and environmental point of view, oxidative couplings between two carbon-hydrogen bonds would be ideal. Oxidative coupling between phenyl and "inert" alkyl carbon-hydrogen bonds still awaits realization. It is very difficult to develop successful strategies for oxidative coupling of two carbon-hydrogen bonds owning different chemical properties. This article provides a solution to this challenge in a convenient preparation of dihydrobenzofurans from substituted phenyl alkyl ethers. For the phenyl carbon-hydrogen bond activation, our choice falls on the carboxylic acid fragment to form the palladacycle as a key intermediate. Through careful manipulation of an additional ligand, the second "inert" alkyl carbon-hydrogen bond activation takes place to facilitate the formation of structurally diversified dihydrobenzofurans.Cross-dehydrogenative coupling is finding increasing application in synthesis, but coupling two chemically distinct sites remains a challenge. Here, the authors report an oxidative coupling between sp 2 and sp 3 carbons by sequentially activating the more active aryl site followed by the alkyl position.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrash, Daniel A.; Lalonde, Stefan V.; González-Arismendi, Gabriela

The formation of dolomite in modern peritidal environments is linked to the degradation of buried microbial mats, with complexation of Ca and Mg by extracellular polymeric substances (EPSs) and alkalinity generation through organic carbon respiration facilitating the nucleation of dolomite precursors. In the past two decades, microbial sulfate reduction, methanogenesis, and methanotrophy have all been considered as potential drivers of the nucleation process, but it remains unclear why dolomite formation could not also occur in suboxic sediments where abundant alkalinity is produced by processes linked to Mn(IV) and/or Fe(III) reduction coupled with the diffusion and reoxidation of reduced sulfur species.more » Here we report the interstitial occurrence of spheroidal aggregates of nanometer-scale Ca-rich dolomite rhombohedra within suboxic sediments associated with remnant microbial mats that developed in the peritidal zone of the Archipelago Los Roques, Venezuela. Multiple analytical tools, including EPMA, ICP-MS, synchrotron-based XRF and XRD, and spatially resolved XANES microanalyses, show that the dolomite-cemented interval exhibits depleted bulk iron concentrations, but is interstitially enriched in Mn and elemental sulfur (S⁰). Manganese occurs in several oxidation states, indicating that the dolomite-cemented interval was the locus of complex biological redox transformations characterized by coupled Mn and S cycling. The tight correspondence between sedimentary Mn and MgCO₃ concentrations further hints at a direct role for Mn during dolomitization. While additional studies are required to confirm its relevance in natural settings, we propose a model by which coupled Mn–S redox cycling may promote alkalinity generation and thus dolomite formation in manner similar to, or even more efficiently, than bacterial sulfate reduction alone.« less

Synthesis and structural characterization of polyaniline/cobalt chloride composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asha, E-mail: arana5752@gmail.com; Goyal, Sneh Lata; Kishore, Nawal

2016-05-23

Polyaniline (PANI) and PANI /cobalt chloride composites were synthesized by in situ chemical oxidative polymerization of aniline with CoCl{sub 2}.6H{sub 2}O using ammonium peroxidisulphate as an oxidant. These composites were characterized by X-ray diffraction (XRD) and Scanning electron microscopy (SEM). The XRD study reveals that both PANI and composites are amorphous. The XRD and SEM results confirm the presence of cobalt chloride in the composites.

Preparation of redox polymer cathodes for thin film rechargeable batteries

DOEpatents

Skotheim, T.A.; Lee, H.S.; Okamoto, Yoshiyuki.

1994-11-08

The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

A catalyst-free, temperature controlled gelation system for in-mold fabrication of microgels.

PubMed

Krüger, Andreas J D; Köhler, Jens; Cichosz, Stefan; Rose, Jonas C; Gehlen, David B; Haraszti, Tamás; Möller, Martin; De Laporte, Laura

2018-06-19

Anisometric microgels are prepared via thermal crosslinking using an in-mold polymerization technique. Star-shaped poly(ethylene oxide-stat-propylene oxide) polymers, end-modified with amine and epoxy groups, form hydrogels, of which the mechanical properties and gelation rate can be adjusted by the temperature, duration of heating, and polymer concentration. Depending on the microgel stiffness, the rod-shaped microgels self-assemble into ordered or disordered structures.

Systematic Investigations of Biomimetic Catalysts in the Synthesis of Reactive Metal Oxide Nanoparticle Networks

DTIC Science & Technology

2012-09-01

dioxide and aluminum oxide. Numerous polymeric templates (Table 1), such as polyallyamine (PAA), were investigated, along with amine- functionalized ...SephadexTM LH60 (an anionic functionalized resin) and SephadexTM G-100 (unfunctionalized) were used as the functionalized surface. The reaction conditions...formed with all of the polymers tested and from some of the functionalized surface. SEM images (Figure 1) show that with the exception of the

Electroactive Polymeric Materials for Supercapacitors

DTIC Science & Technology

2017-06-16

composites either using transition metal oxides or different 3D carbon structures to maximize the pseudocapacitance. TECHNICAL APPROACH Our... printing /coating. Figure 9. Schematic representation of CNT forest well plate and a photograph of CNT well sample alongside a penny placed for size

Process for recovering filler from polymer

DOEpatents

Smith, Maurice L.; Smith, Robert M.

1978-01-01

This disclosure relates to a process for recovering filler material from a polymeric matrix by reacting the matrix at an elevated temperature in a gas atmosphere with a controlled oxidizing potential and thereafter separating and cleaning the residue from the reaction mixture.

Colloidal polyaniline

DOEpatents

Armes, Steven P.; Aldissi, Mahmoud

1990-01-01

Processable electrically conductive latex polymer compositions including colloidal particles of an oxidized, polymerized amino-substituted aromatic monomer, a stabilizing effective amount of a random copolymer containing amino-benzene type moieties as side chain constituents, and dopant anions, and a method of preparing such polymer compositions are provided.

Magnetic levitating polymeric nano/microparticular substrates for three-dimensional tumor cell culture.

PubMed

Lee, Woong Ryeol; Oh, Kyung Taek; Park, So Young; Yoo, Na Young; Ahn, Yong Sik; Lee, Don Haeng; Youn, Yu Seok; Lee, Deok-Keun; Cha, Kyung-Hoi; Lee, Eun Seong

2011-07-01

Herein, we describe magnetic cell levitation models using conventional polymeric microparticles or nanoparticles as a substrate for the three-dimensional tumor cell culture. When the magnetic force originating from the ring-shaped magnets overcame the gravitational force, the magnetic field-levitated KB tumor cells adhered to the surface area of magnetic iron oxide (Fe(3)O(4))-encapsulated nano/microparticles and concentrated clusters of levitated cells, ultimately developing tumor cells to tumor spheroids. These simple cell culture models may prove useful for the screening of anticancer drugs and their formulations. Copyright © 2011 Elsevier B.V. All rights reserved.

Gadolinium-Encapsulating Iron Oxide Nanoprobe as Activatable NMR/MRI Contrast Agent

PubMed Central

Santra, Santimukul; Jativa, Samuel D.; Kaittanis, Charalambos; Normand, Guillaume; Grimm, Jan; Perez, J. Manuel

2012-01-01

Herein we report a novel gadolinium-encapsulating iron oxide nanoparticle-based activatable NMR/MRI nanoprobe. In our design, Gd-DTPA is encapsulated within the polyacrylic acid (PAA) polymer coating of a superparamagnetic iron oxide nanoparticle (IO-PAA) yielding a composite magnetic nanoprobe (IO-PAA-Gd-DTPA) with quenched longitudinal spin-lattice magnetic relaxation (T1). Upon release of the Gd-DTPA complex from the nanoprobe's polymeric coating in acidic media, an increase in the T1 relaxation rate (1/T1) of the composite magnetic nanoprobe was observed, indicating a dequenching of the nanoprobe with a corresponding increase in the T1-weighted MRI signal. When a folate-conjugated nanoprobe was incubated in HeLa cells, a cancer cell line overexpressing folate receptors, an increase in the 1/T1 signal was observed. This result suggests that upon receptor-mediated internalization, the composite magnetic nanoprobe degraded within the cell's lysosome acidic (pH = 5.0) environment, resulting in an intracellular release of Gd-DTPA complex with subsequent T1 activation. No change in T1 was observed when the Gd-DTPA complex was chemically conjugated on the surface of the nanoparticle's polymeric coating or when encapsulated in the polymeric coating of a non-magnetic nanoparticle. These results confirmed that the observed (T1) quenching of the composite magnetic nanoprobe is due to the encapsulation and close proximity of the Gd ion to the nanoparticles superparamagnetic iron oxide (IO) core. In addition, when an anticancer drug (Taxol) was co-encapsulated with the Gd-DTPA within the folate receptor targeting composite magnetic nanoprobe, the T1 activation of the probe coincide with the rate of drug release and corresponding cytotoxic effect in cell culture studies. Taken together, these results suggest that our activatable T1 nanoagent could be of great importance for the detection of acidic tumors and assessment of drug targeting and release by MRI. PMID:22809405

Bio-Functional, Lanthanide-Labeled Polymer Particles by Seeded Emulsion Polymerization and their Characterization by Novel ICP-MS Detection.

PubMed

Thickett, Stuart C; Abdelrahman, Ahmed I; Ornatsky, Olga; Bandura, Dmitry; Baranov, Vladimir; Winnik, Mitchell A

2010-01-01

We present the synthesis and characterization of monodisperse, sub-micron poly(styrene) (PS) particles loaded with up to and including 10(7) lanthanide (Ln) ions per particle. These particles have been synthesized by seeded emulsion polymerization with a mixture of monomer and a pre-formed Ln complex, and analyzed on a particle-by-particle basis by a unique inductively coupled plasma mass cytometer. Seed particles were prepared by surfactant-free emulsion polymerization (SFEP) to obtain large particle sizes in aqueous media. Extensive surface acid functionality was introduced using the acid-functional initiator ACVA, either during seed latex synthesis or in the second stage of polymerization. The loading of particles with three different Ln ions (Eu, Tb, and Ho) has proven to be close to 100 % efficient on an individual and combined basis. Covalent attachment of metal-tagged peptides and proteins such as Neutravidin to the particle surface was shown to be successful and the number of bound species can be readily determined. We believe these particles can serve as precursors for multiplexed, bead-based bio-assays utilizing mass cytometric detection.

Bio-Functional, Lanthanide-Labeled Polymer Particles by Seeded Emulsion Polymerization and their Characterization by Novel ICP-MS Detection

PubMed Central

Thickett, Stuart C.; Abdelrahman, Ahmed I.; Ornatsky, Olga; Bandura, Dmitry; Baranov, Vladimir; Winnik, Mitchell A.

2010-01-01

We present the synthesis and characterization of monodisperse, sub-micron poly(styrene) (PS) particles loaded with up to and including 107 lanthanide (Ln) ions per particle. These particles have been synthesized by seeded emulsion polymerization with a mixture of monomer and a pre-formed Ln complex, and analyzed on a particle-by-particle basis by a unique inductively coupled plasma mass cytometer. Seed particles were prepared by surfactant-free emulsion polymerization (SFEP) to obtain large particle sizes in aqueous media. Extensive surface acid functionality was introduced using the acid-functional initiator ACVA, either during seed latex synthesis or in the second stage of polymerization. The loading of particles with three different Ln ions (Eu, Tb, and Ho) has proven to be close to 100 % efficient on an individual and combined basis. Covalent attachment of metal-tagged peptides and proteins such as Neutravidin to the particle surface was shown to be successful and the number of bound species can be readily determined. We believe these particles can serve as precursors for multiplexed, bead-based bio-assays utilizing mass cytometric detection. PMID:20396648

Graft Polymerization of Acrylic Acid on a Polytetrafluoroethylene Panel by an Inductively Coupled Plasma

NASA Astrophysics Data System (ADS)

Lan, Yan; You, Qingliang; Cheng, Cheng; Zhang, Suzhen; Ni, Guohua; Nagatsu, M.; Meng, Yuedong

2011-02-01

Surface modification on a polytetrafluoroethylene (PTFE) panel was performed with sequential nitrogen plasma treatments and surface-initiated polymerization. By introducing COO- groups to the surface of the PTFE panel through grafting polymerization of acrylic acid (AA), a transparent poly (acrylic acid) (PAA) membrane was achieved from acrylic acid solution. Grafting polymerization initiating from the active groups was achieved on the PTFE panel surface after the nitrogen plasma treatment. Utilizing the acrylic acid as monomers, with COO- groups as cross link sites to form reticulation structure, a transparent poly (acrylic acid) membrane with arborescent macromolecular structure was formed on the PTFE panel surface. Analysis methods, such as fourier transform infrared spectroscopy (FTIR), microscopy and X-ray photoelectron spectroscopy (XPS), were utilized to characterize the structures of the macromolecule membrane on the PTFE panel surface. A contact angle measurement was performed to characterize the modified PTFE panels. The surface hydrophilicities of modified PTFE panels were significantly enhanced after the plasma treatment. It was shown that the grafting rate is related to the treating time and the power of plasma.

Enantioselective oxidative biaryl coupling reactions catalyzed by 1,5-diazadecalin metal complexes.

PubMed

Li, X; Yang, J; Kozlowski, M C

2001-04-19

[reaction: see text]. Chiral 1,5-diaza-cis-decalins have been examined as ligands in the enantioselective oxidative biaryl coupling of substituted 2-naphthol derivatives. Under the optimal conditions employing a 1,5-diaza-cis-decalin copper(I) iodide complex with oxygen as the oxidant, rapid and highly selective couplings could be achieved (90-93% ee, 85% yield).

Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

PubMed Central

Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

2013-01-01

Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

Improved hybrid solar cells via in situ UV-polymerization.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tepavcevic, S.; Darling, S. B.; Dimitrijevic, N. M.

One approach for making inexpensive inorganic-organic hybrid photovoltaic (PV) cells is to fill highly ordered TiO{sub 2} nanotube (NT) arrays with solid organic hole conductors such as conjugated polymers. Here, a new in situ UV polymerization method for growing polythiophene (UV-PT) inside TiO{sub 2} NTs is presented and compared to the conventional approach of infiltrating NTs with pre-synthesized polymer. A nanotubular TiO{sub 2} substrate is immersed in a 2,5-diiodothiophene (DIT) monomer precursor solution and then irradiated with UV light. The selective UV photodissociation of the C-I bond produces monomer radicals with intact {pi}-ring structure that further produce longer oligothiophene/PT molecules.more » Complete photoluminescence quenching upon UV irradiation suggests coupling between radicals created from DIT and at the TiO{sub 2} surface via a charge transfer complex. Coupling with the TiO{sub 2} surface improves UV-PT crystallinity and {pi}-{pi} stacking; flat photocurrent values show that charge recombination during hole transport through the polymer is negligible. A non-ideal, backside-illuminated setup under illumination of 620-nm light yields a photocurrent density of {approx} 5 {micro}A cm{sup -2} - surprisingly much stronger than with comparable devices fabricated with polymer synthesized ex situ. Since in this backside architecture setup we illuminate the cell through the Ag top electrode, there is a possibility for Ag plasmon-enhanced solar energy conversion. By using this simple in situ UV polymerization method that couples the conjugated polymer to the TiO{sub 2} surface, the absorption of sunlight can be improved and the charge carrier mobility of the photoactive layer can be enhanced.« less

Regio-selectivity of the Oxidative C-S Bond Formation in Ergothioneine and Ovothiol Biosyntheses

PubMed Central

Song, Heng; Leninger, Maureen; Lee, Norman

2014-01-01

Ergothioneine (5) and ovothiol (8) are two novel thiol-containing natural products. Their C-S bonds are formed by oxidative coupling reactions catalyzed by EgtB and OvoA enzymes, respectively. In this work, it was discovered that besides catalyzing the oxidative coupling between histidine and cysteine (1 → 6 conversion), OvoA can also catalyze a direct oxidative coupling between hercynine (2) and cysteine (2 → 4 conversion), which can shorten the ergothioneine biosynthetic pathway by two steps. PMID:24016264

Photoinitiated polymerization of PEG-diacrylate with lithium phenyl-2,4,6-trimethylbenzoylphosphinate: polymerization rate and cytocompatibility

PubMed Central

Fairbanks, Benjamin D.; Schwartz, Michael P.; Bowman, Christopher N.; Anseth, Kristi S.

2009-01-01

Due to mild reaction conditions and temporal and spatial control over material formation, photopolymerization has become a valuable technique for the encapsulation of living cells in three dimensional, hydrated, biomimetic materials. For such applications,2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone (I2959) is the most commonly used photoinitiator (by virtue of its moderate water solubility), yet this initiator has an absorption spectrum that is poorly matched with wavelengths of light generally regarded as benign to living cells, limiting the rate at which it may initiate polymerization in their presence. In contrast, acylphosphine oxide photoinitiators, generally exhibit absorption spectra at wavelengths suitable for cell encapsulation, yet commercially available initiators of this class have low water solubility. Here, a water soluble lithium acylphosphinate salt is evaluated for its ability to polymerize diacrylated poly(ethylene glycol) (PEGDA) monomers rapidly into hydrogels, while maintaining high viability during direct encapsulation of cells. Through rheometric measurements, the time to reach gelation of a PEGDA solution with the phosphinate initiator is one tenth the time for that using I2959 at similar concentrations, when exposed to 365 nm light. Further, polymerization with the phosphinate initiator at 405 nm visible light exposure is achieved with low initiator concentrations and light intensities, precluded in polymerizations initiated with I2959 by its absorbance profile. When examined 24 hours after encapsulation, survival rates of human neonatal fibroblasts encapsulated in hydrogels polymerized with the phosphinate initiator exceed 95%, demonstrating the cytocompatibility of this initiating system. PMID:19783300

Preparation of end-grafted polymer brushes by nitroxide-mediated free radical polymerization of vaporized vinyl monomers.

PubMed

Li, Jun; Chen, Xiaoru; Chang, Ying-Chih

2005-10-11

In this work, we report a gas-phase polymerization approach to create end-grafted vinyl based polymer films on silicon oxide based substrates. The "surface-initiated vapor deposition polymerization" (SI-VDP) of vaporized vinyl monomers, via the nitroxide-mediated free radical polymerization mechanism, was developed to fabricate various homo- and block copolymer brushes from surface-bound initiators, 1-(4'-oxa-2'-phenyl-12'-trimethoxysilyldodecyloxy)-2,2,6,6-tetra-methylpiperidine ("TEMPO"). The resulting polymer thin films were characterized by the Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ellipsometry, and contact angle goniometry, respectively, to identify the surface composition, film thickness, surface coverage, and water contact angles. Through the SI-VDP, end-grafted polymer films of polystyrene (PSt), poly(acrylic acid) (PAAc), poly(N-(2-hydroxypropyl) methacrylamide) (PHPMA), and poly(N-isopropylacrylamide) (PNIPAAm) with 10-200 nm thicknesses were fabricated. Furthermore, the block copolymer films of PAAc (1st block)-b-PSt (2nd block), PSt (1st block)-b-PAAc (2nd block), and a triblock copolymer film of PAAc (1st)-b-PSt (2nd)-b-PHPMA (3rd), were also fabricated, suggesting the "renewability" of the TEMPO-initiated polymerization in the SI-VDP scheme. It is also noticed that the SI-VDP is more efficient than the conventional solution phase polymerization in producing functional polymer brushes such as PNIPAAm, PAAc, or PAAc-b-PSt end-grafted films. In summary, our studies have shown clear advantages of the SI-VDP setup for the nitroxide-mediated polymerization scheme in controlling synthesis of end-grafted homo- and copolymer thin films.

In vivo polymerization of poly(3,4-ethylenedioxythiophene) in the living rat hippocampus does not cause a significant loss of performance in a delayed alternation task

NASA Astrophysics Data System (ADS)

Ouyang, Liangqi; Shaw, Crystal L.; Kuo, Chin-chen; Griffin, Amy L.; Martin, David C.

2014-04-01

After extended implantation times, traditional intracortical neural probes exhibit a foreign-body reaction characterized by a reactive glial sheath that has been associated with increased system impedance and signal deterioration. Previously, we have proposed that the local in vivo polymerization of an electronically and ionically conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), might help to rebuild charge transport pathways across the glial scar between the device and surrounding parenchyma (Richardson-Burns et al 2007 J. Neural Eng. 4 L6-13). The EDOT monomer can be delivered via a microcannula/electrode system into the brain tissue of living animals followed by direct electrochemical polymerization, using the electrode itself as a source of oxidative current. In this study, we investigated the long-term effect of local in vivo PEDOT deposition on hippocampal neural function and histology. Rodent subjects were trained on a hippocampus-dependent task, delayed alternation (DA), and implanted with the microcannula/electrode system in the hippocampus. The animals were divided into four groups with different delay times between the initial surgery and the electrochemical polymerization: (1) control (no polymerization), (2) immediate (polymerization within 5 min of device implantation), (3) early (polymerization within 3-4 weeks after implantation) and (4) late (polymerization 7-8 weeks after polymerization). System impedance at 1 kHz was recorded and the tissue reactions were evaluated by immunohistochemistry. We found that under our deposition conditions, PEDOT typically grew at the tip of the electrode, forming an ˜500 µm cloud in the tissue. This is much larger than the typical width of the glial scar (˜150 µm). After polymerization, the impedance amplitude near the neurologically important frequency of 1 kHz dropped for all the groups; however, there was a time window of 3-4 weeks for an optimal decrease in impedance. For all surgery-polymerization time intervals, the polymerization did not cause significant deficits in performance of the DA task, suggesting that hippocampal function was not impaired by PEDOT deposition. However, GFAP+ and ED-1+ cells were also found at the deposition two weeks after the polymerization, suggesting potential secondary scarring. Therefore, less extensive deposition or milder deposition conditions may be desirable to minimize this scarring while maintaining decreased system impedance.

In vivo polymerization of poly(3,4-ethylenedioxythiophene) (PEDOT) in living rat hippocampus does not cause a significant loss of performance in a delayed alternation (DA) task

PubMed Central

Ouyang, Liangqi; Shaw, Crystal L.; Kuo, Chin-chen; Griffin, Amy L.; Martin, David C.

2014-01-01

After extended implantation times, traditional intracortical neural probes exhibit a foreign body reaction characterized by a reactive glial sheath that has been associated with increased system impedance and signal deterioration. Previously, we have proposed that the local in vivo polymerization of an electronically and ionically conducting polymer, poly(3,4 ethylene dioxythiophene) (PEDOT), might help to rebuild charge transport pathways across the glial scar between the device and surrounding parenchyma (Richardson-Burns, Hendricks, & Martin, 2007). The EDOT monomer can be delivered via a microcannula/electrode system into the brain tissue of living animals followed by direct electrochemical polymerization, using the electrode itself as a source of oxidative current. In this study we investigated the long-term effect of local in vivo PEDOT deposition on hippocampal neural function and histology. Rodent subjects were trained on a hippocampus-dependent task, Delayed Alternation (DA), and implanted with the microcannula/electrode system in the hippocampus. The animals were divided into four groups with different delay times between the initial surgery and the electrochemical polymerization: (1) Control (no polymerization), (2) Immediate (polymerization within 5 minutes of device implantation), (3) Early (polymerization within 3–4 weeks after implantation), and (4) Late (polymerization 7–8 weeks after polymerization). System impedance at 1 kHz was recorded and the tissue reactions were evaluated by immunohistochemistry. We found that under our deposition conditions, PEDOT typically grew at the tip of the electrode, forming a ~500 μm cloud into the tissue. This is much larger than the typical width of the glial scar (~150 μm). After polymerization, the impedance amplitude near the neurologically important frequency of 1 kHz dropped for all the groups, however, there was a time window of 3–4 weeks for optimal decrease in impedance. For all surgery-polymerization time intervals, the polymerization did not cause significant deficits in performance of the DA task, suggesting that hippocampal function was not impaired by PEDOT deposition. However, GFAP+ and ED-1+ cells were also found at the deposition 2 weeks after the polymerization, suggesting potential secondary scarring. Therefore less extensive deposition or milder deposition conditions may be desirable to minimize this scarring while maintaining decreased system impedance. PMID:24503720

In situ STM investigation of aromatic poly(azomethine) arrays constructed by "on-site" equilibrium polymerization.

PubMed

Tanoue, Ryota; Higuchi, Rintaro; Ikebe, Kiryu; Uemura, Shinobu; Kimizuka, Nobuo; Stieg, Adam Z; Gimzewski, James K; Kunitake, Masashi

2012-10-02

Two-dimensional (2D) arrays of π-conjugated aromatic polymers produced by surface-selective Schiff base coupling reactions between an aromatic diamine and an aromatic dialdehyde were investigated in detail using in situ scanning tunneling microscopy. Surface-selective coupling was achieved for almost all diamine/dialdehyde combinations attempted, although several combinations did not proceed even in homogeneous aqueous alkaline solution. Most of the combinations of an aromatic diamine and a dialdehyde, except the combinations of 4,4'-azodianiline with mono/bithiophenedicarboxaldehyde, formed highly ordered π-conjugated polymer arrays on an iodine-modified Au(111) surface in aqueous solution at a suitable pH. The simplest polymer of the various combinations tested, obtained from the combination of 1,4-diaminobenzene with terephthaldicarboxaldehyde, gave a 2D array consisting of linearly connected benzene units. Poly(azomethine) adlayers caused a positive shift in the electrochemical potential of the butterfly shaped oxidative adsorption and reductive desorption of iodine. The acceleration of the reductive desorption of iodine suggests the existence of a weak interaction between the polymer layer and iodine. Not only the first polymer adlayers but also partially adsorbed secondary adlayers with "on-top" epitaxial behavior were frequently observed for all polymer systems. The alignment of the polymer chains in the adlayers possessed a certain regularity in terms of a regular interval between polymer chains because of repulsive interpolymer interactions.

Enhanced mechanical properties of self-polymerized polydopamine-coated recycled PLA filament used in 3D printing

NASA Astrophysics Data System (ADS)

Zhao, Xing Guan; Hwang, Kyung-Jun; Lee, Dongoh; Kim, Taemin; Kim, Namsu

2018-05-01

Dopamine readily adsorbs onto almost all kinds of surfaces and develops cohesive strength through self-polymerization; hence, aqueous solutions of dopamine can be used as adhesives. These properties were used to prevent the degradation in the mechanical properties of recycled PLA fabricated by 3D printer. The mechanical properties of 3D printed PLA play a critical role in determining its applications. To reduce the manufacturing cost as well as environmental pollutants, recycling of 3D printed materials has attracted many attentions. However, recycling of polymeric materials causes the degradation of the mechanical properties. Our study is aimed at advancing the current knowledge on the adhesion behavior of polydopamine coatings on PLA pellets used in 3D printing process. Polydopamine was synthesized by oxidative polymerization and used to coat PLA specimens. The adhesion behavior and mechanical properties of the 3D printed specimens were evaluated by tensile tests. It was found that the mechanical properties of recycled specimen with polydopamine coating have been improved. Microstructural and chemical characterization of the coated specimens was carried out using FE-SEM, FTIR, and XPS analyses.

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

PubMed Central

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; Zhao, Jie; Yan, Kai; Cui, Yi

2016-01-01

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm−2 in both carbonate and ether electrolyte. The advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes. PMID:26987481

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

DOE PAGES

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; ...

2016-03-18

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yayuan; Lin, Dingchang; Liang, Zheng

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

High-sensitivity chemical derivatization NMR analysis for condition monitoring of aged elastomers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Assink, Roger Alan; Celina, Mathias C.; Skutnik, Julie Michelle

2004-06-01

An aged polybutadiene-based elastomer was reacted with trifluoroacetic anhydride (TFAA) and subsequently analyzed via 19F NMR spectroscopy. Derivatization between the TFAA and hydroxyl functionalities produced during thermo-oxidative aging was achieved, resulting in the formation of trifluoroester groups on the polymer. Primary and secondary alcohols were confirmed to be the main oxidation products of this material, and the total percent oxidation correlated with data obtained from oxidation rate measurements. The chemical derivatization appears to be highly sensitive and can be used to establish the presence and identity of oxidation products in aged polymeric materials. This methodology represents a novel condition monitoringmore » approach for the detection of chemical changes that are otherwise difficult to analyze.« less

Photo-catalytic Activities of Plant Hormones on Semiconductor Nanoparticles by Laser-Activated Electron Tunneling and Emitting

PubMed Central

Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Jiang, Ruowei; Zhong, Hongying

2015-01-01

Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO2), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach, photo-activities of phytohormones have been investigated. PMID:25749635

Photo-catalytic Activities of Plant Hormones on Semiconductor Nanoparticles by Laser-Activated Electron Tunneling and Emitting

NASA Astrophysics Data System (ADS)

Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Jiang, Ruowei; Zhong, Hongying

2015-03-01

Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO2), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach, photo-activities of phytohormones have been investigated.

Chemical factors that control lignin polymerization.

PubMed

Sangha, Amandeep K; Davison, Brian H; Standaert, Robert F; Davis, Mark F; Smith, Jeremy C; Parks, Jerry M

2014-01-09

Lignin is a complex, branched polymer that reinforces plant tissue. Understanding the factors that govern lignin structure is of central importance to the development of technologies for converting lignocellulosic biomass into fuels because lignin imparts resistance to chemical, enzymatic, and mechanical deconstruction. Lignin is formed by enzymatic oxidation of phenolic monomers (monolignols) of three main types, guaiacyl (G), syringyl (S), and p-hydroxyphenyl (H) subunits. It is known that increasing the relative abundance of H subunits results in lower molecular weight lignin polymers and hence more easily deconstructed biomass, but it is not known why. Here, we report an analysis of frontier molecular orbitals in mono-, di-, and trilignols, calculated using density functional theory, which points to a requirement of strong p-electron density on the reacting phenolic oxygen atom of the neutral precursor for enzymatic oxidation to occur. This model is consistent with a proton-coupled electron transfer (PCET) mechanism and for the first time explains why H subunits in certain linkages (β-β or β-5) react poorly and tend to "cap" the polymer. In general, β-5 linkages with either a G or H terminus are predicted to inhibit elongation. More broadly, the model correctly accounts for the reactivity of the phenolic groups in a diverse set of dilignols comprising H and G subunits. Thus, we provide a coherent framework for understanding the propensity toward growth or termination of different terminal subunits in lignin.

Chemical Compatibility of Polymeric Materials.

ERIC Educational Resources Information Center

Solen, Kenneth A.; Kuchar, Marvin C.

1990-01-01

Presents some principles for specifying general classes of polymers for predicting relative chemical attack from acids, bases, oxidants, and certain common antagonists. Also discusses predicting relative solvent effects. Suggests uses of this information in two or three lectures in a chemical engineering materials course. (YP)

Synthesis of imine bond containing insoluble polymeric ligand and its transition metal complexes, structural characterization and catalytic activity on esterification reaction.

PubMed

Gönül, İlyas; Ay, Burak; Karaca, Serkan; Saribiyik, Oguz Yunus; Yildiz, Emel; Serin, Selahattin

2017-01-01

In this study, synthesis of insoluble polymeric ligand (L) and its transition metal complexes [Cu(L)Cl 2 ]·2H 2 O (1) , [Co(L)Cl 2 (H 2 O) 2 ] (2) and [Ni(L)Cl 2 (H 2 O) 2 ] (3) , having the azomethine groups, were synthesized by the condensation reactions of the diamines and dialdehydes. The structural properties were characterized by the analytical and spectroscopic methods using by elemental analysis, Fourier Transform Infrared, Thermo Gravimetric Analysis, Powder X-ray Diffraction, magnetic susceptibility and Inductively Coupled Plasma. The solubilities of the synthesized polymeric materials were also investigated and found as insoluble some organic and inorganic solvents. Additionally, their catalytic performance was carried out for the esterification reaction of acetic acid and butyl acetate. The highest conversion rate is 75.75% by using catalyst 1 . The esterification of butanol gave butyl acetate with 100% selectivity.

Enhancement of Fluorescence-Based Sandwich Immunoassay Using Multilayered Microplates Modified with Plasma-Polymerized Films

PubMed Central

Yano, Kazuyoshi; Iwasaki, Akira

2016-01-01

A functional modification of the surface of a 96-well microplate coupled with a thin layer deposition technique is demonstrated for enhanced fluorescence-based sandwich immunoassays. The plasma polymerization technique enabling the deposition of organic thin films was employed for the modification of the well surface of a microplate. A silver layer and a plasma-polymerized film were consecutively deposited on the microplate as a metal mirror and the optical interference layer, respectively. When Cy3-labeled antibody was applied to the wells of the resulting multilayered microplate without any immobilization step, greatly enhanced fluorescence was observed compared with that obtained with the unmodified one. The same effect could be also exhibited for an immunoassay targeting antigen directly adsorbed on the multilayered microplate. Furthermore, a sandwich immunoassay for the detection of interleukin 2 (IL-2) was performed with the multilayered microplates, resulting in specific and 88-fold–enhanced fluorescence detection. PMID:28029144

In vitro biocompatibility of plasma-aided surface-modified 316L stainless steel for intracoronary stents.

PubMed

Bayram, Cem; Mizrak, Alpay Koray; Aktürk, Selçuk; Kurşaklioğlu, Hurkan; Iyisoy, Atila; Ifran, Ahmet; Denkbaş, Emir Baki

2010-10-01

316L-type stainless steel is a raw material mostly used for manufacturing metallic coronary stents. The purpose of this study was to examine the chemical, wettability, cytotoxic and haemocompatibility properties of 316L stainless steel stents which were modified by plasma polymerization. Six different polymeric compounds, polyethylene glycol, 2-hydroxyethyl methacrylate, ethylenediamine, acrylic acid, hexamethyldisilane and hexamethyldisiloxane, were used in a radio frequency glow discharge plasma polymerization system. As a model antiproliferative drug, mitomycin-C was chosen for covalent coupling onto the stent surface. Modified SS 316L stents were characterized by water contact angle measurements (goniometer) and x-ray photoelectron spectroscopy. C1s binding energies showed a good correlation with the literature. Haemocompatibility tests of coated SS 316L stents showed significant latency (t-test, p < 0.05) with respect to SS 316L and control groups in each test.

Polymerization of tellurophene derivatives via microwave-assisted palladium-catalyzed ipso-arylative polymerization**

PubMed Central

Park, Young S.; Wu, Qin; Nam, Chang-Yong; Grubbs, Robert B.

2014-01-01

We report the synthesis of a tellurophene-containing low bandgap polymer, PDPPTe2T, via microwave-assisted palladium-catalyzed ipso-arylative polymerization of 2,5-bis[(α-hydroxy-α,α-diphenyl)methyl]tellurophene with a diketopyrrolopyrrole (DPP) monomer. Compared with the corresponding thiophene analog, PDPPTe2T absorbs light of longer wavelengths and has a smaller bandgap. Bulk heterojunction solar cells prepared from PDPPTe2T and PC71BM show PCE values of up to 4.4%. External quantum efficiency measurements show that PDPPTe2T produces photocurrent at wavelengths up to 1 μm. DFT calculations suggest that the atomic substitution from sulfur to tellurium increases electronic coupling to decrease the length of the carbon-carbon bonds between the tellurophene and thiophene rings, which results in the red-shift in absorption upon substitution of tellurium for sulfur. PMID:25145499

Polymer-grafted gold nanorods in polymer thin films: Dispersion and plasmonic coupling

NASA Astrophysics Data System (ADS)

Hore, Michael-Jon Ainsley

This dissertation describes complementary experimental and theoretical studies to deter- mine the thermodynamic factors that affect the dispersion of polymer-grafted Au nanorods within polymer thin films. Au nanorods exhibit a uniform dispersion with a regular spacing for favorable brush / matrix interactions, such as poly(ethylene glycol) (PEG)-Au / poly(methyl methacrylate) (PMMA) and polystyrene (PS)-Au / poly(2,6-dimethyl-p-phenylene oxide) (PPO). For PEG-Au / PMMA, the nanorods are locally oriented and their dispersion is independent of the ratio of the degree of polymerization of the matrix (P) to that of the brush (N), α = P/N, whereas for chemically similar brush / matrix combinations, such as PS-Au / PS and PEG-Au / poly(ethylene oxide) (PEO), nanorods are randomly dispersed for α 2. For aggregated systems (α > 2), nanorods are found primarily within aggregates containing side-by-side aligned nanorods with a spacing that scales with N. UV-visible spectroscopy and discrete dipole approximation (DDA) calculations demonstrate that coupling between surface plasmons within the aggregates leads to a blue shift in the optical absorption as α increases, indicating the sensitivity of spectroscopy for determining nanorod dispersion in polymer nanocomposite films. Self-consistent field theory (SCFT) calculations and Monte Carlo (MC) simulations show that the aggregation of nanorods for α > 2 can be attributed to depletion-attraction forces caused by autophobic dewetting of the brush and matrix. Finally, miscible blends of PS and PPO are investigated as a route to control depletion-attraction interactions between PS-Au nanorods. Initially, nanorods aggregate in matrices having 50 vol. % PPO and then gradually disperse as PPO becomes the majority component. The brush and matrix density profiles, determined by SCFT, show that PPO segregates into the PS brush, and acts as a compatibilizer, which improves dispersion. As dispersion improves, coupling between surface plasmons is reduced, leading to a red shift in the optical absorption. The outcome of these systematic structure-property-modeling studies is the ability to control nanorod dispersion, orientation, and optical absorption by manipulating brush/matrix interactions and entropic depletion-attraction forces.

Effects of gas flow rate on the etch characteristics of a low- k sicoh film with an amorphous carbon mask in dual-frequency CF4/C4F8/Ar capacitively-coupled plasmas

NASA Astrophysics Data System (ADS)

Kwon, Bong-Soo; Lee, Hea-Lim; Lee, Nae-Eung; Kim, Chang-Young; Choi, Chi Kyu

2013-01-01

Highly selective nanoscale etching of a low-dielectric constant (low- k) organosilicate (SiCOH) layer using a mask pattern of chemical-vapor-deposited (CVD) amorphous carbon layer (ACL) was carried out in CF4/C4F8/Ar dual-frequency superimposed capacitively-coupled plasmas. The etching characteristics of the SiCOH layers, such as the etch rate, etch selectivity, critical dimension (CD), and line edge roughness (LER) during the plasma etching, were investigated by varying the C4F8 flow rate. The C4F8 gas flow rate primarily was found to control the degree of polymerization and to cause variations in the selectivity, CD and LER of the patterned SiCOH layer. Process windows for ultra-high etch selectivity of the SiCOH layer to the CVD ACL are formed due to the disproportionate degrees of polymerization on the SiCOH and the ACL surfaces.

Changes in characteristics of soluble microbial products and extracellular polymeric substances in membrane bioreactor coupled with worm reactor: relation to membrane fouling.

PubMed

Tian, Yu; Li, Zhipeng; Lu, Yaobin

2012-10-01

The study focused on the membrane fouling mitigation observed in a membrane bioreactor (MBR) coupled with worm reactor system. During the operation time of 100 days, the transmembrane pressure (TMP) in the combined system was maintained less than 5 kPa, while the final TMP in the Control-MBR increased to 30 kPa. The changes in properties of soluble microbial products (SMP) and extracellular polymeric substances (EPS) after worm predation were investigated by means of various analytical techniques. It was found that due to the worm predation, the reduced amount of EPS was far more than the increased amount of SMP leading to a significant decrease of protein-like substances which were dominant in the membrane foulants. Except for the content decrease, worm predation destroyed the functional groups of simple aromatic proteins and tryptophan protein-like substances in EPS, making them have lower tendency attaching to the membrane in the combined system. Copyright © 2012 Elsevier Ltd. All rights reserved.

Friction-induced surface activity of some hydrocarbons with clean and oxide-covered iron

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Sliding friction studies were conducted on a clean and oxide-covered iron surface with exposure of that surface to various hydrocarbons. The hydrocarbons included ethane, ethylene ethyl chloride, methyl chloride, and vinyl chloride. Auger cylindrical mirror analysis was used to follow interactions of the hydrocarbon with the iron surface. Results with vinyl chloride indicate friction induced surface reactivity, adsorption to surface oxides, friction sensitivity to concentration and polymerization. Variation in the loads employed influence adsorption and accordingly friction. In contrast with ethyl and vinyl chloride, friction induced surface reactivity was not observed with ethane and ethylene.

Polyurethane nanofiber strain sensors via in situ polymerization of polypyrrole and application to monitoring joint flexion

NASA Astrophysics Data System (ADS)

Kim, Inhwan; Cho, Gilsoo

2018-07-01

Strain sensors made of intrinsically conductive polymers (ICPs) and nanofibers were fabricated and tested for suitability for use in wearable technology. The sensors were fabricated and evaluated based on their surface appearances, and electrical, tensile, and chemical/thermal properties. Polypyrrole (PPy) was in situ polymerized onto polyurethane (PU) nanofiber substrates by exposing pyrrole monomers to ammonium persulfate as oxidant and 2,6-naphthalenedisulfonic acid disodium salt as doping agents in an aqueous bath. The PPy treated PU nanofibers were then coated with polydimethylsiloxane (PDMS). Both pyrrole concentrations and layer numbers were significantly related to change in electrical conductivity. Specimen treated with 0.1 M of PPy and having three layered structure showed the best electrical conductivity. Regarding tensile strength, the in situ polymerization process decreased tensile strength because the oxidant chemically degraded the PU fibers. Adding layers and PDMS treatment generally improved tensile properties while adding layers created fracture parts in the stress–strain curves. The treatment condition of 0.1 M of PPy, two layered, and PDMS treated specimen showed the best tensile properties as a strain sensor. The chemical property evaluation with Fourier transform infrared and x-ray photoelectron spectroscopy tests showed successful PPy polymerization and PDMS treatments. The functional groups and chemical bonds in polyol, urethane linkage, backbone ring structure in PPy, silicon-based functional groups in PDMS, and elemental content changes by treatment at each stage were characterized. The real-time data acquired from the dummy and five human subjects with repetition of motion at three different speeds of 0.16, 0.25 and 0.5 Hz generated similar trends and tendencies. The PU nanofiber sensors based on PPy and PDMS treatments in this study point to the possibility of developing textiles based wearable strain sensors developed using ICPs.

Conjugation of arginine-glycine-aspartic acid peptides to poly(ethylene oxide)-b-poly(epsilon-caprolactone) micelles for enhanced intracellular drug delivery to metastatic tumor cells.

PubMed

Xiong, Xiao-Bing; Mahmud, Abdullah; Uludağ, Hasan; Lavasanifar, Afsaneh

2007-03-01

An arginine-glycine-aspartic acid (RGD) containing model peptide was conjugated to the surface of poly(ethylene oxide)-block-poly(epsilon-caprolactone) (PEO-b-PCL) micelles as a ligand that can recognize adhesion molecules overexpressed on the surface of metastatic cancer cells, that is, integrins, and that can enhance the micellar delivery of encapsulated hydrophobic drug into a tumor cell. Toward this goal, PEO-b-PCL copolymers bearing acetal groups on the PEO end were synthesized, characterized, and assembled to polymeric micelles. The acetal group on the surface of the PEO-b-PCL micelles was converted to reactive aldehyde under acidic condition at room temperature. An RGD-containing linear peptide, GRGDS, was conjugated on the surface of the aldehyde-decorated PEO-b-PCL micelles by incubation at room temperature. A hydrophobic fluorescent probe, that is, DiI, was physically loaded in prepared polymeric micelles to imitate hydrophobic drugs loaded in micellar carrier. The cellular uptake of DiI loaded GRGDS-modified micelles by melanoma B16-F10 cells was investigated at 4 and 37 degrees C by fluorescent spectroscopy and confocal microscopy techniques and was compared to the uptake of DiI loaded valine-PEO-b-PCL micelles (as the irrelevant ligand decorated micelles) and free DiI. GRGDS conjugation to polymeric micelles significantly facilitated the cellular uptake of encapsulated hydrophobic DiI most probably by intergrin-mediated cell attachment and endocytosis. The results indicate that acetal-terminated PEO-b-PCL micelles are amenable for introducing targeting moieties on the surface of polymeric micelles and that RGD-peptide conjugated PEO-b-PCL micelles are promising ligand-targeted carriers for enhanced drug delivery to metastatic tumor cells.

Hygienic support of the ISS air quality (main achievements and prospects)

NASA Astrophysics Data System (ADS)

Moukhamedieva, Lana; Tsarkov, Dmitriy; Pakhomova, Anna

Hygienic preventive measures during pre-flight processing of manned spaceships, selection of polymeric materials, sanitary-hygienic evaluation of cargo and scientific hardware to be used on the ISS and life support systems allow to maintain air quality in limits of regulatory requirements. However, graduate increase of total air contamination by harmful chemicals is observed as service life of the ISS gets longer. It is caused by polymeric materials used on the station overall quantity rise, by additional contamination brought by cargo spacecrafts and modules docking to the ISS and by the cargo. At the same time the range of contaminants that are typical for off-gassing from polymeric materials where modern stabilizers, plasticizers, flame retarders and other additives are used gets wider. In resolving the matters of the ISS service life extension the main question of hygienic researches is to determine real safe operation life of the polymeric material used in structures and hardware of the station, including: begin{itemize} research of polymers degradation (ageing) and its effect on intensity of off gassing and its toxicity; begin{itemize} introduction of polymers with minimal volatile organic compounds off gassing under conditions of space flight and thermal-oxidative degradation. In order to ensure human safety during long-term flight it is important to develop: begin{itemize} real-time air quality monitoring systems, including on-line analysis of highly toxic contaminants evolving during thermo-oxidative degradation of polymer materials and during blowouts of toxic contaminants; begin{itemize} hygienic standards of contaminants level for extended duration of flight up to 3 years. It is essential to develop an automated control system for on-line monitoring of toxicological status and to develop hygienic and engineer measures of its management in order to ensure crew members safety during off-nominal situation.

Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization

PubMed Central

2016-01-01

The need for polymers for high-end applications, coupled with the desire to mimic nature’s macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design. PMID:26795940

Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization.

PubMed

Olsén, Peter; Odelius, Karin; Albertsson, Ann-Christine

2016-03-14

The need for polymers for high-end applications, coupled with the desire to mimic nature's macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design.

Porous polymeric materials for hydrogen storage

DOEpatents

Yu, Luping [Hoffman Estates, IL; Liu, Di-Jia [Naperville, IL; Yuan, Shengwen [Chicago, IL; Yang, Junbing [Westmont, IL

2011-12-13

Porous polymers, tribenzohexazatriphenylene, poly-9,9'-spirobifluorene, poly-tetraphenyl methane and their derivatives for storage of H.sub.2 prepared through a chemical synthesis method. The porous polymers have high specific surface area and narrow pore size distribution. Hydrogen uptake measurements conducted for these polymers determined a higher hydrogen storage capacity at the ambient temperature over that of the benchmark materials. The method of preparing such polymers, includes oxidatively activating solids by CO.sub.2/steam oxidation and supercritical water treatment.

Porous polymeric materials for hydrogen storage

DOEpatents

Yu, Luping; Liu, Di-Jia; Yuan, Shengwen; Yang, Junbing

2013-04-02

A porous polymer, poly-9,9'-spirobifluorene and its derivatives for storage of H.sub.2 are prepared through a chemical synthesis method. The porous polymers have high specific surface area and narrow pore size distribution. Hydrogen uptake measurements conducted for these polymers determined a higher hydrogen storage capacity at the ambient temperature over that of the benchmark materials. The method of preparing such polymers, includes oxidatively activating solids by CO.sub.2/steam oxidation and supercritical water treatment.

TRANSPARENT TESTA10 Encodes a Laccase-Like Enzyme Involved in Oxidative Polymerization of Flavonoids in Arabidopsis Seed CoatW⃞

PubMed Central

Pourcel, Lucille; Routaboul, Jean-Marc; Kerhoas, Lucien; Caboche, Michel; Lepiniec, Loïc; Debeaujon, Isabelle

2005-01-01

The Arabidopsis thaliana transparent testa10 (tt10) mutant exhibits a delay in developmentally determined browning of the seed coat, also called the testa. Seed coat browning is caused by the oxidation of flavonoids, particularly proanthocyanidins, which are polymers of flavan-3-ol subunits such as epicatechin and catechin. The tt10 mutant seeds accumulate more epicatechin monomers and more soluble proanthocyanidins than wild-type seeds. Moreover, intact testa cells of tt10 cannot trigger H2O2-independent browning in the presence of epicatechin and catechin, in contrast with wild-type cells. UV–visible light detection and mass spectrometry revealed that the major oxidation products obtained with epicatechin alone are yellow dimers called dehydrodiepicatechin A. These products differ from proanthocyanidins in the nature and position of their interflavan linkages. Flavonol composition was also affected in tt10 seeds, which exhibited a higher ratio of quercetin rhamnoside monomers versus dimers than wild-type seeds. We identified the TT10 gene by a candidate gene approach. TT10 encodes a protein with strong similarity to laccase-like polyphenol oxidases. It is expressed essentially in developing testa, where it colocalizes with the flavonoid end products proanthocyanidins and flavonols. Together, these data establish that TT10 is involved in the oxidative polymerization of flavonoids and functions as a laccase-type flavonoid oxidase. PMID:16243908

Differential effects of grape ( Vitis vinifera ) skin polyphenolics on human platelet aggregation and low-density lipoprotein oxidation.

PubMed

Shanmuganayagam, Dhanansayan; Beahm, Mark R; Kuhns, Melissa A; Krueger, Christian G; Reed, Jess D; Folts, John D

2012-06-13

Antioxidant and antiplatelet properties of grape products are thought to be responsible for observed antiatherosclerotic effects. Diverse classes of phenolics are derived from the seed and skin (GSK) of grapes. The relative contributions of the classes of phenolics to observed properties of grape products are unknown. In this paper, GSK fractions were used to examine effects on platelet aggregation, low-density lipoprotein (LDL) oxidation in vitro, and relative binding of phenolics to LDL. GSK was separated into six fractions (fractions 1-6), and primary phenolics were characterized using high-performance liquid chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Fractions 4, 5, and 6, enriched in polygalloyl polyflavan-3-ols (PGPFs) with 3-6, 4-8, and 6-15 degrees of polymerization, respectively, inhibited platelet aggregation. Fractions 1-3, containing various amounts of oligosaccharides, hydroxycinnamic acids, anthocyanins, flavanols, and low molecular weight PGPFs, significantly increased platelet aggregation. Fractions 4-6 were most effective in binding LDL and inhibiting LDL oxidation. Fractions 5 and 6 exhibited the greatest inhibition of platelet aggregation and LDL oxidation, suggesting that polymeric PGPFs are responsible for the beneficial effects of grape products. Conversely, phenolics in fractions 1-3 may reduce the net biological potency of the grape products and have undesirable effects on cardiovascular disease risk factors.

Coupling UV-H2O2 to accelerate dimethyl phthalate (DMP) biodegradation and oxidation.

PubMed

Chen, Bin; Song, Jiaxiu; Yang, Lihui; Bai, Qi; Li, Rongjie; Zhang, Yongming; Rittmann, Bruce E

2015-11-01

Dimethyl phthalate (DMP), an important industrial raw material, is an endocrine disruptor of concern for human and environmental health. DMP exhibits slow biodegradation, and its coupled treatment by means of advanced oxidation may enhance its biotransformation and mineralization. We evaluated two ways of coupling UV-H2O2 advanced oxidation to biodegradation: sequential coupling and intimate coupling in an internal circulation baffled biofilm reactor (ICBBR). During sequential coupling, UV-H2O2 pretreatment generated carboxylic acids that depressed the pH, and subsequent biodegradation generated phthalic acid; both factors inhibited DMP biodegradation. During intimately coupled UV-H2O2 with biodegradation, carboxylic acids and phthalic acid (PA) did not accumulate, and the biodegradation rate was 13 % faster than with biodegradation alone and 78 % faster than with biodegradation after UV-H2O2 pretreatment. Similarly, DMP oxidation with intimate coupling increased by 5 and 39 %, respectively, compared with biodegradation alone and sequential coupling. The enhancement effects during intimate coupling can be attributed to the rapid catabolism of carboxylic acids, which generated intracellular electron carriers that directly accelerated di-oxygenation of PA and relieved the inhibition effect of PA and low pH. Thus, intimate coupling optimized the impacts of energy input from UV irradiation used together with biodegradation.

Pathophysiologically based drug treatment of sickle cell disease.

PubMed

Steinberg, Martin H

2006-04-01

Sickle cell disease is a systemic disorder that is caused by a mutation (Glu6Val) in the gene that encodes beta globin. The sickle hemoglobin molecule (HbS) is a tetramer of two alpha-globin chains and two sickle beta-globin chains, and has the tendency to polymerize when deoxygenated. HbS facilitates abnormal interactions between the sickle erythrocyte and leukocytes and endothelial cells, which trigger a complex pathobiology. This multifaceted pathophysiology provides the opportunity to interrupt the disease at multiple sites, including polymerization of HbS, erythrocyte density and cell-cell interactions. For example, it is possible to induce higher concentrations of fetal hemoglobin, which disrupts the pathology-initiating step of HbS polymerization. Furthermore, it is possible to improve the hydration of sickle erythrocytes and it might be feasible to counteract the endothelial, inflammatory and oxidative abnormalities of sickle cell disease. A therapeutic approach that targets several sites of pathobiology might be most promising.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2003-04-08

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n }.sup.+ {A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, and SnR".sub.3 containing groups (R"=C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2003-12-30

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C containing groups (R".dbd.C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Metal containing polymeric functional microspheres

NASA Technical Reports Server (NTRS)

Yen, Shiao-Ping S. (Inventor); Rembaum, Alan (Inventor); Molday, Robert S. (Inventor)

1979-01-01

Polymeric functional microspheres containing metal or metal compounds are formed by addition polymerization of a covalently bondable olefinic monomer such as hydroxyethylmethacrylate in the presence of finely divided metal or metal oxide particles, such as iron, gold, platinum or magnetite, which are embedded in the resulting microspheres. The microspheres can be covalently bonded to chemotherapeutic agents, antibodies, or other proteins providing a means for labeling or separating labeled cells. Labeled cells or microspheres can be concentrated at a specific body location such as in the vicinity of a malignant tumor by applying a magnetic field to the location and then introducing the magnetically attractable microspheres or cells into the circulatory system of the subject. Labeled cells can be separated from a cell mixture by applying a predetermined magnetic field to a tube in which the mixture is flowing. After collection of the labeled cells, the magnetic field is discontinued and the labeled sub-cell population recovered.

Method for heat treating and sintering metal oxides with microwave radiation

DOEpatents

Holcombe, Cressie E.; Dykes, Norman L.; Meek, Thomas T.

1989-01-01

A method for microwave sintering materials, primarily metal oxides, is described. Metal oxides do not normally absorb microwave radiation at temperatures ranging from about room temperature to several hundred degrees centrigrade are sintered with microwave radiation without the use of the heretofore required sintering aids. This sintering is achieved by enclosing a compact of the oxide material in a housing or capsule formed of a oxide which has microwave coupling properties at room temprature up to at least the microwave coupling temperature of the oxide material forming the compact. The heating of the housing effects the initial heating of the oxide material forming the compact by heat transference and then functions as a thermal insulator for the encased oxide material after the oxide material reaches a sufficient temperature to adequately absorb or couple with microwave radiation for heating thereof to sintering temperature.

Temperature dependent thermoelectric property of reduced graphene oxide-polyaniline composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitra, Mousumi, E-mail: mousumimitrabesu@gmail.com; Banerjee, Dipali, E-mail: dipalibanerjeebesu@gmail.com; Kargupta, Kajari, E-mail: karguptakajari2010@gmail.com

2016-05-06

A composite material of reduced graphene oxide (rG) nanosheets with polyaniline (PANI) protonated by 5-sulfosalicylic acid has been synthesized via in situ oxidative polymerization method. The morphological and spectral characterizations have been done using FESEM and XRD measurements. The thermoelectric (TE) properties of the reduced graphene oxide-polyaniline composite (rG-P) has been studied in the temperature range from 300-400 K. The electrical conductivity and the Seebeck coefficient of rG-P is higher than the of pure PANI, while the thermal conductivity of the composite still keeps much low value ensuing an increase in the dimensionless figure of merit (ZT) in the wholemore » temperature range.« less

Altered native stability is the dominant basis for susceptibility of α1-antitrypsin mutants to polymerization

PubMed Central

Irving, James A.; Haq, Imran; Dickens, Jennifer A.; Faull, Sarah V.; Lomas, David A.

2014-01-01

Serpins are protease inhibitors whose most stable state is achieved upon transition of a central 5-stranded β-sheet to a 6-stranded form. Mutations, low pH, denaturants and elevated temperatures promote this transition, which can result in a growing polymer chain of inactive molecules. Different types of polymer are possible, but, experimentally only heat has been shown to generate polymers in vitro consistent with ex vivo pathological specimens. Many mutations that alter the rate of heat-induced polymerization have been described, but interpretation is problematic because discrimination is lacking between the effect of global changes in native stability and specific effects on structural mechanism. We show that the temperature midpoint (Tm) of thermal denaturation reflects the transition of α1-antitrypsin to the polymerization intermediate, and determine the relationship with fixed-temperature polymerization half-times (t0.5) in the presence of stabilizing additives [TMAO (trimethylamine N-oxide), sucrose and sodium sulfate], point mutations and disulfide bonds. Combined with a retrospective analysis of 31 mutants characterized in the literature, the results of the present study show that global changes to native state stability are the predominant basis for the effects of mutations and osmolytes on heat-induced polymerization, summarized by the equation: ln(t0.5,mutant/t0.5,wild-type)=0.34×ΔTm. It is deviations from this relationship that hold key information about the polymerization process. PMID:24552432

Flexible polymeric rib waveguide with self-align couplers system

PubMed Central

Huang, Cheng-Sheng; Wang, Wei-Chih

2011-01-01

The authors report a polymeric based rib waveguide with U shape self-align fiber couplers system using a simple micromolding process with SU8 as a molding material and polydimethysiloxane as a waveguide material. The material is used for its good optical transparency, low surface tension, biocompatibility, and durability. Furthermore, the material is highly formable. This unique fabrication molding technique provides a means of keeping the material and manufacturing costs to a minimum. The self-align fiber couplers system also proves a fast and simple means of light coupling. The flexible nature of the waveguide material makes this process ideal for a potential wearable optical sensor. PMID:22171151

Biological studies and electrical conductivity of paper sheet based on PANI/PS/Ag-NPs nanocomposite.

PubMed

Youssef, A M; Mohamed, S A; Abdel-Aziz, M S; Abdel-Aziz, M E; Turky, G; Kamel, S

2016-08-20

Polyaniline (PANI) with/without polystyrene (PS), was successfully manufactured in the occurrence of dispersed pulp fibers via the oxidative polymerization reaction of aniline monomer to produce conductive paper sheets containing PANI, PANI/PS composites. Additionally, sliver nitrate (Ag-NO3) was added by varied loadings to the oxidative polymerization of aniline monomer to provide sliver nanoparticles (Ag-NPs) emptied into the prepared paper sheets. The prepared paper sheets were examined using scanning electron microscopy (SEM), X-ray diffraction (XRD) and infrared spectroscopy (IR), the mechanical properties of the prepared paper sheets were evaluated. Moreover, the electrical conductivity and biological studies such as cellulases assay, Microorganism & culture condition and detection of the released of Ag-NPs were evaluated. Furthermore, the prepared paper sheets were displayed good antibacterial properties contrary to gram positive and gram negative bacteria. Consequently, the prepared paper sheet may be used as novel materials for packaging applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reduced Graphene Oxide-Hybridized Polymeric High-Internal Phase Emulsions for Highly Efficient Removal of Polycyclic Aromatic Hydrocarbons from Water Matrix.

PubMed

Huang, Yipeng; Zhang, Wenjuan; Ruan, Guihua; Li, Xianxian; Cong, Yongzheng; Du, Fuyou; Li, Jianping

2018-03-27

Reduced graphene oxide (RGO)-hybridized polymeric high-internal phase emulsions (RGO/polyHIPEs) with an open-cell structure and hydrophobicity have been successfully prepared using 2-ethylhexyl acrylate and ethylene glycol dimethacrylate as the monomer and the cross-linker, respectively. The adsorption mechanism and performance of this RGO/polyHIPEs to polycyclic aromatic hydrocarbons (PAHs) were investigated. Adsorption isotherms of PAHs on RGO/polyHIPEs show that the saturated adsorption capacity is 47.5 mg/g and the equilibrium time is 8 h. Cycling tests show that the adsorption capacity of RGO/polyHIPEs remains stable in 10 adsorption-desorption cycles without observable structure change in RGO/polyHIPEs. Moreover, the PAH residues in water samples after being purified by RGO/polyHIPEs are lower than the limit values in drinking water set by the European Food Safety Authority. These results demonstrate that the RGO/polyHIPEs have great potentiality in PAH removal and water purification.

Europium-doped aluminum oxide phosphors as indicators for frontal polymerization dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carranza, Arturo; Gewin, Mariah; Pojman, John A., E-mail: japojman@lsu.edu

2014-06-15

In this study, we present an inexpensive and practical method that allows the monitoring and visualization of front polymerization, propagation, and dynamics. Commercially available europium-doped aluminum oxide powders were combined with video imaging to visualize free-radical propagating polymer fronts. In order to demonstrate the applicability of this method, frontal copolymerization reactions of propoxylated glycerin triacrylate (EB53), pentaerythritol triacrylate (PETA), and pentaerythritol tetra-acrylate (PETEA) with 1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane (Luperox 231®) as an initiator were studied and compared to the results obtained by IR imaging. Systems exhibiting higher filler loading, higher EB53 content, and less acrylated monomers showed a marked decrease in front velocity,more » while those with more acrylated monomers and higher crosslinking density showed a marked increase in front velocity. Finally, in order to show the potential of the imaging technique, we studied fronts propagating in planar and spherical geometries.« less

Influence of graphene-oxide nanosheets impregnation on properties of sterculia gum-polyacrylamide hydrogel formed by radiation induced polymerization.

PubMed

Singh, Baljit; Singh, Baldev

2017-06-01

Present work is an attempt, to explore the potential of graphene oxide nanoplates impregnation, on the mechanical and drug delivery properties of sterculia gum-polyacrylamide composite hydrogel formed by radiation induced polymerization. These polymers were characterized by SEM, cryo-SEM, AFM, FTIR's, 13 C NMR and swelling studies. Release profile of an anticancer drug 'gemcitabine' was studied to determine the drug release mechanism and best fit kinetic model. Furthermore, some important biomedical properties of the polymers such as blood compatibility, mucoadhesion, antioxidant properties and gel strength were also studied. Impregnation of GO into sterculia gum-poly(AAm) hydrogels decreased the swelling of hydrogels but improved the mechanical, drug loading and drug release properties of the hydrogels. Release of gemcitabine from drug loaded hydrogels occurred through non-Fickian diffusion mechanism and release profile was best fitted in first order kinetic model. These hydrogels have been found as haemocompatible, mucoadhesive, and antioxidant in nature. Copyright © 2017 Elsevier B.V. All rights reserved.

Novel "anchor modification" of polymeric biomaterial surfaces by the utilization of cyclodextrin inclusion complex supramolecules.

PubMed

Zhao, Xiaobin; Courtney, James M

2009-07-01

In this article, a novel approach for the surface modification of polymeric biomaterials by the utilization of supramolecules was studied. The supramolecules selected were cyclodextrin inclusion complexes (CICs). The biomaterial selected for surface modification was plasticized poly (vinyl chloride) (PVC-P). Results indicate that when the CICs were blended into PVC-P, they tend to migrate and "anchor" on the surface to achieve a remarkable protein-resistant surface, with improved blood compatibility. In comparison with a physical mixture of cyclodextrins and a "guest" molecule, such as poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO and PPO-PEO-PPO for PVC-P modification, CICs modified PVC-P are more consistent in processing and achieve reproducible surface characteristics. Based on this study, a novel "anchor modification" was proposed regarding CICs modified surface. This "anchor modification" is likely to reduce plasticizer extraction from PVC-P and also can be utilized for the modification of polymers other than PVC-P.

Tetra(p-tolyl)borate-functionalized solvent polymeric membrane: a facile and sensitive sensing platform for peroxidase and peroxidase mimetics.

PubMed

Wang, Xuewei; Qin, Wei

2013-07-22

The determination of peroxidase activities is the basis for enzyme-labeled bioaffinity assays, peroxidase-mimicking DNAzymes- and nanoparticles-based assays, and characterization of the catalytic functions of peroxidase mimetics. Here, a facile, sensitive, and cost-effective solvent polymeric membrane-based peroxidase detection platform is described that utilizes reaction intermediates with different pKa values from those of substrates and final products. Several key but long-debated intermediates in the peroxidative oxidation of o-phenylenediamine (o-PD) have been identified and their charge states have been estimated. By using a solvent polymeric membrane functionalized by an appropriate substituted tetraphenylborate as a receptor, those cationic intermediates could be transferred into the membrane from the aqueous phase to induce a large cationic potential response. Thus, the potentiometric indication of the o-PD oxidation catalyzed by peroxidase or its mimetics can be fulfilled. Horseradish peroxidase has been detected with a detection limit at least two orders of magnitude lower than those obtained by spectrophotometric techniques and traditional membrane-based methods. As an example of peroxidase mimetics, G-quadruplex DNAzymes were probed by the intermediate-sensitive membrane and a label-free thrombin detection protocol was developed based on the catalytic activity of the thrombin-binding G-quadruplex aptamer. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic-inorganic random copolymers from methacrylate-terminated poly(ethylene oxide) with 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane: synthesis via RAFT polymerization and self-assembly behavior.

PubMed

Wei, Kun; Li, Lei; Zheng, Sixun; Wang, Ge; Liang, Qi

2014-01-14

In this contribution, we report the synthesis of organic-inorganic random polymers from methacrylate-terminated poly(ethylene oxide) (MAPEO) (Mn = 950) and 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane (MAPOSS) macromers via reversible addition-fragmentation chain transfer (RAFT) polymerization with 4-cyano-4-(thiobenzoylthio) valeric acid (CTBTVA) as the chain transfer agent. The organic-inorganic random copolymers were characterized by means of (1)H NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The results of GPC indicate that the polymerizations were carried out in a controlled fashion. Transmission electron microscopy (TEM) showed that the organic-inorganic random copolymers in bulk were microphase-separated and the POSS microdomains were formed via POSS-POSS interactions. In aqueous solutions the organic-inorganic random copolymers were capable of self-assembling into spherical nanoobjects as evidenced by transmission electron microscopy (TEM) and dynamic laser scattering (DLS). The self-assembly behavior of the organic-inorganic random copolymers was also found to occur in the mixtures with the precursors of epoxy. The nanostructures were further fixed via subsequent curing reaction and thus the organic-inorganic nanocomposites were obtained. The formation of nanophases in epoxy thermosets was confirmed by transmission electron microscopy (TEM) and dynamic mechanical thermal analysis (DMTA). The organic-inorganic nanocomposites displayed the enhanced surface hydrophobicity as evidenced by surface contact angle measurements.

Chemical sensors

DOEpatents

Lowell, Jr., James R.; Edlund, David J.; Friesen, Dwayne T.; Rayfield, George W.

1991-01-01

Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising (a) a mechanochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, operatively coupled to (b) a transducer capable of directly converting said expansion or contraction to a measurable electrical response.

Ultra-thin solid oxide fuel cells: Materials and devices

NASA Astrophysics Data System (ADS)

Kerman, Kian

Solid oxide fuel cells are electrochemical energy conversion devices utilizing solid electrolytes transporting O2- that typically operate in the 800 -- 1000 °C temperature range due to the large activation barrier for ionic transport. Reducing electrolyte thickness or increasing ionic conductivity can enable lower temperature operation for both stationary and portable applications. This thesis is focused on the fabrication of free standing ultrathin (<100 nm) oxide membranes of prototypical O 2- conducting electrolytes, namely Y2O3-doped ZrO2 and Gd2O3-doped CeO2. Fabrication of such membranes requires an understanding of thin plate mechanics coupled with controllable thin film deposition processes. Integration of free standing membranes into proof-of-concept fuel cell devices necessitates ideal electrode assemblies as well as creative processing schemes to experimentally test devices in a high temperature dual environment chamber. We present a simple elastic model to determine stable buckling configurations for free standing oxide membranes. This guides the experimental methodology for Y 2O3-doped ZrO2 film processing, which enables tunable internal stress in the films. Using these criteria, we fabricate robust Y2O3-doped ZrO2 membranes on Si and composite polymeric substrates by semiconductor and micro-machining processes, respectively. Fuel cell devices integrating these membranes with metallic electrodes are demonstrated to operate in the 300 -- 500 °C range, exhibiting record performance at such temperatures. A model combining physical transport of electronic carriers in an insulating film and electrochemical aspects of transport is developed to determine the limits of performance enhancement expected via electrolyte thickness reduction. Free standing oxide heterostructures, i.e. electrolyte membrane and oxide electrodes, are demonstrated. Lastly, using Y2O3-doped ZrO2 and Gd2O 3-doped CeO2, novel electrolyte fabrication schemes are explored to develop oxide alloys and nanoscale compositionally graded membranes that are thermomechanically robust and provide added interfacial functionality. The work in this thesis advances experimental state-of-the-art with respect to solid oxide fuel cell operation temperature, provides fundamental boundaries expected for ultrathin electrolytes, develops the ability to integrate highly dissimilar material (such as oxide-polymer) heterostructures, and introduces nanoscale compositionally graded electrolyte membranes that can lead to monolithic materials having multiple functionalities.

Copper-catalyzed oxidative homo- and cross-coupling of Grignard reagents using diaziridinone.

PubMed

Zhu, Yingguang; Xiong, Tao; Han, Wenyong; Shi, Yian

2014-12-05

Transition-metal-catalyzed cross-coupling reactions are among the most powerful synthetic transformations. This paper describes an efficient copper-catalyzed homo- and cross-coupling of Grignard reagents with di-tert-butyldiaziridinone as oxidant under mild conditions, giving the coupling products in good to excellent yields. The reaction process has a broad substrate scope and is also effective for the C(sp)-C(sp(3)) coupling.

Mechanisms of transport and electron transfer at conductive polymer/liquid interfaces

NASA Astrophysics Data System (ADS)

Ratcliff, Erin

Organic semiconductors (OSCs) have incredible prospects for next-generation, flexible electronic devices including bioelectronics, thermoelectrics, opto-electronics, and energy storage and conversion devices. Yet many fundamental challenges still exist. First, solution processing prohibits definitive control over microstructure, which is fundamental for controlling electrical, ionic, and thermal transport properties. Second, OSCs generally suffer from poor electrical conductivities due to a combination of low carriers and low mobility. Third, polymeric semiconductors have potential-dependent, dynamically evolving electronic and chemical states, leading to complex interfacial charge transfer properties in contact with liquids. This talk will focus on the use of alternative synthetic strategies of oxidative chemical vapor deposition and electrochemical deposition to control physical, electronic, and chemical structure. We couple our synthetic efforts with energy-, time-, and spatially resolved spectroelectrochemical and microscopy techniques to understand the critical interfacial chemistry-microstructure-property relationships: first at the macroscale, and then moving towards the nanoscale. In particular, approaches to better understand electron transfer events at polymer/liquid interfaces as a function of: 1.) chemical composition; 2.) electronic density of states (DOS); and 3.) crystallinity and microstructure will be discussed.

Rapid determination of pyridine derivatives by dispersive liquid-liquid microextraction coupled with gas chromatography/gas sensor based on nanostructured conducting polypyrrole.

PubMed

Pirsa, Sajad; Alizadeh, Naader

2011-12-15

Polypyrrole (PPy) gas sensor has been prepared by polymerization of pyrrole on surfaces of commercial polymer fibers in the presence of an oxidizing agent. The sensing behavior of PPy gas sensor was investigated in the presence of pyridine derivatives. The resistive responses of the PPy gas sensor to pyridine derivatives were in the order of quinoline>pyridine>4-methyl pyridine and 2-methyl pyridine. The PPy gas sensor was used as gas chromatography (GC) detector and exhibited linear responses to pyridine derivatives in the ranges 40-4,000 ng. Dispersive liquid-liquid microextraction (DLLME) combined with GC/PPy gas sensor has been developed for simultaneous determination of pyridine derivatives and quinoline. The purposed method was used for determination of pyridine derivatives from cigarette smoke. The GC runs were completed in 4 min. The reproducibility of this method is suitable and good standard deviations were obtained. RSD value is less than 10% for all analytes. Copyright © 2011 Elsevier B.V. All rights reserved.

Creating biomimetic polymeric surfaces by photochemical attachment and patterning of dextran

PubMed Central

Ferrer, M. Carme Coll; Yang, Shu; Eckmann, David M.; Composto, Russell J.

2010-01-01

In this work, we report the preparation of photoactive dextran and demonstrate its utility by photochemically attaching it onto various polymeric substrates. The attachment of homogeneous and patterned dextran films was performed on polyurethane and polystyrene, with detailed analysis of surface morphology, swelling behavior, and the protein resistance of these substrates. The described photoactive dextran and attachment procedure is applicable to a wide variety of substrates while accommodating surfaces with complex surface and geometries. Dextran with azide content between 22 to 0.3 wt% was produced by esterification with p-azidobenzoic acid. Dextran (1.2 wt% azide) was photografted onto plasma oxidized polyurethane and polystyrene and displayed thicknesses of 5 ± 3 nm and 7 ± 3 nm, respectively. The patterned dextran on oxidized polyurethane was patchy with a nominal height difference between dextranized and non-dextranized regions. The azidated dextran on oxidized polystyrene exhibited a distinct step in height. In the presence of PBS buffer, the dextranized regions became smoother and more uniform without affecting the height difference at the oxidized polyurethane boundary. However, the dextranized regions on oxidized polyurethane were observed to swell by a factor of 3 relative to the dried thickness. These dissimilarities were attributed to hydrogen bonding between the dextran and oxidized polyurethane and were confirmed by the photoimmobiliization in the presence of LiCl. The resulting surface was the smoothest of all the azidated dextran samples (RRMS = 1 ± 0.3 nm) and swelled up to 2 times its dried thickness in PBS buffer. The antifouling properties of dextran functionalized surfaces were verified by the selective adsorption of FITC-labeled human albumin only on the non-dextranized regions of the patterned polyurethane and polystyrene substrates. PMID:20712352

Nanostructure and Dynamics of Ionic and Non-Ionic PEO-Containing Polyureas

NASA Astrophysics Data System (ADS)

Chuayprakong, Sunanta; Runt, James

2013-03-01

A series of polyethylene oxide (PEO) - based diamines with molecular weights ranging from 250 - 6000 g/mol were polymerized in solution with 4,4'-methylene diphenyl diisocyanate (MDI). In addition, PEO soft segment diamines where modified to incorporate ionomeric species and also polymerized with MDI. The role of PEO soft segment molecular weight and the presence of ionic species on nanoscale segregation and cation conductivity were explored. The former was investigated using small-angle X-ray scattering and atomic force microscopy. Dielectric relaxation spectroscopy was used to investigate polymer and ion dynamics. Local environment and hydrogen bonding were identified by using FTIR spectroscopy.

Doxorubicin-loaded micelles of reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers as efficient "active" chemotherapeutic agents.

PubMed

Cambón, A; Rey-Rico, A; Mistry, D; Brea, J; Loza, M I; Attwood, D; Barbosa, S; Alvarez-Lorenzo, C; Concheiro, A; Taboada, P; Mosquera, V

2013-03-10

Five reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers, BOnEOmBOn, with BO ranging from 8 to 21 units and EO from 90 to 411 were synthesized and evaluated as efficient chemotherapeutic drug delivery nanocarriers and inhibitors of the P-glycoprotein (P-gp) efflux pump in a multidrug resistant (MDR) cell line. The copolymers were obtained by reverse polymerization of poly(butylene oxide), which avoids transfer reaction and widening of the EO block distribution, commonly found in commercial poly(ethylene oxide)-poly(propylene oxide) block copolymers (poloxamers). BOnEOmBOn copolymers formed spherical micelles of 10-40 nm diameter at lower concentrations (one order of magnitude) than those of equivalent poloxamers. The influence of copolymer block lengths and BO/EO ratios on the solubilization capacity and protective environment for doxorubicin (DOXO) was investigated. Micelles showed drug loading capacity ranging from ca. 0.04% to 1.5%, more than 150 times the aqueous solubility of DOXO, and protected the cargo from hydrolysis for more than a month due to their greater colloidal stability in solution. Drug release profiles at various pHs, and the cytocompatibility and cytotoxicity of the DOXO-loaded micelles were assessed in vitro. DOXO loaded in the polymeric micelles accumulated more slowly inside the cells than free DOXO due to its sustained release. All copolymers were found to be cytocompatible, with viability extents larger than 95%. In addition, the cytotoxicity of DOXO-loaded micelles was higher than that observed for free drug solutions in a MDR ovarian NCI-ADR-RES cell line which overexpressed P-gp. The inhibition of the P-gp efflux pump by some BOnEOmBOn copolymers, similar to that measured for the common P-gp inhibitor verapamil, favored the retention of DOXO inside the cell increasing its cytotoxic activity. Therefore, poly(butylene oxide)-poly(ethylene oxide) block copolymers offer interesting features as cell response modifiers to complement their role as efficient nanocarriers for cancer chemotherapy. Copyright © 2013 Elsevier B.V. All rights reserved.

Nonaqueous polypyrrole colloids

DOEpatents

Armes, Steven P.; Aldissi, Mahmoud

1991-01-01

Processable conductive polymers including an oxidized, polymerized aromatic heterocyclic monomer, e.g., pyrrole, an stabilizing effective amount of a poly(vinyl acetate) and dopant anions, and a process of preparing said processable conductive polymers directly in a nonaqueous medium such as methyl acetate, methyl formate, ethyl formate, and propyl formate are disclosed.

Supramolecular Inclusion in Cyclodextrins: A Pictorial Spectroscopic Demonstration

ERIC Educational Resources Information Center

Haldar, Basudeb; Mallick, Arabinda; Chattopadhyay, Nitin

2008-01-01

A spectroscopic experiment is presented that reveals that the hydrophobically end-modified water-soluble polymeric fluorophore, pyrene end-capped poly(ethylene oxide) (PYPY), interacts differently with [alpha], [beta], and [gamma]-cyclodextrins (CD) to form supramolecular inclusion complexes. The emission spectrum of PYPY in aqueous solution shows…

Discovering Volatile Chemicals from Window Weatherstripping through Solid-Phase Microextraction/Gas Chromatography-Mass Spectrometry

ERIC Educational Resources Information Center

Rosu, Cornelia; Cueto, Rafael; Veillion, Lucas; David, Connie; Laine, Roger A.; Russo, Paul S.

2017-01-01

Volatile compounds from polymeric materials such as weatherstripping were identified by solid-phase microextraction (SPME), a solvent-free analytical method, coupled to gas chromatography-mass spectrometry (GC-MS). These compounds, originating from additives and fillers used in weatherstripping processing, were mostly polycyclic aromatic…

Chemical sensors

DOEpatents

Lowell, J.R. Jr.; Edlund, D.J.; Friesen, D.T.; Rayfield, G.W.

1991-07-02

Sensors responsive to small changes in the concentration of chemical species are disclosed. The sensors comprise a mechanochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment. They are operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical response. 9 figures.

A Discovery-Oriented Approach to Solid-Phase Peptide Synthesis

ERIC Educational Resources Information Center

Bockman, Matthew R.; Miedema, Christopher J.; Brennan, Brian B.

2012-01-01

In this discovery-oriented laboratory experiment, students use solid-phase synthesis techniques to construct a dipeptide containing an unknown amino acid. Following synthesis and cleavage from the polymeric support, electrospray ionization-mass spectrometry is employed to identify the unknown amino acid that was used in the peptide coupling. This…

Nitrous Oxide-dependent Iron-catalyzed Coupling Reactions of Grignard Reagents.

PubMed

Döhlert, Peter; Weidauer, Maik; Enthaler, Stephan

2015-01-01

The formation of carbon-carbon bonds is one of the fundamental transformations in chemistry. In this regard the application of palladium-based catalysts has been extensively investigated during recent years, but nowadays research focuses on iron catalysis, due to sustainability, costs and toxicity issues; hence numerous examples for iron-catalyzed cross-coupling reactions have been established, based on the coupling of electrophiles (R(1)-X, X = halide) with nucleophiles (R(2)-MgX). Only a small number of protocols deals with the iron-catalyzed oxidative coupling of nucleophiles (R(1)-MgX + R(2)-MgX) with the aid of oxidants (1,2-dihaloethanes). However, some issues arise with these oxidants; hence more recently the potential of the industrial waste product nitrous oxide (N(2)O) was investigated, because the unproblematic side product N(2) is formed. Based on that, we demonstrate the catalytic potential of easily accessible iron complexes in the oxidative coupling of Grignard reagents. Importantly, nitrous oxide was essential to obtain yields up to >99% at mild conditions (e.g. 1 atm, ambient temperature) and low catalyst loadings (0.1 mol%) Excellent catalyst performance is realized with turnover numbers of up to 1000 and turnover frequencies of up to 12000 h(-1). Moreover, a good functional group tolerance is observed (e.g. amide, ester, nitrile, alkene, alkyne). Afterwards the reaction of different Grignard reagents revealed interesting results with respect to the selectivity of cross-coupling product formation.

Copper-Catalyzed Oxidative Homo- and Cross-Coupling of Grignard Reagents Using Diaziridinone

PubMed Central

2015-01-01

Transition-metal-catalyzed cross-coupling reactions are among the most powerful synthetic transformations. This paper describes an efficient copper-catalyzed homo- and cross-coupling of Grignard reagents with di-tert-butyldiaziridinone as oxidant under mild conditions, giving the coupling products in good to excellent yields. The reaction process has a broad substrate scope and is also effective for the C(sp)–C(sp3) coupling. PMID:25420218

Plasma-Chemical Synthesis of Oxide Powders Using Transformer-Coupled Discharge

NASA Astrophysics Data System (ADS)

M. Ulanov, I.; V. Isupov, M.; Yu Litvinsev, A.; A. Mischenko, P.

2013-04-01

An experimental investigation of transformer-coupled discharge in an Ar-O2 mixture with the addition of SiCl4, TiCl4 and ZrCl4 has been carried out under the atmospheric pressure of plasma-forming gases. Discharge power and discharge heat losses have been determined, and the dispersion and phase composition of reaction products (oxide powders) has been analyzed with SEM and X-ray diffraction analysis. Investigations reveal the formation of ultrafine oxide powders in the case of vaporized chloride (SiCl4 and TiCl4) injecting into the transformer coupled discharge. In the case of fine powder (ZrCl4) injection, full oxidation was not observed and reaction products consisted of a mixture of ZrO2 and ZrOCl2. A conclusion has been made regarding the perspectives of using transformer-coupled discharge to produce ultrafine oxide powders.

Polarized Exocytosis Induces Compensatory Endocytosis by Sec4p-Regulated Cortical Actin Polymerization

PubMed Central

Johansen, Jesper; Alfaro, Gabriel; Beh, Christopher T.

2016-01-01

Polarized growth is maintained by both polarized exocytosis, which transports membrane components to specific locations on the cell cortex, and endocytosis, which retrieves these components before they can diffuse away. Despite functional links between these two transport pathways, they are generally considered to be separate events. Using live cell imaging, in vivo and in vitro protein binding assays, and in vitro pyrene-actin polymerization assays, we show that the yeast Rab GTPase Sec4p couples polarized exocytosis with cortical actin polymerization, which induces endocytosis. After polarized exocytosis to the plasma membrane, Sec4p binds Las17/Bee1p (yeast Wiskott—Aldrich Syndrome protein [WASp]) in a complex with Sla1p and Sla2p during actin patch assembly. Mutations that inactivate Sec4p, or its guanine nucleotide exchange factor (GEF) Sec2p, inhibit actin patch formation, whereas the activating sec4-Q79L mutation accelerates patch assembly. In vitro assays of Arp2/3-dependent actin polymerization established that GTPγS-Sec4p overrides Sla1p inhibition of Las17p-dependent actin nucleation. These results support a model in which Sec4p relocates along the plasma membrane from polarized sites of exocytic vesicle fusion to nascent sites of endocytosis. Activated Sec4p then promotes actin polymerization and triggers compensatory endocytosis, which controls surface expansion and kinetically refines cell polarization. PMID:27526190

Electro-mechanical coupling of semiconductor film grown on stainless steel by oxidation

NASA Astrophysics Data System (ADS)

Lin, M. C.; Wang, G.; Guo, L. Q.; Qiao, L. J.; Volinsky, Alex A.

2013-09-01

Electro-mechanical coupling phenomenon in oxidation film on stainless steel has been discovered by using current-sensing atomic force microscopy, along with the I-V curves measurements. The oxidation films exhibit either ohmic, n-type, or p-type semiconductor properties, according to the obtained I-V curves. This technique allows characterizing oxidation films with high spatial resolution. Semiconductor properties of oxidation films must be considered as additional stress corrosion cracking mechanisms.

Oxidation Numbers in the Study of Metabolism

ERIC Educational Resources Information Center

Bentley, Ronald; Franzen, James; Chasteen, Thomas G.

2002-01-01

The calculation and use of oxidation numbers in the study of metabolic reactions are discussed for normal oxidations (alcohol dehydrogenase and the NAD+/NADH couple, propanediol dehydratase) and for enzymatic reactions with a "hidden" redox component (transamination, the coupled conversion of ethylamine to ethanol, and the biomethylation of…

Locating a silane coupling agent in silica-filled rubber composites by EFTEM.

PubMed

Dohi, Hidehiko; Horiuchi, Shin

2007-11-20

A silane coupling agent (SA) was added to silica/rubber composites at different mixing temperatures and the formation of a coupling layer at the silica/rubber interface was investigated by energy-filtering transmission electron microscopy. Bis(triethoxysilypropyl)tetrasulfane (TESPT), which was used as the SA, reacted with the silanol groups on the silica surface and with styrene-butadiene rubber to form an interfacial coupling layer. The silicon and sulfur elemental distributions were analyzed by electron energy loss spectroscopy (EELS) and elemental mapping. The amount of TESPT trapped in the rubber matrix could be qualitatively estimated by EELS, and the in situ formed coupling layer could be characterized by elemental mapping. The result indicated that the formation of the coupling layer was affected by the mixing temperature. The technique described here will contribute to the study of interface-property relationships and the evaluation of the role of SAs in polymeric composites.

Adsorption of ethoxylated styrene oxide and polyacrylic acid and mixtures there of on organic pigment.

PubMed

Wijting, W K; Laven, J; van Benthem, R A T M; de With, G

2008-11-01

The adsorption of two polymeric surfactants on an organic pigment was investigated. As surfactants the anionic polyacrylic acid sodium salt (PANa, M(W)=15,000) and a non-ionic block copolymer surfactant based on styrene oxide (SO) and ethylene oxide (EO) (M(W)=1500) were used. The adsorption behavior was analyzed by size exclusion chromatography of the supernatant after centrifugation of the pigment dispersions. It was found that PANa has no affinity to the pigment, whereas SO-EO has a strong affinity to the pigment surface. Competitive adsorption of PANa and SO-EO was not observed. Addition of SO-EO yields stable dispersions.

Facile fabrication of core cross-linked micelles by RAFT polymerization and enzyme-mediated reaction.

PubMed

Wu, Yukun; Lai, Quanyong; Lai, Shuqi; Wu, Jing; Wang, Wei; Yuan, Zhi

2014-06-01

Polymeric micelles formed in aqueous solution by assembly of amphiphilic block copolymers have been extensively investigated due to their great potential as drug carriers. However, the stability of polymeric assembly is still one of the major challenges in delivering drugs to tissues and cells. Here, we report a facile route to fabricate core cross-linked (CCL) micelles using an enzymatic polymerization as the cross-linking method. We present synthesis of poly(ethylene glycol)-block-poly(N-isopropyl acrylamide-co-N-(4-hydroxyphenethyl) acrylamide) diblock copolymer PEG-b-P(NIPAAm-co-NHPAAm) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The diblock copolymer was then self-assembled into non-cross-linked (NCL) micelles upon heating above the lower critical solution temperature (LCST), and subsequently cross-linked using horseradish peroxidase (HRP) and hydrogen peroxide (H2O2) as enzyme and oxidant. The characterization of the diblock copolymer and micelles were studied by NMR, DLS, UV-vis, and fluorescence spectroscopy. The fluorescence study reveals that the cross-linking process endows the micelles with much lower critical micelle concentration (CMC). In addition, the drug release study shows that the CCL micelles have lower release amount of doxorubicin (DOX) than the NCL micelles due to the enhanced stability of the CCL micelles by core cross-linking process. Copyright © 2014 Elsevier B.V. All rights reserved.

Nitric oxide-releasing polymeric nanoparticles against Trypanosoma cruzi

NASA Astrophysics Data System (ADS)

Seabra, A. B.; Kitice, N. A.; Pelegrino, M. T.; Lancheros, C. A. C.; Yamauchi, L. M.; Pinge-Filho, P.; Yamada-Ogatta, S. F.

2015-05-01

Chagas disease, also known as American trypanosomiasis, is a potentially life-threatening illness caused by the protozoan parasite, Trypanosoma cruzi (T. cruzi), and the disease remains a major health problem in many Latin American countries. Several papers report that the killing of the parasite is dependent on the production of nitric oxide (NO). The endogenous free radical NO is an important cellular signalling molecule that plays a key role in the defense against pathogens, including T. cruzi. As T. cruzi is able to compromise host macrophages decreasing endogenous NO production, the administration of exogenous NO donors represents an interesting strategy to combat Chagas disease. Thus, the aims of this study were to prepare and evaluate the antimicrobial activity of NO-releasing polymeric nanoparticles against T. cruzi. Biocompatible polymeric nanoparticles composed of chitosan/sodium tripolyphosphate(TPP) were prepared and used to encapsulate mercaptosuccinic acid (MSA), which is a thiol-containing molecule. Nitrosation of free thiols (SH) groups of MSA were performed by the addition of equimolar amount of sodium nitrite (NaNO2), leading to the formation of S-nitroso-MSA-containing nanoparticles. These polymeric nanoparticles act as spontaneous NO donors, with free NO release. The results show the formation of nanoparticles with average hydrodynamic diameter ranging from 270 to 500 nm, average of polydispersity index of 0.35, and encapsulation efficiency in the range of 99%. The NO release kinetics from the S-nitroso-MSA-containing nanoparticles showed sustained and controlled NO release over several hours. The microbicidal activity of S-nitroso-MSA-containing nanoparticles was evaluated by incubating NO-releasing nanoparticles (200 - 600 μg/mL) with replicative and non-infective epimastigote, and non-replicative and infective trypomastigote forms of T. cruzi. In addition, a significant decrease in the percentage of macrophage-infected (with amastigotes) and NO-releasing nanoparticle-treated cells was observed. Taken together, our results reveal a potent toxic effect of NO-releasing polymeric nanoparticles against different life cycle forms of T. cruzi, indicating that the encapsulation of the NO donor S-nitroso-MSA represents an interesting approach to combat and to prevent Chagas disease.

Chemical Oxidative Polymerization of Polyaniline: A Practical Approach for Preparation of Smart Conductive Textiles

ERIC Educational Resources Information Center

Abu-Thabit, Nedal Y.

2016-01-01

Electrically conducting polymers are one of the promising alternative materials for technological applications in many interdisciplinary areas, including chemistry, material sciences, and engineering. This experiment was designed for providing undergraduate students with a quick and practical approach for preparation of a polyaniline-conducting…

A comparative study of cellulose nanofibrils disintegrated via multiple processing approaches

Treesearch

Yan Qing; Ronald Sabo; J.Y. Zhu; Umesh Agarwal; Zhiyong Cai; Yiqiang Wu

2013-01-01

Various cellulose nanofibrils (CNFs) created by refining and microfluidization, in combination withenzymatic or 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidized pretreatment were compared. Themorphological properties, degree of polymerization, and crystallinity for the obtained nanofibrils, aswell as physical and mechanical properties of the corresponding films...

ROOM TEMPERATURE BULK SYNTHESIS OF SILVER NANOCABLES WRAPPED WITH POLYPYRROLE

EPA Science Inventory

Wet chemical synthesis of silver cables wrapped with polypyrrole is reported in aqueous media without use of any surfactant/capping agent and/or template. The method employs direct polymerization of pyrrole of an aqueous solution with AgNO3 as an oxidizing agent. The four probe c...

EFFECT OF MOLECULAR ARCHITECTURE ON DBS-INDUCED BLOCK COPOLYMER GELS: A RHEOLOGICAL STUDY

EPA Science Inventory

Dibenzylidene sorbitol (DBS) is capable of gelling a variety of organic solvents and polymeric materials by forming a rigid, 3-D hydrogen-bonded network. In this work, two poly(siloxane)/poly(propylene oxide) segmented copolymers of equal composition and molecular weight, but di...

Li/Ag 2VO 2PO 4 batteries: the roles of composite electrode constituents on electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bock, David C.; Bruck, Andrea M.; Pelliccione, Christopher J.

2016-11-01

Silver vanadium phosphorous oxide, Ag 2V 2OPO 4, was used as a model system to systematically study the impact on the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Three different electrode compositions were investigated.

Large-scale synthesis of reduced graphene oxides with uniformly coated polyaniline for supercapacitor applications.

PubMed

Salunkhe, Rahul R; Hsu, Shao-Hui; Wu, Kevin C W; Yamauchi, Yusuke

2014-06-01

We report an effective route for the preparation of layered reduced graphene oxide (rGO) with uniformly coated polyaniline (PANI) layers. These nanocomposites are synthesized by chemical oxidative polymerization of aniline monomer in the presence of layered rGO. SEM, TEM, X-ray photoelectron spectroscopy (XPS), FTIR, and Raman spectroscopy analysis results demonstrated that reduced graphene oxide-polyaniline (rGO-PANI) nanocomposites are successfully synthesized. Because of synergistic effects, rGO-PANI nanocomposites prepared by this approach exhibit excellent capacitive performance with a high specific capacitance of 286 F g(-1) and high cycle reversibility of 94 % after 2000 cycles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

PubMed Central

Metaxas, Ioannis; Vasilikogiannaki, Eleni

2017-01-01

A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv) and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv) and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12%) from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity. PMID:29231853

High ethylene to ethane processes for oxidative coupling

DOEpatents

Chafin, R.B.; Warren, B.K.

1991-12-17

Oxidative coupling of lower alkane to higher hydrocarbon is conducted using a catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

High ethylene to ethane processes for oxidative coupling

DOEpatents

Chafin, Richard B.; Warren, Barbara K.

1991-01-01

Oxidative coupling of lower alkane to higher hydrocarbon is conducted using catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

One-step synthesis and characterization of polyaniline nanofiber/silver nanoparticle composite networks as antibacterial agents.

PubMed

Poyraz, Selcuk; Cerkez, Idris; Huang, Tung Shi; Liu, Zhen; Kang, Litao; Luo, Jujie; Zhang, Xinyu

2014-11-26

Through a facile and effective seeding polymerization reaction via a one-step redox/complexation process, which took place in aqueous medium at ambient temperature, silver nanoparticles (Ag NPs) embedded polyaniline nanofiber (PANI NF) networks were synthesized as antibacterial agents. During the reaction, not only NF morphology formation of the resulting conducting polymers (CPs) but also amplification of the aqueous silver nitrate (AgNO3) solutions' oxidative potentials were managed by vanadium pentoxide (V2O5) sol-gel nanofibers, which acted as well-known nanofibrous seeding agents and the auxiliary oxidative agent at the same time. The PANI/Ag nanocomposites were proven to exhibit excellent antibacterial property against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Antibacterial property performance and average life span of the nanocomposite network were optimized through the homogeneous distribution/embedment of Ag NPs within one-dimensional (1-D) PANI NF matrix. The antibacterial efficacy tests and nanocomposite material characterization results further indicated that the sole components of PANI/Ag have a synergistic effect to each other in terms of antibacterial property. Thus, this well-known catalytic seeding approach via a one-step oxidative polymerization reaction can be considered as a general methodology and a substantial fabrication tool to synthesize Ag NP decorated nanofibrillar PANI networks as advanced antibacterial agents.

Enhanced the performance of graphene oxide/polyimide hybrid membrane for CO2 separation by surface modification of graphene oxide using polyethylene glycol

NASA Astrophysics Data System (ADS)

Wu, Li-guang; Yang, Cai-hong; Wang, Ting; Zhang, Xue-yang

2018-05-01

Polyethylene glycol (PEG) with different molecular weights was first used to modify graphene oxide (GO) samples. Subsequently, polyimide (PI) hybrid membranes containing modified-GO were fabricated via in situ polymerization. The separation performance of these hybrid membranes was evaluated using permeation experiments for CO2 and N2 gases. The morphology characterization showed that PEG with suitable molecular weight could be successfully grafted on the GO surface. PEG modification altered the surface properties of GO and introduced defective structures onto GO surface. This caused strong surface polarity and high free volume of membranes containing PEG-modified GO, thereby improving the separation performance of membranes. The addition of PEG-GO with low molecular weight effectively increased gas diffusion through hybrid membranes. The hybrid membranes containing PEG-GO with large molecular weight had high solubility performance for CO2 gas due to the introduction of numerous polar groups into polymeric membranes. With the loading content of modified GO, the CO2 gas permeability of hybrid membranes initially increased but eventually decreased. The optimal content of modified GO in membranes reached 3.0 wt%. When too much PEG added (exceeding 30 g), some impurities formed on GO surface and some aggregates appeared in the resulting hybrid membrane, which depressed the membrane performance.

Processable dodecylbenzene sulfonic acid (DBSA) doped poly(N-vinyl carbazole)-poly(pyrrole) for optoelectronic applications

PubMed Central

Hammed, W. A.; Rahman, M. S.; Mahmud, H. N. M. E.; Yahya, R.; Sulaiman, K.

2017-01-01

Abstract A soluble poly (n-vinyl carbazole)–polypyrrole (PNVC–Ppy) copolymer was prepared through oxidative chemical polymerization wherein dodecyl benzene sulfonic acid (DBSA) was used as a dopant to facilitate polymer-organic solvent interaction and ammonium persulfate (APS) was used as an oxidant. Compared with undoped PNVC–Ppy, the DBSA-doped PNVC–Ppy copolymer showed higher solubility in some selected organic solvents. The composition and structural characteristics of the DBSA-doped PNVC–Ppy were determined by Fourier transform infrared, ultraviolet–visible, and X-ray diffraction spectroscopic methods. Field emission scanning electron microscopic method was employed to observe the morphology of the DBSA-doped PNVC–Ppy copolymer. The electrical conductivity of the DBSA-doped PNVC–Ppy copolymer was measured at room temperature. The conductivity increased with increasing concentration of APS oxidant, and the highest conductivity was recorded at 0.004 mol/dm3 APS at a polymerization temperature of −5 °C. The increased conductivity can be explained by the extended half-life of pyrrole free radical at a lower temperature and a gradual increase in chain length over a prolonged time due to the slow addition of APS. Furthermore, the obtained soluble copolymer exhibits unique optical and thermal properties different from those of PNVC and Ppy. PMID:29491808

Fabrication of high-capacity polyelectrolyte brush-grafted porous AAO-silica composite membrane via RAFT polymerization.

PubMed

Song, Cunfeng; Wang, Meijie; Liu, Xin; Wang, He; Chen, Xiaoling; Dai, Lizong

2017-09-01

Surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization has been utilized to fabricate high-capacity strong anion-exchange (AEX) membrane for the separation of protein. By means of RAFT polymerization, quaternized poly(3-(methacrylamidomethyl)-pyridine) brushes formed 3-dimensional nanolayers on the surface of porous anodic aluminum oxide (AAO)-silica composite membrane. The surface properties of the membranes were analyzed by SEM, water contact angle, ATR-FTIR, XPS and TGA. To investigate the adsorption performance, the new AEX membranes were applied to recover a model protein, ovalbumin (OVA). High adsorption capacities of 95.8mg/g membranes (static) and 65.3mg/g membranes (dynamic) were obtained at ambient temperature. In the further studies, up to 90% of the adsorbed OVA was efficiently eluted by using phosphate buffer-1M NaCl as elution medium. The successful separation of OVA with high purity from a mixture protein solution was also achieved by using the AEX membranes. The present study demonstrated that under mild reaction condition, RAFT polymerization can be used to fabricate ion-exchange membrane which has many remarkable features, such as high capacity and selectivity, easy elution and so on. Copyright © 2017. Published by Elsevier B.V.

Coloristic and antimicrobial behaviour of polymeric substrates using bioactive substances

NASA Astrophysics Data System (ADS)

Coman, D.; Vrînceanu, N.; Oancea, S.; Rîmbu, C.

2016-08-01

A major concern in reducing microbial contamination of healthcare and hygiene products motivated us to seek viable alternatives in order to create such barriers. The antimicrobial and anti-oxidant effects of natural extracts are well-known, their application onto polymeric supports is still challenging in terms of investigation. To our knowledge, the method of natural dyeing of different polymeric substrates using bioactive substances derived from black currant and green walnut shells, in conjunction with biomordants, and their long term effects have not been very consistently reported. The main objective of the study is based on the comparative study of different polymeric fibrous substrates dyed by means of laboratory scaled classic methodology with extracts from black currant fruits and green walnut shells, with the assistance of conventional and biomordants (copper sulphate, citric and tannic acids). The assistance of biomordant in the dyeing process seems to conduct to improved synergetic colouring and antibacterial performances. The main results demonstrated that the extract of green walnut shells reinforced by the biomordants solutions expressed the best antimicrobial behaviour. The present research is a milestone in the identification of potential technological alternatives applied in dyeing of synthetic and natural textile supports, quantified and controlled by antimicrobial response correlated with colorimetric features.

The properties conferred upon triple-helical collagen-mimetic peptides by the presence of cysteine residues

PubMed Central

Slatter, David A.; Bihan, Dominique G.; Jarvis, Gavin E.; Stone, Rachael; Pugh, Nicholas; Giddu, Sumana; Farndale, Richard W.

2012-01-01

Recently, the ability of polymeric collagen-like peptides to regulate cell behavior has generated great interest. A triple-helical peptide known as collagen-related peptide (CRP) contains the sequence (Gly-Pro-Hyp)10. With Gly-Pro-Cys triplets appended to both of its termini, designated CRPcys, chemical cross-linking using heterobifunctional reagents generates CRPcys-XL, a potent, widely used, polymeric agonist for platelet Glycoprotein VI, whereas non-cross-linked, monomeric CRPcys antagonizes Glycoprotein VI. Here, we describe how cysteine in these triplets may also undergo random air-induced oxidation, especially upon prolonged storage or repeated freeze–thawing, to form disulphide bonds, resulting in a lesser degree of polymerization than with chemical cross-linking. We investigated the monomeric and polymeric states of these and other cysteine-containing collagen-derived peptides, using gel filtration and dynamic light scattering, allowing the size of a CRP-XL aggregate to be estimated. The effect of cysteine thiols upon peptide adsorption to surfaces and subsequent platelet responses was investigated. This demonstrated that cysteine is required for strong binding to glass coverslips and to plastic plates used in ELISA assays. PMID:22555281

The properties conferred upon triple-helical collagen-mimetic peptides by the presence of cysteine residues.

PubMed

Slatter, David A; Bihan, Dominique G; Jarvis, Gavin E; Stone, Rachael; Pugh, Nicholas; Giddu, Sumana; Farndale, Richard W

2012-07-01

Recently, the ability of polymeric collagen-like peptides to regulate cell behavior has generated great interest. A triple-helical peptide known as collagen-related peptide (CRP) contains the sequence (Gly-Pro-Hyp)(10). With Gly-Pro-Cys triplets appended to both of its termini, designated CRP(cys), chemical cross-linking using heterobifunctional reagents generates CRP(cys)-XL, a potent, widely used, polymeric agonist for platelet Glycoprotein VI, whereas non-cross-linked, monomeric CRP(cys) antagonizes Glycoprotein VI. Here, we describe how cysteine in these triplets may also undergo random air-induced oxidation, especially upon prolonged storage or repeated freeze-thawing, to form disulphide bonds, resulting in a lesser degree of polymerization than with chemical cross-linking. We investigated the monomeric and polymeric states of these and other cysteine-containing collagen-derived peptides, using gel filtration and dynamic light scattering, allowing the size of a CRP-XL aggregate to be estimated. The effect of cysteine thiols upon peptide adsorption to surfaces and subsequent platelet responses was investigated. This demonstrated that cysteine is required for strong binding to glass coverslips and to plastic plates used in ELISA assays. Copyright © 2012 Elsevier Inc. All rights reserved.

Microwave absorption properties of reduced graphene oxide strontium hexaferrite/poly(methyl methacrylate) composites

NASA Astrophysics Data System (ADS)

Acharya, Sanghamitra; Ray, J.; Patro, T. U.; Alegaonkar, Prashant; Datar, Suwarna

2018-03-01

The key factors to consider when designing microwave absorber materials for eradication of electromagnetic (EM) pollution are absorption of incident EM waves and good impedance matching. By keeping these things in mind, flexible microwave absorber composite films can be fabricated by simple gel casting techniques using reduced graphene oxide (RGO) and strontium ferrite (SF) in a poly(methyl methacrylate) (PMMA) matrix. SF nanoparticles are synthesized by the well known sol-gel method. Subsequently, reduced graphene oxide (RGO) and SF nanocomposite (RGOSF) are prepared through a chemical reduction method using hydrazine. The structure, morphology, chemical composition, thermal stability and magnetic properties of the nanocomposite are characterized in detail by various techniques. The SF particles are found to be nearly 500 nm and decorated on RGO sheets as revealed by field emission scanning electron microscopy and transmission electron microscopy analysis. Fourier transform infrared and and Raman spectroscopy clearly show the presence of SF in the graphene sheet by the lower peak positions. Finally, ternary polymer composites of RGO/SF/PMMA are prepared by an in situ polymerization method. Magnetic and dielectric studies of the composite reveal that the presence of RGO/SF/PMMA lead to polarization effects contributing to dielectric loss. Also, RGO surrounding SF provides a conductive network in the polymer matrix which is in turn responsible for the magnetic loss in the composite. Thus, the permittivity as well as the permeability of the composite can be controlled by an appropriate combination of RGO and SF in PMMA. More than 99% absorption efficiency is achieved by a suitable combination of magneto-dielectric coupling in the X-band frequency range by incorporating 9 wt% of RGO and 1 wt% of SF in the polymer matrix.

Construction of Hierarchical Polymer Brushes on Upconversion Nanoparticles via NIR-Light-Initiated RAFT Polymerization.

PubMed

Xie, Zhongxi; Deng, Xiaoran; Liu, Bei; Huang, Shanshan; Ma, Pingan; Hou, Zhiyao; Cheng, Ziyong; Lin, Jun; Luan, Shifang

2017-09-13

Photoinduced reversible addition-fragmentation chain transfer (RAFT) polymerization generally adopts high-energy ultraviolet (UV) or blue light. In combination with photoredox catalyst, the excitation light wavelength was extended to the visible and even near-infrared (NIR) region for photoinduced electron transfer RAFT polymerization. In this report, we introduce for the first time a surface NIR-light-initiated RAFT polymerization on upconversion nanoparticles (UCNPs) without adding any photocatalyst and construct a functional inorganic core/polymer shell nanohybrid for application in cancer theranostics. The multilayer core-shell UCNPs (NaYF 4 :Yb/Tm@NaYbF 4 :Gd@NaNdF 4 :Yb@NaYF 4 ), with surface anchorings of chain transfer agents, can serve as efficient NIR-to-UV light transducers for initiating the RAFT polymerization. A hierarchical double block copolymer brush, consisting of poly(acrylic acid) (PAA) and poly(oligo(ethylene oxide)methacrylate-co-2-(2-methoxy-ethoxy)ethyl methacrylate) (PEG for short), was grafted from the surface in sequence. The targeting arginine-glycine-aspartic (RGD) peptide was modified at the end of the copolymer through the trithiolcarbonate end group. After loading of doxorubicin, the UCNPs@PAA-b-PEG-RGD exhibited an enhanced U87MG cancer cell uptake efficiency and cytotoxicity. Besides, the unique upconversion luminescence of the nanohybrids was used for the autofluoresence-free cell imaging and labeling. Therefore, our strategy verified that UCNPs could efficiently activate RAFT polymerization by NIR photoirradiation and construct the complex nanohybrids, exhibiting prospective biomedical applications due to the low phototoxicity and deep penetration of NIR light.

Reduced graphene oxide-NH2 modified low pressure nanofiltration composite hollow fiber membranes with improved water flux and antifouling capabilities

NASA Astrophysics Data System (ADS)

Li, Xipeng; Zhao, Changwei; Yang, Mei; Yang, Bin; Hou, Deyin; Wang, Tao

2017-10-01

Reduced graphene oxide-NH2 (R-GO-NH2), a kind of amino graphene oxide, was embedded into the polyamide (PA) layer of nanofiltration (NF) composite hollow fiber membranes via interfacial polymerization to enhance the permeate flux and antifouling properties of NF membranes under low pressure conditions. In addition, it could mitigate the poor compatibility issue between graphene oxide materials and PA layer. To evaluate the influence of R-GO-NH2 on the performance of the NF composite hollow fiber membrane, SEM, AFM, FTIR, XPS and Zeta potentials were used to characterize the membranes. The results indicated that the compatibility and interactions between R-GO-NH2 and PA layer were enhanced, which was mainly due to the polymerization reaction between amino groups of R-GO-NH2 and acyl chloride groups of TMC. Therefore, salts rejection of the current membranes was improved significantly, and the modified membranes with 50 mg/L R-GO-NH2 demonstrated highest performance in terms of the rejections, which were 26.9%, 98.5%, 98.1%, and 96.1%, for NaCl, Na2SO4, MgSO4, and CaCl2 respectively. It was found that with the R-GO-NH2 contents rasing from 0 to 50 mg/L, pure water flux increased from 30.44 ± 1.71 to 38.57 ± 2.01 L/(m2.h) at 2 bar. What's more, the membrane demonstrated improved antifouling properties.