Fabrication of Hyperbranched Block-Statistical Copolymer-Based Prodrug with Dual Sensitivities for Controlled Release.

PubMed

Zheng, Luping; Wang, Yunfei; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Ji, Xiangling; Wei, Hua

2018-01-17

Dendrimer with hyperbranched structure and multivalent surface is regarded as one of the most promising candidates close to the ideal drug delivery systems, but the clinical translation and scale-up production of dendrimer has been hampered significantly by the synthetic difficulties. Therefore, there is considerable scope for the development of novel hyperbranched polymer that can not only address the drawbacks of dendrimer but maintain its advantages. The reversible addition-fragmentation chain transfer self-condensing vinyl polymerization (RAFT-SCVP) technique has enabled facile preparation of segmented hyperbranched polymer (SHP) by using chain transfer monomer (CTM)-based double-head agent during the past decade. Meanwhile, the design and development of block-statistical copolymers has been proven in our recent studies to be a simple yet effective way to address the extracellular stability vs intracellular high delivery efficacy dilemma. To integrate the advantages of both hyperbranched and block-statistical structures, we herein reported the fabrication of hyperbranched block-statistical copolymer-based prodrug with pH and reduction dual sensitivities using RAFT-SCVP and post-polymerization click coupling. The external homo oligo(ethylene glycol methyl ether methacrylate) (OEGMA) block provides sufficient extracellularly colloidal stability for the nanocarriers by steric hindrance, and the interior OEGMA units incorporated by the statistical copolymerization promote intracellular drug release by facilitating the permeation of GSH and H + for the cleavage of the reduction-responsive disulfide bond and pH-liable carbonate link as well as weakening the hydrophobic encapsulation of drug molecules. The delivery efficacy of the target hyperbranched block-statistical copolymer-based prodrug was evaluated in terms of in vitro drug release and cytotoxicity studies, which confirms both acidic pH and reduction-triggered drug release for inhibiting proliferation of HeLa cells. Interestingly, the simultaneous application of both acidic pH and GSH triggers promoted significantly the cleavage and release of CPT compared to the exertion of single trigger. This study thus developed a facile approach toward hyperbranched polymer-based prodrugs with high therapeutic efficacy for anticancer drug delivery.

Synthesis and properties of amphiphilic hyperbranched polyethers as pigment dispersant

NASA Astrophysics Data System (ADS)

Xu, Q.; Zhou, Y. J.; Long, S. J.; Liu, Y. G.; Li, J. H.

2018-01-01

Hyperbranched polymers possess prominent properties such as low viscosity, good solubility, high rheological property, environmental non-toxic, and so on, which have potential applications in coatings. In this study, the amphiphilic hyperbranched polyethers (AHPs) consisting of hydrophobic hyperbranched polyethers core and hydrophilic poly (ethylene glycol) arms with different degree of branching (DB) under various reaction temperatures was prepared by the cation ring-opening polymerization. Their structures were characterized by IR, 13CNMR and GPC. Their dispersion properties for pigment particles were investigated. The AHP47 with 0.47 DB was found to have good dispersion properties for Yellow HGR. This work would provide experimental data and theoretical foundation for the application of hyperbranched polyethers in environmental protection coating.

CO2 capture by polymeric membranes composed of hyper-branched polymers with dense poly(oxyethylene) comb and poly(amidoamine)

NASA Astrophysics Data System (ADS)

Taniguchi, Ikuo; Wada, Norihisa; Kinugasa, Kae; Higa, Mitsuru

2017-11-01

Due to CO2-philic nature of polyoxyethylene (POE), a dense POE comb structure was tethered onto PMMA backbone to develop CO2 separation membranes over N2. The resulting hyper-branched polymers displayed preferential CO2 permeation. When the polymer thin layer was formed on a high gas permeable polydimethylsiloxane (PDMS) support by a spray-coating manner, the resulting thin film composite (TFC) membranes displayed very high CO2 permeability. However, the CO2 selectivity, which was the permeability ratio of CO2 over N2, was moderate and lower than 50. To enhance the selectivity, poly(amidoamine) (PAMAM) was introduced to the hyper-branched polymers in the CO2-selective layer of the TFC membranes. The CO2 selectivity increased from 47 to 90 with increasing PAMAM content to 40 wt%, and it was drastically enhanced to 350 with PAMAM content of 50 wt%. Differential scanning calorimetry (DSC) and laser microscope revealed formation of PAMAM-rich domain at the higher amine content, where CO2 could readily migrate in comparison to the other polymeric fractions.

The Lewis-acid-catalyzed synthesis of hyperbranched poly(glycerol-diacid)s in toluene

USDA-ARS?s Scientific Manuscript database

The first examples of monomeric glycerol-derived hyperbranched polyesters produced in a non-polar solvent system are reported here. The polymers were made by the Lewis acid (dibutyltin(IV)oxide)-catalyzed polycondensation of glycerol with either succinic acid (n (aliphatic chain length)=2), glutari...

Degree of branching in hyperbranched poly(glycerol-co-diacid)s synthesized in toluene

USDA-ARS?s Scientific Manuscript database

Hyperbranched polymers were synthesized by using a Lewis acid (dibutyltin(IV)oxide) to catalyze the polycondensation of glycerol with either succinic acid (n (aliphatic chain length)=2), glutaric acid (n=3) or azelaic acid (n=7) in toluene. These are the first examples of diacid-glycerol hyperbranc...

Structural and Interfacial Properties of Hyperbranched-Linear Polymer Surfactant.

PubMed

Qiang, Taotao; Bu, Qiaoqiao; Huang, Zhaofeng; Wang, Xuechuan

2014-01-01

With oleic acid grafting modification, a series of hyperbranched-linear polymer surfactants (HLPS) were prepared by hydroxyl-terminated hyperbranched polymer (HBP), which was gained through a step synthesis method using trimethylolpropane and AB 2 monomer. The AB 2 monomers were obtained through the Michael addition reaction of methyl acrylate and diethanol amine. The structures of HLPS were characterised by Fourier transform infrared spectrophotometer and nuclear magnetic resonance (NMR), which indicated that HBP was successfully modified by oleic acid. Furthermore, the properties of surface tension and critical micelle concentration of HLPS solution showed that HLPS can significantly reduce the surface tension of water. The morphology of the HLPS solution was characterised by dynamic light scattering, which revealed that HLPS exhibited a nonmonotonic appearance in particle size at different scattering angles owing to the different replaced linear portions. The relationships of the surface pressure to monolayer area and time were measured using the Langmuir-Blodgett instrument, which showed that the surface tension of monolayer molecules increased with the increasing of hydrophobic groups. In addition, the interface conditions of different replaced HLPS solutions were simulated.

Ferrocene-Based Hyperbranched Polytriazoles: Synthesis by Click Polymerization and Application as Precursors to Nanostructured Magnetoceramics.

PubMed

Li, Hongkun; Chi, Weiwen; Liu, Yajing; Yuan, Wei; Li, Yaowen; Li, Yongfang; Tang, Ben Zhong

2017-09-01

Ferrocene-based polymers have drawn much attention in the past decades due to their unique properties and promising applications. However, the synthesis of hyperbranched polymers is still a great challenge. Here, two ferrocene-based hyperbranched polytriazoles with high molecular weights are facilely prepared by the click polymerization reactions of ferrocene-containing diazides (1) and tris(4-ethynylphenyl)amine (2) using Cu(PPh 3 ) 3 Br as catalyst in dimethylformamide at 60 °C for 5 and 9 h in satisfactory yields of 54.0% and 52.3%. The resulting polytriazoles are soluble in common organic solvents and thermally stable, with 5% weight loss temperatures up to 307 °C. They can be used as precursors to produce nanostructured ceramics with good magnetizability by pyrolysis at elevated temperature. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal Coordination Stoichiometry Controlled Formation of Linear and Hyperbranched Supramolecular Polymers.

PubMed

Lin, Cuiling; Xu, Luonan; Huang, Libo; Chen, Jia; Liu, Yuanyuan; Ma, Yifan; Ye, Feixiang; Qiu, Huayu; He, Tian; Yin, Shouchun

2016-09-01

Controlling the topologies of polymers is a hot topic in polymer chemistry because the physical and/or chemical properties of polymers are determined (at least partially) by their topologies. This study exploits the host-guest interactions between dibenzo-24-crown-8 and secondary ammonium salts and metal coordination interactions between 2,6-bis(benzimidazolyl)-pyridine units with metal ions (Zn(II) and/or Eu(III) ) as orthogonal non-covalent interactions to prepare supramolecular polymers. By changing the ratios of the metal ion additives (Zn(NO3 )2 and Eu(NO3 )3 ) linkers to join the host-guest dimeric complex, the linear supramolecular polymers (100 mol% Zn(NO3 )2 per ligand) and hyperbranched supramolecular polymers (97 mol% Zn(NO3 )2 and 3 mol% Eu(NO3 )3 per ligand) are separately and successfully constructed. This approach not only expands topological control over polymeric systems, but also paves the way for the functionalization of smart and adaptive materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Protoenzymes: the case of hyperbranched polyesters

NASA Astrophysics Data System (ADS)

Mamajanov, Irena; Cody, George D.

2017-11-01

Enzymes are biopolymeric complexes that catalyse biochemical reactions and shape metabolic pathways. Enzymes usually work with small molecule cofactors that actively participate in reaction mechanisms and complex, usually globular, polymeric structures capable of specific substrate binding, encapsulation and orientation. Moreover, the globular structures of enzymes possess cavities with modulated microenvironments, facilitating the progression of reaction(s). The globular structure is ensured by long folded protein or RNA strands. Synthesis of such elaborate complexes has proven difficult under prebiotically plausible conditions. We explore here that catalysis may have been performed by alternative polymeric structures, namely hyperbranched polymers. Hyperbranched polymers are relatively complex structures that can be synthesized under prebiotically plausible conditions; their globular structure is ensured by virtue of their architecture rather than folding. In this study, we probe the ability of tertiary amine-bearing hyperbranched polyesters to form hydrophobic pockets as a reaction-promoting medium for the Kemp elimination reaction. Our results show that polyesters formed upon reaction between glycerol, triethanolamine and organic acid containing hydrophobic groups, i.e. adipic and methylsuccinic acid, are capable of increasing the rate of Kemp elimination by a factor of up to 3 over monomeric triethanolamine. This article is part of the themed issue 'Reconceptualizing the origins of life'.

Interactions between cells and ionized dendritic biomaterials: Flow cytometry and fluorescence spectroscopic studies

NASA Astrophysics Data System (ADS)

Kannan, R. M.; Kolhe, Parag; Khandare, Jayant; Kannan, Sujatha; Lieh-Lai, Mary

2004-03-01

Dendrimers and hyperbranched polymers are a new class of macromolecules characterized by large density of "tunable" peripheral functional groups. Therefore dendrimers can serve as a model macromolecular system to study the influence of molecular geometry and charge density on transport across biological barriers, especially cellular interfaces. The effect of size, end-functionality, surface charge (pH), and the nature of the cell surface are expected to play an important role in transport, and are investigated using flow cytometry, fluorescene microscopy and UV/Vis spectroscopy. Our results suggest that at physiological pH, cationic polyamidoamine (PAMAM) dendrimers can enter the A549 cancer lung epithelial cells within 5 minutes, perhaps due to the favorable interaction between anionic surface receptors of cells and cationic PAMAM dendrimer, through adsorptive endocytosis. On the other hand, hyperbranched polyol, which is a neutral polymer at physiological pH, enters cells at a much slower rate. The entry of hyperbranched polyol may be because of fluid-phase pinocytosis. Our results also indicate that the dendritic polymers enter the cell surface much more rapidly than linear polymers, and some small drugs, suggesting that the high density of functional groups plays a key role in the interaction with the cell surface, and the subsequent transport inside.

Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

NASA Astrophysics Data System (ADS)

Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J. Timothy; Cosimbescu, Lelia

2016-01-01

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.

Preparation of novel polyamine-type chelating resin with hyperbranched structures and its adsorption performance

NASA Astrophysics Data System (ADS)

Chen, Youning; Zhao, Wei; Wang, Huan; Li, Yuhong; Li, Chenxi

2018-02-01

This paper explored the method of combining atom transfer radical polymerization (ATRP) technology and hyperbranched polymer principle to prepare the high capacity chelating resin. First, surface-initiated atom transfer radical polymerization (SI-ATRP) method was used to graft glycidyl methacrylate (GMA) on chloromethylated cross-linked styrene-divinylbenzene resin, and then the novel polyamine chelating resin with a kind of hyperbranched structure was prepared through the amination reaction between amino group of (2-aminoethyl) triamine and epoxy group in GMA. This resin had a selective effect on As(V) and Cr(VI) at a relatively low pH and can be used for the disposal of waste water containing As(V) and Cr(VI). It had a relatively strong adsorption effect on Cu(II), Pb(II), Cd(II) and Cr(III) and can be used for the disposal of heavy metal ion waste water. The finding was that, the adsorption capacity of resin on the studied heavy metal ions was higher than that of the chelating resin synthesized by traditional technology and also higher than that of the resin modified by ATRP technology and bifunctional chelator, indicating that the combination of ATRP and hyperbranched polymer concept is an effective method to prepare chelating resin with high capacity.

Preparation of novel polyamine-type chelating resin with hyperbranched structures and its adsorption performance

PubMed Central

Zhao, Wei; Wang, Huan; Li, Yuhong; Li, Chenxi

2018-01-01

This paper explored the method of combining atom transfer radical polymerization (ATRP) technology and hyperbranched polymer principle to prepare the high capacity chelating resin. First, surface-initiated atom transfer radical polymerization (SI-ATRP) method was used to graft glycidyl methacrylate (GMA) on chloromethylated cross-linked styrene-divinylbenzene resin, and then the novel polyamine chelating resin with a kind of hyperbranched structure was prepared through the amination reaction between amino group of (2-aminoethyl) triamine and epoxy group in GMA. This resin had a selective effect on As(V) and Cr(VI) at a relatively low pH and can be used for the disposal of waste water containing As(V) and Cr(VI). It had a relatively strong adsorption effect on Cu(II), Pb(II), Cd(II) and Cr(III) and can be used for the disposal of heavy metal ion waste water. The finding was that, the adsorption capacity of resin on the studied heavy metal ions was higher than that of the chelating resin synthesized by traditional technology and also higher than that of the resin modified by ATRP technology and bifunctional chelator, indicating that the combination of ATRP and hyperbranched polymer concept is an effective method to prepare chelating resin with high capacity. PMID:29515875

New hyperbranched polytriazoles containing isolation chromophore moieties derived from AB4 monomers through click chemistry under copper(I) catalysis: improved optical transparency and enhanced NLO effects.

PubMed

Wu, Wenbo; Ye, Cheng; Yu, Gui; Liu, Yunqi; Qin, Jingui; Li, Zhen

2012-04-02

By modifying a synthetic procedure, two new hyperbranched polytriazoles (HP1 and HP2) containing isolation chromophores were synthesized successfully through click chemistry reactions under copper(I) catalysis. For the first time, these two polymers were derived from an AB(4)-type monomer, although they contain different end-capping chromophores. They are soluble in normal polar organic solvents and are well characterized. Thanks to the presence of the isolation chromophore, the two polymers demonstrate good nonlinear optical (NLO) properties and optical transparency, making them promising candidates for practical applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of antibacterial PVA nanocomposite films containing dendritic polymer functionalized multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Sapalidis, Andreas; Sideratou, Zili; Panagiotaki, Katerina N.; Sakellis, Elias; Kouvelos, Evangelos P.; Papageorgiou, Sergios; Katsaros, Fotios

2018-03-01

A series of Poly(vinyl alcohol) (PVA) nanocomposite films containing quaternized hyperbranched polyethyleneimine (PEI) functionalized multi-walled carbon nanotubes (ox-CNTs@QPEI) are prepared by solvent casting technique. The modified carbon based material exhibits high aqueous solubility, due to the hydrophilic character of the functionalized hyperbranched dendritic polymer. The quaternized PEI successfully wraps around nanotube walls, as polycations provide electrostatic repulsion. Various contents of ox-CNTs@QPEI ranging from 0.05 to 1.0 % w/w were employed to prepare functionalized PVA nanocomposites. The developed films exhibit adequate optical transparency, improved mechanical properties and extremely high antibacterial behavior due to the excellent dispersion of the functionalized carbon nanotubes into the PVA matrix.

Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

PubMed Central

Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J. Timothy; Cosimbescu, Lelia

2016-01-01

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach. PMID:26727881

Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

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

Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acidsmore » (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.« less

Dynamics of Hyperbranched Polymers under Confinement

NASA Astrophysics Data System (ADS)

Androulaki, Krystallenia; Chrissopoulou, Kiriaki; Anastasiadis, Spiros H.; Prevosto, Daniele; Labardi, Massimiliano

2015-03-01

The effect of severe confinement on the dynamics of three different generations of hyperbranched polyesters (Boltorns) is investigated by Dielectric Spectroscopy. The polymers are intercalated within the galleries of natural Na+-MMT, thus, forming 1nm polymer films confined between solid walls. The Tg's of the polymers determined by DSC show a clear dependence on the generation whereas the transition is completely suppressed when all the polymer chains are intercalated. The dynamic investigation of the bulk polymers reveals two sub-Tg processes, with similar behavior for the three polymers with the segmental relaxation observed above the Tg of each. For the nanocomposites, where all polymers are severely confined, the dynamics show significant differences compared to that of the bulk polymers. The sub-Tg processes are similar for the three generations but significantly faster and with weaker temperature dependence than those in the bulk. The segmental process appears at temperatures below the bulk polymer Tg, it exhibits an Arrhenius temperature dependence and shows differences for the three generations. A slow process that appears at higher temperatures is due to interfacial polarization. Co-financed by the EU and Greek funds through the Operational Program ``Education and Lifelong Learning'' of the NSRF-Research Funding Program: THALES-Investing in knowledge society through the Eur. Social Fund (MIS 377278) and COST Action MP0902-COINAPO.

Truxene-Based Hyperbranched Conjugated Polymers: Fluorescent Micelles Detect Explosives in Water.

PubMed

Huang, Wei; Smarsly, Emanuel; Han, Jinsong; Bender, Markus; Seehafer, Kai; Wacker, Irene; Schröder, Rasmus R; Bunz, Uwe H F

2017-01-25

We report two hyperbranched conjugated polymers (HCP) with truxene units as core and 1,4-didodecyl-2,5-diethynylbenzene as well as 1,4-bis(dodecyloxy)-2,5-diethynylbenzene as comonomers. Two analogous poly(para-phenyleneethynylene)s (PPE) are also prepared as comparison to demonstrate the difference between the truxene and the phenyl moieties in their optical properties and their sensing performance. The four polymers are tested for nitroaromatic analytes and display different fluorescence quenching responses. The quenching efficiencies are dependent upon the spectral overlap between the absorbance of the analyte and the emission of the fluorescent polymer. Optical fingerprints are obtained, based on the unique response patterns of the analytes toward the polymers. With this small sensor array, one can distinguish nine nitroaromatic analytes with 100% accuracy. The amphiphilic polymer F127 (a polyethylene glycol-polypropylene glycol block copolymer) carries the hydrophobic HCPs and self-assembles into micelles in water, forming highly fluorescent HCP micelles. The micelle-bound conjugated polymers detect nitroaromatic analytes effectively in water and show an increased sensitivity compared to the sensing of nitroaromatics in organic solvents. The nitroarenes are also discriminated in water using this four-element chemical tongue.

Photo-enhanced performance and photo-tunable degradation in LC ecopolymers

NASA Astrophysics Data System (ADS)

Kaneko, Tatsuo

2007-05-01

Photosensitive, liquid crystalline (LC) polymers were prepared by in-bulk polymerization of phytomonomers such as cinnamic acid derivatives. The p-coumaric acid (4HCA) homopolymer showed a thermotropic LC phase where a photoreaction of [2+2] cycloaddition occurred by ultraviolet irradiation. LC phase was exhibited only in a low molecular weight state but the polymer was too brittle to materialize. Then we copolymerized 4HCA with multifunctional cinnamate, 3,4 dihydroxycinnamic acid (caffeic acid; DHCA), to prepare the hyperbranching architecture. Many branches increased the apparent size of the polymer chain but kept the low number-average molecular weight. P(4HCA-co-DHCA)s showed high performances which may be attained through the entanglement by in-bulk formation of hyperbranching, rigid structures. P(4HCA-co-DHCA)s showed a smooth hydrolysis, an in-soil degradation and a photoreaction cross-linking from conjugated cinnamate esters to aliphatic esters. The change in photoconversion degree tuned the polymer performance and chain hydrolysis.

Vegetable Oil-Based Hyperbranched Thermosetting Polyurethane/Clay Nanocomposites

PubMed Central

2009-01-01

The highly branched polyurethanes and vegetable oil-based polymer nanocomposites have been showing fruitful advantages across a spectrum of potential field of applications.Mesua ferreaL. seed oil-based hyperbranched polyurethane (HBPU)/clay nanocomposites were prepared at different dose levels by in situ polymerization technique. The performances of epoxy-cured thermosetting nanocomposites are reported for the first time. The partially exfoliated structure of clay layers was confirmed by XRD and TEM. FTIR spectra indicate the presence of H bonding between nanoclay and the polymer matrix. The present investigation outlines the significant improvement of tensile strength, scratch hardness, thermostability, water vapor permeability, and adhesive strength without much influencing impact resistance, bending, and elongation at break of the nanocomposites compared to pristine HBPU thermoset. An increment of two times the tensile strength, 6 °C of melting point, and 111 °C of thermo-stability were achieved by the formation of nanocomposites. An excellent shape recovery of about 96–99% was observed for the nanocomposites. Thus, the formation of partially exfoliated clay/vegetable oil-based hyperbranched polyurethane nanocomposites significantly improved the performance. PMID:20596546

Vegetable Oil-Based Hyperbranched Thermosetting Polyurethane/Clay Nanocomposites.

PubMed

Deka, Harekrishna; Karak, Niranjan

2009-04-25

The highly branched polyurethanes and vegetable oil-based polymer nanocomposites have been showing fruitful advantages across a spectrum of potential field of applications. Mesua ferrea L. seed oil-based hyperbranched polyurethane (HBPU)/clay nanocomposites were prepared at different dose levels by in situ polymerization technique. The performances of epoxy-cured thermosetting nanocomposites are reported for the first time. The partially exfoliated structure of clay layers was confirmed by XRD and TEM. FTIR spectra indicate the presence of H bonding between nanoclay and the polymer matrix. The present investigation outlines the significant improvement of tensile strength, scratch hardness, thermostability, water vapor permeability, and adhesive strength without much influencing impact resistance, bending, and elongation at break of the nanocomposites compared to pristine HBPU thermoset. An increment of two times the tensile strength, 6 degrees C of melting point, and 111 degrees C of thermo-stability were achieved by the formation of nanocomposites. An excellent shape recovery of about 96-99% was observed for the nanocomposites. Thus, the formation of partially exfoliated clay/vegetable oil-based hyperbranched polyurethane nanocomposites significantly improved the performance.

Facile modification of nanodiamonds with hyperbranched polymers based on supramolecular chemistry and their potential for drug delivery.

PubMed

Huang, Hongye; Liu, Meiying; Jiang, Ruming; Chen, Junyu; Mao, Liucheng; Wen, Yuanqing; Tian, Jianwen; Zhou, Naigen; Zhang, Xiaoyong; Wei, Yen

2018-03-01

Due to their excellent chemical stability and remarkable biocompatibility, nanodiamonds (NDs) have received widespread research attention by the biomedical field. The excellent water dispersibility of NDs has significant importance for biomedical applications. Therefore, surface modification of NDs with hydrophilic polymers has been extensively investigated over the past few decades. In this study, we synthesize β-CD containing hyperbranched polymer functionalized ND (ND-β-CD-HPG) composites with high water dispersibility via supramolecular chemistry based on the host-guest interactions between β-Cyclodextrin (β-CD) and adamantine (Ad). The hydroxyl groups of NDs first reacted with 1, 1-adamantanecarbonyl chloride to obtain ND-Ad, which was further functionalized with β-CD containing hyperbranched polymers to form the final ND-β-CD-HPG composites. The successful preparation of ND-β-CD-HPG composites was confirmed by several characterization techniques. Furthermore, the loading and release of the anticancer agent doxorubicin hydrochloride (DOX) on ND-β-CD-HPG composites was also examined to explore its potential in drug delivery. When compared with traditional methods of surface modification of NDs, this method was convenient, fast and efficient. We demonstrated that ND-β-CD-HPG composites have great water dispersibility, low toxicity, high drug-loading capacity and controlled drug-release behavior. Based on these characteristics, ND-β-CD-HPG composites are expected to have high potential for biomedical applications. Copyright © 2017 Elsevier Inc. All rights reserved.

Hyperbranched PEGmethacrylate linear pDMAEMA block copolymer as an efficient non-viral gene delivery vector.

PubMed

Mathew, Asha; Cao, Hongliang; Collin, Estelle; Wang, Wenxin; Pandit, Abhay

2012-09-15

A unique hyperbranched polymeric system with a linear poly-2-dimethylaminoethyl methacrylate (pDMAEMA) block and a hyperbranched polyethylene glycol methyl ether methacrylate (PEGMEMA) and ethylene dimethacrylate (EGDMA) block was designed and synthesized via deactivation enhanced atom transfer radical polymerisation (DE-ATRP) for efficient gene delivery. Using this unique structure, with a linear pDMAEMA block, which efficiently binds to plasmid DNA (pDNA) and hyperbranched polyethylene glycol (PEG) based block as a protective shell, we were able to maintain high transfection levels without sacrificing cellular viability even at high doses. The transfection capability and cytotoxicity of the polymers over a range of pDNA concentration were analysed and the results were compared to commercially available transfection vectors such as polyethylene imine (branched PEI, 25 kDa), partially degraded poly(amido amine)dendrimer (dPAMAM; commercial name: SuperFect(®)) in fibroblasts and adipose tissue derived stem cells (ADSCs). Copyright © 2012 Elsevier B.V. All rights reserved.

Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

DOE PAGES

Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; ...

2016-01-05

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acidsmore » (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. Increased branching and degree of polymerization, and thus molecular weight, were found to reduce the solubility of these systems in the base oil. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated improved viscosity index and reduced friction coefficient, validating the basic approach.« less

Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

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

Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acidsmore » (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. Increased branching and degree of polymerization, and thus molecular weight, were found to reduce the solubility of these systems in the base oil. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated improved viscosity index and reduced friction coefficient, validating the basic approach.« less

Carboxylated hyperbranched poly(glycidol)s for preparation of pH-sensitive liposomes.

PubMed

Yuba, Eiji; Harada, Atsushi; Sakanishi, Yuichi; Kono, Kenji

2011-01-05

Previous reports by the authors described intracellular delivery using liposomes modified with various carboxylated poly(glycidol) derivatives. These linear polymer-modified liposomes exhibited a pH-dependent membrane fusion behavior in cellular acidic compartments. However, the effect of the backbone structure on membrane fusion activity remains unknown. Therefore, this study specifically investigated the backbone structure to obtain pH-sensitive polymers with much higher fusogenic activity and to reveal the effect of the polymer backbone structure on the interaction with the membrane. Hyperbranched poly(glycidol) (HPG) derivatives were prepared as a new type of pH-sensitive polymer and used for the modification of liposomes. The resultant HPG derivatives exhibited high hydrophobicity and intensive interaction with the membrane concomitantly with the increasing degree of polymerization (DP). Furthermore, HPG derivatives showed a stronger interaction with the membrane than the linear polymers show. Liposomes modified with HPG derivatives of high DP delivered contents into the cytosol of DC2.4 cells, a dendritic cell line, more effectively than the linear polymer-modified liposomes do. Results show that the backbone structure of pH-sensitive polymers affected their pH-sensitivity and interaction with liposomal and cellular membranes. Copyright © 2010 Elsevier B.V. All rights reserved.

Hyperbranched polyglycerols at the biointerface

NASA Astrophysics Data System (ADS)

Moore, Eli; Thissen, Helmut; Voelcker, Nicolas H.

2013-08-01

The control over biointerfacial interactions is the key to a broad range of biomedical applications, ranging from implantable devices to drug delivery and nanomedicine. In many of these applications, coatings are required that reduce or prevent non-specific interactions with the biological environment, while at the same time presenting specific bioactive signals. Whilst surface coatings based on polymers such as poly(ethylene glycol) (PEG) have been used successfully, many limitations persist in regard to the biocompatibility, stability and functionality of state-of-the-art polymer coatings. Most of these limitations are related to the fact that, typically, linear polymers are used with associated limited chemical functionality. Here, we examine the development of hyperbranched polyglycerols (HPGs) as promising candidates for the replacement of traditional linear polymers, such as the chemically analogous PEG, for the control of biointerfacial interactions. HPGs are highly branched globular molecules that exhibit a high valency, allow easy access to a variety of functionalities and can present biologically active signals. In this review, a comprehensive overview is provided with respect to the history, synthetic strategies, modifications and applications of HPGs.

Hard and flexible nanocomposite coatings using nanoclay-filled hyperbranched polymers.

PubMed

Fogelström, Linda; Malmström, Eva; Johansson, Mats; Hult, Anders

2010-06-01

The combination of hardness, scratch resistance, and flexibility is a highly desired feature in many coating applications. The aim of this study is to achieve this through the introduction of an unmodified nanoclay, montmorillonite (Na(+)MMT), in a polymer resin based on the hyperbranched polyester Boltorn H30. Smooth and transparent films were prepared from both the neat and the nanoparticle-filled hyperbranched resins. X-ray diffraction (XRD) and transmission electron microscopy (TEM) corroborated a mainly exfoliated structure in the nanocomposite films, which was also supported by results from dynamic mechanical analysis (DMA). Furthermore, DMA measurements showed a 9-16 degrees C increase in Tg and a higher storage modulus-above and below the T(g)-both indications of a more cross-linked network, for the clay-containing film. Thermogravimetric analysis (TGA) demonstrated the influence of the nanofiller on the thermal properties of the nanocomposites, where a shift upward of the decomposition temperature in oxygen atmosphere is attributed to the improved barrier properties of the nanoparticle-filled materials. Conventional coating characterization methods demonstrated an increase in the surface hardness, scratch resistance and flexibility, with the introduction of clay, and all coatings exhibited excellent chemical resistance and adhesion.

Small-angle x-ray scattering study of polymer structure: Carbosilane dendrimers in hexane solution

NASA Astrophysics Data System (ADS)

Shtykova, E. V.; Feigin, L. A.; Volkov, V. V.; Malakhova, Yu. N.; Streltsov, D. R.; Buzin, A. I.; Chvalun, S. N.; Katarzhanova, E. Yu.; Ignatieva, G. M.; Muzafarov, A. M.

2016-09-01

The three-dimensional organization of monodisperse hyper-branched macromolecules of regular structure—carbosilane dendrimers of zero, third, and sixth generations—has been studied by small-angle X-ray scattering (SAXS) in solution. The use of modern methods of SAXS data interpretation, including ab initio modeling, has made it possible to determine the internal architecture of the dendrimers in dependence of the generation number and the number of cyclosiloxane end groups (forming the shell of dendritic macromolecules) and show dendrimers to be spherical. The structural results give grounds to consider carbosilane dendrimers promising objects for forming crystals with subsequent structural analysis and determining their structure with high resolution, as well as for designing new materials to be used in various dendrimer-based technological applications.

Rheological and Thermal Properties of Bio-based Hyperbranched Polyesters

NASA Astrophysics Data System (ADS)

Bubeck, Robert; Dumitrascu, Adina; Zhang, Tracy; Smith, Patrick

Hyperbranched poly(ester)s (HBPEs) of designed molecular structures and targeted molecular weight can be prepared from a variety of multi-functional acids and alcohols. These polymers find application in the areas of coatings and rheology modifiers for coatings. These functional polymers can be synthesized in variety of architectures, possessing either hydroxyl or carboxyl reactive end-groups suitable for the attachment of active entities. The rheological characteristics as related to variation in molecular structure were determined using cone and plate or couette geometries. Viscosities of the HBPEs were found to be near Newtonian. HB polymers permit the control of Tg that is not as readily attained with linear polymers. Accordingly, Tg and viscosity are affected little as a function of Mw but vary dramatically with the nature of the end-groups, are highly dependent on hydrogen bonding of the hydroxyl end groups, and decrease dramatically with the incorporation of aliphatic end-caps. The thermal properties and the degradation characteristics of the HBPEs were determined. Thermal degradation of the hydroxyl-terminal HBPEs is initiated by dehydrative ether formation (crosslinking) while decarboxylation is the initial decomposition event for the carboxyl-terminal polymers. Midland, MI Campus.

Thermodynamic properties of hyperbranched polymer, Boltorn U3000, using inverse gas chromatography.

PubMed

Domańska, Urszula; Zołek-Tryznowska, Zuzanna

2009-11-19

Mass-fraction activity coefficients at infinite dilution (Omega13(infinity)) of alkanes (C5-C10), cycloalkanes (C5-C8), alkenes (C5-C8), alkynes (C5-C8), aromatic hydrocarbons (benzene, toluene, ethylbenzene, o-, m-, p-xylene, thiophene), alcohols (C1-C5), water, ethers (tetrahydrofuran (THF), methyl-tert-butylether (MTBE), diethyl-, di-n-propyl-, di-n-butyl ether), and ketones (propanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclopentanone) in the hyperbranched polymer, Boltorn U3000 (B-U3000), have been determined by inverse gas chromatography (IGC) using the polymer as the stationary phase. The measurements were carried out at different temperatures between 308.15 and 348.15 K. The density and thermophysical properties of polymer were described. The specific retention volume (V(g)), the Flory-Huggins interaction parameter (chi13(infinity)), the molar enthalpy of sorption (the partial molar enthalpies of solute dissolution) (Delta(s)H), the partial molar excess enthalpy at infinite dilution of the solute and polymer (DeltaH1(E,infinity)), the partial molar Gibbs excess energy at infinite dilution (DeltaG1(E,infinity)), and the solubility parameter (delta3) were calculated.

Glycodendritic structures based on Boltorn hyperbranched polymers and their interactions with Lens culinaris lectin.

PubMed

Arce, Eva; Nieto, Pedro M; Díaz, Vicente; Castro, Rossana García; Bernad, Antonio; Rojo, Javier

2003-01-01

Multivalent scaffolds bearing carbohydrates have been prepared to mediate biological processes where carbohydrates are involved. These systems consist of dendritic structures based on Boltorn H20 and H30 hyperbranched polymers to which carbohydrates are linked through a convenient spacer. Mannose has been chosen as a sugar unit to test the viability of this strategy. These glycodendritic compounds have been prepared in a few steps with good yields, showing a high solubility in physiological media and low toxicity. The binding of these dendritic polymers to the mannose-binding lectin Lens culinaris (LCA) was studied using STD-NMR experiments and quantitative precipitation assays. The results demonstrate the existence of a clear interaction between the mannose derivative systems and the Lens lectin where the dendritic scaffold does not have an important role in mannose binding but supplies the necessary multivalence for lectin cluster formation. These glycodendritic structures are able to interact with a receptor, and therefore they can be considered as promising tools for biological studies.

Hyperbranched polymer functional cotton fabric for its in situ deposition of silver nanoparticles

NASA Astrophysics Data System (ADS)

Zhang, Desuo; Jiao, Chenlu; Xiong, Jiaqing; Lin, Hong; Chen, Yuyue

2015-06-01

This paper describes a strategy of fabricating silver nanoparticles (Ag NPs) finished cotton fabric through in situ synthesis method. In order to endow the cotton fabric with the capability of in situ synthesis of Ag NPs without any other reagents, an amino-terminated hyperbranched polymer (HBP-NH2) was employed to functionalize the cotton fabric. To this end, cotton fabric was oxidized to generate aldehyde groups and then HBP-NH2 was grafted on the oxidized cotton fabric based on the reaction between amino groups and aldehyde groups. Due to numerous imino and amino groups in the polymer and its special three-dimensional structure, the functional cotton fabric could take initiative to capture and reduce silver ions, control the formation of Ag NPs and fix them on the cotton fabric. The sizes of Ag NPs in situ synthesized on cotton fibers range from 4 to 10 nm. The prepared Ag NPs finished cotton fabric has excellent laundering durability.

Self-Controlled Synthesis of Hyperbranched Poly(etherketone)s from A2 + B3 Approach in Poly(phosphoric acid)

DTIC Science & Technology

2009-01-01

aromatic keto -band arisen from carboxylic acids, which could be part of terminal groups of HPEKs, ranged from 1708 to 1719 cm1. The carbonyl bands from...1999, 143 , 1–34; (d) Inoue, K. Prog Polym Sci 2000, 25, 453–571; (e) Voit, B. J Polym Sci Part A: Polym Chem 2000, 36, 2505–2525; (f) Hult, A

Preparation of a novel hyperbranched carbosilane-silica hybrid coating for trace amount detection by solid phase microextraction/gas chromatography.

PubMed

Chen, Guowen; Li, Wenjie; Zhang, Chen; Zhou, Chuanjian; Feng, Shengyu

2012-09-21

Phenyl-ended hyperbranched carbosilane (HBC) is synthesized and immobilized onto the inner wall of a fused silica capillary column using a sol-gel process. The hybrid coating layer formed is used as a stationary phase for gas chromatography (GC) and as an adsorption medium for solid phase microextraction (SPME). Trifluoroacetic acid, as a catalyst in this process, helps produce a homogeneous hybrid coating layer. This result is beneficial for better column chromatographic performances, such as high efficiency and high resolution. Extraction tests using the novel hybrid layer show an extraordinarily large adsorption capacity and specific adsorption behavior for aromatic compounds. A 1 ppm trace level detectability is obtained with the SPME/GC work model when both of the stationary phase and adsorption layer bear a hyperbranched structure. A large amount of phenyl groups and a low viscosity of hyperbranched polymers contribute to these valuable properties, which are important to environment and safety control, wherein detection sensitivity and special adsorption behavior are usually required. Copyright © 2012 Elsevier B.V. All rights reserved.

Thinking Outside the 'Block': Alternative Polymer Compositions for Micellar Drug Delivery.

PubMed

Jones, Marie-Christine

2015-01-01

With a number of formulations currently in clinical trials, the interest in polymer micelles as drug carriers in unlikely to subside. Historically, linear diblock copolymers have been used as the building blocks for micelle preparation. Yet, recent advances in polymer chemistry have meant that a wider variety of polymer architectures and compositions have become available and been trialed for pharmaceutical applications. This mini-review aims to provide an overview of recent, exciting developments in triblock, graft and hyperbranched polymer chemistries that may change the way polymeric micelles drug formulations are prepared.

Research progress on synthesis and characteristic about dendrimers

NASA Astrophysics Data System (ADS)

Tang, Zitao

2017-12-01

Dendrimers are hyper-branched polymers which have perfectly defined structures. Different from the common polymers, dendrimers are synthesized by a step-by-step iterative style, which starts from a central core and forms branching parts outward. The dendrimers also have different physical and chemical characteristics from common polymers. In this paper, contributions to dendrimer synthesis from different researchers with different scientific background, synthesis of different dendrimers, and applications of them will be reviewed.

Drug Self-Delivery Systems Based on Hyperbranched Polyprodrugs towards Tumor Therapy.

PubMed

Duan, Xiao; Chen, Jianxin; Wu, Yalan; Wu, Si; Shao, Dongyan; Kong, Jie

2018-04-16

Amphiphilic hyperbranched polyprodrugs (DOX-S-S-PEG) with drug repeat units in hydrophobic core linked by disulfide bonds were developed as drug self-delivery systems for cancer therapy. The hydroxyl groups and the amine group in doxorubicin (DOX) were linked by 3,3'-dithiodipropanoic acid as hydrophobic hyperbranched cores, then amino-terminated polyethylene glycol monomethyl ether (mPEG-NH 2 ) as hydrophilic shell was linked to hydrophobic cores to form amphiphilic and glutathione (GSH)-responsive micelle of hyperbranched polyprodrugs. The amphiphilic micelles can be disrupted under GSH (1 mg mL -1 ) circumstance. Cell viability of A549 cells and 293T cells was evaluated by CCK-8 and Muse Annexin V & Dead Cell Kit. The disrupted polyprodrugs maintained drug activity for killing tumor cells. Meanwhile, the undisrupted polyprodrugs possessed low cytotoxicity to normal cells. The cell uptake experiments showed that the micelles of DOX-S-S-PEG were taken up by A549 cells and distributed to cell nuclei. Thus, the drug self-delivery systems with drug repeat units in hydrophobic cores linked by disulfide bonds showed significant special advantages: 1) facile one-pot synthesis; 2) completely without toxic or non-degradable polymers; 3) DOX itself functions as fluorescent labeled molecule and self-delivery carrier; 4) drug with inactive form in hyperbranched cores and low cytotoxicity to normal cells. These advantages make them excellent drug self-delivery systems for potential high efficient cancer therapy. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stabilization of Lipid Membranes With Dendritic Polymers

DTIC Science & Technology

2004-12-01

Langmuir - Blodgett (Takamato, et al., 2001) and solution techniques (Johnson, et al., 2002). However, BLMs are too unstable to be used to make effective...J.A., Ivanova, A.T., Schwartz, D.K., Yang, T., and Cremer, P.S., 2001: Stable Ordering in Langmuir - Blodgett Films, Science, 293, 1292-1295. Tully...Various dendrimers and hyperbranched polymers were evaluated. In addition, lipids with different head groups were used to probe the underlying

Covalent attachment of a bioactive hyperbranched polymeric layer to titanium surface for the biomimetic growth of calcium phosphates

PubMed Central

Tsiourvas, D.; Arkas, M.; Diplas, S.; Mastrogianni, E.

2010-01-01

This work is investigating the chemical grafting on Ti surface of a polymer/calcium phosphate coating of improved adhesion for enhanced bioactivity. For this purpose, a whole new methodology was developed based on covalently attaching a hyperbranched poly(ethylene imine) layer on Ti surface able to promote calcium phosphate formation in a next deposition stage. This was achieved through an intermediate surface silanization step. The research included optimization both of the reaction conditions for covalently grafting the intermediate organosilicon and the subsequent hyperbranched poly(ethylene imine) layers, as well as of the conditions for the mechanical and chemical pretreatment of Ti surface before coating. The reaction steps were monitored employing FTIR and XPS analyses, whereas the surface morphology and structure of the successive coating layers were studied by SEM combined with EDS. The analysis confirmed the successful grafting of the hybrid layer which demonstrated very good ability for hydroxyapatite growth in simulated body fluid. PMID:21069559

Covalent attachment of a bioactive hyperbranched polymeric layer to titanium surface for the biomimetic growth of calcium phosphates.

PubMed

Tsiourvas, D; Tsetsekou, A; Arkas, M; Diplas, S; Mastrogianni, E

2011-01-01

This work is investigating the chemical grafting on Ti surface of a polymer/calcium phosphate coating of improved adhesion for enhanced bioactivity. For this purpose, a whole new methodology was developed based on covalently attaching a hyperbranched poly(ethylene imine) layer on Ti surface able to promote calcium phosphate formation in a next deposition stage. This was achieved through an intermediate surface silanization step. The research included optimization both of the reaction conditions for covalently grafting the intermediate organosilicon and the subsequent hyperbranched poly(ethylene imine) layers, as well as of the conditions for the mechanical and chemical pretreatment of Ti surface before coating. The reaction steps were monitored employing FTIR and XPS analyses, whereas the surface morphology and structure of the successive coating layers were studied by SEM combined with EDS. The analysis confirmed the successful grafting of the hybrid layer which demonstrated very good ability for hydroxyapatite growth in simulated body fluid.

Development of hyperbranched polymers with non-covalent interactions for extraction and determination of aflatoxins in cereal samples.

PubMed

Liu, Xiaoyan; Li, Huihui; Xu, Zhigang; Peng, Jialin; Zhu, Shuqiang; Zhang, Haixia

2013-10-03

A novel approach for assembling homogeneous hyperbranched polymers based on non-covalent interactions with aflatoxins was developed; the polymers were used to evaluate the extraction of aflatoxins B1, B2, G1 and G2 (AFB1, AFB2, AFG1 and AFG2) in simulant solutions. The results showed that the extraction efficiencies of three kinds of synthesized polymers for the investigated analytes were not statistically different; as a consequence, one of the representative polymers (polymer I) was used as the solid-phase extraction (SPE) sorbent to evaluate the influences of various parameters, such as desorption conditions, pH, ionic strength, concentration of methanol in sample solutions, and the mass of the sorbent on the extraction efficiency. In addition, the extraction efficiencies for these aflatoxins were compared between the investigated polymer and the traditional sorbent C18. The results showed that the investigated polymer had superior extraction efficiencies. Subsequently, the proposed polymer for the SPE packing material was employed to enrich and analyze four aflatoxins in the cereal powder samples. The limits of detection (LODs) at a signal-to-noise (S/N) ratio of 3 were in the range of 0.012-0.120 ng g(-1) for four aflatoxins, and the limits of quantification (LOQs) calculated at S/N=10 were from 0.04 to 0.40 ng g(-1) for four aflatoxins. The recoveries of four aflatoxins from cereal powder samples were in the range of 82.7-103% with relative standard deviations (RSDs) lower than 10%. The results demonstrate the suitability of the SPE approach for the analysis of trace aflatoxins in cereal powder samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Thioether-Bearing Hyperbranched Polyether Polyols with Methionine-Like Side-Chains: A Versatile Platform for Orthogonal Functionalization.

PubMed

Seiwert, Jan; Herzberger, Jana; Leibig, Daniel; Frey, Holger

2017-01-01

The synthesis of thioether-bearing hyperbranched polyether polyols based on an AB/AB 2 type copolymerization (cyclic latent monomers) is introduced. The polymers are prepared by anionic ring-opening multibranching copolymerization of glycidol and 2-(methylthio)ethyl glycidyl ether (MTEGE), which is conveniently accessible in a single etherification step. Slow monomer addition provides control over molecular weights. Moderate dispersities (Đ = 1.48-1.85) are obtained, given the hyperbranched structure. In situ 1 H NMR copolymerization kinetics reveal reactivity ratios of r G = 3.7 and r MTEGE = 0.27. Using slow monomer addition, copolymer composition can be systematically varied, allowing for the adjustment of the hydroxyl/thioether ratio, the degree of branching (DB = 0.36-0.48), thermal properties, and cloud point temperatures in aqueous solution in the range of 29-75 °C. Thioether oxidation to sulfoxides enables to tailor the copolymers' solubility profile. Use of these copolymers as a versatile, multifunctional platform for orthogonal modification is highlighted. The methyl sulfide groups can be selectively alkoxylated, using propylene oxide, allyl glycidyl ether, or furfuryl glycidyl ether, resulting in functional hyperbranched polyelectrolytes. Reaction of the alcohol groups with benzyl isocyanate demonstrates successful orthogonal functionalization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mussel-inspired hyperbranched poly(amino ester) polymer as strong wet tissue adhesive.

PubMed

Zhang, Hong; Bré, Lígia P; Zhao, Tianyu; Zheng, Yu; Newland, Ben; Wang, Wenxin

2014-01-01

Current medical adhesives based on cyanoacrylates typically exhibit cellular toxicity. In contrast, fibrin adhesives are non-toxic but have poor adhesive properties. To overcome these drawbacks we designed a simple and scalable adhesive precursor inspired by marine mussel adhesion that functioned with strong adhesion in wet conditions and with low cytotoxicity. Dopamine, an-amine derivative of an amino acid abundantly present in mussel adhesive proteins, was co-polymerised with a tri-functional vinyl monomer, to form a hyperbranched poly(β-amino ester) polymer termed poly(dopamine-co-acrylate) (PDA). A variety of molecular weights and crosslinking methods were analysed using an ex vivo porcine skin model and an almost 4 fold increase in wet adhesion strength was observed compared to TISSEEL(®) fibrin sealant. With a fast curing time, degradable properties and low cytotoxicity, PDA is highly attractive for medical purposes and could have a broad impact on surgeries where surgical tissue adhesives, sealants, and haemostatic agents are used. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effects of nanoparticle shape on the morphology and properties of porous CdSe assemblies (aerogels).

PubMed

Yu, Hongtao; Brock, Stephanie L

2008-08-01

We demonstrate the effect of differently shaped CdSe nanoscale building blocks (dots, rods, branched nanoparticles, and hyperbranched nanoparticles) on the morphologies, surface characteristics, and optical properties of resultant porous CdSe nanostructured aerogels. Monolithic CdSe aerogels were produced by controlled oxidative removal of surface thiolate ligands from differently shaped CdSe nanoparticles to yield a wet gel, followed by CO(2) supercritical drying. The X-ray diffraction data show that the resultant CdSe aerogels maintain the crystalline phase of the building blocks without significant grain growth. However, the transmission electron microscopy images indicate that the morphology of CdSe aerogels changes from a colloid-type morphology to a polymer-type morphology when the building block changes from dot to rod or the branched nanoparticle. The morphology of the CdSe aerogel assembled from hyperbranched nanoparticles appears to be intermediate between the colloid-type and the polymer-type. Nitrogen physisorption measurements suggest that the surface areas and porosity are a direct function of the shape of the primary building blocks, with aerogels formed from rods or branched particles exhibiting the greatest surface areas (>200 m(2)/g) and those prepared from hyperbranched nanoparticles exhibiting the least (<100 m(2)/g). Band gap measurements and photoluminescence studies show that the as-prepared CdSe aerogels retain to a large extent the intrinsic quantum confinement of the differently shaped building blocks, despite being connected into a 3D network.

Quantitation of monomers in poly(glyerol-co-diacid) gels using gas chromatography

USDA-ARS?s Scientific Manuscript database

The validation of a gas chromatography (GC) method developed to quantify amounts of starting material from the synthesis of hyperbranched polymers made from glycerol and either succinic acid, glutaric acid, or azelaic acid is described. The GC response to concentration was linear for all starting r...

Aliphatic hyperbranched polyester: A new building block in the construction of multifunctional nanoparticles and nanocomposites**

PubMed Central

Santra, Santimukul; Kaittanis, Charalambos; Perez, J. Manuel

2009-01-01

Herein we report the design and synthesis of multifunctional hyperbranched polyester-based nanoparticles and nanocomposites with properties ranging from magnetic, fluorescence, antioxidant and X-ray contrast. The fabrication of these nanostructures was achieved using a novel aliphatic and biodegradable hyperbranched polyester (HBPE) synthesized from readily available diethylmalonate. The polymer’s globular structure with functional surface carboxylic groups and hydrophobic cavities residing in the polymer’s interior allows for the formation of multifunctional polymeric nanoparticles, which are able to encapsulate a diversity of hydrophobic cargos. Via simple surface chemistry modifications, the surface carboxylic acid groups were modified to yield nanoparticles with a variety of surface functionalizations, such as amino, azide and propargyl groups, which mediated the conjugation of small molecules. This capability achieved the engineering of the HBPE nanoparticle surface for specific cell internalization studies and the formation of nanoparticle assemblies for the creation of novel nanocomposites that retained, and in some cases enhanced, the properties of the parental nanoparticle building blocks. Considering these results, the HBPE polymer, nanoparticles and composites should be ideal for biomedical, pharmaceutical, nanophotonics and material applications. PMID:19957939

Modified Thermoresponsive Hyperbranched Polymers for Improved Viscosity and Enhanced Lubricity of Engine Oils

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

Cosimbescu, Lelia; Robinson, Joshua W.; Bays, John Timothy

The manuscript captures the chronological succession of the molecular design progression through multiple architectures and topologies of the polymeric viscosity index improvers and their rheology bench test performance. Tribology testing was also performed on selected analogs and their friction and wear was evaluated. Finally, a top performing polymer was selected for engine testing, scaled-up, and its rheological performance in a complete formulation was assessed. The engine performance of the viscosity index improver was examined against an industry-established baseline.

Synthesis and characterization of novel fluoroalkyl-terminated hyperbranched polyurethane latex

NASA Astrophysics Data System (ADS)

Xu, Wei; Zhao, Weijia; Hao, Lifen; Wang, Sha; Pei, Mengmeng; Wang, Xuechuan

2018-04-01

Waterborne polyurethane (PU) emulsions are widely used in various fields and the demand for them is ever-increasing over the years. However, the hydrophilic chain extender inevitably bonded into the PU backbone can affect the water tolerance of PU. Thus, it is of great importance to improve PU water resistance effectively. Herein, novel fluoroalkyl-terminated hyperbranched polyurethane (HBPUF) latex was accordingly synthesized by graft reaction of perfluorohexyl ethyl alcohol and hyperbranched polyurethane (HBPU), which was previously obtained from interaction between hydroxyl-terminated hyperbranched polymer and PU prepolymer manufactured via the acetone process, as well as using neutralization, adding water, and high-speed stirring operations. We characterized the resultants and investigated its surface properties by IR, NMR, TEM, XRD, TGA, DSC, FE-SEM, AFM, XPS, and contact angle measurements, etc. IR and NMR tests confirmed that the fluorinated fragments had been grafted onto the tail end of HBPU. TEM, XRD, DSC, and FE-SEM results all accounted for the fact that there were multi-crystals in PU, HBPU and HBPUF. TGA results showed that thermal stabilities of the PU, HBPU, and HBPUF latex films were enhanced in turn. XPS and AFM analyses demonstrated that the fluorine-containing segments from the HBPUF terminals were prone to migrate and enrich on the film-air surface of the HBPUF latex film, which made water contact angle and water absorption of the HBPUF film be as 113.9° and 11.1%, respectively, compared to those of the PU film (77.8° and 136.2%). This research indicates that water resistance of the PU film can be efficiently enhanced by fluorinated polyurethane with novel fluoroalkyl-terminated hyperbranched structure.

Ductile electroactive biodegradable hyperbranched polylactide copolymers enhancing myoblast differentiation.

PubMed

Xie, Meihua; Wang, Ling; Guo, Baolin; Wang, Zhong; Chen, Y Eugene; Ma, Peter X

2015-12-01

Myotube formation is crucial to restoring muscular functions, and biomaterials that enhance the myoblast differentiation into myotubes are highly desirable for muscular repair. Here, we report the synthesis of electroactive, ductile, and degradable copolymers and their application in enhancing the differentiation of myoblasts to myotubes. A hyperbranched ductile polylactide (HPLA) was synthesized and then copolymerized with aniline tetramer (AT) to produce a series of electroactive, ductile and degradable copolymers (HPLAAT). The HPLA and HPLAAT showed excellent ductility with strain to failure from 158.9% to 42.7% and modulus from 265.2 to 758.2 MPa. The high electroactivity of the HPLAAT was confirmed by UV spectrometer and cyclic voltammogram measurements. These HPLAAT polymers also showed improved thermal stability and controlled biodegradation rate compared to HPLA. Importantly, when applying these polymers for myotube formation, the HPLAAT significantly improved the proliferation of C2C12 myoblasts in vitro compared to HPLA. Furthermore, these polymers greatly promoted myogenic differentiation of C2C12 cells as measured by quantitative analysis of myotube number, length, diameter, maturation index, and gene expression of MyoD and TNNT. Together, our study shows that these electroactive, ductile and degradable HPLAAT copolymers represent significantly improved biomaterials for muscle tissue engineering compared to HPLA. Copyright © 2015 Elsevier Ltd. All rights reserved.

A New Epoxy-Based Layered Silicate Nanocomposite Using a Hyperbranched Polymer: Study of the Curing Reaction and Nanostructure Development.

PubMed

Cortés, Pilar; Fraga, Iria; Calventus, Yolanda; Román, Frida; Hutchinson, John M; Ferrando, Francesc

2014-03-04

Polymer layered silicate (PLS) nanocomposites have been prepared with diglycidyl ether of bisphenol-A (DGEBA) epoxy resin as the matrix and organically modified montmorillonite (MMT) as the clay nanofiller. Resin-clay mixtures with different clay contents (zero, two, five and 10 wt%) were cured, both isothermally and non-isothermally, using a poly(ethyleneimine) hyperbranched polymer (HBP), the cure kinetics being monitored by differential scanning calorimetry (DSC). The nanostructure of the cured nanocomposites was characterized by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and their mechanical properties were determined by dynamic mechanical analysis (DMA) and impact testing. The results are compared with an earlier study of the structure and properties of the same DGEBA-MMT system cured with a polyoxypropylene diamine, Jeffamine. There are very few examples of the use of HBP as a curing agent in epoxy PLS nanocomposites; here, it is found to enhance significantly the degree of exfoliation of these nanocomposites compared with those cured with Jeffamine, with a corresponding enhancement in the impact energy for nanocomposites with the low clay content of 2 wt%. These changes are attributed to the different cure kinetics with the HBP, in which the intra-gallery homopolymerization reaction is accelerated, such that it occurs before the bulk cross-linking reaction.

Ductile electroactive biodegradable hyperbranched polylactide copolymers enhancing myoblast differentiation

PubMed Central

Xie, Meihua; Wang, Ling; Guo, Baolin; Wang, Zhong; Chen, Y. Eugene; Ma, Peter X.

2015-01-01

Myotube formation is crucial to restoring muscular functions, and biomaterials that enhance the myoblast differentiation into myotubes are highly desirable for muscular repair. Here, we report the synthesis of electroactive, ductile, and degradable copolymers and their application in enhancing the differentiation of myoblasts to myotubes. A hyperbranched ductile polylactide (HPLA) was synthesized and then copolymerized with aniline tetramer (AT) to produce a series of electroactive, ductile and degradable copolymers (HPLAAT). The HPLA and HPLAAT showed excellent ductility with strain to failure from 158.9% to 42.7% and modulus from 265.2 to 758.2 MPa. The high electroactivity of the HPLAAT was confirmed by UV spectrometer and cyclic voltammogram measurements. These HPLAAT polymers also showed improved thermal stability and controlled biodegradation rate compared to HPLA. Importantly, when applying these polymers for myotube formation, the HPLAAT significantly improved the proliferation of C2C12 myoblasts in vitro compared to HPLA. Furthermore, these polymers greatly promoted myogenic differentiation of C2C12 cells as measured by quantitative analysis of myotube number, length, diameter, maturation index, and gene expression of MyoD and TNNT. Together, our study shows that these electroactive, ductile and degradable HPLAAT copolymers represent significantly improved biomaterials for muscle tissue engineering compared to HPLA. PMID:26335860

Enhanced cellular transport and drug targeting using dendritic nanostructures

NASA Astrophysics Data System (ADS)

Kannan, R. M.; Kolhe, Parag; Kannan, Sujatha; Lieh-Lai, Mary

2003-03-01

Dendrimers and hyperbranched polymers possess highly branched architectures, with a large number of controllable, tailorable, peripheral' functionalities. Since the surface chemistry of these materials can be modified with relative ease, these materials have tremendous potential in targeted drug delivery. The large density of end groups can also be tailored to create enhanced affinity to targeted cells, and can also encapsulate drugs and deliver them in a controlled manner. We are developing tailor-modified dendritic systems for drug delivery. Synthesis, drug/ligand conjugation, in vitro cellular and in vivo drug delivery, and the targeting efficiency to the cell are being studied systematically using a wide variety of experimental tools. Results on PAMAM dendrimers and polyol hyperbranched polymers suggest that: (1) These materials complex/encapsulate a large number of drug molecules and release them at tailorable rates; (2) The drug-dendrimer complex is transported very rapidly through a A549 lung epithelial cancel cell line, compared to free drug, perhaps by endocytosis. The ability of the drug-dendrimer-ligand complexes to target specific asthma and cancer cells is currently being explored using in vitro and in vivo animal models.

Active site formation mechanism of carbon-based oxygen reduction catalysts derived from a hyperbranched iron phthalocyanine polymer.

PubMed

Hiraike, Yusuke; Saito, Makoto; Niwa, Hideharu; Kobayashi, Masaki; Harada, Yoshihisa; Oshima, Masaharu; Kim, Jaehong; Nabae, Yuta; Kakimoto, Masa-Aki

2015-01-01

Carbon-based cathode catalysts derived from a hyperbranched iron phthalocyanine polymer (HB-FePc) were characterized, and their active-site formation mechanism was studied by synchrotron-based spectroscopy. The properties of the HB-FePc catalyst are compared with those of a catalyst with high oxygen reduction reaction (ORR) activity synthesized from a mixture of iron phthalocyanine and phenolic resin (FePc/PhRs). Electrochemical measurements demonstrate that the HB-FePc catalyst does not lose its ORR activity up to 900°C, whereas that of the FePc/PhRs catalyst decreases above 700°C. Hard X-ray photoemission spectra reveal that the HB-FePc catalysts retain more nitrogen components than the FePc/PhRs catalysts between pyrolysis temperatures of 600°C and 800°C. This is because the linked structure of the HB-FePc precursor has high thermostability against nitrogen desorption. Consequently, effective doping of active nitrogen species into the sp (2) carbon network of the HB-FePc catalysts may occur up to 900°C.

Processing of poly(hydroxybutyrate-co-hydroxyvalerate)-based bionanocomposite foams using supercritical fluids

Treesearch

Alireza Javadi; Yottha Srithep; Craig C. Clemons; L-S. Turng; Shaoqin Gong

2012-01-01

Supercritical fluid (SCF) N2 was used as a physical foaming agent to fabricate microcellular injection-molded poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)–poly(butylene adipate-co-terephthalate) (PBAT)–hyperbranched-polymer (HBP)–nanoclay (NC) bionanocomposites. The effects of incorporating HBP and NC on the morphological, mechanical, and...

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.

2007-01-01

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Three-Dimensional Polypeptide Architectures Through Tandem Catalysis and Click Chemistry

NASA Astrophysics Data System (ADS)

Rhodes, Allison Jane

Rapid renal clearance, liver accumulation, proteolytic degradation and non-specificity are challenges small molecule drugs, peptides, proteins and nucleic acid therapeutics encounter en route to their intended destination within the body. Nanocarriers (i.e. dendritric polymers, vesicles, and micelles) of approximately 100 nm in diameter, shuttle small molecule drugs to their desired location through passive (EPR effect) and active (ligand-mediated) targeting, maximizing therapeutic efficiency. Polypeptide-based polymers are water-soluble, biocompatible, non-toxic and are therefore excellent candidates for nanocarriers. Dendritic polymers, including dendrimers, cylindrical brushes, and star polymers, are the newest class of nanomedicine drug delivery vehicles. The synthesis and characterization of dendritic polymers is challenging, with tedious and costly procedures. Dendritic polymers possess peripheral pendent functional groups that can potentially be used in ligand-mediated drug delivery vehicles and bioimaging applications. More specifically, cylindrical brushes are dendritic polymers where a single linear polymer (primary chain) has polymer chains (secondary chains) grafted to it. Recently, research groups have shown that cylindrical brush polymers are capable of nanoparticle and supramolecular structure self-assembly. The facile preparation of high-density brush copolypeptides by the "grafting from" approach will be discussed. This approach utilizes a novel, tandem catalytic methodology where alloc-alpha-aminoamide groups are installed within the side-chains of the alpha-amino-N-carboxyanhydride (NCA) monomer serving as masked initiators. These groups are inert during cobalt initiated NCA polymerization, and give alloc-alpha-aminoamide substituted polypeptide main-chains. The alloc-alpha-aminoamide groups are activated in situ using nickel to generate initiators for growth of side-chain brush segments. This method proves to be efficient, yielding well-defined, high-density brushes for applications in drug delivery and imaging. Here, we also report a method for the synthesis of soluble, well-defined, azido functionalized polypeptides in a straightforward, 3-step synthesis. Homo and diblock azidopolypeptides were prepared with controlled segment lengths via living polymerization using Co(PMe3)4 initiator. Through copper azide alkyne click chemistry (CuAAC) in organic solvent, azidopolypeptides were regioselectively and quantitatively modified with carboxylic acid (pH-responsive), amino acid and sugar functional groups. Finally, the advances towards well-defined hyperbranched polypeptides through alpha-amino-acid-N-thiocarboxyanhydrides (NTAs) will be discussed. Within the past 10 years, controlled NCA (alpha-amino acid-N-carboxyanhydride) ring-opening polymerization (ROP) has emerged, expanding the application of copolypeptide polymers in various drug delivery and tissue engineering motifs. Modification of NCA monomers to the corresponding alpha-amino-acid-N-thiocarboxyanhydride (NTA) will diversify ROP reactions, leading to more complex polypeptides (such as hyperbranched polymers), in addition to the possibility of performing these polymerizations under ambient conditions, which would greatly expand their potential utility. The project focuses on the preparation of hyperbranched polypeptides with well-defined architectures and controlled branching density in a one-pot reaction. This will be accomplished by taking advantage of the different selectivities of Co(PMe3)4 and depeNi(COD) polymerization initiators, and by exploiting the reactivity difference between NCA and the more stable NTA monomers.

Thermodynamics of coil-hyperbranched poly(styrene-b-acrylated epoxidized soybean oil) block copolymers

NASA Astrophysics Data System (ADS)

Lin, Fang-Yi; Hohmann, Austin; Hernández, Nacú; Cochran, Eric

Here we present the phase behavior of a new type of coil-hyperbranched diblock copolymer: poly(styrene- b-acrylated epoxidized soybean oil), or PS-PAESO. PS-PAESO is an example of a biorenewable thermoplastic elastomer (bio-TPE). To date, we have shown that bio-TPEs can be economical commercial substitutes for their petrochemically derived analogues--such as poly(styrene- b-butadiene- b-styrene) (SBS)--in a range of applications including pressure sensitive adhesives and bitumen modification. From a polymer physics perspective, PS-PAESO is an interesting material in that it couples a linear coil-like block with a highly branched block. Thus in contrast to the past five decades of studies on linear AB diblock copolymers, coil-hyperbranched block copolymers are relatively unknown to the community and can be expected to deviate substantially from the standard ``universal'' phase behavior in the AB systems. To explore these new materials, we have constructed a library of PS-PAESO materials spanning a range of molecular weight and composition values. The phase transition behavior and the morphology information will be interpreted by isochronal temperature scanning in dynamic shear rheology, small angle X-ray scattering and the corresponding transmission electron microscopy.

A New Epoxy-Based Layered Silicate Nanocomposite Using a Hyperbranched Polymer: Study of the Curing Reaction and Nanostructure Development

PubMed Central

Cortés, Pilar; Fraga, Iria; Calventus, Yolanda; Román, Frida; Hutchinson, John M.; Ferrando, Francesc

2014-01-01

Polymer layered silicate (PLS) nanocomposites have been prepared with diglycidyl ether of bisphenol-A (DGEBA) epoxy resin as the matrix and organically modified montmorillonite (MMT) as the clay nanofiller. Resin-clay mixtures with different clay contents (zero, two, five and 10 wt%) were cured, both isothermally andnon-isothermally, using a poly(ethyleneimine) hyperbranched polymer (HBP), the cure kinetics being monitored by differential scanning calorimetry (DSC). The nanostructure of the cured nanocomposites was characterized by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and their mechanical properties were determined by dynamic mechanical analysis (DMA) and impact testing. The results are compared with an earlier study of the structure and properties of the same DGEBA-MMT system cured with a polyoxypropylene diamine, Jeffamine. There are very few examples of the use of HBP as a curing agent in epoxy PLS nanocomposites; here, it is found to enhance significantly the degree of exfoliation of these nanocomposites compared with those cured with Jeffamine, with a corresponding enhancement in the impact energy for nanocomposites with the low clay content of 2 wt%. These changes are attributed to the different cure kinetics with the HBP, in which the intra-gallery homopolymerization reaction is accelerated, such that it occurs before the bulk cross-linking reaction. PMID:28788542

Bio-based hyperbranched thermosetting polyurethane/triethanolamine functionalized multi-walled carbon nanotube nanocomposites as shape memory materials.

PubMed

Kalita, Hemjyoti; Karak, Niranjan

2014-07-01

Here, bio-based shape memory polymers have generated immense interest in recent times. Here, Bio-based hyperbranched polyurethane/triethanolamine functionalized multi-walled carbon nanotube (TEA-f-MWCNT) nanocomposites were prepared by in-situ pre-polymerization technique. The Fourier transform infrared spectroscopy and the transmission electron microscopic studies showed the strong interfacial adhesion and the homogeneous distribution of TEA-f-MWCNT in the polyurethane matrix. The prepared epoxy cured thermosetting nanocomposites exhibited enhanced tensile strength (6.5-34.5 MPa), scratch hardness (3.0-7.5 kg) and thermal stability (241-288 degrees C). The nanocomposites showed excellent shape fixity and shape recovery. The shape recovery time decreases (24-10 s) with the increase of TEA-f-MWCNT content in the nanocomposites. Thus the studied nanocomposites have potential to be used as advanced shape memory materials.

FY08 Chemical Synthesis for the Self-Decontaminating Coatings Project

DTIC Science & Technology

2013-08-01

These synthesized materials consist of Boltorn hyperbranched polymers that are functionalized with hydantoin, alkyl, and perfluorinated groups. 15...envisioned that completely prevents sorption of chemical agents, enables autonomous decontamination, reduces the volume of cleaning solution...modified with perfluorinated octanoic acid (PFOA), lauric acid, and a hydantoin moiety. HO OH CH3 HO O 3 Figure 2. Synthetic targets 1–3

pH-Mediated Fluorescent Polymer Particles and Gel from Hyperbranched Polyethylenimine and the Mechanism of Intrinsic Fluorescence.

PubMed

Liu, Shi Gang; Li, Na; Ling, Yu; Kang, Bei Hua; Geng, Shuo; Li, Nian Bing; Luo, Hong Qun

2016-02-23

We report that fluorescence properties and morphology of hyperbranched polyethylenimine (hPEI) cross-linked with formaldehyde are highly dependent on the pH values of the cross-linking reaction. Under acidic and neutral conditions, water-soluble fluorescent copolymer particles (CPs) were produced. However, under basic conditions, white gels with weak fluorescence emission would be obtained. The water-soluble hPEI-formaldehyde (hPEI-F) CPs show strong intrinsic fluorescence without the conjugation to any classical fluorescent agents. By the combination of spectroscopy and microscopy techniques, the mechanism of fluorescence emission was discussed. We propose that the intrinsic fluorescence originates from the formation of a Schiff base in the cross-linking process between hPEI and formaldehyde. Schiff base bonds are the fluorescence-emitting moieties, and the compact structure of hPEI-F CPs plays an important role in their strong fluorescence emission. The exploration on fluorescence mechanism may provide a new strategy to prepare fluorescent polymer particles. In addition, the investigation shows that the hPEI-F CPs hold potential as a fluorescent probe for the detection of copper ions in aqueous media.

Wanted: Scalable Tracers for Diffusion Measurements

PubMed Central

2015-01-01

Scalable tracers are potentially a useful tool to examine diffusion mechanisms and to predict diffusion coefficients, particularly for hindered diffusion in complex, heterogeneous, or crowded systems. Scalable tracers are defined as a series of tracers varying in size but with the same shape, structure, surface chemistry, deformability, and diffusion mechanism. Both chemical homology and constant dynamics are required. In particular, branching must not vary with size, and there must be no transition between ordinary diffusion and reptation. Measurements using scalable tracers yield the mean diffusion coefficient as a function of size alone; measurements using nonscalable tracers yield the variation due to differences in the other properties. Candidate scalable tracers are discussed for two-dimensional (2D) diffusion in membranes and three-dimensional diffusion in aqueous solutions. Correlations to predict the mean diffusion coefficient of globular biomolecules from molecular mass are reviewed briefly. Specific suggestions for the 3D case include the use of synthetic dendrimers or random hyperbranched polymers instead of dextran and the use of core–shell quantum dots. Another useful tool would be a series of scalable tracers varying in deformability alone, prepared by varying the density of crosslinking in a polymer to make say “reinforced Ficoll” or “reinforced hyperbranched polyglycerol.” PMID:25319586

Novel Low-Density Ablators Containing Hyperbranched Poly(azomethine)s

NASA Technical Reports Server (NTRS)

Tigelaar, Dean

2011-01-01

An ablative composite is low-density (0.25 to 0.40 g/cu cm), easy to fabricate, and superior to the current state-of-the-art ablator (phenolic impregnated carbon ablator, PICA) in terms of decomposition temperature, char yield, and mechanical strength. Initial ablative testing with a CO2 laser under high-heat-flux (1,100 W/sq cm) conditions showed these new ablators are over twice as effective as PICA in terms of weight loss, as well as transfer of heat through the specimen. The carbon fiber/poly(azomethine) composites have the same density as PICA, but are 8 to 11 times stronger to irreversible breaking by tensile compression. In addition, polyazomethine char yields by thermogravimetric analysis are 70 to 80 percent at 1,000 C. This char yield is 10 to 20 percent higher than phenolic resins, as well as one of the highest char yields known for any polymer. A high char yield holds the composite together better toward shearing forces on reentry, as well as reradiates high heat fluxes. This innovative composite is stronger than PICA, so multiple pieces can be sealed together without fracture. Researchers have also studied polyazomethines before as linear polymers. Due to poor solubility, these polymers precipitate from the polymerization solvent as a low-molecular-weight (2 to 4 repeat units) powder. The only way found to date to keep linear polyazomethines in solution is by adding solubilizing side groups. However, these groups sacrifice certain polymer properties. These hyperbranched polyazomethines are high molecular weight and fully aromatic.

Tethering of hyperbranched polyols using PEI as a building block to synthesize antifouling PVDF membranes

NASA Astrophysics Data System (ADS)

Wang, Xushan; Wang, Zihong; Wang, Zhe; Cao, Yu; Meng, Jianqiang

2017-10-01

Antifouling PVDF membranes were prepared by grafting hyperbranched polyols on the membrane surface via a three-step modification method. The membrane was first prepared by alkaline treatment to introduce alkenyl groups, then chemically immobilizing hyperbranched poly(ethyleneimine) (HPEI) on membrane surface through Michael reaction followed by ring opening reaction of the glycidol with amine groups. Chemical compositions, surface morphology and physicochemical properties of the original and modified membranes were characterized via attenuated total refection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), water contact angle (WCA) and zeta potential measurements. The antifouling property of the modified membrane was assessed by the static bovine serum albumin (BSA) and lysozyme (LZM) adsorption as well as cross-flow filtration of BSA aqueous solution. The results explicate that surface modification using hyperbranched polymers can alter membrane chemistry and morphology significantly. In contrast to the original PVDF membrane, the modified membrane shows superhydrophilic property and relatively high capability to resist nonspecific protein adsorption. Three HPEIs were used for modification and the obtained PVDFA-g-PG60,000 membrane has a static BSA protein adsorption of 45 μg/cm2 and shows the highest protein resistance. However, the PVDF-g-PG membrane is positively charged due to the unreacted amine groups. As a result, the PVDF-g-PG membranes also show high flux decline during the filtration of BSA aqueous solution due to the electrostatic interaction. In spite of that, the PVDF-g-PG membranes still maintain high flux recovery ratio and good washing properties.

Modified Hyperbranched Polymers for Fluorescence Sensing Applications

DTIC Science & Technology

2012-06-01

sensors. The HBPs transported the fluorescent groups to the fiber mat surface where they interacted with mercury (Hg(II)) or cytochrome c as the analyte...coworkers (27, 28) have employed fluorescence quenching using a binol-based dendrimer sensor, which exhibited differential sensitivity to enantiomeric...based sensors using HBP-based fluorophores was demonstrated in this report. Low concentrations of fluorophore were transported to the surface of

Hyperbranched quasi-1D nanostructures for solid-state dye-sensitized solar cells.

PubMed

Passoni, Luca; Ghods, Farbod; Docampo, Pablo; Abrusci, Agnese; Martí-Rujas, Javier; Ghidelli, Matteo; Divitini, Giorgio; Ducati, Caterina; Binda, Maddalena; Guarnera, Simone; Li Bassi, Andrea; Casari, Carlo Spartaco; Snaith, Henry J; Petrozza, Annamaria; Di Fonzo, Fabio

2013-11-26

In this work we demonstrate hyperbranched nanostructures, grown by pulsed laser deposition, composed of one-dimensional anatase single crystals assembled in arrays of high aspect ratio hierarchical mesostructures. The proposed growth mechanism relies on a two-step process: self-assembly from the gas phase of amorphous TiO2 clusters in a forest of tree-shaped hierarchical mesostructures with high aspect ratio; oriented crystallization of the branches upon thermal treatment. Structural and morphological characteristics can be optimized to achieve both high specific surface area for optimal dye uptake and broadband light scattering thanks to the microscopic feature size. Solid-state dye sensitized solar cells fabricated with arrays of hyperbranched TiO2 nanostructures on FTO-glass sensitized with D102 dye showed a significant 66% increase in efficiency with respect to a reference mesoporous photoanode and reached a maximum efficiency of 3.96% (among the highest reported for this system). This result was achieved mainly thanks to an increase in photogenerated current directly resulting from improved light harvesting efficiency of the hierarchical photoanode. The proposed photoanode overcomes typical limitations of 1D TiO2 nanostructures applied to ss-DSC and emerges as a promising foundation for next-generation high-efficiency solid-state devices comprosed of dyes, polymers, or quantum dots as sensitizers.

Molecularly Engineered Polymer-Based Systems in Drug Delivery and Regenerative Medicine.

PubMed

Piluso, Susanna; Soultan, Al Halifa; Patterson, Jennifer

2017-01-01

Polymer-based systems are attractive in drug delivery and regenerative medicine due to the possibility of tailoring their properties and functions to a specific application. The present review provides several examples of molecularly engineered polymer systems, including stimuli responsive polymers and supramolecular polymers. The advent of controlled polymerization techniques has enabled the preparation of polymers with controlled molecular weight and well-defined architecture. By using these techniques coupled to orthogonal chemical modification reactions, polymers can be molecularly engineered to incorporate functional groups able to respond to small changes in the local environment or to a specific biological signal. This review highlights the properties and applications of stimuli-responsive systems and polymer therapeutics, such as polymer-drug conjugates, polymer-protein conjugates, polymersomes, and hyperbranched systems. The applications of polymeric membranes in regenerative medicine are also discussed. The examples presented in this review suggest that the combination of membranes with polymers that are molecularly engineered to respond to specific biological functions could be relevant in the field of regenerative medicine. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Glycodendritic structures: promising new antiviral drugs.

PubMed

Rojo, Javier; Delgado, Rafael

2004-09-01

DC-SIGN, a C-type lectin expressed by dendritic cells, is able to recognize high mannosylated glycoproteins at the surface of a broad range of pathogens including viruses, bacteria, fungi and parasites. For at least some of these agents this interaction appears to be an important part of the infection process. Therefore, this lectin might be considered in the design of new antiviral drugs. In this manner, multivalent carbohydrate systems based on dendrimers and dendritic polymers are promising candidates as antiviral drugs. Boltorn hyperbranched dendritic polymers functionalized with mannose have been used to inhibit DC-SIGN-mediated infection in an Ebola-pseudotyped viral model. Their physiological solubility, lack of toxicity and especially their low price suggest the application of these glycodendritic polymers for possible formulation as microbicides.

Synthesis of a Chloroamide-Hyperbranched Polymer Additive for Self-Decontaminating Surfaces

DTIC Science & Technology

2012-04-01

dissolved in dichloromethane (DCM) (30 mL) and the solution was dried with anhydrous sodium sulfate (Na2SO4) before being used in the next step...infrared spectroscopy N2 nitrogen Na2SO4 anhydrous sodium sulfate NMP 1-methyl-2-pyrrolidinone PFOA perfluorinated octanoic acid PMMA poly(methyl...16 3.6.1 Synthesis and Characterization of Chlorinated 5,5-Dimethylhydantoin Sodium Salt

Advanced Materials by Atom Transfer Radical Polymerization.

PubMed

Matyjaszewski, Krzysztof

2018-06-01

Atom transfer radical polymerization (ATRP) has been successfully employed for the preparation of various advanced materials with controlled architecture. New catalysts with strongly enhanced activity permit more environmentally benign ATRP procedures using ppm levels of catalyst. Precise control over polymer composition, topology, and incorporation of site specific functionality enables synthesis of well-defined gradient, block, comb copolymers, polymers with (hyper)branched structures including stars, densely grafted molecular brushes or networks, as well as inorganic-organic hybrid materials and bioconjugates. Examples of specific applications of functional materials include thermoplastic elastomers, nanostructured carbons, surfactants, dispersants, functionalized surfaces, and biorelated materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Positively Charged Hyperbranched Polymers with Tunable Fluorescence and the Cell Imaging Application.

PubMed

Ma, Hengchang; Qin, Yanfang; Yang, Zenming; Yang, Manyi; Ma, Yucheng; Yin, Pei; Yang, Yuan; Wang, Tao; Lei, Ziqiang; Yao, Xiaoqiang

2018-04-25

Fluorescence-tunable materials are becoming increasingly attractive for their potential application in optics, electronics, and biomedical technology. Herein, a multi-color molecular pixel system is realized using simple copolymerization method. Bleeding both of complementary colors from blue and yellow fluorescence segments, reproduced a serious multicolor fluorescence materials. Interestingly, the emission colors of the polymers can be fine-tuned in solid state, solution phase, and in hydrogel state. More importantly, the positive fluorescent polymers exhibited cell-membrane permeable ability, and were found to accumulate on the cell nucleus, exhibiting remarkable selectivity to give bright fluorescence. The DNA/RNA selectivity experiments in vitro and in vivo verified that [tris(4-(pyridin-4-yl)phenyl)amine]-[1,8-dibromooctane] (TPPA-DBO) has prominent selectivity to DNA over RNA inside cells.

Molecular Mobility in Hyperbranched Polymers and Their Interaction with an Epoxy Matrix

PubMed Central

Román, Frida; Colomer, Pere; Calventus, Yolanda; Hutchinson, John M.

2016-01-01

The molecular mobility related to the glass transition and secondary relaxations in a hyperbranched polyethyleneimine, HBPEI, and its relaxation behaviour when incorporated into an epoxy resin matrix are investigated by dielectric relaxation spectroscopy (DRS) and dynamic mechanical analysis (DMA). Three systems are analysed: HBPEI, epoxy and an epoxy/HBPEI mixture, denoted ELP. The DRS behaviour is monitored in the ELP system in three stages: prior to curing, during curing, and in the fully cured system. In the stage prior to curing, DRS measurements show three dipolar relaxations: γ, β and α, for all systems (HBPEI, epoxy and ELP). The α-relaxation for the ELP system deviates significantly from that for HBPEI, but superposes on that for the epoxy resin. The fully cured thermoset displays both β- and α-relaxations. In DMA measurements, both α- and β-relaxations are observed in all systems and in both the uncured and fully cured systems, similar to the behaviour identified by DRS. PMID:28773319

Synthesis and characterization of curcumin loaded PLA-Hyperbranched polyglycerol electrospun blend for wound dressing applications.

PubMed

Perumal, Govindaraj; Pappuru, Sreenath; Chakraborty, Debashis; Maya Nandkumar, A; Chand, Dillip Kumar; Doble, Mukesh

2017-07-01

This study is aimed to develop curcumin (Cur) incorporated electrospun nanofibers of a blend of poly (lactic acid) (PLA) and hyperbranched polyglycerol (HPG) for wound healing applications. Both the polymers are synthesized and fabricated by electrospinning technique. The produced nanofibers were characterized by Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Colorimetry (DSC) and Thermogravimetric Analysis (TGA). Electrospun scaffolds (PLA/HPG/Cur) exhibits very high hydrophilicity, high swelling and drug uptake and promotes better cell viability, adhesion and proliferation when compared to PLA/Cur electrospun nanofibers. Biodegradation study revealed that the morphology of the nanofibers were unaffected even after 14days immersion in Phosphate Buffered Saline. In vitro scratch assay indicates that migration of the cells in the scratch treated with PLA/HPG/Cur is complete within 36h. These results suggest that PLA/HPG/Cur nanofibers can be a potential wound patch dressing for acute and chronic wound applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Composite Electrolyte Membranes from Partially Fluorinated Polymer and Hyperbranched, Sulfonated Polysulfone

PubMed Central

Subianto, Surya; Roy Choudhury, Namita; Dutta, Naba

2013-01-01

Macromolecular modification of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF) was done with various proportions of sulfonic acid terminated, hyperbranched polysulfone (HPSU) with a view to prepare ion conducting membranes. The PVDF-co-HFP was first chemically modified by dehydrofluorination and chlorosulfonation in order to make the membrane more hydrophilic as well as to introduce unsaturation, which would allow crosslinking of the PVDF-co-HFP matrix to improve the stability of the membrane. The modified samples were characterized for ion exchange capacity, morphology, and performance. The HPSU modified S-PVDF membrane shows good stability and ionic conductivity of 5.1 mS cm−1 at 80 °C and 100% RH for blends containing 20% HPSU, which is higher than the literature values for equivalent blend membranes using Nafion. SEM analysis of the blend membranes containing 15% or more HPSU shows the presence of spherical domains with a size range of 300–800 nm within the membranes, which are believed to be the HPSU-rich area. PMID:28348282

Polymer Brushes: Synthesis, Characterization, Applications

NASA Astrophysics Data System (ADS)

Advincula, Rigoberto C.; Brittain, William J.; Caster, Kenneth C.; Rühe, Jürgen

2004-09-01

Materials scientists, polymer chemists, surface physicists and materials engineers will find this book a complete and detailed treatise on the field of polymer brushes, their synthesis, characterization and manifold applications. In a first section, the various synthetic pathways and different surface materials are introduced and explained, followed by a second section covering important aspects of characterization and analysis in both flat surfaces and particles. These specific surface initiated polymerization (SIP) systems such as linear polymers, homopolymers, block copolymers, and hyperbranched polymers are unique compared to previously reported systems by chemisorption or physisorption. They have found their way in both large-scale and miniature applications of polymer brushes, which is covered in the last section. Such 'hairy' surfaces offer fascinating opportunities for addressing numerous problems of both academic and, in particular, industrial interest: high-quality, functional or protective coatings, composite materials, surface engineered particles, metal-organic interfaces, biological applications, micro-patterning, colloids, nanoparticles, functional devices, and many more. It is the desire of the authors that this book will be of benefit to readers who want to "brush-up on polymers".

Effect of chain topology on crystallization within nanoporous alumina

NASA Astrophysics Data System (ADS)

Yao, Yang; Suzuki, Yasuhito; Sakai, Takamasa; Seiwert, Jan; Frey, Holger; Steinhart, Martin; Butt, Hans-Juergen; Floudas, George

Polymer topology has inevitable influence on the structure, packing, and dynamic of chains. Herein, we investigate for the first time the impact of polymer architecture on crystallization under 2D confinement, the latter provided by nanoporous alumina (AAO). We employ two poly(ethylene oxide) (PEO) star polymers to study the effect of (i) end groups and (ii) molecular weight on polymer crystallization in the bulk and under confinement. Bulk end groups reduce the crystallization/melting temperatures and the corresponding equilibrium melting point. Under confinement, in the absence of catalyst, homogeneous nucleation prevails as with linear PEOs. The homogeneous nucleation temperatures for the star polymers agree with that of linear ones provided that the arm molecular weight is used instead. Long-range dynamics pertinent to star relaxation are affecting the homogeneous nucleation temperature. On the other hand, the segmental dynamics speed up on confinement. In addition to star PEO, we study the effect of another topology, i.e. hyperbranched PEO, on the nucleation mechanism.

Conjugated Organosilicon Materials for Organic Electronics and Photonics

NASA Astrophysics Data System (ADS)

Ponomarenko, Sergei A.; Kirchmeyer, Stephan

In this chapter different types of conjugated organosilicon materials possessing luminescent and/or semiconducting properties will be described. Such macromolecules have various topologies and molecular structures: linear, branched and hyperbranched oligomers, polymers, and dendrimers. Specific synthetic approaches to access these structures will be discussed. Special attention is devoted to the role of silicon in these structures and its influence on their optical and electrical properties, leading to their potential application in the emerging areas of organic and hybrid electronics.

Hyperbranched Polycarbosilanes via Nucleophilic Substitution Reactions

NASA Astrophysics Data System (ADS)

Interrante, L.; Shen, Q.

Nucleophilic substitution reactions involving organomagnesium (Grignard) [1] and organolithium reagents have been used extensively for many years to form Si—C bonds (see Reaction Scheme 12.1). However, their use for the construction of hyperbranched polymers whose backbone contains, as a major structural component, silicon—carbon bonds, i.e., polycarbosilanes [2] is relatively more recent. (12.1) begin{array}{l} {{R}}_3 {{SiX + MR'}} to {{R}}_3 {{SiR' + MX}} \\ left({{{R,R' = alkyl}} {{or aryl;}} {{M = Mg(X),}} {{Li,}} {{Na}};{{X = halogen, OR''}}} right) \\ This chapter focuses on the application of such nucleophilic substitution reactions toward the synthesis of hyperbranched polycarbosilanes, with particular emphasis on those preparations that have resulted in relatively well characterized products. These syntheses are organized by the type of ABn monomer unit used (see Section 1.2), where A and B refer to the (C)X and (Si)Xn, respectively, functional ends of the monomer unit and where the nature of the coupling reaction leads to entirely or primarily Si—C bond formation. In most cases, these are “one-pot” reactions that employ monomers that bear halogen or alkoxy groups on the C and Si ends of the unit. Indeed, hyperbranched polycarbosilanes have been described, in general, as “obtained in one synthetic step via a random, one-pot polymerization of multifunctional monomers of AB n type” [2]. Treatment of the ABn monomer with either elemental Mg or an organolithium reagent, ideally (but not always) forms a complexed carbanion (the nucleophile) by reaction with the C-X end of the monomer unit, resulting in an intermediate of the type, (XxM)CSiXn, where M = Mg or Li, X = halogen or alkoxy, and x = 1 (Mg) or 0 (Li). Self-coupling of this reagent via reactions of the type shown in Reaction Scheme 12.1 leads to oligomeric and polymeric products that are connected primarily through Si—C bonds and yield an inorganic MXx by-product.

Removal of some organic pollutants in water employing ceramic membranes impregnated with cross-linked silylated dendritic and cyclodextrin polymers.

PubMed

Allabashi, Roza; Arkas, Michael; Hörmann, Gerold; Tsiourvas, Dimitris

2007-01-01

Triethoxysilylated derivatives of poly(propylene imine) dendrimer, polyethylene imine and polyglycerol hyperbranched polymers and beta-cyclodextrin have been synthesized and characterized. These compounds impregnated ceramic membranes made from Al(2)O(3), SiC and TiO(2) and subsequently sol-gel reaction led to their polymerization and chemical bond formation with the ceramic substrates. The resulting organic-inorganic filters were tested for the removal of a variety of organic pollutants from water. They were found to remove of polycyclic aromatic hydrocarbons (up to 99%), of monocyclic aromatic hydrocarbons (up to 93%), trihalogen methanes (up to 81%), pesticides (up to 43%) and methyl-tert-butyl ether (up to 46%).

Chain conformation and immunomodulatory activity of a hyperbranched polysaccharide from Cordyceps sinensis.

PubMed

Wu, Ding-Tao; Meng, Lan-Zhen; Wang, Lan-Ying; Lv, Guang-Ping; Cheong, Kit-Leong; Hu, De-Jun; Guan, Jia; Zhao, Jing; Li, Shao-Ping

2014-09-22

A polysaccharide, named as cordysinan, extracted from natural Cordyceps sinensis, was identified as a hyperbranched heteropolysaccharide from the results of FT-IR, GC-MS, and carbohydrate analysis by carbohydrate gel electrophoresis analysis, as well as the degree of branching of cordysinan was 43.3%. The solution properties of cordysinan were investigated by using size exclusion chromatography coupled with multi-angle laser light scattering and triple detector array, respectively. The molecular weights, the radius of gyration and the intrinsic viscosity of cordysinan were determined as 22.45±0.26 kDa and 22.37 kDa, 15.4±2.4 nm and 1.41 mL/g, respectively. By applying the polymer solution theory, the exponent (ν and α) values of g1/2=kMwv and [η]=kMwα were calculated as 0.28 and 0.42, respectively, which firstly revealed that cordysinan existed as a globular shape in 0.9% NaCl aqueous solution. Moreover, the results showed that cordysinan could obviously stimulate macrophages functions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Aerosol delivery of folate-decorated hyperbranched polyspermine complexes to suppress lung tumorigenesis via Akt signaling pathway.

PubMed

Luo, Cheng-Qiong; Jang, Yoonjeong; Xing, Lei; Cui, Peng-Fei; Qiao, Jian-Bin; Lee, Ah Young; Kim, Hyeon-Jeong; Cho, Myung-Haing; Jiang, Hu-Lin

2016-11-20

Lung cancer has been a leading cause of cancer mortality worldwide and aerosol-mediated gene therapy endows numerous advantages compared to other traditional modalities. Here, we reported a folic acid (FA)-modified hyperbranched polyspermine (HPSPE) with prominent biocompatibility for lung cancer cell targeted gene therapy. FA was decorated to the HPSPE via an amidation reaction and the physicochemical properties of nanoplexes formed with DNA were characterized. Gel electrophoresis study elucidated that the designed polymer was capable to condense DNA and protect it from degradation by DNase I. Cell viability and transfection efficiency assay in vitro and in vivo indicated its increased transfection performance with lower toxicity. Furthermore, reduced tumor numbers and down-regulation of Akt1 protein after aerosol treatment containing FA-HPSPE/shAkt1 complexes proved its therapeutic potential for lung cancer suppression. Results obtained in this study suggested that FA-HPSPE with highly biocompatibility and targeting capability while forming complexes with shAkt1 and administrated through noninvasive aerosol could be prospective for inhibiting lung tumorigenesis. Copyright © 2016 Elsevier B.V. All rights reserved.

High-performance functional ecopolymers based on flora and fauna.

PubMed

Kaneko, Tatsuo

2007-01-01

Liquid crystalline (LC) polymers of rigid monomers based on flora and fauna were prepared by in-bulk polymerization. Para-coumaric (p-coumaric) acid [4-hydroxycinnamic acid (4HCA)] and its derivatives were selected as phytomonomers and bile acids were selected as biomonomers. The 4HCA homopolymer showed a thermotropic LC phase only in a state of low molecular weight. The copolymers of 4HCA with bile acids such as lithocholic acid (LCA) and cholic acid (CA) showed excellent cell compatibilities but low molecular weights. However, P(4HCA-co-CA)s allowed LC spinning to create molecularly oriented biofibers, presumably due to the chain entanglement that occurs during in-bulk chain propagation into hyperbranching architecture. P[4HCA-co-3,4-dihydroxycinnamic acid (DHCA)]s showed high molecular weight, high mechanical strength, high Young's modulus, and high softening temperature, which may be achieved through the entanglement by in-bulk formation of hyperbranching, rigid structures. P(4HCA-co-DHCA)s showed a smooth hydrolysis, in-soil degradation, and photo-tunable hydrolysis. Thus, P(4HCA-co-DHCA)s might be applied as an environmentally degradable plastic with extremely high performance.

Microfluidic approaches for the fabrication of gradient crosslinked networks based on poly(ethylene glycol) and hyperbranched polymers for manipulation of cell interactions

PubMed Central

Pedron, S; Peinado, C; Bosch, P; Benton, J A; Anseth, K S

2011-01-01

High-throughput methods allow rapid examination of parameter space to characterize materials and develop new polymeric formulations for biomaterials applications. One limitation is the difficulty of preparing libraries and performing high-throughput screening with conventional instrumentation and sample preparation. Here, we describe the fabrication of substrate materials with controlled gradients in composition by a rapid method of micromixing followed by a photopolymerization reaction. Specifically, poly(ethylene glycol) dimethacrylate was copolymerized with a hyperbranched multimethacrylate (P1000MA or H30MA) in a gradient manner. The extent of methacrylate conversion and the final network composition were determined by near-infrared spectroscopy, and mechanical properties were measured by nanoindentation. A relationship was observed between the elastic modulus and network crosslinking density. Roughness and hydrophilicity were increased on surfaces with a higher concentration of P1000MA. These results likely relate to a phase segregation process of the hyperbranched macromer that occurs during the photopolymerization reaction. On the other hand, the decrease in the final conversion in H30MA polymerization reactions was attributed to the lower termination rate as a consequence of the softening of the network. Valvular interstitial cell attachment was evaluated on these gradient substrates as a demonstration of studying cell morphology as a function of the local substrate properties. Data revealed that the presence of P1000MA affects cell–material interaction with a higher number of adhered cells and more cell spreading on gradient regions with a higher content of the multifunctional crosslinker. PMID:21105168

A liposome-based antigen delivery system using pH-sensitive fusogenic polymers for cancer immunotherapy.

PubMed

Yuba, Eiji; Harada, Atsushi; Sakanishi, Yuichi; Watarai, Shinobu; Kono, Kenji

2013-04-01

Highly pH-sensitive liposomes that deliver antigenic molecules into cytosol through fusion with or destabilization of endosome were prepared by surface modification of egg yolk phosphatidylcholine/dioleoylphosphatidylethanolamine (1/1, mol/mol) liposomes with 3-methylglutarylated poly(glycidol) of linear (MGlu-LPG) or hyperbranched structure (MGlu-HPG). These polymer-modified liposomes were stable at neutral pH, but they became strongly destabilized below pH 6, which corresponds to the pH of endosome. These polymer-modified liposomes were taken up by murine dendritic cells (DCs) more efficiently than the unmodified liposomes were through an endocytic pathway. They introduced entrapped ovalbumin (OVA) molecules into cytosol. Subcutaneous or nasal administration of the polymer-modified liposomes loaded with OVA induced generation of OVA-specific cytotoxic T cells (CTL) much more effectively than the unmodified liposomes loaded with OVA. Furthermore, administration of the polymer-modified OVA-loaded liposomes to mice bearing E.G7-OVA tumor significantly reduced the tumor burden, although the OVA-loaded unmodified liposomes only slightly affected tumor growth. Results suggest that the polymer-modified liposomes with highly pH-sensitive destabilizing property are promising as antigen carriers for efficient cancer immunotherapy. Copyright © 2012 Elsevier Ltd. All rights reserved.

Synthesis and Characterization of a Hyperbranched Hydrogen Bond Acidic Carbosilane Sorbent Polymer

DTIC Science & Technology

2010-01-01

double bond of HCSA2 (1) electrophilically attacks the ketone carbon of the HFA. The bonds are formed via a pericyclic mechanism which requires formation...val- ues for H, 3.1% and C, 35.4% compared with the theoretical weight percents of H, 2.2%, and C, 34.3%. Fluorine composi- tion numbers were...Srcic, S. Acta Chim Solv 2004, 51, 373–394. 43 Bhadury, P. S.; Dubey, V.; Singh, S.; Saxena, C. J. Fluorine Chem 2005, 126, 1252–1256. 44 Grate, J. W

Dendritic polymer-based nanodevices for targeted drug delivery applications

NASA Astrophysics Data System (ADS)

Kannan, R. M.; Kolhe, Parag; Gurdag, Sezen; Khandare, Jayant; Lieh-Lai, Mary

2004-03-01

Dendrimers and hyperbranched polymers are unimolecular micellar nanostructures, characterized by globular shape ( ˜ 20 nm) and large density of functional groups at periphery. The tailorable end groups make them ideal for conjugation with drugs, ligands, and imagining agents, making them an attractive molecular nanodevices for drug delivery. Compared to linear polymers and nanoparticles, these nanodevices enter cells rapidly, carrying drugs and delivering them inside cells. Performance of nanodevices prepared for asthma and cancer drug delivery will be discussed. Our conjugation procedure produced very high drug payloads. Dendritic polymer-drug conjugates were very effective in transporting methotrexate (a chemotherapy drug) into both sensitive (CCRF-CEM cell line) and resistant cell line (CEM-MTX). The conjugate nanodevice was 3 times more effective than free drug in the sensitive line, and 9 times more effective in the resistant cell line (based on IC50). The physics of cell entry and drug release from these nanodevices are being investigated. The conjugates appear to enter cells through endocytosis, with the rate of entry dependent on end-group, molecular weight, the pH of the medium, and the cancerous nature of the cells.

Designing Dendrimer and Miktoarm Polymer Based Multi-Tasking Nanocarriers for Efficient Medical Therapy.

PubMed

Sharma, Anjali; Kakkar, Ashok

2015-09-17

To address current complex health problems, there has been an increasing demand for smart nanocarriers that could perform multiple complimentary biological tasks with high efficacy. This has provoked the design of tailor made nanocarriers, and the scientific community has made tremendous effort in meeting daunting challenges associated with synthetically articulating multiple functions into a single scaffold. Branched and hyper-branched macromolecular architectures have offered opportunities in enabling carriers with capabilities including location, delivery, imaging etc. Development of simple and versatile synthetic methodologies for these nanomaterials has been the key in diversifying macromolecule based medical therapy and treatment. This review highlights the advancement from conventional "only one function" to multifunctional nanomedicine. It is achieved by synthetic elaboration of multivalent platforms in miktoarm polymers and dendrimers by physical encapsulation, covalent linking and combinations thereof.

Multifunctional Nanomaterials: Design, Synthesis and Application Properties.

PubMed

Martinelli, Marisa; Strumia, Miriam Cristina

2017-02-07

The immense scope of variation in dendritic molecules (hyper-branching, nano-sized, hydrophobicity/hydrophilicity, rigidity/flexibility balance, etc.) and their versatile functionalization, with the possibility of multivalent binding, permit the design of highly improved, novel materials. Dendritic-based materials are therefore viable alternatives to conventional polymers. The overall aim of this work is to show the advantages of dendronization processes by presenting the synthesis and characterization of three different dendronized systems: (I) microbeads of functionalized chitosan; (II) nanostructuration of polypropylene surfaces; and (III) smart dendritic nanogels. The particular properties yielded by these systems could only be achieved thanks to the dendronization process.

Inorganic dendrimers: recent advances for catalysis, nanomaterials, and nanomedicine.

PubMed

Caminade, Anne-Marie

2016-10-07

Dendrimers are hyperbranched polymers having a perfectly defined structure because they are synthesized step-by-step in an iterative fashion, and not by polymerization reactions. Some dendrimers are considered as inorganic, as they possess inorganic atoms at each branching point. Among numerous examples, two families of inorganic dendrimers have emerged as particularly promising: silicon-containing dendrimers, particularly carbosilanes, and phosphorus-containing dendrimers, particularly phosphorhydrazones. This tutorial review will display the main properties of both families of dendrimers in the fields of catalysis, materials and biology/nanomedicine. Emphasis will be put on the most recent and promising examples.

Improved epoxy thermosets by the use of poly(ethyleneimine) derivatives

NASA Astrophysics Data System (ADS)

Acebo, Cristina; Ramis, Xavier; Serra, Angels

2017-07-01

Epoxy resins are commonly used as thermosetting materials due to their excellent mechanical properties, high adhesion to many substrates and good heat and chemical resistances. This type of thermosets is intensively used in a wide range of fields, where they act as fiber-reinforced materials, general-purpose adhesives, high-performance coatings and encapsulating materials. These materials are formed by the chemical reaction of multifunctional epoxy monomers forming a polymer network produced through an irreversible way. In this article the improvement of the characteristics of epoxy thermosets using different hyperbranched poly(ethyleneimine) (PEI) derivatives will be explained.

Heat conduction tuning by hyperbranched nanophononic metamaterials

NASA Astrophysics Data System (ADS)

Li, Bing; Tan, K. T.; Christensen, Johan

2018-05-01

Phonon dispersion and thermal conduction properties of hyperbranched nanostructures with unique topological complexity are theoretically and numerically investigated in this research. We present analytical cantilever-in-mass models to analyze and control the inherent resonance hybridization in hyperbranched nanomembranes containing different configurations and cross sections. We show that these local resonances hosted by hyperbranched nanopillars can generate numerous flat bands in the phonon dispersion relation and dramatically lower the group velocities, consequently resulting in a significant reduction of the thermal conductivity. The applicability of the proposed analytical models in thermal conductivity tuning is demonstrated, and a superior performance in reducing the heat flux in nano-structured membranes is exhibited, which can potentially lead to improved thermoelectric energy conversion devices.

Enhanced energy density and thermal conductivity in poly(fluorovinylidene-co-hexafluoropropylene) nanocomposites incorporated with boron nitride nanosheets exfoliated under assistance of hyperbranched polyethylene.

PubMed

Ye, Huijian; Lu, Tiemei; Xu, Chunfeng; Zhong, Mingqiang; Xu, Lixin

2018-03-02

Polymer dielectric film with a large dielectric constant, high energy density and enhanced thermal conductivity are of significance for the development of impulse capacitors. However, the fabrication of polymer dielectrics combining high energy density and thermal conductivity is still a challenge at the moment. Here we demonstrate the facile exfoliation of hexagonal boron nitride nanosheets (BNNSs) in common organic solvents under sonication with the assistance of hyperbranched polyethylene (HBPE). The noncovalent CH-π interactions between the nanosheets and HBPE ensure the dispersion of BNNSs in organic solvents with high concentrations, because of the highly branched chain structure of HBPE. Subsequently, the resultant BNNSs with a few defects are distributed uniformly in the poly(fluorovinylidene-co-hexafluoropropylene) (P(VDF-HFP)) nanocomposite films prepared via simple solution casting. The BNNS/P(VDF-HFP) nanocomposite exhibits outstanding dielectric properties, high energy density and high thermal conductivity. The dielectric constant of the 0.5 wt% nanocomposite film is 35.5 at 100 Hz with an energy density of 5.6 J cm -3 at 325 MV m -1 and a high charge-discharge efficiency of 79% due to the depression of the charge injection and chemical species ionization in a high field. Moreover, a thermal conductivity of 1.0 wt% nanocomposite film reaches 0.91 W·m -1  · K -1 , which is 3.13 times higher than that of the fluoropolymer matrix. With dipole accumulation and orientation in the interfacial zone, lightweight, flexible BNNS/P(VDF-HFP) nanocomposite films with high charge-discharge performance and thermal conductivity, exhibit promising applications in relatively high-temperature electronics and energy storage devices.

Enhanced energy density and thermal conductivity in poly(fluorovinylidene-co-hexafluoropropylene) nanocomposites incorporated with boron nitride nanosheets exfoliated under assistance of hyperbranched polyethylene

NASA Astrophysics Data System (ADS)

Ye, Huijian; Lu, Tiemei; Xu, Chunfeng; Zhong, Mingqiang; Xu, Lixin

2018-03-01

Polymer dielectric film with a large dielectric constant, high energy density and enhanced thermal conductivity are of significance for the development of impulse capacitors. However, the fabrication of polymer dielectrics combining high energy density and thermal conductivity is still a challenge at the moment. Here we demonstrate the facile exfoliation of hexagonal boron nitride nanosheets (BNNSs) in common organic solvents under sonication with the assistance of hyperbranched polyethylene (HBPE). The noncovalent CH-π interactions between the nanosheets and HBPE ensure the dispersion of BNNSs in organic solvents with high concentrations, because of the highly branched chain structure of HBPE. Subsequently, the resultant BNNSs with a few defects are distributed uniformly in the poly(fluorovinylidene-co-hexafluoropropylene) (P(VDF-HFP)) nanocomposite films prepared via simple solution casting. The BNNS/P(VDF-HFP) nanocomposite exhibits outstanding dielectric properties, high energy density and high thermal conductivity. The dielectric constant of the 0.5 wt% nanocomposite film is 35.5 at 100 Hz with an energy density of 5.6 J cm-3 at 325 MV m-1 and a high charge-discharge efficiency of 79% due to the depression of the charge injection and chemical species ionization in a high field. Moreover, a thermal conductivity of 1.0 wt% nanocomposite film reaches 0.91 W·m-1 · K-1, which is 3.13 times higher than that of the fluoropolymer matrix. With dipole accumulation and orientation in the interfacial zone, lightweight, flexible BNNS/P(VDF-HFP) nanocomposite films with high charge-discharge performance and thermal conductivity, exhibit promising applications in relatively high-temperature electronics and energy storage devices.

Controlled growth of novel hyper-branched nanostructures in nanoporous alumina membrane.

PubMed

Zhang, Junping; Day, Cynthia S; Carroll, David L

2009-12-07

This paper proposes a novel approach to fabricate hyper-branched anodic aluminium oxide (AAO) nanostructures with different branches on the vertically-aligned trunk and at the trunk terminal. Silver nanowires with different dimensional and multifunctional complexity have been prepared from this hyper-branched AAO template by varying the electrodeposition time. These kinds of novel nanostructure may be used to build blocks for nanoelectronic and nanophotonic devices.

Nature of alpha and beta particles in glycogen using molecular size distributions.

PubMed

Sullivan, Mitchell A; Vilaplana, Francisco; Cave, Richard A; Stapleton, David; Gray-Weale, Angus A; Gilbert, Robert G

2010-04-12

Glycogen is a randomly hyperbranched glucose polymer. Complex branched polymers have two structural levels: individual branches and the way these branches are linked. Liver glycogen has a third level: supramolecular clusters of beta particles which form larger clusters of alpha particles. Size distributions of native glycogen were characterized using size exclusion chromatography (SEC) to find the number and weight distributions and the size dependences of the number- and weight-average masses. These were fitted to two distinct randomly joined reference structures, constructed by random attachment of individual branches and as random aggregates of beta particles. The z-average size of the alpha particles in dimethylsulfoxide does not change significantly with high concentrations of LiBr, a solvent system that would disrupt hydrogen bonding. These data reveal that the beta particles are covalently bonded to form alpha particles through a hitherto unsuspected enzyme process, operative in the liver on particles above a certain size range.

Cell-free 3D scaffold with two-stage delivery of miRNA-26a to regenerate critical-sized bone defects

PubMed Central

Zhang, Xiaojin; Li, Yan; Chen, Y. Eugene; Chen, Jihua; Ma, Peter X.

2016-01-01

MicroRNAs (miRNAs) are being developed to enhance tissue regeneration. Here we show that a hyperbranched polymer with high miRNA-binding affinity and negligible cytotoxicity can self-assemble into nano-sized polyplexes with a ‘double-shell' miRNA distribution and high transfection efficiency. These polyplexes are encapsulated in biodegradable microspheres to enable controllable two-stage (polyplexes and miRNA) delivery. The microspheres are attached to cell-free nanofibrous polymer scaffolds that spatially control the release of miR-26a. This technology is used to regenerate critical-sized bone defects in osteoporotic mice by targeting Gsk-3β to activate the osteoblastic activity of endogenous stem cells, thus addressing a critical challenge in regenerative medicine of achieving cell-free scaffold-based miRNA therapy for tissue engineering. PMID:26765931

Simultaneous growth of pure hyperbranched Zn3As2 structures and long Ga2O3 nanowires.

PubMed

Li, Jianye; Wang, Lung-Shen; Buchholz, D Bruce; Chang, Robert P H

2009-05-01

Through a facile and highly repeatable chemical vapor method, pure three-dimensional hyperbranched Zn(3)As(2) structures and ultralong Ga(2)O(3) nanowires were simultaneously grown with controllable locations in the same experiment. The hyperbranched Zn(3)As(2) consists of cone-shaped submicro-/nanowires and has a single-crystalline tetragonal structure. This is the first report of nano Zn(3)As(2) and hyperbranched Zn(3)As(2) structures. The as-grown Ga(2)O(3) nanowires are monoclinic single crystals. A vapor-solid-solid mechanism is suggested for the growth of the Ga(2)O(3) nanowires, and a vapor-solid mechanism, for the Zn(3)As(2) structures.

Conjugation of cytochrome c with ferrocene-terminated hyperbranched polymer and its influence on protein structure, conformation and function.

PubMed

Xiao, Fengjuan; Yue, Lin; Li, Song; Li, Xinxin

2016-06-05

Interaction mechanism of a new hyperbranched polyurethane-based ferrocene (HPU-Fc) with cytochrome c (cyt c) and cyt c structure and conformation change induced by HPU-Fc were investigated using cyclic voltammogram(CV), differential pulse voltammetry (DPV), circular dichroism (CD), fluorescence, synchronous fluorescence and absorbance spectroscopy technique. The peroxidase activity of cyt c in the presence of HPU-Fc was also studied. The structure and conformation of protein are relatively stable at moderate concentration of HPU-Fc without obvious perturbation of the heme pocket and significant changes in protein secondary structure. Conjugation of cyt c with excessive HPU-Fc (over about 3 times of cyt c) slightly changed the α-helix structure in protein, disturbed the microenvironment around heme as well as away from the heme crevice, which caused the changes of the electrochemical behavior and the absorption spectra. Reasonable amount of HPU-Fc has no significant influence on the protein enzymatic activity, while excess HPU-Fc may cause a conformation not suitable for H2O2 activation and guaiacol oxidation. The interaction of HPU-Fc with cyt c and the conservation of protein function at suitable HPU-Fc amount make prepared complex promising for the synergistic anticancer therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Using inositol as a biocompatible ligand for efficient transgene expression

PubMed Central

Zhang, Lei; Bellis, Susan L; Fan, Yiwen; Wu, Yunkun

2015-01-01

Transgene transfection techniques using cationic polymers such as polyethylenimines (PEIs) and PEI derivatives as gene vectors have shown efficacy, although they also have shortcomings. PEIs have decent DNA-binding capability and good cell internalization performance, but they cannot deliver gene payloads very efficiently to cell nuclei. In this study, three hyperbranched polyglycerol-polyethylenimine (PG6-PEI) polymers conjugated with myo-inositol (INO) molecules were developed. The three resulting PG6-PEI-INO polymers have an increased number of INO ligands per molecule. PG6-PEI-INO 1 had only 14 carboxymethyl INO (CMINO) units per molecule. PG6-PEI-INO 2 had approximately 130 CMINO units per molecule. PG6-PEI-INO 3 had as high as 415 CMINO units approximately. Mixing PG6-PEI-INO polymers with DNA produced compact nanocomposites. We then performed localization studies using fluorescent microscopy. As the number of conjugated inositol ligands increased in PG6-PEI-INO polymers, there was a corresponding increase in accumulation of the polymers within 293T cell nuclei. Transfection performed with spherical 293T cells yielded 82% of EGFP-positive cells when using PG6-PEI-INO 3 as the vehicle. Studies further revealed that extracellular adenosine triphosphate (eATP) can inhibit the transgene efficiency of PG6-PEI-INO polymers, as compared with PEI and PG6-PEI that were not conjugated with inositol. Our work unveiled the possibility of using inositol as an effective ligand for transgene expression. PMID:25926732

Origin of Broad Visible Emission from Branched Polysilane and Polygermane Chains

NASA Astrophysics Data System (ADS)

Watanabe, Akira; Sato, Takaaki; Matsuda, Minoru

2001-11-01

The emission properties of branched polysilane and polygermane are studied using time-resolved emission spectroscopy. As branched polymers, the organosilicon cluster (OSI) and organogermanium cluster (OGE) are investigated, which are prepared from tetrachlorosilane and tetrachlorogermane, respectively, and have a hyperbranched structure. The broad visible emissions of OSI and OGE are explained by the energy diagram based on a configuration coordinate model, and the excited states are attributed to a localized state around the branching point. The molecular orbital (MO) calculation suggested the formation of a localized state by the distortion around the branching point in the excited state. The potential barrier for the nonradiative relaxation process was determined from the temperature dependence of the emission lifetime.

RHEOLOGY OF CONCENTRATED SOLUTIONS OF HYPERBRANCHED POLYESTERS

EPA Science Inventory

The solution rheology of different generations of hyperbranched polyesters in N-methyl-2- pyrrolidinone (NMP) solvent was examined in this study. The solutions exhibited Newtonian behavior over a wide range of polyester concentrations. Also, the relative viscosities of poly(amido...

Study of Hyperbranched Poly(ethyleneimine) Polymers of Different Molecular Weight and Their Interaction with Epoxy Resin

PubMed Central

2018-01-01

Two different commercial hyperbranched poly(ethyleneimine)s (HBPEI), with molecular weights (MW) of 800 and 25,000 g/mol, and denoted as PEI800 and PEI25000, respectively, as well as the mixtures with a Diglycidyl Ether of Bisphenol-A (DGEBA) epoxy resin, have been studied using thermal analysis techniques (DSC, TGA), dielectric relaxation spectroscopy (DRS), and dynamic mechanical analysis (DMA). Only a single glass transition is observed in these mixtures by DSC. DRS of the HBPEIs shows three dipolar relaxations: γ, β, and α. The average activation energy for the γ-relaxation is similar for all HBPEIs and is associated with the motion of the terminal groups. The β-relaxation has the same average activation energy for both PEI800 and PEI25000; this relaxation is attributed to the mobility of the branches. The α-relaxation peak for all the HBPEIs is an asymmetric peak with a shoulder on the high temperature side. This shoulder suggests the existence of ionic charge trapped in the PEI. For the mixtures, the γ- and β-relaxations follow the behaviour of the epoxy resin alone, indicating that the epoxy resin dominates the molecular mobility. The α-relaxation by DRS is observed only as a shoulder, as a consequence of an overlap with conductivity effects, whereas by DMA, it is a clear peak. PMID:29522480

Impedimetric Aptasensor for Ochratoxin A Determination Based on Au Nanoparticles Stabilized with Hyper-Branched Polymer

PubMed Central

Evtugyn, Gennady; Porfireva, Anna; Stepanova, Veronika; Kutyreva, Marianna; Gataulina, Alfiya; Ulakhovich, Nikolay; Evtugyn, Vladimir; Hianik, Tibor

2013-01-01

An impedimetric aptasensor for ochratoxin A (OTA) detection has been developed on the base of a gold electrode covered with a new modifier consisting of electropolymerized Neutral Red and a mixture of Au nanoparticles suspended in the dendrimeric polymer Botlorn H30®. Thiolated aptamer specific to OTA was covalently attached to Au nanoparticles via Au-S bonding. The interaction of the aptamer with OTA induced the conformational switch of the aptamer from linear to guanine quadruplex form followed by consolidation of the surface layer and an increase of the charge transfer resistance. The aptasensor makes it possible to detect from 0.1 to 100 nM of OTA (limit of detection: 0.02 nM) in the presence of at least 50 fold excess of ochratoxin B. The applicability of the aptasensor for real sample assay was confirmed by testing spiked beer samples. The recovery of 2 nM OTA was found to be 70% for light beer and 78% for dark beer. PMID:24287535

Composites Based on Core-Shell Structured HBCuPc@CNTs-Fe3O4 and Polyarylene Ether Nitriles with Excellent Dielectric and Mechanical Properties

NASA Astrophysics Data System (ADS)

Pu, Zejun; Zhong, Jiachun; Liu, Xiaobo

2017-10-01

Core-shell structured magnetic carbon nanotubes (CNTs-Fe3O4) coated with hyperbranched copper phthalocyanine (HBCuPc) (HBCuPc@CNTs-Fe3O4) hybrids were prepared by the solvent-thermal method. The results indicated that the HBCuPc molecules were decorated on the surface of CNTs-Fe3O4 through coordination behavior of phthalocyanines, and the CNTs-Fe3O4 core was completely coaxial wrapped by a functional intermediate HBCuPc shell. Then, polymer-based composites with a relatively high dielectric constant and low dielectric loss were fabricated by using core-shell structured HBCuPc@CNTs-Fe3O4 hybrids as fillers and polyarylene ether nitriles (PEN) as the polymer matrix. The cross-sectional scanning electron microscopy (SEM) images of composites showed that there is almost no agglomeration and internal delamination. In addition, the rheological analysis reveals that the core-shell structured HBCuPc@CNTs-Fe3O4 hybrids present better dispersion and stronger interface adhesion with the PEN matrix than CNTs-Fe3O4, thus resulting in significant improvement of the mechanical, thermal and dielectric properties of polymer-based composites.

Synthesis and supramolecular assembly of biomimetic polymers

NASA Astrophysics Data System (ADS)

Marciel, Amanda Brittany

A grand challenge in materials chemistry is the synthesis of macromolecules and polymers with precise shapes and architectures. Polymer microstructure and architecture strongly affect the resulting functionality of advanced materials, yet understanding the static and dynamic properties of these complex macromolecules in bulk has been difficult due to their inherit polydispersity. Single molecule studies have provided a wealth of information on linear flexible and semi-flexible polymers in dilute solutions. However, few investigations have focused on industrially relevant complex topologies (e.g., star, comb, hyperbranched polymers) in industrially relevant solution conditions (e.g., semi-dilute, concentrated). Therefore, from this perspective there is a strong need to synthesize precision complex architectures for bulk studies as well as complex architectures compatible with current single molecule techniques to study static and dynamic polymer properties. In this way, we developed a hybrid synthetic strategy to produce branched polymer architectures based on chemically modified DNA. Overall, this approach enables control of backbone length and flexibility, as well as branch grafting density and chemical identity. We utilized a two-step scheme based on enzymatic incorporation of non-natural nucleotides containing bioorthogonal dibenzocyclooctyne (DBCO) functional groups along the main polymer backbone, followed by copper-free "click" chemistry to graft synthetic polymer branches or oligonucleotide branches to the DNA backbone, thereby allowing for the synthesis of a variety of polymer architectures, including three-arm stars, H-polymers, graft block copolymers, and comb polymers for materials assembly and single molecule studies. Bulk materials properties are also affected by industrial processing conditions that alter polymer morphology. Therefore, in an alternative strategy we developed a microfluidic-based approach to assemble highly aligned synthetic oligopeptides nanostructures using microscale extensional flows. This strategy enabled reproducible, reliable fabrication of aligned hierarchical constructs that do not form spontaneously in solution. In this way, fluidic-directed assembly of supramolecular structures allows for unprecedented manipulation at the nano- and mesoscale, which has the potential to provide rapid and efficient control of functional materials properties.

Hyperbranched Polyglycerol as a Colloid in Cold Organ Preservation Solutions

PubMed Central

Gao, Sihai; Guan, Qiunong; Chafeeva, Irina; Brooks, Donald E.; Nguan, Christopher Y. C.; Kizhakkedathu, Jayachandran N.; Du, Caigan

2015-01-01

Hydroxyethyl starch (HES) is a common colloid in organ preservation solutions, such as in University of Wisconsin (UW) solution, for preventing graft interstitial edema and cell swelling during cold preservation of donor organs. However, HES has undesirable characteristics, such as high viscosity, causing kidney injury and aggregation of erythrocytes. Hyperbranched polyglycerol (HPG) is a branched compact polymer that has low intrinsic viscosity. This study investigated HPG (MW-0.5 to 119 kDa) as a potential alternative to HES for cold organ preservation. HPG was synthesized by ring-opening multibranching polymerization of glycidol. Both rat myocardiocytes and human endothelial cells were used as an in vitro model, and heart transplantation in mice as an in vivo model. Tissue damage or cell death was determined by both biochemical and histological analysis. HPG polymers were more compact with relatively low polydispersity index than HES in UW solution. Cold preservation of mouse hearts ex vivo in HPG solutions reduced organ damage in comparison to those in HES-based UW solution. Both size and concentration of HPGs contributed to the protection of the donor organs; 1 kDa HPG at 3 wt% solution was superior to HES-based UW solution and other HPGs. Heart transplants preserved with HPG solution (1 kDa, 3%) as compared with those with UW solution had a better functional recovery, less tissue injury and neutrophil infiltration in syngeneic recipients, and survived longer in allogeneic recipients. In cultured myocardiocytes or endothelial cells, significantly more cells survived after cold preservation with the HPG solution than those with the UW solution, which was positively correlated with the maintenance of intracellular adenosine triphosphate and cell membrane fluidity. In conclusion, HPG solution significantly enhanced the protection of hearts or cells during cold storage, suggesting that HPG is a promising colloid for the cold storage of donor organs and cells in transplantation. PMID:25706864

Hyperbranched polyglycerol as a colloid in cold organ preservation solutions.

PubMed

Gao, Sihai; Guan, Qiunong; Chafeeva, Irina; Brooks, Donald E; Nguan, Christopher Y C; Kizhakkedathu, Jayachandran N; Du, Caigan

2015-01-01

Hydroxyethyl starch (HES) is a common colloid in organ preservation solutions, such as in University of Wisconsin (UW) solution, for preventing graft interstitial edema and cell swelling during cold preservation of donor organs. However, HES has undesirable characteristics, such as high viscosity, causing kidney injury and aggregation of erythrocytes. Hyperbranched polyglycerol (HPG) is a branched compact polymer that has low intrinsic viscosity. This study investigated HPG (MW-0.5 to 119 kDa) as a potential alternative to HES for cold organ preservation. HPG was synthesized by ring-opening multibranching polymerization of glycidol. Both rat myocardiocytes and human endothelial cells were used as an in vitro model, and heart transplantation in mice as an in vivo model. Tissue damage or cell death was determined by both biochemical and histological analysis. HPG polymers were more compact with relatively low polydispersity index than HES in UW solution. Cold preservation of mouse hearts ex vivo in HPG solutions reduced organ damage in comparison to those in HES-based UW solution. Both size and concentration of HPGs contributed to the protection of the donor organs; 1 kDa HPG at 3 wt% solution was superior to HES-based UW solution and other HPGs. Heart transplants preserved with HPG solution (1 kDa, 3%) as compared with those with UW solution had a better functional recovery, less tissue injury and neutrophil infiltration in syngeneic recipients, and survived longer in allogeneic recipients. In cultured myocardiocytes or endothelial cells, significantly more cells survived after cold preservation with the HPG solution than those with the UW solution, which was positively correlated with the maintenance of intracellular adenosine triphosphate and cell membrane fluidity. In conclusion, HPG solution significantly enhanced the protection of hearts or cells during cold storage, suggesting that HPG is a promising colloid for the cold storage of donor organs and cells in transplantation.

Rheology of Hyperbranched Poly(triglyceride)-Based Thermoplastic Elastomers via RAFT polymerization

NASA Astrophysics Data System (ADS)

Yan, Mengguo; Cochran, Eric

2014-03-01

In this contribution we discuss how melt- and solid-state properties are influenced by the degree of branching and molecular weight in a family of hyperbranched thermoplastics derived from soybean oil. Acrylated epoxidized triglycerides from soybean oils have been polymerized to hyperbranched thermoplastic elastomers using reversible addition-fragmentation chain transfer (RAFT) polymerization. With the proper choice of chain transfer agent, both homopolymer and block copolymer can be synthesized. By changing the number of acrylic groups per triglycerides, the chain architectures can range from nearly linear to highly branched. We show how the fundamental viscoelastic properties (e.g. entanglement molecular weight, plateau modulus, etc.) are influenced by chain architecture and molecular weight.

Microcellular processing of polylactide-hyperbranched polyester-nanoclay composites

Treesearch

Srikanth Pilla; Adam Kramschuster; Jungjoo Lee; Craig Clemons; Shaoqin Gong; Lih-Sheng Turng

2010-01-01

The effects of addition of hyperbranched polyesters (HBPs) and nanoclay on the material properties of both solid and microcellular polylactide (PLA) produced via a conventional and microcellular injection-molding process, respectively, were investigated. The effects of two different types of HBPs (i.e., Boltorn H2004® and Boltorn H20®) at the same...

Magnetoceramics from the bulk pyrolysis of polysilazane cross-linked by polyferrocenylcarbosilanes with hyperbranched topology.

PubMed

Kong, Jie; Kong, Minmin; Zhang, Xiaofei; Chen, Lixin; An, Linan

2013-10-23

In this contribution, we report a novel strategy for the synthesis of nanocrystal-containing magnetoceramics with an ultralow hysteresis loss by the pyrolysis of commercial polysilazane cross-linked with a functional metallopolymer possessing hyperbranched topology. The usage of hyperbranched polyferrocenylcarbosilane offers either enhanced ceramic yield or magnetic functionality of pyrolyzed ceramics. The ceramic yield was enhanced accompanied by a decreased evolution of hydrocarbons and NH3 because of the cross-linking of precursors and the hyperbranched cross-linker. The nucleation of Fe5Si3 from the reaction of iron atoms with Si-C-N amorphous phase promoted the formation of α-Si3N4 and SiC crystals. After annealing at 1300 °C, stable Fe3Si crystals were generated from the transformation of the metastable Fe5Si3 phase. The nanocrystal-containing ceramics showed good ferromagnetism with an ultralow (close to 0) hysteresis loss. This method is convenient for the generation of tunable functional ceramics using a commercial polymeric precursor cross-linked by a metallopolymer with a designed topology.

Multistack integration of three-dimensional hyperbranched anatase titania architectures for high-efficiency dye-sensitized solar cells.

PubMed

Wu, Wu-Qiang; Xu, Yang-Fan; Rao, Hua-Shang; Su, Cheng-Yong; Kuang, Dai-Bin

2014-04-30

An unprecedented attempt was conducted on suitably functionalized integration of three-dimensional hyperbranched titania architectures for efficient multistack photoanode, constructed via layer-by-layer assembly of hyperbranched hierarchical tree-like titania nanowires (underlayer), branched hierarchical rambutan-like titania hollow submicrometer-sized spheres (intermediate layer), and hyperbranched hierarchical urchin-like titania micrometer-sized spheres (top layer). Owing to favorable charge-collection, superior light harvesting efficiency and extended electron lifetime, the multilayered TiO2-based devices showed greater J(sc) and V(oc) than those of a conventional TiO2 nanoparticle (TNP), and an overall power conversion efficiency of 11.01% (J(sc) = 18.53 mA cm(-2); V(oc) = 827 mV and FF = 0.72) was attained, which remarkably outperformed that of a TNP-based reference cell (η = 7.62%) with a similar film thickness. Meanwhile, the facile and operable film-fabricating technique (hydrothermal and drop-casting) provides a promising scheme and great simplicity for high performance/cost ratio photovoltaic device processability in a sustainable way.

Surface engineering of nanoparticles with macromolecules for epoxy curing: Development of super-reactive nitrogen-rich nanosilica through surface chemistry manipulation

NASA Astrophysics Data System (ADS)

Jouyandeh, Maryam; Jazani, Omid Moini; Navarchian, Amir H.; Shabanian, Meisam; Vahabi, Henri; Saeb, Mohammad Reza

2018-07-01

Curing behavior of epoxy-based nanocomposites depends on dispersion state of nanofillers and their physical and chemical interactions with the curing moieties. In this work, a systematic approach was introduced for chemical functionalization of nanoparticles with macromolecules in order to enrich crosslinking potential of epoxy/amine systems, particularly at late stages of cure where the curing is diffusion-controlled. Super-reactive hyperbranched polyethylenimine (PEI)-attached nanosilica was materialized in this work to facilitate epoxy-amine curing. Starting from coupling [3-(2,3-epoxypropoxy) propyl] trimethoxysilane (EPPTMS) with hyperbranched PEI, a super-reactive macromolecule was obtained and subsequently grafted onto the nanosilica surface. Eventually, a thermally-stable highly-curable nanocomposite was attained by replacement of amine and imine groups of the PEI with imide and amide groups through the reaction with pyromellitic acid dianhydride. Fourier-transform infrared spectrophotometry, X-ray diffractometry, X-ray photoelectron spectroscopy and transmission electron microscopy approved successful grafting of polymer chains onto the nanosilica surface. Thermogravimetric analyses approved a relatively high grafting ratio of ca. 21%. Curing potential of the developed super-reactive nanoparticle was uncovered through nonisothermal differential scanning calorimetry signifying an enthalpy rise of ca. 120 J/g by addition of 2 wt.% to epoxy at 5 °C/min heating rate. Even at low concentration of 0.5 wt.%, the glass transition temperature of epoxy increased from 128 to 156 °C, demonstrating prolonged crosslinking.

Triggered and catalyzed self-assembly of hyperbranched DNA structures for logic operations and homogeneous CRET biosensing of microRNA.

PubMed

Bi, Sai; Yue, Shuzhen; Wu, Qiang; Ye, Jiayan

2016-04-07

Toehold-mediated strand displacement-based nanocircuits are developed by integrating catalytic hairpin assembly (CHA) with hybridization chain reaction (HCR), which achieves self-assembly of hyperbranched DNA structures and is readily utilized as an enzyme-free amplifier for homogeneous CRET detection of microRNA with high sensitivity and selectivity.

Maximizing omnidirectional light harvesting in metal oxide hyperbranched array architectures

NASA Astrophysics Data System (ADS)

Wu, Wu-Qiang; Feng, Hao-Lin; Rao, Hua-Shang; Xu, Yang-Fan; Kuang, Dai-Bin; Su, Cheng-Yong

2014-05-01

The scrupulous design of nanoarchitectures and smart hybridization of specific active materials are closely related to the overall photovoltaic performance of an anode electrode. Here we present a solution-based strategy for the fabrication of well-aligned metal oxide-based nanowire-nanosheet-nanorod hyperbranched arrays on transparent conducting oxide substrates. For these hyperbranched arrays, we observe a twofold increment in dye adsorption and enhanced light trapping and scattering capability compared with the pristine titanium dioxide nanowires, and thus a power conversion efficiency of 9.09% is achieved. Our growth approach presents a strategy to broaden the photoresponse and maximize the light-harvesting efficiency of arrays architectures, and may lead to applications for energy conversion and storage, catalysis, water splitting and gas sensing.

Maximizing omnidirectional light harvesting in metal oxide hyperbranched array architectures.

PubMed

Wu, Wu-Qiang; Feng, Hao-Lin; Rao, Hua-Shang; Xu, Yang-Fan; Kuang, Dai-Bin; Su, Cheng-Yong

2014-05-29

The scrupulous design of nanoarchitectures and smart hybridization of specific active materials are closely related to the overall photovoltaic performance of an anode electrode. Here we present a solution-based strategy for the fabrication of well-aligned metal oxide-based nanowire-nanosheet-nanorod hyperbranched arrays on transparent conducting oxide substrates. For these hyperbranched arrays, we observe a twofold increment in dye adsorption and enhanced light trapping and scattering capability compared with the pristine titanium dioxide nanowires, and thus a power conversion efficiency of 9.09% is achieved. Our growth approach presents a strategy to broaden the photoresponse and maximize the light-harvesting efficiency of arrays architectures, and may lead to applications for energy conversion and storage, catalysis, water splitting and gas sensing.

Hydrothermal growth of cross-linked hyperbranched copper dendrites using copper oxalate complex

NASA Astrophysics Data System (ADS)

Truong, Quang Duc; Kakihana, Masato

2012-06-01

A facile and surfactant-free approach has been developed for the synthesis of cross-linked hyperbranched copper dendrites using copper oxalate complex as a precursor and oxalic acid as a reducing and structure-directing agent. The synthesized particles are composed of highly branched nanostructures with unusual cross-linked hierarchical networks. The formation of copper dendrites can be explained in view of both diffusion control and aggregation-based growth model accompanied by the chelation-assisted assembly. Oxalic acid was found to play dual roles as reducing and structure-directing agent based on the investigation results. The understanding on the crystal growth and the roles of oxalic acid provides clear insight into the formation mechanism of hyperbranched metal dendrites.

Progesterone binding nano-carriers based on hydrophobically modified hyperbranched polyglycerols

NASA Astrophysics Data System (ADS)

Alizadeh Noghani, M.; Brooks, D. E.

2016-02-01

Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models.Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models. Electronic supplementary information (ESI) available: Fig. S-1: chemical structure of progesterone (Pro). Fig. S-2: 1H NMR spectrum of HPG-C8-MPEG. Fig. S-3: GPC chromatogram of HPG-C8-MPEG. Fig. S-4: 1H NMR spectrum of HPG-C12-MPEG. Fig. S-5: GPC chromatogram of HPG-C8-MPEG. Fig. S-6: FTIR spectrum of HPG-C8-MPEG. Fig. S-7: inverse-gated 13C NMR spectrum of HPG-C8-MPEG in methanol-d4. Fig. S-8: semi-log plot to determine initial rapid release kinetics for HPG-C8-MPEG/Pro in PBS. Fig. S-9: semi-log plot to determine secondary slow release kinetics for HPG-C8-MPEG/Pro in PBS. Fig. S-10: semi-log plot illustrating the kinetics of Pro release from HPG-C8-MPEG/Pro in plasma. Fig. S-11: dependence of k1 and Vp - Va. Fig. S-12: correlation between the maximum binding capacity of HPG-Cn-MPEG polymeric systems for binding Pro and their total mass of alkyl carbon external to the oxygen (R2 = 0.77 and p < 0.025). Table S-1: effect of loaded Pro on HPG-Cn-MPEG size. Fig. S-13. DLS size determination of HPG-C10-MPEG at 2 mg ml-1 (on the left) and HPG-C10-MPEG/Pro at 2 mg ml-1 of polymer and 25 μg ml-1 of Pro (on the right). The minor population of larger particles was reduced in diameter by Pro binding, illustrated above, consistent with an earlier report.11 See DOI: 10.1039/c5nr08175k

High dielectric hyperbranched polyaniline materials.

PubMed

Yan, X Z; Goodson, T

2006-08-03

New organic materials for the purpose of high speed capacitor applications are discussed. The effect of the microcrystalline size dependence of different polyaniline polymeric systems on the dielectric constant is investigated. Two different methods are described for the preparation of the polyaniline dielectric materials. By sonication polymerization, the prepared polyaniline with a suggested hyperbranched structure showed much larger microcrystalline domains in comparison to the conventional linear polyaniline. Investigations of the dielectric constant and capacitance at a relatively high frequency (>100 kHz) suggested that the system with the larger microcrystalline domains (hyperbranched) gives rise to a larger dielectric constant. The mechanism of the increased dielectric response at higher frequencies is investigated by EPR spectroscopy, and these results suggest that delocalized polarons may provide a way to enhance the dielectric response at high frequency.

Biodegradable shape-memory block co-polymers for fast self-expandable stents.

PubMed

Xue, Liang; Dai, Shiyao; Li, Zhi

2010-11-01

Block co-polymers PCTBVs (M(n) of 36,300-65,300 g/mol, T(m) of 39-40 and 142 degrees C) containing hyperbranched three-arm poly(epsilon-caprolactone) (PCL) as switching segment and microbial polyester PHBV as crystallizable hard segment were designed as biodegradable shape-memory polymer (SMP) for fast self-expandable stent and synthesized in 96% yield by the reaction of three-arm PCL-triol (M(n) of 4200 g/mol, T(m) of 47 degrees C) with methylene diphenyl 4,4'-diisocyanate isocynate (MDI) to form the hyperbrached MDI-linked PCL (PTCM; M(n) of 25,400 g/mol and a T(m) of 38 degrees C), followed by further polymerization with PHBV-diol (M(n) of 2200 g/mol, T(m) of 137 and 148 degrees C). The polymers were characterized by (1)H NMR, GPC, DSC, tensile test, and cyclic thermomechanical tensile test. PCTBVs showed desired thermal properties, mechanical properties, and ductile nature. PCTBV containing 25 wt% PHBV (PCTBV-25) demonstrated excellent shape-memory property at 40 degrees C, with R(f) of 94%, R(r) of 98%, and shape recovery within 25s. PCTBV-25 was also shown as a safe material with good biocompatibility by cytotoxicity tests and cell growth experiments. The stent made from PCTBV-25 film showed nearly complete self-expansion at 37 degrees C within only 25 s, which is much better and faster than the best known self-expandable stents. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Drug-loaded nanoparticles induce gene expression in human pluripotent stem cell derivatives

NASA Astrophysics Data System (ADS)

Gajbhiye, Virendra; Escalante, Leah; Chen, Guojun; Laperle, Alex; Zheng, Qifeng; Steyer, Benjamin; Gong, Shaoqin; Saha, Krishanu

2013-12-01

Tissue engineering and advanced manufacturing of human stem cells requires a suite of tools to control gene expression spatiotemporally in culture. Inducible gene expression systems offer cell-extrinsic control, typically through addition of small molecules, but small molecule inducers typically contain few functional groups for further chemical modification. Doxycycline (DXC), a potent small molecule inducer of tetracycline (Tet) transgene systems, was conjugated to a hyperbranched dendritic polymer (Boltorn H40) and subsequently reacted with polyethylene glycol (PEG). The resulting PEG-H40-DXC nanoparticle exhibited pH-sensitive drug release behavior and successfully controlled gene expression in stem-cell-derived fibroblasts with a Tet-On system. While free DXC inhibited fibroblast proliferation and matrix metalloproteinase (MMP) activity, PEG-H40-DXC nanoparticles maintained higher fibroblast proliferation levels and MMP activity. The results demonstrate that the PEG-H40-DXC nanoparticle system provides an effective tool to controlling gene expression in human stem cell derivatives.Tissue engineering and advanced manufacturing of human stem cells requires a suite of tools to control gene expression spatiotemporally in culture. Inducible gene expression systems offer cell-extrinsic control, typically through addition of small molecules, but small molecule inducers typically contain few functional groups for further chemical modification. Doxycycline (DXC), a potent small molecule inducer of tetracycline (Tet) transgene systems, was conjugated to a hyperbranched dendritic polymer (Boltorn H40) and subsequently reacted with polyethylene glycol (PEG). The resulting PEG-H40-DXC nanoparticle exhibited pH-sensitive drug release behavior and successfully controlled gene expression in stem-cell-derived fibroblasts with a Tet-On system. While free DXC inhibited fibroblast proliferation and matrix metalloproteinase (MMP) activity, PEG-H40-DXC nanoparticles maintained higher fibroblast proliferation levels and MMP activity. The results demonstrate that the PEG-H40-DXC nanoparticle system provides an effective tool to controlling gene expression in human stem cell derivatives. Electronic supplementary information (ESI) available: ESI containing 1H NMR spectra and additional fibroblast characterization data. See DOI: 10.1039/c3nr04794f

Hyperbranched TiO2-CdS nano-heterostructures for highly efficient photoelectrochemical photoanodes.

PubMed

Mezzetti, Alessandro; Balandeh, Mehrdad; Luo, Jingshan; Bellani, Sebastiano; Tacca, Alessandra; Divitini, Giorgio; Cheng, Chuanwei; Ducati, Caterina; Meda, Laura; Fan, Hongjin; Di Fonzo, Fabio

2018-08-17

Quasi-1D-hyperbranched TiO 2 nanostructures are grown via pulsed laser deposition and sensitized with thin layers of CdS to act as a highly efficient photoelectrochemical photoanode. The device properties are systematically investigated by optimizing the height of TiO 2 scaffold structure and thickness of the CdS sensitizing layer, achieving photocurrent values up to 6.6 mA cm -2 and reaching saturation with applied biases as low as 0.35 V RHE . The high internal conversion efficiency of these devices is to be found in the efficient charge generation and injection of the thin CdS photoactive film and in the enhanced charge transport properties of the hyperbranched TiO 2 scaffold. Hence, the proposed device represents a promising architecture for heterostructures capable of achieving high solar-to-hydrogen efficiency.

Organic/inorganic hybrid filters based on dendritic and cyclodextrin "nanosponges" for the removal of organic pollutants from water.

PubMed

Arkas, Michael; Allabashi, Roza; Tsiourvas, Dimitris; Mattausch, Eva-Maria; Perfler, Reinhard

2006-04-15

Long-alkyl chain functionalized poly(propylene imine) dendrimer, poly(ethylene imine) hyperbranched polymer, and beta-cyclodextrin derivatives, which are completely insoluble in water, have the property of encapsulating organic pollutants from water. Ceramic porous filters can be impregnated with these compounds resulting in hybrid organic/ inorganic filter modules. These hybrid filter modules were tested for the effective purification of water, by continuous filtration experiments, employing a variety of water pollutants. It has been established that polycyclic aromatic hydrocarbons (PAHs) can be removed very efficiently (more than 95%), and final concentrations of several ppb (microg/ L) are easily obtained. Representatives of the pollutant group of trihalogen methanes (THMs), monoaromatic hydrocarbons (BTX), and pesticides (simazine) can also be removed (>80%), although the filters are saturated considerably faster in these cases.

Influence of polymer architecture on antigens camouflage, CD47 protection and complement mediated lysis of surface grafted red blood cells.

PubMed

Chapanian, Rafi; Constantinescu, Iren; Rossi, Nicholas A A; Medvedev, Nadia; Brooks, Donald E; Scott, Mark D; Kizhakkedathu, Jayachandran N

2012-11-01

Hyperbranched polyglycerol (HPG) and polyethylene glycol (PEG) polymers with similar hydrodynamic sizes in solution were grafted to red blood cells (RBCs) to investigate the impact of polymer architecture on the cell structure and function. The hydrodynamic sizes of polymers were calculated from the diffusion coefficients measured by pulsed field gradient NMR. The hydration of the HPG and PEG was determined by differential scanning calorimetry analyses. RBCs grafted with linear PEG had different properties compared to the compact HPG grafted RBCs. HPG grafted RBCs showed much higher electrophoretic mobility values than PEG grafted RBCs at similar grafting concentrations and hydrodynamic sizes indicating differences in the structure of the polymer exclusion layer on the cell surface. PEG grafting impacted the deformation properties of the membrane to a greater degree than HPG. The complement mediated lysis of the grafted RBCs was dependent on the type of polymer, grafting concentration and molecular size of grafted chains. At higher molecular weights and graft concentrations both HPG and PEG triggered complement activation. The magnitude of activation was higher with HPG possibly due to the presence of many hydroxyl groups per molecule. HPG grafted RBCs showed significantly higher levels of CD47 self-protein accessibility than PEG grafted RBCs at all grafting concentrations and molecular sizes. PEG grafted polymers provided, in general, a better shielding and protection to ABO and minor antigens from antibody recognition than HPG polymers, however, the compact HPGs provided greater protection of certain antigens on the RBC surface. Our data showed that HPG 20 kDa and HPG 60 kDa grafted RBCs exhibited properties that are more comparable to the native RBC than PEG 5 kDa and PEG 10 kDa grafted RBCs of comparable hydrodynamic sizes. The study shows that small compact polymers such as HPG 20 kDa have a greater potential in the generation of functional RBC for therapeutic delivery applications. The intermediate sized polymers (PEG or HPG) which showed greater antigen camouflage at lower grafting concentrations have significant potential in transfusion as universal red blood donor cells. Copyright © 2012 Elsevier Ltd. All rights reserved.

pH-sensitive polymer-modified liposome-based immunity-inducing system: Effects of inclusion of cationic lipid and CpG-DNA.

PubMed

Yoshizaki, Yuta; Yuba, Eiji; Sakaguchi, Naoki; Koiwai, Kazunori; Harada, Atsushi; Kono, Kenji

2017-10-01

Efficient vaccine carriers for cancer immunotherapy require two functions: antigen delivery to dendritic cells (DCs) and the activation of DCs, a so-called adjuvant effect. We previously reported antigen delivery system using liposomes modified with pH-sensitive polymers, such as 3-methylglutarylated hyperbranched poly(glycidol) (MGlu-HPG), for the induction of antigen-specific immune responses. We reported that inclusion of cationic lipids to MGlu-HPG-modified liposomes activates DCs and enhances antitumor effects. In this study, CpG-DNA, a ligand to Toll-like receptor 9 (TLR9) expressing in endosomes of DCs, was introduced to MGlu-HPG-modified liposomes containing cationic lipids using two complexation methods (Pre-mix and Post-mix) for additional activation of antigen-specific immunity. For Pre-mix, thin membrane of lipids and polymers were dispersed by a mixture of antigen/CpG-DNA. For Post-mix, CpG-DNA was added to pre-formed liposomes. Both Pre-mix and Post-mix delivered CpG-DNA to DC endosomes, where TLR9 is expressing, more efficiently than free CpG-DNA solution did. These liposomes promoted cytokine production from DCs and the expression of co-stimulatory molecules in vitro and induced antigen-specific immune responses in vivo. Both Pre-mix and Post-mix exhibited strong antitumor effects compared with conventional pH-sensitive polymer-modified liposomes. Results show that inclusion of multiple adjuvant molecules into pH-sensitive polymer-modified liposomes and suitable CpG-DNA complexation methods are important to design potent vaccine carriers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hierarchial Junction Solar Cells Based on Hyper-Branched Semiconductor Nanocrystals

DTIC Science & Technology

2009-06-30

Hyper-Branched Semiconductor Nanocrystals 4 2. Cu2S- CdS all-inorganic nanocrystal solar cells. We demonstrated the rational synthesis of... Hydrothermal Synthesis of Single Phase Pyrite FeS2 Nanocrystals. We demonstrated a single-source molecular precursor that can be used for the synthesis ... CdS Semiconductor Nanostructures,” Advanced Materials, (2008), 20(22), 4306. Y. Wu, C. Wadia, W. Ma, B. Sadtler, A. P. Alivisatos, “ Synthesis of

Fluorescent aliphatic hyperbranched polyether: chromophore-free and without any N and P atoms.

PubMed

Miao, Xuepei; Liu, Tuan; Zhang, Chen; Geng, Xinxin; Meng, Yan; Li, Xiaoyu

2016-02-14

The strong fluorescence, in both the solution and the bulk state, of a chromophore-free aliphatic hyperbranched polyether which does not contain N and P atoms was reported for the first time. Effects of concentration and solvent solubility were measured. Its ethanol solution shows a strong blue-green fluorescence (Yu = 0.11-0.39), and its fluorescence shows a strong selective quenching with respect to Fe(3+).

Hyperbranched Hybridization Chain Reaction for Triggered Signal Amplification and Concatenated Logic Circuits.

PubMed

Bi, Sai; Chen, Min; Jia, Xiaoqiang; Dong, Ying; Wang, Zonghua

2015-07-06

A hyper-branched hybridization chain reaction (HB-HCR) is presented herein, which consists of only six species that can metastably coexist until the introduction of an initiator DNA to trigger a cascade of hybridization events, leading to the self-sustained assembly of hyper-branched and nicked double-stranded DNA structures. The system can readily achieve ultrasensitive detection of target DNA. Moreover, the HB-HCR principle is successfully applied to construct three-input concatenated logic circuits with excellent specificity and extended to design a security-mimicking keypad lock system. Significantly, the HB-HCR-based keypad lock can alarm immediately if the "password" is incorrect. Overall, the proposed HB-HCR with high amplification efficiency is simple, homogeneous, fast, robust, and low-cost, and holds great promise in the development of biosensing, in the programmable assembly of DNA architectures, and in molecular logic operations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Secondary and primary relaxations in hyperbranched polyglycerol: a comparative study in the frequency and time domains.

PubMed

Garcia-Bernabé, Abel; Dominguez-Espinosa, Gustavo; Diaz-Calleja, Ricardo; Riande, Evaristo; Haag, Rainer

2007-09-28

The non-Debye relaxation behavior of hyperbranched polyglycerol was investigated by broadband dielectric spectroscopy. A thorough study of the relaxations was carried out paying special attention to truncation effects on deconvolutions of overlapping processes. Hyperbranched polyglycerol exhibits two relaxations in the glassy state named in increasing order of frequency beta and gamma processes. The study of the evolution of these two fast processes with temperature in the time retardation spectra shows that the beta absorption is swallowed by the alpha in the glass-liquid transition, the gamma absorption being the only relaxation that remains operative in the liquid state. In heating, a temperature is reached at which the alpha absorption vanishes appearing the alphagamma relaxation. Two characteristics of alpha absorptions, decrease of the dielectric strength with increasing temperature and rather high activation energy, are displayed by the alphagamma process. Williams' ansatz seems to hold for these topologically complex macromolecules.

Facile synthesis of dendritic gold nanostructures with hyperbranched architectures and their electrocatalytic activity toward ethanol oxidation.

PubMed

Huang, Jianshe; Han, Xinyi; Wang, Dawei; Liu, Dong; You, Tianyan

2013-09-25

Gold dendritic nanostructures with hyperbranched architectures were synthesized by the galvanic replacement reaction between nickel wire and HAuCl4 in aqueous solution. The study revealed that the morphology of the obtained nanostructures strongly depended on experimental parameters such as the HAuCl4 solution concentration, reaction temperature, and time, as well as stirring or not. According to the investigation of the growth process, it was proposed that gold nanoparticles with rough surfaces were first deposited on the nickel substrate and that subsequent growth preferentially occurred on the preformed gold nanoparticles, finally leading to the formation of hyperbranched gold dendrites via a self-organization process under nonequilibrium conditions. The electrochemical experiment results demonstrated that the as-obtained gold dendrites exhibited high catalytic activity toward ethanol electrooxidation in alkaline solution, indicating that this nanomaterial may be a potential catalyst for direct ethanol fuel cells.

Probing the cross-effect of strains in non-linear elasticity of nearly regular polymer networks by pure shear deformation.

PubMed

Katashima, Takuya; Urayama, Kenji; Chung, Ung-il; Sakai, Takamasa

2015-05-07

The pure shear deformation of the Tetra-polyethylene glycol gels reveals the presence of an explicit cross-effect of strains in the strain energy density function even for the polymer networks with nearly regular structure including no appreciable amount of structural defect such as trapped entanglement. This result is in contrast to the expectation of the classical Gaussian network model (Neo Hookean model), i.e., the vanishing of the cross effect in regular networks with no trapped entanglement. The results show that (1) the cross effect of strains is not dependent on the network-strand length; (2) the cross effect is not affected by the presence of non-network strands; (3) the cross effect is proportional to the network polymer concentration including both elastically effective and ineffective strands; (4) no cross effect is expected exclusively in zero limit of network concentration in real polymer networks. These features indicate that the real polymer networks with regular network structures have an explicit cross-effect of strains, which originates from some interaction between network strands (other than entanglement effect) such as nematic interaction, topological interaction, and excluded volume interaction.

Directed deposition of inorganic oxide networks on patterned polymer templates

NASA Astrophysics Data System (ADS)

Ford, Thomas James Robert

Inspired by nature, we have successfully directed the deposition of inorganic oxide materials on polymer templates via a combination of top-down and bottom-up fabrication methods. We have functionally mimicked the hierarchical silica exoskeletons of diatoms, where specialized proteins chaperone the condensation of silicic acid into nanoscale silica networks confined by microscopic vesicle walls. We replaced the proteins with functionally analogous polyamines and vesicles with lithographically defined polymer templates. We grafted the polyamines either to the surface or throughout the template by changing the template chemistry and altering our grafting strategy. Exposure to an inorganic oxide precursor solution led to electrostatic aggregation at the polyamine chains, catalyzing hydrolysis and condensation to form long-range inorganic oxide nanoparticle networks. Grafted to epoxy surfaces, swelling effects and the hyperbranched brush morphology lead to the formation of nanofruit features that generated thin, conformal inorganic coatings. When the polyamines were grafted throughout hydrogel templates, we obtained composite networks that yielded faithful inorganic replicas of the original patterns. By varying the polyamine chain length and combustion parameters, we controlled the nanoparticle size, morphology, and crystalline phase. The polyamine morphology affected the resulting inorganic network in both fabrication schemes and we could control the depostion over multiple length scales. Because our methods were compatible with a variety of lithographic methods, we were able to generate inorganic replicas of 1D, 2D, and 3D polymer structures. These may be used for a wide range of applications, including sensing, catalysis, photonic, phononic, photovoltaic, and others that require well-defined inorganic structures.

Biodegradable hyperbranched amphiphilic polyurethane multiblock copolymers consisting of poly(propylene glycol), poly(ethylene glycol), and polycaprolactone as in situ thermogels.

PubMed

Li, Zibiao; Zhang, Zhongxing; Liu, Kerh Li; Ni, Xiping; Li, Jun

2012-12-10

This paper reports the synthesis and characterization of new hyperbranched amphiphilic polyurethane multiblock copolymers consisting of poly(propylene glycol) (PPG), poly(ethylene glycol) (PEG), and polycaprolactone (PCL) segments as in situ thermogels. The hyperbranched poly(PPG/PEG/PCL urethane)s, termed as HBPEC copolymers, were synthesized from PPG-diol, PEG-diol, and PCL-triol by using 1,6-hexamethylene diisocyanate (HMDI) as a coupling agent. The compositions and structures of HBPEC copolymers were determined by GPC and 1H NMR spectroscopy. We carried out comparative studies of the new hyperbranched copolymers with their linear counterparts, the linear poly(PPG/PEG/PCL urethane) (LPEC) copolymer and Pluronic F127 PEG-PPG-PEG block copolymer, in terms of their self-assembly and aggregation behaviors and thermoresponsive properties. HBPEC copolymers were found to show thermoresponsive micelle formation and aggregation behaviors. Particularly, the lower critical solution temperature (LCST) of the copolymers was significantly affected by the copolymer architecture. HBPEC copolymers showed much lower LCST than LPEC, the linear counterpart. Our studies revealed that the effect of hyperbranch architecture was more prominent in the gelation of the copolymers. The aqueous solutions of HBPEC copolymers exhibited thermogelling behaviors at critical gelation concentrations (CGCs) ranging from 4.3 to 7.4 wt %. These values are much lower than those reported on other PCL-contained linear thermogelling copolymers and Pluronic F127 copolymer. In addition, the CGC of HBPEC copolymers is much lower than the control LPEC copolymer. More interestingly, at high temperatures, while LPEC and other linear thermogelling copolymers formed turbid sol, HBPEC formed a dehydrated gel. Our data suggest that these phenomena are caused by the hyperbranched structure of HBPEC copolymers, which could increase the interaction of copolymer branches and enhance the chain association through synergetic hydrogen bonding effect. The thermogelling behavior of HBPEC block copolymers was further evidenced by the 1H NMR molecular dynamic study and rheological study, which further support the above hypothesis. The hydrolytic degradation study showed that the HBPEC copolymer hydrogels are biodegradable under physiological conditions. Together with the good cell biocompatibility demonstrated by the cytotoxicity study, the new thermogelling copolymers reported in this paper could potentially be used as in situ-forming hydrogels for biomedical applications.

Polystyrene/Hyperbranched Polyester Blends and Reactive Polystyrene/Hyperbranched Polyester Blends

DTIC Science & Technology

1999-01-01

interfacial tension between the PE and polystyrene phases. This was brought about by the chemical interaction between the acidic anhydride groups in the...multiple 2,2 dimethylol propionic acid (C5H10O4) chain extenders or repeat units. 11 Core HO \\ HO’ /■ J OH V *OH Pentaerythritol Chain Extender...O 2,2 - Dimethylol propionic acid Figure 11. HBP Building Blocks. These materials were supplied in small quantities with little technical data. The

Solar-Driven Hydrogen Peroxide Production Using Polymer-Supported Carbon Dots as Heterogeneous Catalyst

NASA Astrophysics Data System (ADS)

Gogoi, Satyabrat; Karak, Niranjan

2017-10-01

Safe, sustainable, and green production of hydrogen peroxide is an exciting proposition due to the role of hydrogen peroxide as a green oxidant and energy carrier for fuel cells. The current work reports the development of carbon dot-impregnated waterborne hyperbranched polyurethane as a heterogeneous photo-catalyst for solar-driven production of hydrogen peroxide. The results reveal that the carbon dots possess a suitable band-gap of 2.98 eV, which facilitates effective splitting of both water and ethanol under solar irradiation. Inclusion of the carbon dots within the eco-friendly polymeric material ensures their catalytic activity and also provides a facile route for easy catalyst separation, especially from a solubilizing medium. The overall process was performed in accordance with the principles of green chemistry using bio-based precursors and aqueous medium. This work highlights the potential of carbon dots as an effective photo-catalyst.

Bioinspired synthesis of calcium carbonate hollow spheres with a nacre-type laminated microstructure.

PubMed

Dong, Wenyong; Cheng, Haixing; Yao, Yuan; Zhou, Yongfeng; Tong, Gangsheng; Yan, Deyue; Lai, Yijian; Li, Wei

2011-01-04

In this Article, we combine the characters of hyperbranched polymers and the concept of double-hydrophilic block copolymer (DHBC) to design a 3D crystal growth modifier, HPG-COOH. The novel modifier can efficiently control the crystallization of CaCO(3) from amorphous nanoparticles to vaterite hollow spheres by a nonclassical crystallization process. The obtained vaterite hollow spheres have a special puffy dandelion-like appearance; that is, the shell of the hollow spheres is constructed by platelet-like vaterite mesocrystals, perpendicular to the globe surface. The cross-section of the wall of a vaterite hollow sphere is similar to that of nacres in microstructure, in which platelet-like calcium carbonate mesocrystals pile up with one another. These results reveal the topology effect of the crystal growth modifier on biomineralization and the essential role of the nonclassical crystallization for constructing hierarchical microstructures.

Combining unique properties of dendrimers and magnetic nanoparticles towards cancer theranostics.

PubMed

Chandra, Sudeshna; Nigam, Saumya; Bahadur, Dhirendra

2014-01-01

Magnetic nanoparticles (MNPs) are a well explored class of nanomaterials, known for their high magnetization and biocompatibility thus finding their way in several biomedical applications viz., drug delivery, magnetic resonance imaging contrast agent, immunoassay, detoxification of biological fluids and cell separation, biosensing and hyperthermia. On other hand, dendrimers are a class of hyperbranched, mostly symmetrical polymers that originate from a central core with repetitive branching units, called monomers, thus forming a globular structure. Due to their structural properties and controlled size, dendrimers have emerged as an attractive material for biomedical applications particularly as carriers for therapeutic cargo. Of late, researchers have started attempting to combine the unique features of dendrimer chemistry with the versatile magnetic nanoparticles to provide a facile platform for enhanced therapeutics and biomedical applications. This review intends to present the advances made towards fabrication of dendrimer based magnetic nanoparticles with varied surface architecture and their contribution towards theranostics, particularly for cancer.

A Course in Polymer Processing.

ERIC Educational Resources Information Center

Soong, David S.

1985-01-01

A special-topics course in polymer processing has acquired regular course status. Course goals, content (including such new topics as polymer applications in microelectronics), and selected term projects are described. (JN)

Synthesis of One-Dimensional and Hyperbranched Nanomaterials for Lithium-Ion Battery Solid Electrolytes

NASA Astrophysics Data System (ADS)

Yang, Ting

Lithium-ion batteries can fail and catch fire when overcharged, exposed to high temperatures or short-circuited due to the highly flammable organic liquid used in the electrolyte. Using inorganic solid electrolyte materials can potentially improve the safety factor. Additionally, nanostructured electrolyte materials may further enhanced performance by taking advantage of their large aspect ratio. In this work, the synthesis of two promising nanostructured solid electrolyte materials was explored. Amorphous lithium niobate nanowires were synthesized through the decomposition of a niobium-containing complex in a structure-directing solvent using a reflux method. Lithium lanthanum titanate was obtained via solid state reaction with titanium oxide nanowires as the titanium precursor, but the nanowire morphology could not be preserved due to high temperature sintering. Hyperbranched potassium lanthanum titanate was synthesized through hydrothermal route. This was the first time that hyperbranched nanowires with perovskite structure were made without any catalyst or substrate. This result has the potential to be applied to other perovskite materials.

Succinate Functionalization of Hyperbranched Polyglycerol-Coated Magnetic Nanoparticles as a Draw Solute During Forward Osmosis.

PubMed

Yang, Hee-Man; Choi, Hye Min; Jang, Sung-Chan; Han, Myeong Jin; Seo, Bum-Kyoung; Moon, Jei-Kwon; Lee, Kune-Woo

2015-10-01

Hyperbranched polyglycerol-coated magnetic nanoparticles (SHPG-MNPs) were functionalized with succinate groups to form a draw solute for use in a forward osmosis (FO). After the one-step synthesis of hyperbranched polyglycerol-coated magnetic nanoparticles (HPG-MNPs), the polyglycerol groups on the surfaces of the HPG-MNPs were functionalized with succinic anhydride moieties. The resulting SHPG-MNPs showed no change of size and magnetic property compared with HPG-MNPs and displayed excellent dispersibility in water up to the concentration of 400 g/L. SHPG-MNPs solution showed higher osmotic pressure than that of HPG-MNPs solution due to the presence of surface carboxyl groups in SHPG-MNPs and could draw water from a feed solution across an FO membrane without any reverse draw solute leakage during FO process. Moreover, the water flux remained nearly constant over several SHPG-MNP darw solute regeneration cycles applied to the ultrafiltration (UF) process. The SHPG-MNPs demonstrate strong potential for use as a draw solute in FO processes.

Polyglycerol coatings of glass vials for protein resistance.

PubMed

Höger, Kerstin; Becherer, Tobias; Qiang, Wei; Haag, Rainer; Friess, Wolfgang; Küchler, Sarah

2013-11-01

Proteins are surface active molecules which undergo non-specific adsorption when getting in contact with surfaces such as the primary packaging material. This process is critical as it may cause a loss of protein content or protein aggregation. To prevent unspecific adsorption, protein repellent coatings are of high interest. We describe the coating of industrial relevant borosilicate glass vials with linear methoxylated polyglycerol, hyperbranched polyglycerol, and hyperbranched methoxylated polyglycerol. All coatings provide excellent protein repellent effects. The hyperbranched, non-methoxylated coating performed best. The protein repellent properties were maintained also after applying industrial relevant sterilization methods (≥200 °C). Marginal differences in antibody stability between formulations stored in bare glass vials and coated vials were detected after 3 months storage; the protein repellent effect remained largely stable. Here, we describe a new material suitable for the coating of primary packaging material of proteins which significantly reduces the protein adsorption and thus could present an interesting new possibility for biomedical applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Water-Stable Nanoporous Polymer Films with Excellent Proton Conductivity.

PubMed

Wang, Zhengbang; Liang, Cong; Tang, Haolin; Grosjean, Sylvain; Shahnas, Artak; Lahann, Joerg; Bräse, Stefan; Wöll, Christof

2018-03-01

Achieving high values for proton conductivity in a material critically depends on providing hopping sites arranged in a regular fashion. Record values reported for regular, molecular crystals cannot yet be reached by technologically relevant systems, and the best values measured for polymer membranes suited for integration into devices are almost two orders of magnitude lower. Here, an alternative polymer membrane synthesis strategy based on the chemical modification of surface-mounted, monolithic, crystalline metal-organic framework thin films is demonstrated. Due to chemical crosslinking and subsequent removal of metal ions, these surface-mounted gels (SURGELs) are found to exhibit high proton conductivity (0.1 S cm -1 at 30 °C and 100% RH (relative humidity). These record values are attributed to the highly ordered polymer network structure containing regularly spaced carboxylic acid side groups. These covalently bound organic frameworks outperform conventional, ion-conductive polymers with regard to ion conductivity and water stability. Pronounced water-induced swelling, which causes severe mechanical instabilities in commercial membranes, is not observed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potentiation of pH-sensitive polymer-modified liposomes with cationic lipid inclusion as antigen delivery carriers for cancer immunotherapy.

PubMed

Yoshizaki, Yuta; Yuba, Eiji; Sakaguchi, Naoki; Koiwai, Kazunori; Harada, Atsushi; Kono, Kenji

2014-09-01

Cationic lipid-incorporated liposomes modified with pH-sensitive polymers were prepared by introducing 3, 5-didodecyloxybenzamidine as a cationic lipid to egg yolk phosphatidylcholine liposomes modified with 3-methylglutarylated hyperbranched poly(glycidol) (MGlu-HPG) as a pH-sensitive polymer. These liposomes were stable at neutral pH, but were destabilized below pH 6.0 because MGlu-HPG changed its characteristics from hydrophilic to hydrophobic in response to the pH decrease. Cationic lipid inclusion improved their pH sensitivity at weakly acidic pH and association of liposomes with murine dendritic cell (DC) lines. Cationic lipid-incorporated liposomes delivered entrapped ovalbumin (OVA) molecules not only to cytosol but also to endosome/lysosome. Treatment with cationic lipid-incorporated liposomes induced up-regulation of antigen presentation-involved molecules on DCs, the promotion of cytokine production, and antigen presentation via both major histocompatibility complex (MHC) class I and II molecules. Especially, antigen presentation via MHC class II was promoted by cationic lipid inclusion, which might correspond to efficient endosome/lysosome delivery of OVA. Subcutaneous administration of OVA-loaded cationic lipid-incorporated liposomes induced antigen-specific antibody production in serum and Th1-dominant immune responses in the spleen. Furthermore, administration of the cationic lipid-incorporated liposomes to mice bearing E.G7-OVA tumor more significantly reduced the tumor volume than liposomes without cationic lipids. Therefore, cationic lipid inclusion into pH-sensitive polymer-modified liposomes, which can achieve both efficient antigen intracellular delivery and activation of antigen presenting cell, is an effective approach to develop antigen carriers for efficient cancer immunotherapy. Copyright © 2014 Elsevier Ltd. All rights reserved.

Polymer Vesicle Sensor for Visual and Sensitive Detection of SO2 in Water.

PubMed

Huang, Tong; Hou, Zhilin; Xu, Qingsong; Huang, Lei; Li, Chuanlong; Zhou, Yongfeng

2017-01-10

This study reports the first polymer vesicle sensor for the visual detection of SO 2 and its derivatives in water. A strong binding ability between tertiary alkanolamines and SO 2 has been used as the driving force for the detection by the graft of tertiary amine alcohol (TAA) groups onto an amphiphilic hyperbranched multiarm polymer, which can self-assemble into vesicles with enriched TAA groups on the surface. The polymer vesicles will undergo proton exchange with cresol red (CR) to produce CR-immobilized vesicles (CR@vesicles). Subsequently, through competitive binding with the TAA groups between CR and SO 2 or HSO 3 - , the CR@vesicles (purple) can quickly change into SO 2 @vesicles (colorless) with the release of protonated CR (yellow). Such a fast purple to yellow transition in the solution allows the visual detection of SO 2 or its derivatives in water by the naked eye. A visual test paper for SO 2 gas has also been demonstrated by the adsorption of CR@vesicles onto paper. Meanwhile, the detection limit of CR@vesicles for HSO 3 - is approximately 25 nM, which is improved by approximately 30 times when compared with that of small molecule-based sensors with a similar structure (0.83 μM). Such an enhanced detection sensitivity should be related to the enrichment of TAA groups as well as the CR in CR@vesicles. In addition, the CR@vesicle sensors also show selectivity and specificity for the detection of SO 2 or HSO 3 - among anions such as F - , Br - , Cl - , SO 4 2- , NO 2 - , C 2 O 4 2- , S 2 O 3 2- , SCN - , AcO - , SO 3 2- , S 2- , and HCO 3 - .

Water-Soluble Nonconjugated Polymer Nanoparticles with Strong Fluorescence Emission for Selective and Sensitive Detection of Nitro-Explosive Picric Acid in Aqueous Medium.

PubMed

Liu, Shi Gang; Luo, Dan; Li, Na; Zhang, Wei; Lei, Jing Lei; Li, Nian Bing; Luo, Hong Qun

2016-08-24

Water-soluble nonconjugated polymer nanoparticles (PNPs) with strong fluorescence emission were prepared from hyperbranched poly(ethylenimine) (PEI) and d-glucose via Schiff base reaction and self-assembly in aqueous phase. Preparation of the PEI-d-glucose (PEI-G) PNPs was facile (one-pot reaction) and environmentally friendly under mild conditions. Also, PEI-G PNPs showed a high fluorescence quantum yield in aqueous solution, and the fluorescence properties (such as concentration- and solvent-dependent fluorescence) and origin of intrinsic fluorescence were investigated and discussed. PEI-G PNPs were then used to develop a fluorescent probe for fast, selective, and sensitive detection of nitro-explosive picric acid (PA) in aqueous medium, because the fluorescence can be easily quenched by PA whereas other nitro-explosives and structurally similar compounds only caused negligible quenching. A wide linear range (0.05-70 μM) and a low detection limit (26 nM) were obtained. The fluorescence quenching mechanism was carefully explored, and it was due to a combined effect of electron transfer, resonance energy transfer, and inner filter effect between PA and PEI-G PNPs, which resulted in good selectivity and sensitivity for PA. Finally, the developed sensor was successfully applied to detection of PA in environmental water samples.

An efficient nonviral gene-delivery vector based on hyperbranched cationic glycogen derivatives.

PubMed

Liang, Xuan; Ren, Xianyue; Liu, Zhenzhen; Liu, Yingliang; Wang, Jue; Wang, Jingnan; Zhang, Li-Ming; Deng, David Yb; Quan, Daping; Yang, Liqun

2014-01-01

The purpose of this study was to synthesize and evaluate hyperbranched cationic glycogen derivatives as an efficient nonviral gene-delivery vector. A series of hyperbranched cationic glycogen derivatives conjugated with 3-(dimethylamino)-1-propylamine (DMAPA-Glyp) and 1-(2-aminoethyl) piperazine (AEPZ-Glyp) residues were synthesized and characterized by Fourier-transform infrared and hydrogen-1 nuclear magnetic resonance spectroscopy. Their buffer capacity was assessed by acid-base titration in aqueous NaCl solution. Plasmid deoxyribonucleic acid (pDNA) condensation ability and protection against DNase I degradation of the glycogen derivatives were assessed using agarose gel electrophoresis. The zeta potentials and particle sizes of the glycogen derivative/pDNA complexes were measured, and the images of the complexes were observed using atomic force microscopy. Blood compatibility and cytotoxicity were evaluated by hemolysis assay and MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) assay, respectively. pDNA transfection efficiency mediated by the cationic glycogen derivatives was evaluated by flow cytometry and fluorescence microscopy in the 293T (human embryonic kidney) and the CNE2 (human nasopharyngeal carcinoma) cell lines. In vivo delivery of pDNA in model animals (Sprague Dawley rats) was evaluated to identify the safety and transfection efficiency. The hyperbranched cationic glycogen derivatives conjugated with DMAPA and AEPZ residues were synthesized. They exhibited better blood compatibility and lower cytotoxicity when compared to branched polyethyleneimine (bPEI). They were able to bind and condense pDNA to form the complexes of 100-250 nm in size. The transfection efficiency of the DMAPA-Glyp/pDNA complexes was higher than those of the AEPZ-Glyp/pDNA complexes in both the 293T and CNE2 cells, and almost equal to those of bPEI. Furthermore, pDNA could be more safely delivered to the blood vessels in brain tissue of Sprague Dawley rats by the DMAPA-Glyp derivatives, and then expressed as green fluorescence protein, compared with the control group. The hyperbranched cationic glycogen derivatives, especially the DMAPA-Glyp derivatives, showed high gene-transfection efficiency, good blood compatibility, and low cyto toxicity when transfected in vitro and in vivo, which are novel potential nonviral gene vectors.

Hyper-branched CdTe nanostructures based on the self-assembling of quantum dots and their optical properties.

PubMed

Pan, Ling-Yun; Pan, Gen-Cai; Zhang, Yong-Lai; Gao, Bing-Rong; Dai, Zhen-Wen

2013-02-01

As the priority of interconnects and active components in nanoscale optical and electronic devices, three-dimensional hyper-branched nanostructures came into focus of research. Recently, a novel crystallization route, named as "nonclassical crystallization," has been reported for three-dimensional nanostructuring. In this process, Quantum dots are used as building blocks for the construction of the whole hyper-branched structures instead of ions or single-molecules in conventional crystallization. The specialty of these nanostructures is the inheritability of pristine quantum dots' physical integrity because of their polycrystalline structures, such as quantum confinement effect and thus the luminescence. Moreover, since a longer diffusion length could exist in polycrystalline nanostructures due to the dramatically decreased distance between pristine quantum dots, the exciton-exciton interaction would be different with well dispersed quantum dots and single crystal nanostructures. This may be a benefit for electron transport in solar cell application. Therefore, it is very necessary to investigate the exciton-exciton interaction in such kind of polycrystalline nanostructures and their optical properites for solar cell application. In this research, we report a novel CdTe hyper-branched nanostructures based on self-assembly of CdTe quantum dots. Each branch shows polycrystalline with pristine quantum dots as the building units. Both steady state and time-resolved spectroscopy were performed to investigate the properties of carrier transport. Steady state optical properties of pristine quantum dots are well inherited by formed structures. While a suppressed multi-exciton recombination rate was observed. This result supports the percolation of carriers through the branches' network.

Hyperbranched epoxy/MWCNT-CuO-nystatin nanocomposite as a high performance, biocompatible, antimicrobial material

NASA Astrophysics Data System (ADS)

Barua, Shaswat; Chattopadhyay, Pronobesh; Phukan, Mayur M.; Konwar, Bolin K.; Karak, Niranjan

2014-12-01

Hyperbranched epoxy MWCNT-CuO-nystatin nanocomposite has been presented here as an advanced antimicrobial high performance material. The material showed significant improvement of mechanical properties (tensile strength from 38 to 63 MPa) over the pristine matrix without effecting elongation. MWCNT was modified by a non-ionic surfactant, triton X-100, wherein copper oxide nanoparticles were anchored in situ by a ‘green’ method. Further, sonochemical immobilization of nystatin enhanced the stability of the system. The immobilized nanohybrid system was incorporated into the hyperbranched matrix in 1, 2 and 3 wt%. The resultant system proved its ability to prevent bacterial, fungal and microalgal fouling against the tested strains, Staphylococcus aureus, Candida albicans and Chlorella sp. Additionally, this system is quite compatible with rat heart cells. Furthermore, in vivo assessment showed that this could be utilized as an implantable antimicrobial biomaterial. Thus, the overall study pointed out that the prepared material may have immense utility in marine industry as well as in biomedical domain to address microbial fouling, without inducing any toxicity to higher organisms.

Synthesis of New Hyperbranched α-Glucans from Sucrose by Lactobacillus reuteri 180 Glucansucrase Mutants.

PubMed

Meng, Xiangfeng; Dobruchowska, Justyna M; Pijning, Tjaard; Gerwig, Gerrit J; Dijkhuizen, Lubbert

2016-01-20

α-Glucans produced by glucansucrase enzymes of lactic acid bacteria attract strong attention as novel ingredients and functional biopolymers in the food industry. In the present study, α-helix 4 amino acid residues D1085, R1088, and N1089 of glucansucrase GTF180 of Lactobacillus reuteri 180 were targeted for mutagenesis both jointly and separately. Analysis of the mutational effects on enzyme function revealed that all D1085 and R1088 mutants catalyzed the synthesis of hyperbranched α-glucans with 15-22% branching (α1→3,6) linkages, compared to 13% in the wild-type GTF180. In addition, besides native (α1→6) and (α1→3) linkages, all of the mutations introduced a small amount of (α1→4) linkages (5% at most) in the polysaccharides produced. We conclude that α-helix 4 residues, especially D1085 and R1088, constituting part of the +2 acceptor binding subsite, are important determinants for the linkage specificity. The new hyperbranched α-glucans provide very interesting structural diversities and may find applications in the food industry.

Nano-Bio Engineered Carbon Dot-Peptide Functionalized Water Dispersible Hyperbranched Polyurethane for Bone Tissue Regeneration.

PubMed

Gogoi, Satyabrat; Maji, Somnath; Mishra, Debasish; Devi, K Sanjana P; Maiti, Tapas Kumar; Karak, Niranjan

2017-03-01

The present study delves into a combined bio-nano-macromolecular approach for bone tissue engineering. This approach relies on the properties of an ideal scaffold material imbued with all the chemical premises required for fostering cellular growth and differentiation. A tannic acid based water dispersible hyperbranched polyurethane is fabricated with bio-nanohybrids of carbon dot and four different peptides (viz. SVVYGLR, PRGDSGYRGDS, IPP, and CGGKVGKACCVPTKLSPISVLYK) to impart target specific in vivo bone healing ability. This polymeric bio-nanocomposite is blended with 10 wt% of gelatin and examined as a non-invasive delivery vehicle. In vitro assessment of the developed polymeric system reveals good osteoblast adhesion, proliferation, and differentiation. Aided by this panel of peptides, the polymeric bio-nanocomposite exhibits in vivo ectopic bone formation ability. The study on in vivo mineralization and vascularization reveals the occurrence of calcification and blood vessel formation. Thus, the study demonstrates carbon dot/peptide functionalized hyperbranched polyurethane gel for bone tissue engineering application. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Vivo Biological Evaluation of High Molecular Weight Multifunctional Acid-Degradable Polymeric Drug Carriers with Structurally Different Ketals.

PubMed

Shenoi, Rajesh A; Abbina, Srinivas; Kizhakkedathu, Jayachandran N

2016-11-14

Understanding the influence of degradable chemical moieties on in vivo degradation, tissue distribution, and excretion is critical for the design of novel biodegradable drug carriers. Polyketals have recently emerged as a promising therapeutic delivery platform due to their ability to degrade under mild acidic intracellular compartments and generation of nontoxic degradation products. However, the effect of chemical structure of the ketal groups on the in vivo degradation, biodistribution, and pharmacokinetics of water-soluble ketal-containing polymers has not been explored. In the present work, we synthesized high molecular weight, water-soluble biodegradable hyperbranched polyglycerols (BHPGs) through the incorporation of structurally different ketal groups into the main chain of highly biocompatible polyglycerols. BHPGs showed pH and ketal group structure dependent degradation in buffer solutions. When the polymers were intravenously administered in mice, a strong dependence of in vivo degradation, biodistribution, and clearance on the ketal group structure was observed. All the BHPGs demonstrated degradation and clearance in vivo, with minimal tissue accumulation. Interestingly, an unanticipated degradation behavior of BHPGs with structurally different ketal groups was observed in vivo in comparison to their degradation in buffer solutions. BHPGs with cyclohexyl ketal (CHK) and cyclopentyl ketal (CPK) groups degraded much faster and were cleared from circulation much rapidly, while BHPG with glycerol hydroxy butanone ketal (GHBK) group degraded at a much slower rate and exhibited similar plasma half-life as that of nondegradable HPG. BHPG-GHBK also showed significantly lower tissue accumulation than nondegradable HPG after 30 days of administration. The difference in in vivo degradation may be attributed to the difference in hydrophobic characteristics of different ketal containing polymers, which may change their interaction with proteins and cells in vivo. This is the first study that demonstrates the influence of chemical structure of ketal groups on in vivo degradation and circulation profile of polymers, and through proper surface modifications, these polymers would be useful as multifunctional drug carriers.

Efficient field-theoretic simulation of polymer solutions

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

Villet, Michael C.; Fredrickson, Glenn H., E-mail: ghf@mrl.ucsb.edu; Department of Materials, University of California, Santa Barbara, California 93106

2014-12-14

We present several developments that facilitate the efficient field-theoretic simulation of polymers by complex Langevin sampling. A regularization scheme using finite Gaussian excluded volume interactions is used to derive a polymer solution model that appears free of ultraviolet divergences and hence is well-suited for lattice-discretized field theoretic simulation. We show that such models can exhibit ultraviolet sensitivity, a numerical pathology that dramatically increases sampling error in the continuum lattice limit, and further show that this pathology can be eliminated by appropriate model reformulation by variable transformation. We present an exponential time differencing algorithm for integrating complex Langevin equations for fieldmore » theoretic simulation, and show that the algorithm exhibits excellent accuracy and stability properties for our regularized polymer model. These developments collectively enable substantially more efficient field-theoretic simulation of polymers, and illustrate the importance of simultaneously addressing analytical and numerical pathologies when implementing such computations.« less

Tunable Electromagnetic Coupling in Plasmonic Nanostructures Mediated by Thermoresponsive Polymer Brushes.

PubMed

Nguyen, Mai; Kanaev, Andrei; Sun, Xiaonan; Lacaze, Emmanuelle; Lau-Truong, Stéphanie; Lamouri, Aazdine; Aubard, Jean; Felidj, Nordin; Mangeney, Claire

2015-11-24

A smart and highly SERS-active plasmonic platform was designed by coupling regular arrays of nanotriangles to colloidal gold nanorods via a thermoresponsive polymer spacer (poly(N-isopropylacrylamide), PNIPAM). The substrates were prepared by combining a top-down and a bottom-up approach based on nanosphere lithography, surface-initiated controlled radical polymerization, and colloidal assembly. This multistep strategy provided regular hexagonal arrays of nanotriangles functionalized by polymer brushes and colloidal gold nanorods, confined exclusively on the nanotriangle surface. Interestingly, one could finely tune the gold nanorod impregnation on the polymer-coated nanostructures by adjusting the polymer layer thickness, leading to highly coupled plasmonic systems for intense SERS signal. Moreover, the thermoresponsive properties of the PNIPAM brushes could be wisely handled in order to monitor the SERS activity of the nanostructures coupled via this polymer spacer. The coupled hybrid plasmonic nanostructures designed in this work are therefore very promising smart platforms for the sensitive detection of analytes by SERS.

Dendrimer-protein interactions versus dendrimer-based nanomedicine.

PubMed

Shcharbin, Dzmitry; Shcharbina, Natallia; Dzmitruk, Volha; Pedziwiatr-Werbicka, Elzbieta; Ionov, Maksim; Mignani, Serge; de la Mata, F Javier; Gómez, Rafael; Muñoz-Fernández, Maria Angeles; Majoral, Jean-Pierre; Bryszewska, Maria

2017-04-01

Dendrimers are hyperbranched polymers belonging to the huge class of nanomedical devices. Their wide application in biology and medicine requires understanding of the fundamental mechanisms of their interactions with biological systems. Summarizing, electrostatic force plays the predominant role in dendrimer-protein interactions, especially with charged dendrimers. Other kinds of interactions have been proven, such as H-bonding, van der Waals forces, and even hydrophobic interactions. These interactions depend on the characteristics of both participants: flexibility and surface charge of a dendrimer, rigidity of protein structure and the localization of charged amino acids at its surface. pH and ionic strength of solutions can significantly modulate interactions. Ligands and cofactors attached to a protein can also change dendrimer-protein interactions. Binding of dendrimers to a protein can change its secondary structure, conformation, intramolecular mobility and functional activity. However, this strongly depends on rigidity versus flexibility of a protein's structure. In addition, the potential applications of dendrimers to nanomedicine are reviwed related to dendrimer-protein interactions. Copyright © 2017 Elsevier B.V. All rights reserved.

Characterization of new drug delivery nanosystems using atomic force microscopy

NASA Astrophysics Data System (ADS)

Spyratou, Ellas; Mourelatou, Elena A.; Demetzos, C.; Makropoulou, Mersini; Serafetinides, A. A.

2015-01-01

Liposomes are the most attractive lipid vesicles for targeted drug delivery in nanomedicine, behaving also as cell models in biophotonics research. The characterization of the micro-mechanical properties of drug carriers is an important issue and many analytical techniques are employed, as, for example, optical tweezers and atomic force microscopy. In this work, polyol hyperbranched polymers (HBPs) have been employed along with liposomes for the preparation of new chimeric advanced drug delivery nanosystems (Chi-aDDnSs). Aliphatic polyester HBPs with three different pseudogenerations G2, G3 and G4 with 16, 32, and 64 peripheral hydroxyl groups, respectively, have been incorporated in liposomal formulation. The atomic force microscopy (AFM) technique was used for the comparative study of the morphology and the mechanical properties of Chi-aDDnSs and conventional DDnS. The effects of both the HBPs architecture and the polyesters pseudogeneration number in the stability and the stiffness of chi-aDDnSs were examined. From the force-distance curves of AFM spectroscopy, the Young's modulus was calculated.

Controlled synthesis of multi-arm star polyether-polycarbonate polyols based on propylene oxide and CO2.

PubMed

Hilf, Jeannette; Schulze, Patricia; Seiwert, Jan; Frey, Holger

2014-01-01

Multi-arm star copolymers based on a hyperbranched poly(propylene oxide) polyether-polyol (hbPPO) as a core and poly(propylene carbonate) (PPC) arms are synthesized in two steps from propylene oxide (PO), a small amount of glycidol and CO2 . The PPC arms are prepared via carbon dioxide (CO2 )/PO copolymerization, using hbPPO as a multifunctional macroinitiator and the (R,R)-(salcy)CoOBzF5 catalyst. Star copolymers with 14 and 28 PPC arms, respectively, and controlled molecular weights in the range of 2700-8800 g mol(-1) are prepared (Mw /Mn = 1.23-1.61). Thermal analysis reveals lowered glass transition temperatures in the range of -8 to 10 °C for the PPC star polymers compared with linear PPC, which is due to the influence of the flexible polyether core. Successful conversion of the terminal hydroxyl groups with phenylisocyanate demonstrates the potential of the polycarbonate polyols for polyurethane synthesis. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of branched polymers from lipase-catalyzed trimethylolpropane copolymerizations.

PubMed

Kulshrestha, Ankur S; Gao, Wei; Fu, Hongyong; Gross, Richard A

2007-06-01

Lipase-catalyzed terpolymerizations were performed with the monomers trimethylolpropane (B3), 1,8-octanediol (B2), and adipic acid (A2). Polymerizations were performed in bulk, at 70 degrees C, for 42 h, using immobilized lipase B from Candida antartica (Novozyme-435) as a catalyst. To determine the substitution pattern of trimethylolpropane (TMP) in copolymers, model compounds with variable degrees of acetylation were synthesized. Inverse-gated 13C NMR spectra were recorded to first determine the chemical shift positions for mono-, di-, and trisubstituted TMP units and, subsequently, to determine substitution of TMP units along chains. Variation of TMP in the monomer feed gave copolymers with degrees of branching (DB) from 20% to 67%. In one example, a hyperbranched copolyester with 53 mol % TMP adipate units was formed in 80% yield, with Mw 14 100 (relative to polystyrene standards), Mw/Mn 5.3, and DB 36%. Thermal and crystalline properties of the copolyesters were studied by thermogravimetric analysis and differential scanning calorimetry.

Targeted Cellular Drug Delivery using Tailored Dendritic Nanostructures

NASA Astrophysics Data System (ADS)

Kannan, Rangaramanujam; Kolhe, Parag; Kannan, Sujatha; Lieh-Lai, Mary

2002-03-01

Dendrimers and hyperbranched polymers possess highly branched architectures, with a large number of controllable, tailorble, ‘peripheral’ functionalities. Since the surface chemistry of these materials can be modified with relative ease, these materials have tremendous potential in targeted drug and gene delivery. The large number of end groups can also be tailored to create special affinity to targeted cells, and can also encapsulate drugs and deliver them in a controlled manner. We are developing tailor-modified dendritic systems for drug delivery. Synthesis, in-vitro drug loading, in-vitro drug delivery, and the targeting efficiency to the cell are being studied systematically using a wide variety of experimental tools. Polyamidoamine and Polyol dendrimers, with different generations and end-groups are studied, with drugs such as Ibuprofen and Methotrexate. Our results indicate that a large number of drug molecules can be encapsulated/attached to the dendrimers, depending on the end groups. The drug-encapsulated dendrimer is able to enter the cells rapidly and deliver the drug. Targeting strategies being explored

Synthesis, characterization and application of polyglycerol coated Fe3O4 nanoparticles as a nano-theranostics agent

NASA Astrophysics Data System (ADS)

Jahandar, Marzieh; Zarrabi, Ali; Shokrgozar, Mohammad Ali; Mousavi, Hajar

2015-12-01

Superparamagnetic iron oxide nanoparticles (SPIONs) with an average size of 10 nm have been successfully synthesized by the polyol method. Then, hyperbranched polyglycerol (HPG) branches have been introduced on the surface of SPIONs through ring opening polymerization of glycidol as a biocompatible surface modifier with a more hydrophilic nature than other biomedical polymers. The as-synthesized SPION-HPGs were analyzed by FT-IR, CHNS and TGA analysis which all exhibited the successful HPG grafting onto the SPION surface. The anticancer herbal drug, curcumin, was loaded on the resultant nanocarrier. The MTT assay demonstrated the non-cytotoxicity effect of SPION-HPGs and the low cytotoxicity effect of curcumin at low concentrations on L929 and MCF-7 cell lines as normal and cancerous cells, respectively. Moreover, these nanoparticles exhibited an improved effect as a contrast agent in magnetic resonance imaging. Thus, it is concluded that SPION-HPG has the potential to be used in theranostics applications due to its simultaneous drug delivery and imaging capabilities.

Chemically grafted polymeric filters for chemical sensors: Hyperbranched poly(acrylic acid) films incorporating {Beta}-cyclodextrin receptors and amine-functionalized filter layers

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

Dermody, D.L.; Peez, R.F.; Bergbreiter, D.E.

1999-02-02

The authors report a new molecular-filter approach for enhancing the selectivity of chemical sensors. Specifically, they describe electrochemical sensors prepared from Au electrodes coated with {beta}-cyclodextrin-functionalized, hyperbranched poly(acrylic acid)(PAA) films capped with a chemically grafted, ultrathin polyamine layer. The hyperbranched PAA film is a highly functionalized framework for covalently binding the {beta}-cyclodextrin molecular receptors. The thin, grafted polyamine overlayer acts as a pH-sensitive molecular filter that selectively passes suitably charged analytes. Poly(amidoamine) dendrimers or poly-D-lysine is used as 10--15-nm-thick filter layers. The results show that at low pH, when the polyamines are fully protonated, positively charged redox probe molecules, suchmore » as benzyl viologen (BV), do not permeate the filter layer. However, at high pH, when the filter layer is uncharged, BV penetrates the filter layer and is reduced at the electrode. The opposite pH dependence is observed for negatively charged redox molecules such as anthraquinone-2-sulfonate (AQS). Both BV and AQS specifically interact with the {beta}-cyclodextrin receptors underlying the polyamine filter layers.« less

Normetex Pump Alternatives Study

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

Clark, Elliot A.

2013-04-25

A mainstay pump for tritium systems, the Normetex scroll pump, is currently unavailable because the Normetex company went out of business. This pump was an all-metal scroll pump that served tritium processing facilities very well. Current tritium system operators are evaluating replacement pumps for the Normetex pump and for general used in tritium service. An all-metal equivalent alternative to the Normetex pump has not yet been identified. 1. The ideal replacement tritium pump would be hermetically sealed and contain no polymer components or oils. Polymers and oils degrade over time when they contact ionizing radiation. 2. Halogenated polymers (containing fluorine,more » chlorine, or both) and oils are commonly found in pumps. These materials have many properties that surpass those of hydrocarbon-based polymers and oils, including thermal stability (higher operating temperature) and better chemical resistance. Unfortunately, they are less resistant to degradation from ionizing radiation than hydrocarbon-based materials (in general). 3. Polymers and oils can form gaseous, condensable (HF, TF), liquid, and solid species when exposed to ionizing radiation. For example, halogenated polymers form HF and HCl, which are extremely corrosive upon reaction with water. If a pump containing polymers or oils must be used in a tritium system, the system must be designed to be able to process the unwanted by-products. Design features to mitigate degradation products include filters and chemical or physical traps (eg. cold traps, oil traps). 4. Polymer components can work in tritium systems, but must be replaced regularly. Polymer components performance should be monitored or be regularly tested, and regular replacement of components should be viewed as an expected normal event. A radioactive waste stream must be established to dispose of used polymer components and oil with an approved disposal plan developed based on the facility location and its regulators. Polymers have varying resistances to ionizing radiation - aromatic polymers such as polyimide Vespel (TM) and the elastomer EPDM (ethylene propylene diene monomer) have been found to be more resistant to degradation in tritium than other polymers. This report presents information to help select replacement pumps for Normetex pumps in tritium systems. Several pumps being considered as Normetex replacement pumps are discussed.« less

Improvement of Peptide-Based Tumor Immunotherapy Using pH-Sensitive Fusogenic Polymer-Modified Liposomes.

PubMed

Yoshizaki, Yuta; Yuba, Eiji; Komatsu, Toshihiro; Udaka, Keiko; Harada, Atsushi; Kono, Kenji

2016-09-26

To establish peptide vaccine-based cancer immunotherapy, we investigated the improvement of antigenic peptides by encapsulation with pH-sensitive fusogenic polymer-modified liposomes for induction of antigen-specific immunity. The liposomes were prepared by modification of egg yolk phosphatidylcholine and l-dioleoyl phosphatidylethanolamine with 3-methyl-glutarylated hyperbranched poly(glycidol) (MGlu-HPG) and were loaded with antigenic peptides derived from ovalbumin (OVA) OVA-I (SIINFEKL), and OVA-II (PSISQAVHAAHAEINEAP β A), which bind, respectively, to major histocompatibility complex (MHC) class I and class II molecules on dendritic cell (DCs). The peptide-loaded liposomes were taken up efficiently by DCs. The peptides were delivered into their cytosol. Administration of OVA-I-loaded MGlu-HPG-modified liposomes to mice bearing OVA-expressing E.G7-OVA tumors induced the activation of OVA-specific CTLs much more efficiently than the administration of free OVA-I peptide did. Mice strongly rejected E.G7-OVA cells after immunization with OVA-I peptide-loaded MGlu-HPG liposomes, although mice treated with free OVA-I peptide only slightly rejected the cells. Furthermore, efficient suppression of tumor volume was observed when tumor-bearing mice were immunized with OVA-I-peptide-loaded liposomes. Immunization with OVA-II-loaded MGlu-HPG-modified liposomes exhibited much lower tumor-suppressive effects. Results indicate that MGlu-HPG liposomes might be useful for improvement of CTL-inducing peptides for efficient cancer immunotherapy.

Systemic delivery of blood-brain barrier-targeted polymeric nanoparticles enhances delivery to brain tissue.

PubMed

Saucier-Sawyer, Jennifer K; Deng, Yang; Seo, Young-Eun; Cheng, Christopher J; Zhang, Junwei; Quijano, Elias; Saltzman, W Mark

2015-01-01

Delivery of therapeutic agents to the central nervous system is a significant challenge, hindering progress in the treatment of diseases such as glioblastoma. Due to the presence of the blood-brain barrier (BBB), therapeutic agents do not readily transverse the brain endothelium to enter the parenchyma. Previous reports suggest that surface modification of polymer nanoparticles (NPs) can improve their ability to cross the BBB, but it is unclear whether the observed enhancements in transport are large enough to enhance therapy. In this study, we synthesized two degradable polymer NP systems surface-modified with ligands previously suggested to improve BBB transport, and tested their ability to cross the BBB after intravenous injection in mice. All the NP preparations were able to cross the BBB, although generally in low amounts (<0.5% of the injected dose), which was consistent with prior reports. One NP produced significantly higher brain uptake (∼0.8% of the injected dose): a block copolymer of polylactic acid and hyperbranched polyglycerol, surface modified with adenosine (PLA-HPG-Ad). PLA-HPG-Ad NPs provided controlled release of camptothecin, killing U87 glioma cells in culture. When administered intravenously in mice with intracranial U87 tumors, they failed to increase survival. These results suggest that enhancing NP transport across the BBB does not necessarily yield proportional pharmacological effects.

Can deformation of a polymer film with a rigid coating model geophysical processes?

NASA Astrophysics Data System (ADS)

Volynskii, A. L.; Bazhenov, S. L.

2007-12-01

The structural and mechanical behavior of polymer films with a thin rigid coating is analyzed. The behavior of such systems under applied stress is accompanied by the formation of a regular wavy surface relief and by regular fragmentation of the coating. The above phenomena are shown to be universal. Both phenomena (stress-induced development of a regular wavy surface relief and regular fragmentation of the coating) are provided by the specific features of mechanical stress transfer from a compliant soft support to a rigid thin coating. The above phenomena are associated with a specific structure of the system, which is referred to as “a rigid coating on a soft substratum” system (RCSS). Surface microrelief in RCSS systems is similar to the ocean floor relief in the vicinity of mid-oceanic ridges. Thus, the complex system composed of a young oceanic crust and upper Earth's mantle may be considered as typically “a solid coating on a soft substratum” system. Specific features of the ocean floor relief are analyzed in terms of the approach advanced for the description of the structural mechanical behavior of polymer films with a rigid coating. This analysis allowed to estimate the strength of an ocean floor.

Water-soluble pH-responsive dendritic core-shell nanocarriers for polar dyes based on poly(ethylene imine).

PubMed

Xu, Shangjie; Luo, Ying; Haag, Rainer

2007-08-07

A simple general synthetic concept to build dendritic core-shell architectures with pH-labile linkers based on hyperbranched PEI cores and biocompatible PEG shells is presented. Using these dendritic core-shell architectures as nanocarriers, the encapsulation and transport of polar dyes of different sizes is studied. The results show that the acid-labile nanocarriers exhibit much higher transport capacities for dyes than unfunctionalized hyperbranched PEI. The cleavage of imine bonds and controlled release of the polar dyes revealed that weak acidic condition (pH approximately 5.0) could cleave the imine bonds linker and release the dyes up to five times faster than neutral conditions (pH = 7.4).

An epistemology on the nature of polymers.

PubMed

Laridjani, Mortéza; Leboucher, Pierre

2014-01-01

Liquids have neither a periodic structure nor the completely random character of gases therefore the detailed study of their x-ray scattering diagram encounters many difficulties. The idea of periodic regularity in molecules of liquid polymers has been an attractive proposition for the simple interpretation of liquid polymer x-ray diagrams. The categorisation of polymer substances as being between a crystal phase with a perfect order and an amorphous disordered state is an over simplification of the complex reality. For obtaining structural information, during the early stages of the application of x-ray diffraction, a near crystalline model of the molecular arrangements in liquids was utilised. However, the results from these investigations led to just an approximation of the crystalline state. Our studies have analysed the real image of Fourier space of liquid polymers, for the first time, using anomalous diffractometry. The findings show the precise atomic structure of liquid polymers when transformed, by cooling, to solid polymers. We demonstrate that there is an intermediate ordered structure, characterised by the real full image of Fourier space. This prominent state of matter, an intermediate ordered structure, is defined by a regular unit cell with a five-fold symmetry. These structural atomic studies contribute to a more detailed understanding of the properties of polymers than the traditional studies of the degree of crystallinity.

An Epistemology on the Nature of Polymers

PubMed Central

Laridjani, Mortéza; Leboucher, Pierre

2014-01-01

Liquids have neither a periodic structure nor the completely random character of gases therefore the detailed study of their x-ray scattering diagram encounters many difficulties. The idea of periodic regularity in molecules of liquid polymers has been an attractive proposition for the simple interpretation of liquid polymer x-ray diagrams. The categorisation of polymer substances as being between a crystal phase with a perfect order and an amorphous disordered state is an over simplification of the complex reality. For obtaining structural information, during the early stages of the application of x-ray diffraction, a near crystalline model of the molecular arrangements in liquids was utilised. However, the results from these investigations led to just an approximation of the crystalline state. Our studies have analysed the real image of Fourier space of liquid polymers, for the first time, using anomalous diffractometry. The findings show the precise atomic structure of liquid polymers when transformed, by cooling, to solid polymers. We demonstrate that there is an intermediate ordered structure, characterised by the real full image of Fourier space. This prominent state of matter, an intermediate ordered structure, is defined by a regular unit cell with a five-fold symmetry. These structural atomic studies contribute to a more detailed understanding of the properties of polymers than the traditional studies of the degree of crystallinity. PMID:25329440

Derivatizing weak polyelectrolytes--solution properties, self-aggregation, and association with anionic surfaces of hydrophobically modified poly(ethylene imine).

PubMed

Griffiths, Peter C; Paul, Alison; Fallis, Ian A; Wellappili, Champa; Murphy, Damien M; Jenkins, Robert; Waters, Sarah J; Nilmini, Renuka; Heenan, Richard K; King, Stephen M

2007-10-15

The physical properties of weak polyelectrolytes may be tailored via hydrophobic modification to exhibit useful properties under appropriate pH and ionic strength conditions as a consequence of the often inherently competing effects of electrostatics and hydrophobicity. Pulsed-gradient spin-echo NMR (PGSE-NMR), electron paramagnetic resonance (EPR), small-angle neutron scattering (SANS) surface tension, fluorescence, and pH titration have been used to examine the solution conformation and aggregation behavior of a series of hydrophobically modified hyperbranched poly(ethylene imine) (PEI) polymers in aqueous solution, and their interaction with sodium dodecylsulfate (SDS). PGSE-NMR gave a particularly insightful picture of the apparent molecular weight distribution. The presence of the hydrophobes led to a lower effective charge on the polymer at any given pH, compared to the (parent) nonmodified samples. Analysis of the SANS data showed that the propensity to form highly elliptical or rod-like aggregates at higher pHs, reflecting both the changes in protonation behavior induced by the hydrophobic modification and an hydrophobic interaction, but that these structures were disrupted with decreasing pH (increasing charge). The parent samples were not surface active yet the hydrophobically modified samples show pronounced surface activity and the presence of small hydrophobic domains. The surface activity increased with an increase in the degree of modification. On addition of SDS, the onset of the formation of polymer/surfactant complexes was insensitive to the degree of modification with the resultant PEI/SDS complexes resembling the size and shape of simple SDS micelles. Indeed, the presence of the SDS effectively nullifies the effects of the hydrophobe. Hydrophobic modification is therefore a viable option to tailor pH dependent properties, whose effects may be removed by the presence of surfactant.

A Facile in Situ and UV Printing Process for Bioinspired Self-Cleaning Surfaces

PubMed Central

González Lazo, Marina A.; Katrantzis, Ioannis; Dalle Vacche, Sara; Karasu, Feyza; Leterrier, Yves

2016-01-01

A facile in situ and UV printing process was demonstrated to create self-cleaning synthetic replica of natural petals and leaves. The process relied on the spontaneous migration of a fluorinated acrylate surfactant (PFUA) within a low-shrinkage acrylated hyperbranched polymer (HBP) and its chemical immobilization at the polymer-air interface. Dilute concentrations of 1 wt. % PFUA saturated the polymer-air interface within 30 min, leading to a ten-fold increase of fluorine concentration at the surface compared with the initial bulk concentration and a water contact angle (WCA) of 108°. A 200 ms flash of UV light was used to chemically crosslink the PFUA at the HBP surface prior to UV printing with a polydimethylsiloxane (PDMS) negative template of red and yellow rose petals and lotus leaves. This flash immobilization hindered the reverse migration of PFUA within the bulk HBP upon contacting the PDMS template, and enabled to produce texturized surfaces with WCA well above 108°. The synthetic red rose petal was hydrophobic (WCA of 125°) and exhibited the adhesive petal effect. It was not superhydrophobic due to insufficient concentration of fluorine at its surface, a result of the very large increase of the surface of the printed texture. The synthetic yellow rose petal was quasi-superhydrophobic (WCA of 143°, roll-off angle of 10°) and its self-cleaning ability was not good also due to lack of fluorine. The synthetic lotus leaf did not accurately replicate the intricate nanotubular crystal structures of the plant. In spite of this, the fluorine concentration at the surface was high enough and the leaf was superhydrophobic (WCA of 151°, roll-off angle below 5°) and also featured self-cleaning properties. PMID:28773860

Natural dendrimers: Synthesis and in vitro characterization of glycogen-cysteamine conjugates.

PubMed

Perrone, Mara; Lopedota, Angela; Liberati, Elisa; Russo, Vincenzo; Cutrignelli, Annalisa; Laquintana, Valentino; de Sousa, Irene Pereira; Franco, Massimo; Tongiani, Serena; Denora, Nunzio; Bernkop-Schnürch, Andreas

2017-06-01

The aim of this study was to synthesize, characterize and evaluate the mucoadhesive properties of the first thiolated hyperbranched natural polysaccharide with biodegradability and biocompatibility features. In detail, glycogen-cysteamine conjugates were synthesized through a first step of oxidative ring opening applying increasing concentrations of sodium periodate, to obtain polymers with different degrees of oxidation, and a second step of reductive amination with a constant amount of cysteamine. The obtained glycogen-cysteamine conjugates were characterized regarding their content of free and total thiol groups by Ellman's assay, biocompatibility, swelling/erosion behavior, rheological synergism and mucoadhesive properties in comparison to the unmodified glycogen. The higher the concentration of periodate was, the higher was the content of total thiol groups being in the range of 255.7±12-1194.5±82μmol/g, biocompatibility remained unaffected by these structural changes. On the contrary, the mucoadhesive properties, evaluated by tensile, rheological synergism and rotating cylinder studies, appear to be influenced by the thiol groups concentration on the glycogen. In particular the glycogen-cysteamine conjugate exhibiting the highest degree of thiolation showed a 79-fold increase in viscosity over a time period of 8h, as well as, remained attached on freshly excised porcine mucosa 32-fold longer than the unmodified polymer. The higher was the amount of conjugated thiol groups, the higher was the water absorption capacity of glycogen-cysteamine tablets in Simulated Intestinal Fluid pH 6.8 (SIF). The introduction of thiol moieties on polymer changed the characteristics of the polysaccharide by improving mucoadhesion properties. Therefore, this work represents the first study describing thiolated natural dendrimers as potential platform useful to realize appropriate mucoadhesive nanocarrier systems suitable to prolong mucosal residence time. Copyright © 2017 Elsevier B.V. All rights reserved.

Design of dendrimer-based drug delivery nanodevices with enhanced therapeutic efficacies

NASA Astrophysics Data System (ADS)

Kannan, Rangaramanujam

2007-03-01

Dendrimers and hyperbranched polymers possess highly branched architectures, with a large number of controllable, tailorable, `peripheral' functionalities. Since the surface chemistry of these materials can be modified with relative ease, these materials have tremendous potential in targeted drug delivery. They have significant potential compared to liposomes and nanoparticles, because of the reduced macrophage update, increased cellular transport, and the ability to modulate the local environment through functional groups. We are developing nanodevices based on dendritic systems for drug delivery, that contain a high drug payload, ligands, and imaging agents, resulting in `smart' drug delivery devices that can target, deliver, and signal. In collaboration with the Children's Hospital of Michigan, Karmanos Cancer Institute, and College of Pharmacy, we are testing the in vitro and in vivo response of these nanodevices, by adapting the chemistry for specific clinical applications such as asthma and cancer. These materials are characterized by UV/Vis spectroscopy, flow cytometry, fluorescence/confocal microscopy, and appropriate animal models. Our results suggest that: (1) We can prepare drug-dendrimer conjugates with drug payloads of greater than 50%, for a variety of drugs; (2) The dendritic polymers are capable of transporting and delivering drugs into cells faster than free drugs, with superior therapeutic efficiency. This can be modulated by the surface functionality of the dendrimer; (3) For chemotherapy drugs, the conjugates are a factor of 6-20 times more effective even in drug-resistant cell lines; (4) For corticosteroidal drugs, the dendritic polymers provide higher drug residence times in the lung, allowing for passive targeting. The ability of the drug-dendrimer-ligand conjugates to target specific asthma and cancer cells is currently being explored using in vitro and in vivo animal models.

Preparation of hyperbranched poly (amidoamine)-grafted graphene nanolayers as a composite and curing agent for epoxy resin

NASA Astrophysics Data System (ADS)

Gholipour-Mahmoudalilou, Meysam; Roghani-Mamaqani, Hossein; Azimi, Reza; Abdollahi, Amin

2018-01-01

Thermal properties of epoxy resin were improved by preparation of a curing agent of poly (amidoamine) (PAMAM) dendrimer-grafted graphene oxide (GO). Hyperbranched PAMAM-modified GO (GD) was prepared by a divergent dendrimer synthesis methodology. Modification of GO with (3-Aminopropyl)triethoxysilane (APTES), Michael addition of methacrylic acid, and amidation reaction with ethylenediamine results in the curing agent of GD. Then, epoxy resin was cured in the presence of different amounts of GD and the final products were compared with ethylenediamine-cured epoxy resin (E) in their thermal degradation temperature and char contents. Functionalization of GO with APTES and hyperbranched dendrimer formation at the surface of GO were evaluated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and thermogravimetric analysis (TGA) results. TGA results showed that the weight loss associated with chemical moieties in GONH2, GOMA, and GD is estimated to be 10.1, 12.2, and 14.1%, respectively. Covalent attachment of dendrimer at the surface of GO increases its thermal stability. TGA also showed that decomposition temperature and char content are higher for composites compared with E. Scanning and transmission electron microscopies show that flat and smooth graphene nanolayers are wrinkled in GO and re-stacking and flattening of nanolayers is observed in GD.

Biocompatible high performance hyperbranched epoxy/clay nanocomposite as an implantable material.

PubMed

Barua, Shaswat; Dutta, Nipu; Karmakar, Sanjeev; Chattopadhyay, Pronobesh; Aidew, Lipika; Buragohain, Alak K; Karak, Niranjan

2014-04-01

Polymeric biomaterials are in extensive use in the domain of tissue engineering and regenerative medicine. High performance hyperbranched epoxy is projected here as a potential biomaterial for tissue regeneration. Thermosetting hyperbranched epoxy nanocomposites were prepared with Homalomena aromatica rhizome oil-modified bentonite as well as organically modified montmorillonite clay. Fourier transformed infrared spectroscopy, x-ray diffraction and scanning and transmission electron microscopic techniques confirmed the strong interfacial interaction of clay layers with the epoxy matrix. The poly(amido amine)-cured thermosetting nanocomposites exhibited high mechanical properties like impact resistance (>100 cm), scratch hardness (>10 kg), tensile strength (48-58 MPa) and elongation at break (11.9-16.6%). Cytocompatibility of the thermosets was found to be excellent as evident by MTT and red blood cell hemolytic assays. The nanocomposites exhibited antimicrobial activity against Staphylococcus aureus (ATCC 11632), Escherichia coli (ATCC 10536), Mycobacterium smegmatis (ATCC14468) and Candida albicans (ATCC 10231) strains. In vivo biocompatibility of the best performing nanocomposite was ascertained by histopathological study of the brain, heart, liver and skin after subcutaneous implantation in Wistar rats. The material supported the proliferation of dermatocytes without induction of any sign of toxicity to the above organs. The adherence and proliferation of cells endorse the nanocomposite as a non-toxic biomaterial for tissue regeneration.

Label-free immunosensor based on hyperbranched polyester for specific detection of α-fetoprotein.

PubMed

Niu, Yanlian; Yang, Tian; Ma, Shangshang; Peng, Fang; Yi, Meihui; Wan, Mimi; Mao, Chun; Shen, Jian

2017-06-15

A novel label-free immunosensor based on hyperbranched polyester nanoparticles with nitrite groups (HBPE-NO 2 ), which were synthesized through a simple one-step chemical reaction, was first developed for specific detection of α-fetoprotein (AFP), the tumor marker for liver cancer. The obtained HBPE-NO 2 nanoparticles (NPs) were characterized by the proton nuclear magnetic resonance spectroscopy ( 1 H NMR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). And the fabricated process of immunosensor was investigated by attenuated total reflection Fourier-transform infrared spectra (ATR-FTIR), static water contact angles, scanning electron microscope (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electrochemical performances of the AFP immunosensor were studied. Results indicated the prepared HBPE-NO 2 -modified immunosensor showed excellent electrochemical properties and satisfactory accuracy for the detection of AFP of the real clinical samples that attributed to the properties of the HBPE-NO 2 NPs, which had nanosized structure to increase the specific surface area and unique chemical reactivity for loading capacity of protein molecules. Construction of biosensors using the structure and properties of hyperbranched molecules will offer ideal electrode substrates, which provided more possibilities for the design of biosensor. Copyright © 2017 Elsevier B.V. All rights reserved.

Cationic Copolymerization of 3,3-Bis(hydroxymethyl)oxetane and Glycidol: Biocompatible Hyperbranched Polyether Polyols with High Content of Primary Hydroxyl Groups.

PubMed

Christ, Eva-Maria; Hobernik, Dominika; Bros, Matthias; Wagner, Manfred; Frey, Holger

2015-10-12

The cationic ring-opening copolymerization of 3,3-bis(hydroxymethyl)oxetane (BHMO) with glycidol using different comonomer ratios (BHMO content from 25 to 90%) and BF3OEt2 as an initiator has been studied. Apparent molecular weights of the resulting hyperbranched polyether copolymers ranged from 1400 to 3300 g mol(-1) (PDI: 1.21-1.48; method: SEC, linear PEG standards). Incorporation of both comonomers is evidenced by MALDI-TOF mass spectroscopy. All hyperbranched polyether polyols with high content of primary hydroxyl groups portray good solubility in water, which correlates with an increasing content of glycerol units. Detailed NMR characterization was employed to elucidate the copolymer microstructures. Kinetic studies via FTIR demonstrated a weak gradient-type character of the copolymers. MTT assays of the copolymers (up to 100 μg mL(-1)) on HEK and fibroblast cell lines (3T3, L929, WEHI) as well as viability tests on the fibroblast cells were carried out to assess the biocompatibility of the materials, confirming excellent biocompatibility. Transfection efficiency characterization by flow cytometry and confocal laser microscopy demonstrated cellular uptake of the copolymers. Antiadhesive properties of the materials on surfaces were assessed by adhesion assays with fibroblast cells.

Molecular Design for Preparation of Hexagonal-Ordered Porous Films Based on Side-chain Type Liquid-Crystalline Star Polymer.

PubMed

Naka, Yumiko; Takayama, Hiromu; Koyama, Teruhisa; Le, Khoa V; Sasaki, Takeo

2018-05-02

Fabrication of regularly porous films by the breath-figure method has attracted much attention. The simple, low-cost technique uses the condensation of water droplets to produce these structures, but the phenomenon itself is complex, requiring control over many interacting parameters that change throughout the process. Developing a unified understanding for the molecular design of polymers to prepare ordered porous films is challenging, but required for further advancements. In this article, the effects of the chemical structure of polymers in the breath-figure technique were systematically explored using side-chain type liquid-crystalline (LC) star polymers. The formation of porous films was affected by the structure of the polymers. Although the entire film surface of poly(11-[4-(4-cyanobiphenyl)oxy]undecyl methacrylate) (P11CB) had a hexagonal ordered porous structure over a certain Mn value, regularly arranged holes did not easily form in poly(methyl methacrylate) (PMMA), even though the main chain of PMMA is similar to that of P11CB. Comparing P11CB and poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11B) (P11CB without cyano groups) showed that the local polar groups in hydrophobic polymers promoted the formation of ordered porous films. No holes formed in poly(4-cyanobiphenyl methacrylate) (P0CB) (P11CB without alkyl spacers) films due to its hydrophilicity. The introduction of alkyl chains in P0CB allowed the preparation of honeycomb-structured films by increasing the internal tension. However, alkyl chains in the side chain alone did not result in a porous structure, as in the case of poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11). Aromatic rings are also required to increase the Tg and improve film formability. In the present study, suitable molecular designs of polymers were found, specifically hydrophobic polymers with local polar groups, to form a regularly porous structure. Development of clear guidelines for the molecular design of polymers is the subject of our current research, which will enable the fabrication of porous films using various functional polymers.

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.

Regular Arrays of Germanium Nanoparticles Assisted by Thermoset Polymer Composites for High Capacity Lithium Ion Battery

NASA Astrophysics Data System (ADS)

Jo, Gyuha; Park, Moon Jeong

2012-02-01

In recent years Li-batteries have attracted significant interests for a variety of applications such as portable electronics and electric vehicle (EV) batteries due to their high energy densities. Key challenges in advancing the technology lie in specific energy density, the long term cycle properties, and durability at elevated temperature. In present study, we were motivated to prepare high capacity Li-battery by creating regular arrays of germanium nanoparticles (GeNPs, 1600 mAh/g) to replace commercial graphite anode (370 mAh/g). Thermoset polymers were employed to prepare GeNPs/polymer composites with tunable NP loadings and spacings, followed by carbonization process to prepare GeNPs/carbon composite anode material. Due to the large volume change of GeNPs with charge/discharge cycles, the regular arrays of GeNPs are turned out to be a crucial parameter in obtaining enhanced cyclability. The GeNPs/carbon anode materials were cycle tested in a half cell configuration using Lithium foil as a counter electrode and lithium salt doped PS-PEO block copolymers as electrolytes. High capacity and rate capability were achieved, which demonstrate the role of nano-sized and regularly-arrayed anode active materials in obtaining the improved battery performance.

Precipitation of lamellar gold nanocrystals in molten polymers

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

Palomba, M.; Carotenuto, G., E-mail: giancaro@unina.it

Non-aggregated lamellar gold crystals with regular shape (triangles, squares, pentagons, etc.) have been produced by thermal decomposition of gold chloride (AuCl) molecules in molten amorphous polymers (polystyrene and poly(methyl methacrylate)). Such covalent inorganic gold salt is high soluble into non-polar polymers and it thermally decomposes at temperatures compatible with the polymer thermal stability, producing gold atoms and chlorine radicals. At the end of the gold precipitation process, the polymer matrix resulted chemically modified because of the partial cross-linking process due to the gold atom formation reaction.

Exploring monovalent and multivalent peptides for the inhibition of FBP21-tWW.

PubMed

Henning, Lisa Maria; Bhatia, Sumati; Bertazzon, Miriam; Marczynke, Michaela; Seitz, Oliver; Volkmer, Rudolf; Haag, Rainer; Freund, Christian

2015-01-01

The coupling of peptides to polyglycerol carriers represents an important route towards the multivalent display of protein ligands. In particular, the inhibition of low affinity intracellular protein-protein interactions can be addressed by this design. We have applied this strategy to develop binding partners for FBP21, a protein which is important for the splicing of pre-mRNA in the nucleus of eukaryotic cells. Firstly, by using phage display the optimized sequence WPPPPRVPR was derived which binds with K Ds of 80 μM and 150 µM to the individual WW domains and with a K D of 150 μM to the tandem-WW1-WW2 construct. Secondly, this sequence was coupled to a hyperbranched polyglycerol (hPG) that allowed for the multivalent display on the surface of the dendritic polymer. This novel multifunctional hPG-peptide conjugate displayed a K D of 17.6 µM which demonstrates that the new carrier provides a venue for the future inhibition of proline-rich sequence recognition by FBP21 during assembly of the spliceosome.

Exploring monovalent and multivalent peptides for the inhibition of FBP21-tWW

PubMed Central

Bertazzon, Miriam; Marczynke, Michaela; Seitz, Oliver; Volkmer, Rudolf; Haag, Rainer

2015-01-01

Summary The coupling of peptides to polyglycerol carriers represents an important route towards the multivalent display of protein ligands. In particular, the inhibition of low affinity intracellular protein–protein interactions can be addressed by this design. We have applied this strategy to develop binding partners for FBP21, a protein which is important for the splicing of pre-mRNA in the nucleus of eukaryotic cells. Firstly, by using phage display the optimized sequence WPPPPRVPR was derived which binds with K Ds of 80 μM and 150 µM to the individual WW domains and with a K D of 150 μM to the tandem-WW1–WW2 construct. Secondly, this sequence was coupled to a hyperbranched polyglycerol (hPG) that allowed for the multivalent display on the surface of the dendritic polymer. This novel multifunctional hPG-peptide conjugate displayed a K D of 17.6 µM which demonstrates that the new carrier provides a venue for the future inhibition of proline-rich sequence recognition by FBP21 during assembly of the spliceosome. PMID:26124874

Tris[2-(acryloyloxy)ethyl]isocyanurate cross-linked low-molecular-weight polyethylenimine as gene delivery carriers in cell culture and dystrophic mdx mice.

PubMed

Wang, Mingxing; Tucker, Jay D; Lu, Peijuan; Wu, Bo; Cloer, Caryn; Lu, Qilong

2012-04-18

Hyperbranched poly(ester amine)s (PEAs) were successfully synthesized by Michael addition reaction between tris[2-(acryloyloxy)ethyl]isocyanurate (TAEI) and low-molecular-weight polyethylenimine (LPEI, M(w) 0.8k, 1.2k, and 2.0k) and evaluated in vitro and in vivo as gene carriers. PEAs effectively condensed plasmid DNA with particle sizes below 200 nm and surface charges between 11.5 and 33.5 mV under tested doses [at the ratios 2-10:1 of polymer/pDNA(w/w)]. The PEAs showed significantly lower cytotoxicities when compared with PEI 25k in two different cell lines. The PEAs (C series) composed of PEI 2k showed higher transgene expression compared to PEAs of PEI 0.8k (A series) or 1.2k (B series). Highest gene transfection efficiency in CHO, C2C12 myoblast, and human skeletal muscle (HSK) cell lines was obtained with TAEI/PEI-2K (C12) at a ratio of 1:2. Both C12, C14(TAEI/PEI-2K at a ratio of 1:4) demonstrated 5-8-fold higher gene expression as compared with PEI 25k in mdx mice in vivo through intramuscular administration. No obvious muscle damage was observed with these new polymers. Higher transfection efficiency and lower toxicity indicate the potential of the biodegradable PEAs as safe and efficient transgene delivery vectors. © 2012 American Chemical Society

Impact of Dendrimers on Solubility of Hydrophobic Drug Molecules

PubMed Central

Choudhary, Sonam; Gupta, Lokesh; Rani, Sarita; Dave, Kaushalkumar; Gupta, Umesh

2017-01-01

Adequate aqueous solubility has been one of the desired properties while selecting drug molecules and other bio-actives for product development. Often solubility of a drug determines its pharmaceutical and therapeutic performance. Majority of newly synthesized drug molecules fail or are rejected during the early phases of drug discovery and development due to their limited solubility. Sufficient permeability, aqueous solubility and physicochemical stability of the drug are important for achieving adequate bioavailability and therapeutic outcome. A number of different approaches including co-solvency, micellar solubilization, micronization, pH adjustment, chemical modification, and solid dispersion have been explored toward improving the solubility of various poorly aqueous-soluble drugs. Dendrimers, a new class of polymers, possess great potential for drug solubility improvement, by virtue of their unique properties. These hyper-branched, mono-dispersed molecules have the distinct ability to bind the drug molecules on periphery as well as to encapsulate these molecules within the dendritic structure. There are numerous reported studies which have successfully used dendrimers to enhance the solubilization of poorly soluble drugs. These promising outcomes have encouraged the researchers to design, synthesize, and evaluate various dendritic polymers for their use in drug delivery and product development. This review will discuss the aspects and role of dendrimers in the solubility enhancement of poorly soluble drugs. The review will also highlight the important and relevant properties of dendrimers which contribute toward drug solubilization. Finally, hydrophobic drugs which have been explored for dendrimer assisted solubilization, and the current marketing status of dendrimers will be discussed. PMID:28559844

Langmuir and Langmuir-Blodgett films of multifunctional, amphiphilic polyethers with cholesterol moieties.

PubMed

Reuter, Sascha; Hofmann, Anna M; Busse, Karsten; Frey, Holger; Kressler, Jörg

2011-03-01

Langmuir films of multifunctional, hydrophilic polyethers containing a hydrophobic cholesterol group (Ch) were studied by surface pressure-mean molecular area (π-mmA) measurements and Brewster angle microscopy (BAM). The polyethers were either homopolymers or diblock copolymers of linear poly(glycerol) (lPG), linear poly(glyceryl glycidyl ether) (lPGG), linear poly(ethylene glycol) (lPEG), or hyperbranched poly(glycerol) (hbPG). Surface pressure measurements revealed that the homopolymers lPG and hbPG did not stay at the water surface after spreading and solvent evaporation, in contrast to lPEG. Because of the incorporation of the Ch group in the polymer structure, stable Langmuir films were formed by Ch-lPG(n), Ch-lPGG(n), and Ch-hbPG(n). The Ch-hbPG(n), Ch-lPEG(n), Ch-lPEG(n)-b-lPG(m), Ch-lPEG(n)-b-lPGG(m), and Ch-lPEG(n)-b-hbPG(m) systems showed an extended plateau region assigned to a phase transition involving the Ch groups. Typical hierarchically ordered morphologies of the LB films on hydrophilic substrates were observed for all Ch-initiated polymers. All LB films showed that Ch of the Ch-initiated homopolymers is able to crystallize. This strong tendency of self-aggregation then triggers further dewetting effects of the respective polyether entities. Fingerlike morphologies are observed for Ch-lPEG(69), since the lPEG(69) entity is able to undergo crystallization after transfer onto the silicon substrate.

Biocide immobilized OMMT-carbon dot reduced Cu2O nanohybrid/hyperbranched epoxy nanocomposites: Mechanical, thermal, antimicrobial and optical properties.

PubMed

De, Bibekananda; Gupta, Kuldeep; Mandal, Manabendra; Karak, Niranjan

2015-11-01

The present work demonstrated a transparent thermosetting nanocomposite with antimicrobial and photoluminescence attributes. The nanocomposites are fabricated by incorporation of different wt.% (1, 2 and 3) of a biocide immobilized OMMT-carbon dot reduced Cu2O nanohybrid (MITH-NH) in the hyperbranched epoxy matrix. MITH-NH is obtained by immobilization of 2-methyl-4-isothiazolin-3-one hydrochloride (MITH) at room temperature using sonication on OMMT-carbon dot reduced Cu2O nanohybid. The nanohybrid is prepared by reduction of cupric acetate using carbon dot as the reducing agent in the presence of OMMT at 70°C. The significant improvements in tensile strength (~2 fold), elongation at break (3 fold), toughness (4 fold) and initial thermal degradation temperature (30°C) of the pristine hyperbranched epoxy system are achieved by incorporation of 3wt.% of MITH-NH in it. The nanocomposites exhibit strong antimicrobial activity against Staphylococcus aureus, Bacillus subtilis, Klebsiella pneumoniae and Pseudomonas aeruginosa bacteria and Candida albicans, a fungus. The nanocomposite also shows significant activity against biofilm formation compared to the pristine thermoset. Further, the nanocomposite films emit different colors on exposure of different wavelengths of UV light. The properties of these nanocomposites are also compared with the same nanohybrid without OMMT. Copyright © 2015. Published by Elsevier B.V.

Hyperbranched-dendrimer architectural copolymer gene delivery using hyperbranched PEI conjugated to poly(propyleneimine) dendrimers: synthesis, characterization, and evaluation of transfection efficiency

NASA Astrophysics Data System (ADS)

Alavi, Seyyed Jamal; Gholami, Leila; Askarian, Saeedeh; Darroudi, Majid; Massoudi, Abdolhossein; Rezaee, Mehdi; Kazemi Oskuee, Reza

2017-02-01

The applications of dendrimer-based vectors seem to be promising in non-viral gene delivery because of their potential for addressing the problems with viral vectors. In this study, generation 3 poly(propyleneimine) (G3-PPI) dendrimers with 1, 4-diaminobutane as a core initiator was synthesized using a divergent growth approach. To increase the hydrophobicity and reduce toxicity, 10% of primary amines of G3-PPI dendrimers were replaced with bromoalkylcarboxylates with different chain lengths (6-bromohexanoic and 10-bromodecanoic). Then, to retain the overall buffering capacity and enhance transfection, the alkylcarboxylate-PPIs were conjugated to 10 kDa branched polyethylenimine (PEI). The results showed that the modified PPI was able to form complexes with the diameter of less than 60 nm with net-positive surface charge around 20 mV. No significant toxicity was observed in modified PPIs; however, the hexanoate conjugated PPI-PEI (PPI-HEX-10% PEI) and the decanoate conjugated PPI-PEI (PPI-DEC-10%-PEI) showed the best transfection efficiency in murine neuroblastoma (Neuro-2a) cell line, even PPI-HEX-10%-PEI showed transfection efficiency equal to standard PEI 25 kDa with reduced toxicity. This study suggested a new series of hyperbranched (PEI)-dendrimer (PPI) architectural copolymers as non-viral gene delivery vectors with high transfection efficiency and low toxicity.

Preparation and characterization of starch-based loose-fill packaging foams

NASA Astrophysics Data System (ADS)

Fang, Qi

Regular and waxy corn starches were blended in various ratios with biodegradable polymers including polylactic acid (PLA), Eastar Bio Copolyester 14766 (EBC) and Mater-Bi ZF03U (MBI) and extruded with a C. W. Brabender laboratory twin screw extruder using a 3-mm die nozzle at 150°C and 150 rev/min. Physical characteristics including radial expansion, unit density and bulk density and water solubility index, water absorption characteristics, mechanical properties including compressibility, Young's modulus, spring index, bulk compressibility and bulk spring index and abrasion resistance were investigated as affected by the ingredient formulations, i.e. type of polymers, type of starches, polymer to starch ratio and starch moisture content. A completely randomized factorial blocking experimental design was used. Fifty-four treatments resulted. Each treatment was replicated three times. SAS statistical software package was used to analyze the data. Foams made of waxy starch had better radial expansion, lower unit density and bulk density than did foams made of regular starch. Regular starch foams had significantly lower water solubility index than did the waxy starch foams. PLA-starch foams had the lowest compressibility and Young's modulus. MBI-starch foams were the most rigid. All foams had excellent spring indices and bulk spring indices which were comparable to the spring index of commercial expanded polystyrene foam. Correlations were established between the foam mechanical properties and the physical characteristics. Foam compressibility and Young's modulus decreased as increases in radial expansion and decreases in unit and bulk densities. Their relationships were modeled with power law equations. No correlation was observed between spring index and bulk spring index and foam physical characteristics. MBI-starch foams had the highest equilibrium moisture content. EBC-starch and PLA-starch foams had similar water absorption characteristics. No significant difference existed in water absorption characteristics between foams made of regular and waxy starches. Empirical models were developed to correlate foam water absorption characteristics with relative humidity and polymer content. The developed models fit the data well with relatively small standard errors and uniformly scattered residual plots. Foams with higher polymer content had better abrasion resistance than did foams with lower polymer content.

Universal Sequence Replication, Reversible Polymerization and Early Functional Biopolymers: A Model for the Initiation of Prebiotic Sequence Evolution

PubMed Central

Walker, Sara Imari; Grover, Martha A.; Hud, Nicholas V.

2012-01-01

Many models for the origin of life have focused on understanding how evolution can drive the refinement of a preexisting enzyme, such as the evolution of efficient replicase activity. Here we present a model for what was, arguably, an even earlier stage of chemical evolution, when polymer sequence diversity was generated and sustained before, and during, the onset of functional selection. The model includes regular environmental cycles (e.g. hydration-dehydration cycles) that drive polymers between times of replication and functional activity, which coincide with times of different monomer and polymer diffusivity. Template-directed replication of informational polymers, which takes place during the dehydration stage of each cycle, is considered to be sequence-independent. New sequences are generated by spontaneous polymer formation, and all sequences compete for a finite monomer resource that is recycled via reversible polymerization. Kinetic Monte Carlo simulations demonstrate that this proposed prebiotic scenario provides a robust mechanism for the exploration of sequence space. Introduction of a polymer sequence with monomer synthetase activity illustrates that functional sequences can become established in a preexisting pool of otherwise non-functional sequences. Functional selection does not dominate system dynamics and sequence diversity remains high, permitting the emergence and spread of more than one functional sequence. It is also observed that polymers spontaneously form clusters in simulations where polymers diffuse more slowly than monomers, a feature that is reminiscent of a previous proposal that the earliest stages of life could have been defined by the collective evolution of a system-wide cooperation of polymer aggregates. Overall, the results presented demonstrate the merits of considering plausible prebiotic polymer chemistries and environments that would have allowed for the rapid turnover of monomer resources and for regularly varying monomer/polymer diffusivities. PMID:22493682

Hyperbranched quasi-1D TiO2 nanostructure for hybrid organic-inorganic solar cells.

PubMed

Ghadirzadeh, Ali; Passoni, Luca; Grancini, Giulia; Terraneo, Giancarlo; Li Bassi, Andrea; Petrozza, Annamaria; Di Fonzo, Fabio

2015-04-15

The performance of hybrid solar cells is strongly affected by the device morphology. In this work, we demonstrate a poly(3-hexylthiophene-2,5-diyl)/TiO2 hybrid solar cell where the TiO2 photoanode comprises an array of tree-like hyperbranched quasi-1D nanostructures self-assembled from the gas phase. This advanced architecture enables us to increase the power conversion efficiency to over 1%, doubling the efficiency with respect to state of the art devices employing standard mesoporous titania photoanodes. This improvement is attributed to several peculiar features of this array of nanostructures: high interfacial area; increased optical density thanks to the enhanced light scattering; and enhanced crystallization of poly(3-hexylthiophene-2,5-diyl) inside the quasi-1D nanostructure.

Comparison of Linear and Hyperbranched Polyether Lipids for Liposome Shielding by 18F-Radiolabeling and Positron Emission Tomography.

PubMed

Wagener, Karolin; Worm, Matthias; Pektor, Stefanie; Schinnerer, Meike; Thiermann, Raphael; Miederer, Matthias; Frey, Holger; Rösch, Frank

2018-04-27

Multifunctional and highly biocompatible polyether structures play a key role in shielding liposomes from degradation in the bloodstream, providing also multiple functional groups for further attachment of targeting moieties. In this work hyperbranched polyglycerol ( hbPG) bearing lipids with long alkyl chain anchor are evaluated with respect to steric stabilization of liposomes. The branched polyether lipids possess a hydrophobic bis(hexadecyl)glycerol membrane anchor for the liposomal membrane. hbPG was chosen as a multifunctional alternative to PEG, enabling the eventual linkage of multiple targeting vectors. Different hbPG lipids ( M n = 2900 and 5200 g mol -1 ) were examined. A linear bis(hexadecyl)glycerol-PEG lipid ( M n = 3000 g mol -1 ) was investigated as well, comparing hbPG and PEG with respect to shielding properties. Radiolabeling of the polymers was carried out using 1-azido-2-(2-(2-[ 18 F]fluoroethoxy)ethoxy)ethane ([ 18 F]F-TEG-N) 3 via copper-catalyzed alkyne-azide cycloaddition with excellent radiochemical yields exceeding 95%. Liposomes were prepared by the thin-film hydration method followed by repeated extrusion. Use of a custom automatic extrusion device gave access to reproducible sizes of the liposomes (hydrodynamic radius of 60-94 nm). The in vivo fate of the bis(hexadecyl)glycerol polyethers and their corresponding assembled liposome structures were evaluated via noninvasive small animal positron emission tomography (PET) imaging and biodistribution studies (1 h after injection and 4 h after injection) in mice. Whereas the main uptake of the nonliposomal polyether lipids was observed in the kidneys and in the bladder after 1 h due to rapid renal clearance, in contrast, the corresponding liposomes showed uptake in the blood pool as well as in organs with good blood supply, that is, heart and lung over the whole observation period of 4 h. The in vivo behavior of all three liposomal formulations was comparable, albeit with remarkable differences in splenic uptake. Overall, liposomes shielded by the branched polyglycerol lipids show a favorable biodistribution with greatly prolonged blood circulation times, rendering them promising novel nanovesicles for drug transport and targeting.

From statistics of regular tree-like graphs to distribution function and gyration radius of branched polymers

NASA Astrophysics Data System (ADS)

Grosberg, Alexander Y.; Nechaev, Sergei K.

2015-08-01

We consider flexible branched polymer, with quenched branch structure, and show that its conformational entropy as a function of its gyration radius R, at large R, obeys, in the scaling sense, Δ S˜ {R}2/({a}2L), with a bond length (or Kuhn segment) and L defined as an average spanning distance. We show that this estimate is valid up to at most the logarithmic correction for any tree. We do so by explicitly computing the largest eigenvalues of Kramers matrices for both regular and ‘sparse’ three-branched trees, uncovering on the way their peculiar mathematical properties.

[Preparation of poly(methyl acrylate) microfluidic chips surface-modified by hyperbranched polyamide ester and their application in the separation of biomolecules].

PubMed

Liu, Bing; Lin, Donge; Xu, Lin; Lei, Yanhui; Bo, Qianglong; Shou, Chongqi

2012-05-01

The surface of poly (methyl acrylate) (PMMA) microfluidic chips were modified using hyperbranched polyamide ester via chemical bonding. The contact angles of the modified chips were measured. The surface morphology was observed by scanning electron microscope (SEM) and stereo microscope. The results showed that the surface of the modified chips was coated by a dense, uniform, continuous, hydrophilic layer of hyperbranched polyamide ester. The hydrophilic of the chip surface was markedly improved. The contact angle of the chips modified decreased from 89.9 degrees to 29.5 degrees. The electro osmotic flow (EOF) in the modified microchannel was lower than that in the unmodified microchannel. Adenosine and L-lysine were detected and separated via the modified PMMA microfluidic chips. Compared with unmodified chips, the modified chips successfully separated the two biomolecules. The detection peaks were clear and sharp. The separation efficiencies of adenosine and L-lysine were 8.44 x 10(4) plates/m and 9.82 x 10(4) plates/m respectively, and the resolutions (Rs) was 5.31. The column efficiencies and resolutions of the modified chips were much higher than those of the unmodified chips. It was also observed that the modified chips possessed good reproducibility of migration time. This research may provide a new and effective method to improve the hydrophilicity of the PMMA surface and the application of PMMA microfluidic chips in the determination of trace biomolecules.

Wide bandgap OPV polymers based on pyridinonedithiophene unit with efficiency >5%

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

Schneider, Alexander M.; Lu, Luyao; Manley, Eric F.

2015-06-04

We report the properties of a new series of wide band gap photovoltaic polymers based on the N-alkyl 2-pyridone dithiophene (PDT) unit. These polymers are effective bulk heterojunction solar cell materials when blended with phenyl-C 71-butyric acid methyl ester (PC 71BM). They achieve power conversion efficiencies (up to 5.33%) high for polymers having such large bandgaps, ca. 2.0 eV (optical) and 2.5 eV (electrochemical). As a result, grazing incidence wide-angle X-ray scattering (GIWAXS) reveals strong correlations between π–π stacking distance and regularity, polymer backbone planarity, optical absorption maximum energy, and photovoltaic efficiency.

Synthesis, Characterization and Antibacterial Activity of BiVO4 Microstructure

NASA Astrophysics Data System (ADS)

Ekthammathat, Nuengruethai; Phuruangrat, Anukorn; Thongtem, Somchai; Thongtem, Titipun

2018-05-01

Hyperbranched BiVO4 microstructure were successfully synthesized by a hydrothermal method. Upon characterization the products by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, selected area electron diffraction (SAED) and photoluminescence (PL) spectroscopy, pure monoclinic hyperbranched BiVO4 with dominant vibration peak at 810 cm-1 and strong photoemission peak at 360 nm was synthesized in the solution with pH 1. In the solution with pH 2, tetragonal BiVO4 phase was also detected. In this research, antibacterial activity against S. aureus and E. coli was investigated by counting the colony forming unit (CFU). At 37°C within 24 h, the monoclinic BiVO4 phase can play the role in inhibiting S. aureus growth (350 CFU/mL remaining bacteria) better than that against E. coli (a large number of remaining bacteria).

Toughening epoxy acrylate with polyurethane acrylates and hyper-branched polyester in three dimensional printing

NASA Astrophysics Data System (ADS)

Fang, Chao; Li, Ning; Liu, Yang; Lu, Gang

2018-05-01

In order to improve the toughness of epoxy acrylate (EA) in three dimensional printing (3D-printing), bifunctional polyurethane acrylate (PUA) and trifunctional PUA were firstly blended with EA. The multi-indicators orthogonal experiment, designed with the indicators of tensile strength, elongation at break and impact strength, was used to find out the optimal formulation. Then, hyper-branched polyesters (HBPs) was added to improve the toughness of the photocurable system. The microstructures of the cured specimens were characterized by optical microscopy and scanning electron microscopy. By analyzing their mechanical properties and microstructures, it was revealed that the best addition amounts of HBP are 10 wt%. Results indicated that their toughness improved a lot comparing with pure EA. The changes of mechanical properties were characterized by DMA. The addition of HBP could cause a loss in stiffness, elasticity modulus and thermostability.

Quantum dots-hyperbranched polyether hybrid nanospheres towards delivery and real-time detection of nitric oxide.

PubMed

Liu, Shuiping; Gu, Tianxun; Fu, Jiajia; Li, Xiaoqiang; Chronakis, Ioannis S; Ge, Mingqiao

2014-12-01

In this work, novel hybrid nanosphere vehicles were synthesized for nitric oxide (NO) donating and real-time detection. The hybrid nanosphere vehicles consist of cadmium selenide quantum dots (CdSe QDs) as NO fluorescent probes, and the modified hyperbranched polyether (mHP)-based diazeniumdiolates as NO donors, respectively. The nanospheres have spherical outline with dimension of ~127 nm. The data of systematic characterization demonstrated that the mHP-based hybrid nanosphere vehicles (QDs-mHP-NO) can release and real-time detect NO with the low limit of 25 nM, based on fluorescence quenching mechanism. The low cell-toxicity of QDs-mHP-NO nanospheres was verified by means of MTT assay on L929 cells viability. The QDs-mHP-NO nanospheres provide perspectives for designing a new class of biocompatible NO donating and imaging systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation of Fluorination on Donor Moiety of Donor-Acceptor 4,7-Dithienylbenzothiadiazole-Based Conjugated Polymers toward Enhanced Photovoltaic Efficiency.

PubMed

Li, Yonghai; Wang, Junyi; Liu, Yan; Qiu, Meng; Wen, Shuguang; Bao, Xichang; Wang, Ning; Sun, Mingliang; Yang, Renqiang

2016-10-05

It is known that fluorination on π-conjugated donor-acceptor (D-A) polymers can significantly affect the optoelectronic properties and fluorination on A moiety has been well established for design of efficient photovoltaic materials. For example, polymers based on 4,7-dithienyl-5,6-difluorobenzothiadiazole (DTffBT) have been intensively investigated and exhibited excellent performance, but the corresponding DTBT-based polymers without fluorine often display an unfavorable efficiency. With the purpose of improving photovoltaic efficiency of DTBT-based D-A polymers, we design three polymers PDTBT-TxfBT (x = 0, 1, 2) with fluorination on D moiety (TxfBT) and systematically investigate fluorination on the photophysical/electrochemical and photovoltaic properties. The results show that polymer solar cells (PSCs) based on PDTBT-TBT exhibit moderate power conversion efficiency (PCE) of 5.84%. However, the bis-fluorination on TffBT moiety (PDTBT-TffBT) can greatly enhance the molecular planarity and intermolecular interaction, improve the charge transport and heterojunction morphology, and further suppress the charge recombination losses. PSCs based on PDTBT-TffBT demonstrate obviously improved photovoltaic efficiency with the best PCE up to 7.53% without any processing additives, which ranks among the top DTBT-based PSCs. However, it should be noted that unsymmetrical fluorination on TfBT moiety (PDTBT-TfBT) impairs the regularity of polymer backbone and intermolecular interaction, increases the recombination losses, and seriously reduces the short-circuit current density and efficiency (5.44%). The results exhibit that fluorination on D moiety is a helpful strategy for design high-performance photovoltaic materials and the regularity of fluorination is crucial to improving efficiencies.

Poly-amido-saccharides: Synthesis via Anionic Polymerization of a β-Lactam Sugar Monomer

PubMed Central

Dane, Eric L.; Grinstaff, Mark W.

2013-01-01

Chiral poly-amido-saccharides (PASs) with a defined molecular weight and narrow polydispersity are synthesized using an anionic ring-opening polymerization of a β-lactam sugar monomer. The PASs have a previously unreported main chain structure that is composed of pyranose rings linked through the 1- and 2-positions by an amide bond with α-stereochemistry. The monomer is synthesized in one-step from benzyl-protected d-glucal and polymerized using mild reaction conditions to give degrees of polymerization ranging from 25 to >150 in high yield. Computational modeling reveals how the monomer’s structure and steric bulk affect the thermodynamics and kinetics of polymerization. Protected and deprotected polymers and model compounds are characterized using a variety of methods (NMR, GPC, IR, DLS, etc.). Reductive debenzylation provides the deprotected, hydrophilic polymers in high yield. Based on circular dichroism, the deprotected polymers possess a regular secondary structure in aqueous solution, which agrees favorably with the prediction of a helical structure using molecular modeling. Furthermore, we provide evidence suggesting that the polymers bind the lectin concanavalin A at the same site as natural carbohydrates, showing the potential of these polymers to mimic natural polysaccharides. PASs offer the advantages associated with synthetic polymers, such as greater control over structure and derivitization, and less batch-to-batch variation. At the same time, they preserve many of the structural features of natural polysaccharides, such as a stereochemically regular, rigid pyranose backbone, that make natural carbohydrate polymers important materials both for their unique properties and useful applications. PMID:22937875

Laccase-mediated synthesis of lignin-core hyperbranched copolymers

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

Cannatelli, Mark D.; Ragauskas, Arthur J.

Lignin, one of the major chemical constituents of woody biomass, is the second most abundant biopolymer found in nature. The pulp and paper industry has long produced lignin on the scale of millions of tons annually as a by-product of the pulping process, and the dawn of cellulosic ethanol production has further contributed to this amount. Historically, lignin has been perceived as a waste material and burned as a fuel for the pulping process. But, recent research has been geared toward developing cost-effective technologies to convert lignin into valuable commodities. Attributing to the polyphenolic structure of lignin, enzymatic modification ofmore » its surface using laccases (benzenediol:oxygen oxidoreductases, EC 1.10.3.2) has demonstrated to be highly successful. The current study aims at developing lignin-core hyperbranched copolymers via the laccase-assisted copolymerization of kraft lignin with methylhydroquinone and a trithiol. Based on the physical properties of the resulting material, it is likely that crosslinking reactions have taken place during the drying process to produce a copolymeric network rather than discrete hyperbranched copolymers, with NMR data providing evidence of covalent bonding between monomers. A preliminary thermal analysis data reveals that the copolymeric material possesses a moderate glass transition temperature and exhibits good thermostability, thus may have potential application as a lignin-based thermoplastic. Scanning electron microscopy images confirm the smooth, glossy surface of the material and that it is densely packed. Our results are a sustainable, ecofriendly, economic method to create an exciting novel biomaterial from a renewable feedstock while further enhancing lignin valorization.« less

Laccase-mediated synthesis of lignin-core hyperbranched copolymers

DOE PAGES

Cannatelli, Mark D.; Ragauskas, Arthur J.

2017-06-06

Lignin, one of the major chemical constituents of woody biomass, is the second most abundant biopolymer found in nature. The pulp and paper industry has long produced lignin on the scale of millions of tons annually as a by-product of the pulping process, and the dawn of cellulosic ethanol production has further contributed to this amount. Historically, lignin has been perceived as a waste material and burned as a fuel for the pulping process. But, recent research has been geared toward developing cost-effective technologies to convert lignin into valuable commodities. Attributing to the polyphenolic structure of lignin, enzymatic modification ofmore » its surface using laccases (benzenediol:oxygen oxidoreductases, EC 1.10.3.2) has demonstrated to be highly successful. The current study aims at developing lignin-core hyperbranched copolymers via the laccase-assisted copolymerization of kraft lignin with methylhydroquinone and a trithiol. Based on the physical properties of the resulting material, it is likely that crosslinking reactions have taken place during the drying process to produce a copolymeric network rather than discrete hyperbranched copolymers, with NMR data providing evidence of covalent bonding between monomers. A preliminary thermal analysis data reveals that the copolymeric material possesses a moderate glass transition temperature and exhibits good thermostability, thus may have potential application as a lignin-based thermoplastic. Scanning electron microscopy images confirm the smooth, glossy surface of the material and that it is densely packed. Our results are a sustainable, ecofriendly, economic method to create an exciting novel biomaterial from a renewable feedstock while further enhancing lignin valorization.« less

Hyperbranched polyglycerol/graphene oxide nanocomposite reinforced hollow fiber solid/liquid phase microextraction for measurement of ibuprofen and naproxen in hair and waste water samples.

PubMed

Rezaeifar, Zohreh; Es'haghi, Zarrin; Rounaghi, Gholam Hossein; Chamsaz, Mahmoud

2016-09-01

A new design of hyperbranched polyglycerol/graphene oxide nanocomposite reinforced hollow fiber solid/liquid phase microextraction (HBP/GO -HF-SLPME) coupled with high performance liquid chromatography used for extraction and determination of ibuprofen and naproxen in hair and waste water samples. The graphene oxide first synthesized from graphite powders by using modified Hummers approach. The surface of graphene oxide was modified using hyperbranched polyglycerol, through direct polycondensation with thionyl chloride. The ready nanocomposite later wetted by a few microliter of an organic solvent (1-octanol), and then applied to extract the target analytes in direct immersion sampling mode.After the extraction process, the analytes were desorbed with methanol, and then detected via high performance liquid chromatography (HPLC). The experimental setup is very simple and highly affordable. The main factors influencing extraction such as; feed pH, extraction time, aqueous feed volume, agitation speed, the amount of functionalized graphene oxide and the desorption conditions have been examined in detail. Under the optimized experimental conditions, linearity was observed in the range of 5-30,000ngmL(-1) for ibuprofen and 2-10,000ngmL(-1) for naproxen with correlation coefficients of 0.9968 and 0.9925, respectively. The limits of detection were 2.95ngmL(-1) for ibuprofen and 1.51ngmL(-1) for naproxen. The relative standard deviations (RSDs) were found to be less than 5% (n=5). Copyright © 2016 Elsevier B.V. All rights reserved.

Label-Free Sensitive Detection of DNA Methyltransferase by Target-Induced Hyperbranched Amplification with Zero Background Signal.

PubMed

Zhang, Yan; Wang, Xin-Yan; Zhang, Qianyi; Zhang, Chun-Yang

2017-11-21

DNA methyltransferases (MTases) may specifically recognize the short palindromic sequences and transfer a methyl group from S-adenosyl-l-methionine to target cytosine/adenine. The aberrant DNA methylation is linked to the abnormal DNA MTase activity, and some DNA MTases have become promising targets of anticancer/antimicrobial drugs. However, the reported DNA MTase assays often involve laborious operation, expensive instruments, and radio-labeled substrates. Here, we develop a simple and label-free fluorescent method to sensitively detect DNA adenine methyltransferase (Dam) on the basis of terminal deoxynucleotidyl transferase (TdT)-activated Endonuclease IV (Endo IV)-assisted hyperbranched amplification. We design a hairpin probe with a palindromic sequence in the stem as the substrate and a NH 2 -modified 3' end for the prevention of nonspecific amplification. The substrate may be methylated by Dam and subsequently cleaved by DpnI, producing three single-stranded DNAs, two of which with 3'-OH termini may be amplified by hyperbranched amplification to generate a distinct fluorescence signal. Because high exactitude of TdT enables the amplification only in the presence of free 3'-OH termini and Endo IV only hydrolyzes the intact apurinic/apyrimidinic sites in double-stranded DNAs, zero background signal can be achieved. This method exhibits excellent selectivity and high sensitivity with a limit of detection of 0.003 U/mL for pure Dam and 9.61 × 10 -6 mg/mL for Dam in E. coli cells. Moreover, it can be used to screen the Dam inhibitors, holding great potentials in disease diagnosis and drug development.

Laccase-mediated synthesis of lignin-core hyperbranched copolymers.

PubMed

Cannatelli, Mark D; Ragauskas, Arthur J

2017-08-01

Lignin, one of the major chemical constituents of woody biomass, is the second most abundant biopolymer found in nature. The pulp and paper industry has long produced lignin on the scale of millions of tons annually as a by-product of the pulping process, and the dawn of cellulosic ethanol production has further contributed to this amount. Historically, lignin has been perceived as a waste material and burned as a fuel for the pulping process. However, recent research has been geared toward developing cost-effective technologies to convert lignin into valuable commodities. Attributing to the polyphenolic structure of lignin, enzymatic modification of its surface using laccases (benzenediol:oxygen oxidoreductases, EC 1.10.3.2) has demonstrated to be highly successful. The current study aims at developing lignin-core hyperbranched copolymers via the laccase-assisted copolymerization of kraft lignin with methylhydroquinone and a trithiol. Based on the physical properties of the resulting material, it is likely that crosslinking reactions have taken place during the drying process to produce a copolymeric network rather than discrete hyperbranched copolymers, with NMR data providing evidence of covalent bonding between monomers. Preliminary thermal analysis data reveals that the copolymeric material possesses a moderate glass transition temperature and exhibits good thermostability, thus may have potential application as a lignin-based thermoplastic. Scanning electron microscopy images confirm the smooth, glossy surface of the material and that it is densely packed. The presented results are a sustainable, ecofriendly, economic method to create an exciting novel biomaterial from a renewable feedstock while further enhancing lignin valorization.

Efficient CsF interlayer for high and low bandgap polymer solar cell

NASA Astrophysics Data System (ADS)

Mitul, Abu Farzan; Sarker, Jith; Adhikari, Nirmal; Mohammad, Lal; Wang, Qi; Khatiwada, Devendra; Qiao, Qiquan

2018-02-01

Low bandgap polymer solar cells have a great deal of importance in flexible photovoltaic market to absorb sun light more efficiently. Efficient wide bandgap solar cells are always available in nature to absorb visible photons. The development and incorporation of infrared photovoltaics (IR PV) with wide bandgap solar cells can improve overall solar device performance. Here, we have developed an efficient low bandgap polymer solar cell with CsF as interfacial layer in regular structure. Polymer solar cell devices with CsF shows enhanced performance than Ca as interfacial layer. The power conversion efficiency of 4.5% has been obtained for PDPP3T based polymer solar cell with CsF as interlayer. Finally, an optimal thickness with CsF as interfacial layer has been found to improve the efficiency in low bandgap polymer solar cells.

Ultrastructure Processing of Ordered Polymers

DTIC Science & Technology

1990-01-18

from regenerated cellulose , then from synthetic polymer consisting of chemical raw materials derived from oils and coal. Since then, some scientists have...ordered crystal- line material, crystallite, throughout the fiber, which is composed of microfibrils and fibrils. The small crystallites are regularly...these flat ribbons appears to consist of smaller " microfibrils " of lateral dimension varying from 50-80 A, as described before(Figs. 15 and 16). These

Study of the Molecular Dynamics of Multiarm Star Polymers with a Poly(ethyleneimine) Core and Poly(lactide) Multiarms

PubMed Central

Román, Frida; Colomer, Pere; Calventus, Yolanda; Hutchinson, John M.

2017-01-01

Multiarm star polymers, denoted PEIx-PLAy and containing a hyperbranched poly(ethyleneimine) (PEI) core of different molecular weights x and poly(lactide) (PLA) arms with y ratio of lactide repeat units to N links were used in this work. Samples were preconditioned to remove the moisture content and then characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). The glass transition temperature, Tg, is between 48 and 50 °C for all the PEIx-PLAy samples. The dielectric curves show four dipolar relaxations: γ, β, α, and α′ in order of increasing temperature. The temperatures at which these relaxations appear, together with their dependence on the frequency, allows relaxation maps to be drawn, from which the activation energies of the sub-Tg γ- and β-relaxations and the Vogel–Fulcher–Tammann parameters of the α-relaxation glass transition are obtained. The dependence of the characteristic features of these relaxations on the molecular weight of the PEI core and on the ratio of lactide repeat units to N links permits the assignation of molecular motions to each relaxation. The γ-relaxation is associated with local motions of the –OH groups of the poly(lactide) chains, the β-relaxation with motions of the main chain of poly(lactide), the α-relaxation with global motions of the complete assembly of PEI core and PLA arms, and the α′-relaxation is related to the normal mode relaxation due to fluctuations of the end-to-end vector in the PLA arms, without excluding the possibility that it could be a Maxwell–Wagner–Sillars type ionic peak because the material may have nano-regions of different conductivity. PMID:28772486

Study of the Molecular Dynamics of Multiarm Star Polymers with a Poly(ethyleneimine) Core and Poly(lactide) Multiarms.

PubMed

Román, Frida; Colomer, Pere; Calventus, Yolanda; Hutchinson, John M

2017-02-04

Multiarm star polymers, denoted PEI x -PLA y and containing a hyperbranched poly(ethyleneimine) (PEI) core of different molecular weights x and poly(lactide) (PLA) arms with y ratio of lactide repeat units to N links were used in this work. Samples were preconditioned to remove the moisture content and then characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). The glass transition temperature, T g , is between 48 and 50 °C for all the PEI x -PLA y samples. The dielectric curves show four dipolar relaxations: γ, β, α, and α' in order of increasing temperature. The temperatures at which these relaxations appear, together with their dependence on the frequency, allows relaxation maps to be drawn, from which the activation energies of the sub- T g γ- and β-relaxations and the Vogel-Fulcher-Tammann parameters of the α-relaxation glass transition are obtained. The dependence of the characteristic features of these relaxations on the molecular weight of the PEI core and on the ratio of lactide repeat units to N links permits the assignation of molecular motions to each relaxation. The γ-relaxation is associated with local motions of the -OH groups of the poly(lactide) chains, the β-relaxation with motions of the main chain of poly(lactide), the α-relaxation with global motions of the complete assembly of PEI core and PLA arms, and the α'-relaxation is related to the normal mode relaxation due to fluctuations of the end-to-end vector in the PLA arms, without excluding the possibility that it could be a Maxwell-Wagner-Sillars type ionic peak because the material may have nano-regions of different conductivity.

Toughness augmentation by fibrillation and yielding in nanostructured blends with recycled polyurethane as a modifier

NASA Astrophysics Data System (ADS)

Reghunadhan, Arunima; Datta, Janusz; Kalarikkal, Nandakumar; Haponiuk, Jozef T.; Thomas, Sabu

2018-06-01

In the present paper, we have carefully investigated the morphology and fracture mechanism of the recycled polyurethane (RPU)/epoxy blend system. The second phase (RPU) added to the epoxy resin has a positive effect on the overall mechanical properties. Interestingly, the recycled polymer has a remarkable effect on the fracture toughness of epoxy resin. The mechanism behind the fracture toughness improvement up on the addition of RPU was found to be very similar to that of the incorporation of hyperbranched polymers in epoxy resin. Brittle to ductile fracture was clear in the case of higher loadings such as 20 and 40 phr of RPU in the epoxy resin. The mechanism behind improvement of fracture toughness was found to fibrillation of the RPU phase which was evidenced by the fracture morphology. In fact the force applied to the epoxy matrix was effectively transferred to the added RPU phase due to its strong interaction with the epoxy phase. This effective transfer of force to the RPU phase protects the epoxy matrix without catastrophic failure and we observed 44% increase in G1C values at an addition of 40 phr RPU. This results in the extensive fibrillation of RPU which causes the generation of new surfaces. Thus the impact energy has been fully utilized by the RPU phase. The mechanism is termed as simultaneous reinforcing and toughening and normally reported as a result of cavitations and yielding. SEM, HRTEM and AFM analyses clearly demonstrated the fibrillated morphology of the fracture surface and the formation of nanostructures. This report is first of its kind in the case of both epoxy modification and the elastomer toughening.

Tumor-targeted pH/redox dual-sensitive unimolecular nanoparticles for efficient siRNA delivery.

PubMed

Chen, Guojun; Wang, Yuyuan; Xie, Ruosen; Gong, Shaoqin

2017-08-10

A unique pH/redox dual-sensitive cationic unimolecular nanoparticle (NP) enabling excellent endosomal/lysosomal escape and efficient siRNA decomplexation inside the target cells was developed for tumor-targeted delivery of siRNA. siRNA was complexed into the cationic core of the unimolecular NP through electrostatic interactions. The cationic core used for complexing siRNA contained reducible disulfide bonds that underwent intracellular reduction owing to the presence of high concentrations of reduced glutathione (GSH) inside the cells, thereby facilitating the decomplexation of siRNA from the unimolecular NPs. The cationic polymers were conjugated onto the hyperbranched core (H40) via a pH-sensitive bond, which further facilitated the decomplexation of siRNA from the NPs. In vitro studies on the siRNA release behaviors showed that dual stimuli (pH=5.3, 10mM GSH) induced the quickest release of siRNA from the NPs. In addition, the imidazole groups attached to the cationic polymer segments enhanced the endosomal/lysosomal escape of NPs via the proton sponge effect. Intracellular tracking studies revealed that siRNA delivered by unimolecular NPs was efficiently released to the cytosol. Moreover, the GE11 peptide, an anti-EGFR peptide, enhanced the cellular uptake of NPs in MDA-MB-468, an EFGR-overexpressing triple negative breast cancer (TNBC) cell line. The GE11-conjugated, GFP-siRNA-complexed NPs exhibited excellent GFP gene silencing efficiency in GFP-MDA-MB-468 TNBC cells without any significant cytotoxicity. Therefore, these studies suggest that this smart unimolecular NP could be a promising nanoplatform for targeted siRNA delivery to EFGR-overexpressing cancer cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Hyperbranched polyglycerol is an efficacious and biocompatible novel osmotic agent in a rodent model of peritoneal dialysis.

PubMed

Mendelson, Asher A; Guan, Qiunong; Chafeeva, Irina; da Roza, Gerald A; Kizhakkedathu, Jayachandran N; Du, Caigan

2013-01-01

To enhance the effectiveness of peritoneal dialysis (PD), new biocompatible PD solutions may be needed. The present study was designed to test the efficacy and biocompatibility of hyperbranched polyglycerol (HPG)-a nontoxic, nonimmunogenic water-soluble polyether polymer-in PD. Adult Sprague-Dawley rats were instilled with 30 mL HPG solution (molecular weight 3 kDa; 2.5% - 15%) or control glucose PD solution (2.5% Dianeal: Baxter Healthcare Corporation, Deerfield, IL, USA), and intraperitoneal fluid was recovered after 4 hours. Peritoneal injury and cellular infiltration were determined by histologic and flow cytometric analysis. Human peritoneal mesothelial cells were assessed for viability in vitro after 3 hours of PD fluid exposure. The 15% HPG solution achieved a 4-hour dose-related ultrafiltration up to 43.33 ± 5.24 mL and a dose-related urea clearance up to 39.17 ± 5.21 mL, results that were superior to those with control PD solution (p < 0.05). The dialysate-to-plasma (D/P) ratios of urea with 7.5% and 15% HPG solution were not statistically different from those with control PD solution. Compared with fluid recovered from the control group, fluid recovered from the HPG group contained proportionally fewer neutrophils (3.63% ± 0.87% vs 9.31% ± 2.89%, p < 0.0001). Detachment of mesothelial cells positive for human bone marrow endothelial protein 1 did not increase in the HPG group compared with the stain control (p = 0.1832), but it was elevated in the control PD solution group (1.62% ± 0.68% vs 0.41% ± 0.31%, p = 0.0031). Peritoneal biopsies from animals in the HPG PD group, compared with those from control PD animals, demonstrated less neutrophilic infiltration and reduced thickness. Human peritoneal mesothelial cell survival after HPG exposure was superior in vitro (p < 0.0001, 7.5% HPG vs control; p < 0.01, 15% HPG vs control). Exposure to glucose PD solution induced cytoplasmic vacuolation and caspase 3-independent necrotic cell death that was not seen with HPG solution. Our novel HPG PD solution demonstrated effective ultrafiltration and waste removal with reduced peritoneal injury in a rodent model of PD.

pH-responsive unimolecular micelles self-assembled from amphiphilic hyperbranched block copolymer for efficient intracellular release of poorly water-soluble anticancer drugs.

PubMed

Tabatabaei Rezaei, Seyed Jamal; Abandansari, Hamid Sadeghi; Nabid, Mohammad Reza; Niknejad, Hassan

2014-07-01

Novel unimolecular micelles from amphiphilic hyperbranched block copolymer H40-poly(ε-caprolactone)-b-poly(acrylic acid)-b'-methoxy poly(ethylene glycol)/poly(ethylene glycol)-folate (i.e., H40-PCL-b-PAA-b'-MPEG/PEG-FA (HCAE-FA)) as new multifunctional nanocarriers to pH-induced accelerated release and tumor-targeted delivery of poorly water-soluble anticancer drugs were developed. The hydrophobic core of the unimolecular micelle was hyperbranched polyester (H40-poly(ε-caprolactone) (H40-PCL)). The inner hydrophilic layer was composed of PAA segments, while the outer hydrophilic shell was composed of PEG segments. This copolymer formed unimolecular micelles in the aqueous solution with a mean particle size of 33 nm, as determined by dynamic light scattering (DLS) and transmission electron microscopy (TEM). To study the feasibility of micelles as a potential nanocarrier for targeted drug delivery, we encapsulated a hydrophobic anticancer drug, paclitaxel (PTX), in the hydrophobic core, and the loading content was determined by UV-vis analysis to be 10.35 wt.%. In vitro release studies demonstrated that the drug-loaded delivery system is relatively stable at physiologic conditions but susceptible to acidic environments which would trigger the release of encapsulated drugs. Flow cytometry and fluorescent microscope studies revealed that the cellular binding of the FA-conjugated micelles against HeLa cells was higher than that of the neat micelles (without FA). The in vitro cytotoxicity studies showed that the PTX transported by these micelles was higher than that by the commercial PTX formulation Tarvexol®. All of these results show that these unique unimolecular micelles may offer a very promising approach for targeted cancer therapy. Copyright © 2014 Elsevier Inc. All rights reserved.

Polymer-stabilized liquid crystalline topological defect network for micro-pixelated optical devices

NASA Astrophysics Data System (ADS)

Araoka, Fumito; Le, Khoa V.; Fujii, Shuji; Orihara, Hiroshi; Sasaki, Yuji

2018-02-01

Spatially and temporally controlled topological defects in nematic liquid crystals (NLCs) are promising for its potential in optical applications. Utilization of self-organization is a key to fabricate complex micro- and nano-structures which are often difficult to obtain by conventional lithographic tools. Using photo-polymerization technique, here we show a polymer-stabilized NLC having a micro-pixelated structure of regularly ordered umbilical defects which are induced by an electric field. Due to the formation of polymer network, the self-organized pattern is kept stable without deterioration. Moreover, the polymer network allows to template other LCs whose optical properties can be tuned with external stimuli such as temperature and electric fields.

Thermal properties of poly(urethane-ester-siloxane)s based on hyperbranched polyester

NASA Astrophysics Data System (ADS)

Pergal, M. V.; Džunuzović, J. V.; Kićanović, M.; Vodnik, V.; Pergal, M. M.; Jovanović, S.

2011-12-01

Novel polyurethanes (PUs) were synthesized using hydroxy-terminated hyperbranched polyester (BH-20) and 4,4'-methylenediphenyl diisocyanate (MDI) as hard segments and hydroxy-terminated ethylene oxide-poly(dimethylsiloxane)-ethylene oxide triblock copolymer (PDMS-EO) as soft segment, with soft segment content ranging from 30 to 60 wt %. The PUs were synthesized by two-step solution polymerization method. The influence of the soft segment content on the structure, swelling behavior and thermal properties of PUs was investigated. According to the results obtained by swelling measurements, the increase of the hard segment content resulted in the increase of the crosslinking density of synthesized samples. DSC results showed that the glass transition temperatures increase from 36 to 65°C with increasing hard segment content. It was demonstrated using thermogravimetric analysis (TGA) that thermal stability of investigated PUs increases with increase of the soft PDMS-EO content. This was concluded from the temperatures corresponding to the 10 wt % loss, which represents the beginning of thermal degradation of samples.

Reduction-responsive multifunctional hyperbranched polyaminoglycosides with excellent antibacterial activity, biocompatibility and gene transfection capability.

PubMed

Huang, Yajun; Ding, Xiaokang; Qi, Yu; Yu, Bingran; Xu, Fu-Jian

2016-11-01

There is an increasing demand in developing of multifunctional materials with good antibacterial activity, biocompatibility and drug/gene delivery capability for next-generation biomedical applications. To achieve this purpose, in this work series of hydroxyl-rich hyperbranched polyaminoglycosides of gentamicin, tobramycin, and neomycin (HP and SS-HP with redox-responsive disulfide bonds) were readily synthesized via ring-opening reactions in a one-pot manner. Both HP and SS-HP exhibit high antibacterial activity toward Escherichia coli and Staphylococcus aureus. Meanwhile, the hemolysis assay of the above materials shows good biocompatibility. Moreover, SS-HPs show excellent gene transfection efficiency in vitro due to the breakdown of reduction-responsive disulfide bonds. For an in vivo anti-tumor assay, the SS-HP/p53 complexes exhibit potent inhibition capability to the growth of tumors. This study provides a promising approach for the design of next-generation multifunctional biomedical materials. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fabricating pH-stable and swellable very thin hyperbranched poly(ethylene imine)-oligosaccharide films fabricated without precoating: first view on protein adsorption.

PubMed

Warenda, Monika; Richter, Anne; Schmidt, Diana; Janke, Andreas; Müller, Martin; Simon, Frank; Zimmermann, Ralf; Eichhorn, Klaus-Jochen; Voit, Brigitte; Appelhans, Dietmar

2012-09-14

For using successful (ultra)thin dendritic macromolecule films in (bio)sensing and microfluidic devices and for obtaining reproducible film properties, alteration effects arising from precoatings have to be avoided. Here, oligosaccharide-modified hyperbranched poly(ethylene imine)s (PEI-OS) were used to fabricate very thin PEI-OS films (15-20 nm in dry state), cross-linked with citric acid under condensation, and vacuum condition. However, no reactive precoating is necessary to obtain stable films, which allows very simple film preparation and avoids alteration of the PEIS-OS film properties arising from precoating. Several methods [(in situ) ellipsometry, AFM, XPS, (in situ) ATR-IR, streaming potential measurements] were applied to characterize homogeneity, surface morphology, and stability of these PEI-OS films between pH 2 and pH 10, but also the low protein adsorption behavior. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perfluorocyclobutane containing aromatic ether polymers as planarization materials for alternative magnetic media substrates

NASA Astrophysics Data System (ADS)

Perettie, Donald J.; Judy, Jack; Chen, Qixu; Keirstead, Rick

1994-11-01

Perfluorocyclobutane aromatic ether polymers (PFCB) are being researched as planarization materials for alternative magnetic media substrates allowing smoother surfaces for lower head flying recording. The results of current work reported herein have shown that PFCB can be used to affect surfaces on canasite with R(sub A)'s less than 2 nm. In addition, magnetic media can be produced of a quality comparative to that obtained on standard NiP-coated Al as well as that produced on regular canasite with equivalent coercivities at about 1500-1600 Oe and squarenesses of 0.8 or better. In addition to the above magnetic properties the recording performance was excellent with signal-to-noise ratios of planarized media 3.5 dB higher than that on regular canasite.

Facile Synthesis of Highly Aligned Multiwalled Carbon Nanotubes from Polymer Precursors

DOE PAGES

Han, Catherine Y.; Xiao, Zhi-Li; Wang, H. Hau; ...

2009-01-01

We report a facile one-step approach which involves no flammable gas, no catalyst, and no in situ polymerization for the preparation of well-aligned carbon nanotube array. A polymer precursor is placed on top of an anodized aluminum oxide (AAO) membrane containing regular nanopore arrays, and slow heating under Ar flow allows the molten polymer to wet the template through adhesive force. The polymer spread into the nanopores of the template to form polymer nanotubes. Upon carbonization the resulting multi-walled carbon nanotubes duplicate the nanopores morphology precisely. The process is demonstrated for 230, 50, and 20 nm pore membranes. The synthesized carbonmore » nanotubes are characterized with scanning/transmission electron microscopies, Raman spectroscopy, and resistive measurements. Convenient functionalization of the nanotubes with this method is demonstrated through premixing CoPt nanoparticles in the polymer precursors.« less

Polymer-induced compression of biological hydrogels

NASA Astrophysics Data System (ADS)

Datta, Sujit; Preska Steinberg, Asher; Ismagilov, Rustem

Hydrogels - such as mucus, blood clots, and the extracellular matrix - provide critical functions in biological systems. However, little is known about how their structure is influenced by many of the polymeric materials they come into contact with regularly. Here, we focus on one critically important biological hydrogel: colonic mucus. While several biological processes are thought to potentially regulate the mucus hydrogel structure, the polymeric composition of the gut environment has been ignored. We use Flory-Huggins solution theory to characterize polymer-mucus interactions. We find that gut polymers, including those small enough to penetrate the mucus hydrogel, can in fact alter mucus structure, changing its equilibrium degree of swelling and forcing it to compress. The extent of compression increases with increasing polymer concentration and size. We use experiments on mice to verify these predictions with common dietary and therapeutic gut polymers. Our results provide a foundation for investigating similar, previously overlooked, polymer-induced effects in other biological hydrogels.

Recent Advances in Wide-Bandgap Photovoltaic Polymers.

PubMed

Cai, Yunhao; Huo, Lijun; Sun, Yanming

2017-06-01

The past decade has witnessed significant advances in the field of organic solar cells (OSCs). Ongoing improvements in the power conversion efficiency of OSCs have been achieved, which were mainly attributed to the design and synthesis of novel conjugated polymers with different architectures and functional moieties. Among various conjugated polymers, the development of wide-bandgap (WBG) polymers has received less attention than that of low-bandgap and medium-bandgap polymers. Here, we briefly summarize recent advances in WBG polymers and their applications in organic photovoltaic (PV) devices, such as tandem, ternary, and non-fullerene solar cells. Addtionally, we also dissuss the application of high open-circuit voltage tandem solar cells in PV-driven electrochemical water dissociation. We mainly focus on the molecular design strategies, the structure-property correlations, and the photovoltaic performance of these WBG polymers. Finally, we extract empirical regularities and provide invigorating perspectives on the future development of WBG photovoltaic materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic fluorescent dye-based nanomaterials: Advances in the rational design for imaging and sensing applications.

PubMed

Svechkarev, Denis; Mohs, Aaron M

2018-02-25

Self-assembled fluorescent nanomaterials based on small-molecule organic dyes are gaining increasing popularity in imaging and sensing applications over the past decade. This is primarily due to their ability to combine spectral property tunability and biocompatibility of small molecule organic fluorophores with brightness, chemical, and colloidal stability of inorganic materials. Such a unique combination of features comes with rich versatility of dye-based nanomaterials: from aggregates of small molecules to sophisticated core-shell nanoarchitectures involving hyperbranched polymers. Along with the ongoing discovery of new materials and better ways of their synthesis, it is very important to continue systematic studies of fundamental factors that regulate the key properties of fluorescent nanomaterials: their size, polydispersity, colloidal stability, chemical stability, absorption and emission maxima, biocompatibility, and interactions with biological interfaces. In this review, we focus on the systematic description of various types of organic fluorescent nanomaterials, approaches to their synthesis, and ways to optimize and control their characteristics. The discussion is built on examples from reports on recent advances in design and applications of such materials. Conclusions made from this analysis allow a perspective on future development of fluorescent nanomaterials design for biomedical and related applications. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

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.

Self-Assembly of Diblock Molecular Polymer Brushes in the Spherical Confinement of Nanoemulsion Droplets.

PubMed

Steinhaus, Andrea; Pelras, Théophile; Chakroun, Ramzi; Gröschel, André H; Müllner, Markus

2018-05-02

Understanding the self-assembly behavior of polymers of various topologies is key to a reliable design of functional polymer materials. Self-assembly under confinement conditions emerges as a versatile avenue to design polymer particles with complex internal morphologies while simultaneously facilitating scale-up. However, only linear block copolymers have been studied to date, despite the increasing control over macromolecule composition and architecture available. This study extends the investigation of polymer self-assembly in confinement from regular diblock copolymers to diblock molecular polymer brushes (MPBs). Block-type MPBs with polystyrene (PS) and polylactide (PLA) compartments of different sizes are incorporated into surfactant-stabilized oil-in-water (chloroform/water) emulsions. The increasing confinement in the nanoemulsion droplets during solvent evaporation directs the MPBs to form solid nano/microparticles. Microscopy studies reveal an intricate internal particle structure, including interpenetrating networks and axially stacked lamellae of PS and PLA, depending on the PS/PLA ratio of the brushes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Light-responsive micelles of spiropyran initiated hyperbranched polyglycerol for smart drug delivery.

PubMed

Son, Suhyun; Shin, Eeseul; Kim, Byeong-Su

2014-02-10

Light-responsive polymeric micelles have emerged as site-specific and time-controlled systems for advanced drug delivery. Spiropyran (SP), a well-known photochromic molecule, was used to initiate the ring-opening multibranching polymerization of glycidol to afford a series of hyperbranched polyglycerols (SP-hb-PG). The micelle assembly and disassembly were induced by an external light source owing to the reversible photoisomerization of hydrophobic SP to hydrophilic merocyanine (MC). Transmission electron microscopy, atomic force microscopy, UV/vis spectroscopy, and dynamic light scattering demonstrated the successful assembly and disassembly of SP-hb-PG micelles. In addition, the critical micelle concentration (CMC) was determined through the fluorescence analysis of pyrene to confirm the amphiphilicity of respective SP-hb-PGn (n = 15, 29, and 36) micelles, with CMC values ranging from 13 to 20 mg/L, which is correlated to the length of the polar polyglycerol backbone. Moreover, the superior biocompatibility of the prepared SP-hb-PG was evaluated using WI-38 cells and HeLa cells, suggesting the prospective applicability of the micelles in smart drug delivery systems.

Synthesis of Cu/SiO2 Core-Shell Particles Using Hyperbranched Polyester as Template and Dispersant

NASA Astrophysics Data System (ADS)

Han, Wensong

2017-07-01

Third-generation hyperbranched polyester (HBPE3) was synthesized by stepwise polymerization with N, N-diethylol-3-amine methylpropionate as AB2 monomer and pentaerythritol as core molecule. Then, Cu particles were prepared by reduction of copper nitrate with ascorbic acid in aqueous solution using HBPE3 as template. Finally, Cu/SiO2 particles were prepared by coating silica on the surface of Cu particles. The structure and morphology of the samples were characterized by Fourier-transform infrared (FT-IR) spectrometry, x-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results confirmed the formation of the silica coating on the surface of Cu and that the Cu/SiO2 particles had spherical shape with particle size in the range of 0.8 μm to 2 μm. Compared with pure Cu, the synthesized Cu/SiO2 core-shell particles exhibited better oxidation resistance at high temperature. Moreover, the oxidation resistance of the Cu/SiO2 particles increased significantly with increasing tetraethyl orthosilicate (TEOS) concentration.

Waterborne carboxyl-terminated hyperbranched oligomer polyester ligand: Synthesis, characterization and chelation with chromium(III)

NASA Astrophysics Data System (ADS)

Yao, Qi; Li, Chenying; Huang, Henghui; Chen, Hualin; Liu, Bailing

2017-09-01

A series of carboxyl-terminated hyperbranched oligomer polyester (HBP) with different degree of branching (DB) and number average molar mass (Mbarn) have been prepared. The molecular structure, degree of branching, molecular mass and its distribution of HBP were investigated by FTIR, 1H NMR, and GPC, respectively. And the coordination number, stability constant and degree of dissociation (α) between HBP and chromium(Ⅲ) were measured via continuous variation method (Job's plot). Experimental results show that the coordination capability between HBP and chromium(Ⅲ) affected by both DB and molecular mass, and the latter plays a decisive role. Moreover HBP outperforms low molecular weight of organic acids (citric acid, acetic acid) and linear polyacrylic acid with similar molecular mass. The coordination number and stability constants of HBP-3 (Mbarn = 1713 Da, Mbarw /Mbarn (PDI) = 1.11 and DB = 0.72) can reach 4 and 6.55e+008, which demonstrated it can be selected as a good ligand to coordination with chromium(Ⅲ). Therefore HBP can be used as chrome auxiliary in chrome tanning to improve the absorption of chromium.

Silver-embedded modified hyperbranched epoxy/clay nanocomposites as antibacterial materials.

PubMed

Roy, Buddhadeb; Bharali, Pranjal; Konwar, B K; Karak, Niranjan

2013-01-01

Silver-embedded modified hyperbranched epoxy/clay nanocomposites were prepared at different wt.% of octadecyl amine-modified montmorillonite at a constant silver concentration (1 wt.%). UV-visible, XRD and TEM studies confirmed the formation of silver nanoparticles. Compared to the system without silver and clay, the gloss from 70° to 94°, scratch hardness from 4 to 5.8 kg, impact strength from 60 to 90 cm, tensile strength from 8.5 to 15.5 MPa, adhesive strength from 5 to 7.1 × 10(9)N/m, flexibility from >6 to <4mm, and thermostability from 230 to 260 °C increased for the modified system. Resistance to aqueous 10% HCl, 0.5% NaOH, 10% NaCl also increased. The nanocomposites showed antibacterial activity in well diffusion assays against Staphylococcus aureus (ATCC11632), Bacillus subtilis (ATCC11774), Escherichia coli (MTCC40), Pseudomonas aeruginosa (MTCC7814) and Klebsiella pneumoniae (ATCC10031). The results showed that these nanocomposites have potential to be used as antimicrobial materials. Copyright © 2012 Elsevier Ltd. All rights reserved.

Injectable hyperbranched poly(β-amino ester) hydrogels with on-demand degradation profiles to match wound healing processes.

PubMed

Xu, Qian; Guo, Linru; A, Sigen; Gao, Yongsheng; Zhou, Dezhong; Greiser, Udo; Creagh-Flynn, Jack; Zhang, Hong; Dong, Yixiao; Cutlar, Lara; Wang, Fagang; Liu, Wenguang; Wang, Wei; Wang, Wenxin

2018-02-28

Adjusting biomaterial degradation profiles to match tissue regeneration is a challenging issue. Herein, biodegradable hyperbranched poly(β-amino ester)s (HP-PBAEs) were designed and synthesized via "A2 + B4" Michael addition polymerization, and displayed fast gelation with thiolated hyaluronic acid (HA-SH) via a "click" thiol-ene reaction. HP-PBAE/HA-SH hydrogels showed tunable degradation profiles both in vitro and in vivo using diamines with different alkyl chain lengths and poly(ethylene glycol) diacrylates with varied PEG spacers. The hydrogels with optimized degradation profiles encapsulating ADSCs were used as injectable hydrogels to treat two different types of humanized excisional wounds - acute wounds with faster healing rates and diabetic wounds with slower healing and neo-tissue formation. The fast-degrading hydrogel showed accelerated wound closure in acute wounds, while the slow-degrading hydrogel showed better wound healing for diabetic wounds. The results demonstrate that the new HP-PBAE-based hydrogel in combination with ADSCs can be used as a well-controlled biodegradable skin substitute, which demonstrates a promising approach in the treatment of various types of skin wounds.

Can natural polymers assist in delivering insulin orally?

PubMed

Nur, Mokhamad; Vasiljevic, Todor

2017-10-01

Diabetes mellitus is one of the most grave and lethal non communicable diseases. Insulin is normally used to medicate diabetes. Due to bioavailability issues, the most regular route of administration is through injection, which may pose compliance problems to treatment. The oral administration thus appears as a suitable alternative, but with several important problems. Low stability of insulin in the gastrointestinal tract and low intestinal permeation are some of the issues. Encapsulation of insulin into polymer-based particles emerges as a plausible strategy. Different encapsulation approaches and polymers have been used in this regard. Polymers with different characteristics from natural or synthetic origin have been assessed to attain this goal, with natural polymers being preferable. Natural polymers studied so far include chitosan, alginate, carrageenan, starch, pectin, casein, tragacanth, dextran, carrageenan, gelatine and cyclodextrin. While some promising knowledge and results have been gained, a polymeric-based particle system to deliver insulin orally has not been introduced onto the market yet. In this review, effectiveness of different natural polymer materials developed so far along with fabrication techniques are evaluated. Copyright © 2017 Elsevier B.V. All rights reserved.

Nucleation, crystallization, and melting of atactic polystyrene

NASA Astrophysics Data System (ADS)

Chai, Yu; Forrest, James

Here we present the study of using low molecular weight atactic polystyrene (aPS) as the model system to understand the nucleation, crystallization, and meting behaviors of the stereo-regular polymer chains in aPS. The result is consistent with the theoretical calculation proposed by Semenov. In addition, both the crystallization and melting experiments indicate that all crystals are on or near the surface. Finally, the nucleation experiment below the glass transition temperature provides another piece of evidence of the enhanced surface dynamics in glassy polymers.

Efficient sampling of reversible cross-linking polymers: Self-assembly of single-chain polymeric nanoparticles

NASA Astrophysics Data System (ADS)

Oyarzún, Bernardo; Mognetti, Bortolo Matteo

2018-03-01

We present a new simulation technique to study systems of polymers functionalized by reactive sites that bind/unbind forming reversible linkages. Functionalized polymers feature self-assembly and responsive properties that are unmatched by the systems lacking selective interactions. The scales at which the functional properties of these materials emerge are difficult to model, especially in the reversible regime where such properties result from many binding/unbinding events. This difficulty is related to large entropic barriers associated with the formation of intra-molecular loops. In this work, we present a simulation scheme that sidesteps configurational costs by dedicated Monte Carlo moves capable of binding/unbinding reactive sites in a single step. Cross-linking reactions are implemented by trial moves that reconstruct chain sections attempting, at the same time, a dimerization reaction between pairs of reactive sites. The model is parametrized by the reaction equilibrium constant of the reactive species free in solution. This quantity can be obtained by means of experiments or atomistic/quantum simulations. We use the proposed methodology to study the self-assembly of single-chain polymeric nanoparticles, starting from flexible precursors carrying regularly or randomly distributed reactive sites. We focus on understanding differences in the morphology of chain nanoparticles when linkages are reversible as compared to the well-studied case of irreversible reactions. Intriguingly, we find that the size of regularly functionalized chains, in good solvent conditions, is non-monotonous as a function of the degree of functionalization. We clarify how this result follows from excluded volume interactions and is peculiar of reversible linkages and regular functionalizations.

Dual-Input AND Gate From Single-Channel Thin-Film FET

NASA Technical Reports Server (NTRS)

Miranda, F. A.; Pinto, N. J.; Perez, R.; Mueller, C. H.

2008-01-01

A regio-regular poly(3-hexylthiophene) (RRP3HT) thin-film transistor having a split-gate architecture has been fabricated on a doped silicon/silicon nitride substrate and characterized. RRP3HT is a semiconducting polymer that has a carrier mobility and on/off ratio when used in a field effect transistor (FET) configuration. This commercially available polymer is very soluble in common organic solvents and is easily processed to form uniform thin films. The most important polymer-based device fabricated and studied is the FET, since it forms the building block in logic circuits and switches for active matrix (light-emitting-diode) (LED) displays, smart cards, and radio frequency identification (RFID) cards.

In Situ Grafting of Hyperbranched Poly(Etherketone)s onto Multiwalled Carbon Nanotubes Via A3 + B2 Approach (Preprint)

DTIC Science & Technology

2007-04-01

MWNTs.20 These defects would provide sites for the electrophilic substitution reaction. In our previous work, FT-IR had been used to characterize the...various surface functionalities.22 In this study, MWNTs containing polar surface groups such as amino-, hydroxyl-, and fluorine groups displayed similar

Real-time monitoring of anticancer drug release with highly fluorescent star-conjugated copolymer as a drug carrier.

PubMed

Qiu, Feng; Wang, Dali; Zhu, Qi; Zhu, Lijuan; Tong, Gangsheng; Lu, Yunfeng; Yan, Deyue; Zhu, Xinyuan

2014-04-14

Chemotherapy is one of the major systemic treatments for cancer, in which the drug release kinetics is a key factor for drug delivery. In the present work, a versatile fluorescence-based real-time monitoring system for intracellular drug release has been developed. First, two kinds of star-conjugated copolymers with different connections (e.g., pH-responsive acylhydrazone and stable ether) between a hyperbranched conjugated polymer (HCP) core and many linear poly(ethylene glycol) (PEG) arms were synthesized. Owing to the amphiphilic three-dimensional architecture, the star-conjugated copolymers could self-assemble into multimicelle aggregates from unimolecular micelles with excellent emission performance in the aqueous medium. When doxorubicin (DOX) as a model drug was encapsulated into copolymer micelles, the emission of star-conjugated copolymer and DOX was quenched. In vitro biological studies revealed that fluorescent intensities of both star-conjugated copolymer and DOX were activated when the drug was released from copolymeric micelles, resulting in the enhanced cellular proliferation inhibition against cancer cells. Importantly, pH-responsive feature of the star-conjugated copolymer with acylhydrazone linkage exhibited accelerated DOX release at a mildly acidic environment, because of the fast breakage of acylhydrazone in endosome or lysosome of tumor cells. Such fluorescent star-conjugated copolymers may open up new perspectives to real-time study of drug release kinetics of polymeric drug delivery systems for cancer therapy.

Adsorption of modified dextrins on molybdenite: AFM imaging, contact angle, and flotation studies.

PubMed

Beaussart, Audrey; Parkinson, Luke; Mierczynska-Vasilev, Agnieszka; Beattie, David A

2012-02-15

The adsorption of three dextrins (a regular wheat dextrin, Dextrin TY, carboxymethyl (CM) Dextrin, and hydroxypropyl (HP) Dextrin) on molybdenite has been investigated using adsorption isotherms, tapping mode atomic force microscopy (TMAFM), contact angle measurements, and dynamic bubble-surface collisions. In addition, the effect of the polymers on the flotation recovery of molybdenite has been determined. The isotherms revealed the importance of molecular weight in determining the adsorbed amounts of the polymers on molybdenite at plateau coverage. TMAFM revealed the morphology of the three polymers, which consisted of randomly dispersed domains with a higher area fraction of surface coverage for the substituted dextrins. The contact angle of polymer-treated molybdenite indicated that polymer layer coverage and hydration influenced the mineral surface hydrophobicity. Bubble-surface collisions indicated that the polymers affected thin film rupture and dewetting rate differently, correlating with differences in the adsorbed layer morphology. Direct correlations were found between the surface coverage of the adsorbed layers, their impact on thin film rupture time, and their impact on flotation recovery, highlighting the paramount role of the polymer morphology in the bubble/particle attachment process and subsequent flotation. Copyright © 2011 Elsevier Inc. All rights reserved.

Directed Self-Assembly of Gradient Concentric Carbon Nanotube Rings

NASA Astrophysics Data System (ADS)

Hong, Suck Won; Jeong, Wonje; Ko, Hyunhyub; Tsukruk, Vladimir; Kessler, Michael; Lin, Zhiqun

2008-03-01

Hundreds of gradient concentric rings of linear conjugated polymer, (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4- phenylenevinylene], i.e., MEH-PPV) with remarkable regularity over large areas were produced by controlled, repetitive ``stick- slip'' motions of the contact line in a confined geometry consisting of a sphere on a flat substrate (i.e., sphere-on-flat geometry). Subsequently, MEH-PPV rings exploited as template to direct the formation of gradient concentric rings of multiwalled carbon nanotubes (MWNTs) with controlled density. This method is simple, cost effective, and robust, combining two consecutive self-assembly processes, namely, evaporation-induced self- assembly of polymers in a sphere-on-flat geometry, followed by subsequent directed self-assembly of MWNTs on the polymer- templated surfaces.

Polymers in the gut compress the colonic mucus hydrogel.

PubMed

Datta, Sujit S; Preska Steinberg, Asher; Ismagilov, Rustem F

2016-06-28

Colonic mucus is a key biological hydrogel that protects the gut from infection and physical damage and mediates host-microbe interactions and drug delivery. However, little is known about how its structure is influenced by materials it comes into contact with regularly. For example, the gut abounds in polymers such as dietary fibers or administered therapeutics, yet whether such polymers interact with the mucus hydrogel, and if so, how, remains unclear. Although several biological processes have been identified as potential regulators of mucus structure, the polymeric composition of the gut environment has been ignored. Here, we demonstrate that gut polymers do in fact regulate mucus hydrogel structure, and that polymer-mucus interactions can be described using a thermodynamic model based on Flory-Huggins solution theory. We found that both dietary and therapeutic polymers dramatically compressed murine colonic mucus ex vivo and in vivo. This behavior depended strongly on both polymer concentration and molecular weight, in agreement with the predictions of our thermodynamic model. Moreover, exposure to polymer-rich luminal fluid from germ-free mice strongly compressed the mucus hydrogel, whereas exposure to luminal fluid from specific-pathogen-free mice-whose microbiota degrade gut polymers-did not; this suggests that gut microbes modulate mucus structure by degrading polymers. These findings highlight the role of mucus as a responsive biomaterial, and reveal a mechanism of mucus restructuring that must be integrated into the design and interpretation of studies involving therapeutic polymers, dietary fibers, and fiber-degrading gut microbes.

Fabrication of magnetic water-soluble hyperbranched polyol functionalized graphene oxide for high-efficiency water remediation

PubMed Central

Hu, Lihua; Li, Yan; Zhang, Xuefei; Wang, Yaoguang; Cui, Limei; Wei, Qin; Ma, Hongmin; Yan, Liangguo; Du, Bin

2016-01-01

Magnetic water-soluble hyperbranched polyol functionalized graphene oxide nanocomposite (MWHPO-GO) was successfully prepared and applied to water remediation in this paper. MWHPO-GO was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), magnetization curve, zeta potential, scanning electron microscope (SEM) and transmission electron microscope (TEM) analyses. MWHPO-GO exhibited excellent adsorption performance for the removal of synthetic dyes (methylene blue (MB) and methyl violet (MV)) and heavy metal (Pb(II)). Moreover, MWHPO-GO could be simply recovered from water with magnetic separation. The pseudo-second order equation and the Langmuir model exhibited good correlation with the adsorption kinetic and isotherm data, respectively, for these three pollutants. The thermodynamic results (ΔG < 0, ΔH < 0, ΔS < 0) implied that the adsorption process of MB, MV and Pb(II) was feasible, exothermic and spontaneous in nature. A possible adsorption mechanism has been proposed where π-π stacking interactions, H-bonding interaction and electrostatic attraction dominated the adsorption of MB/MV and chelation and electrostatic attraction dominated the adsorption of Pb(II). In addition, the excellent reproducibility endowed MWHPO-GO with the potential for application in water remediation. PMID:27354318

Two-dimensional hyper-branched gold nanoparticles synthesized on a two-dimensional oil/water interface.

PubMed

Shin, Yonghee; Lee, Chiwon; Yang, Myung-Seok; Jeong, Sunil; Kim, Dongchul; Kang, Taewook

2014-08-26

Two-dimensional (2D) gold nanoparticles can possess novel physical and chemical properties, which will greatly expand the utility of gold nanoparticles in a wide variety of applications ranging from catalysis to biomedicine. However, colloidal synthesis of such particles generally requires sophisticated synthetic techniques to carefully guide anisotropic growth. Here we report that 2D hyper-branched gold nanoparticles in the lateral size range of about 50 ~ 120 nm can be synthesized selectively on a 2D immiscible oil/water interface in a few minutes at room temperature without structure-directing agents. An oleic acid/water interface can provide diffusion-controlled growth conditions, leading to the structural evolution of a smaller gold nucleus to 2D nanodendrimer and nanourchin at the interface. Simulations based on the phase field crystal model match well with experimental observations on the 2D branching of the nucleus, which occurs at the early stage of growth. Branching results in higher surface area and stronger near-field enhancement of 2D gold nanoparticles. This interfacial synthesis can be scaled up by creating an emulsion and the recovery of oleic acid is also achievable by centrifugation.

Development of biodegradable hyperbranched core-multishell nanocarriers for efficient topical drug delivery.

PubMed

Du, Fang; Hönzke, Stefan; Neumann, Falko; Keilitz, Juliane; Chen, Wei; Ma, Nan; Hedtrich, Sarah; Haag, Rainer

2016-11-28

The topical application of drugs allows for a local application in skin disease and can reduce side effects. Here we present biodegradable core-multishell (CMS) nanocarriers which are composed of a hyperbranched polyglycerol core functionalized with diblock copolymers consisting of polycaprolactone (PCL) and poly(ethylene glycol) (mPEG) as the outer shell. The anti-inflammatory drug Dexamethasone (Dexa) was loaded into these CMS nanocarriers. DLS results suggested that Dexa loaded nanoparticles mostly act as a unimolecular carrier system. With longer PCL segments, a better transport capacity is observed. In vitro skin permeation studies showed that CMS nanocarriers could improve the Nile red penetration through the skin by up to 7 times, compared to a conventional cream formulation. Interestingly, covalently FITC-labeled CMS nanocarriers remain in the stratum corneum layer. This suggests the enhancement is due to the release of cargo after being transported into the stratum corneum by the CMS nanocarriers. In addition, the hPG-PCL-mPEG CMS nanocarriers exhibited good stability, low cytotoxicity, and their production can easily be scaled up, which makes them promising nanocarriers for topical drug delivery. Copyright © 2016 Elsevier B.V. All rights reserved.

Manufacture of Regularly Shaped Sol-Gel Pellets

NASA Technical Reports Server (NTRS)

Leventis, Nicholas; Johnston, James C.; Kinder, James D.

2006-01-01

An extrusion batch process for manufacturing regularly shaped sol-gel pellets has been devised as an improved alternative to a spray process that yields irregularly shaped pellets. The aspect ratio of regularly shaped pellets can be controlled more easily, while regularly shaped pellets pack more efficiently. In the extrusion process, a wet gel is pushed out of a mold and chopped repetitively into short, cylindrical pieces as it emerges from the mold. The pieces are collected and can be either (1) dried at ambient pressure to xerogel, (2) solvent exchanged and dried under ambient pressure to ambigels, or (3) supercritically dried to aerogel. Advantageously, the extruded pellets can be dropped directly in a cross-linking bath, where they develop a conformal polymer coating around the skeletal framework of the wet gel via reaction with the cross linker. These pellets can be dried to mechanically robust X-Aerogel.

Engineered Film Surfaces Via Spontaneous Phase Segregation

DTIC Science & Technology

2004-12-01

constituents of a Langmuir Blodgett thin Figure 1: Contact angles w/ H2O Contact angles determined from cast films of TPU with (right) 1% wt/wt...Synn, D.; Stelzle, M.; Rabolt, J. F., 2000: Characterization of Orientation of Perfluorostearic Acid Langmuir - Blodgett Multilayers by Infrared...Natick Soldier Center Materials Science Team Natick, MA 01760 ABSTRACT A series of hyperbranched materials have been developed that allow

Controlled assembly of nanoparticle structures: spherical and toroidal superlattices and nanoparticle-coated polymeric beads.

PubMed

Isojima, Tatsushi; Suh, Su Kyung; Vander Sande, John B; Hatton, T Alan

2009-07-21

The emulsion droplet solvent evaporation method has been used to prepare nanoclusters of monodisperse magnetite nanoparticles of varying morphologies depending on the temperature and rate of solvent evaporation and on the composition (solvent, presence of polymer, nanoparticle concentration, etc.) of the emulsion droplets. In the absence of a polymer, and with increasing solvent evaporation temperatures, the nanoparticles formed single- or multidomain crystalline superlattices, amorphous spherical aggregates, or toroidal clusters, as determined by the energetics and dynamics of the solvent evaporation process. When polymers that are incompatible with the nanoparticle coatings were included in the emulsion formulation, monolayer- and multilayer-coated polymer beads and partially coated Janus beads were prepared; the nanoparticles were expelled by the polymer as its concentration increased on evaporation of the solvent and accumulated on the surfaces of the beads in a well-ordered structure. The precise number of nanoparticle layers depended on the polymer/magnetic nanoparticle ratio in the oil droplet phase parent emulsion. The magnetic nanoparticle superstructures responded to the application of a modest magnetic field by forming regular chains with alignment of nonuniform structures (e.g., toroids and Janus beads) that are in accord with theoretical predictions and with observations in other systems.

Fabrication of ferroelectric polymer nanostructures on flexible substrates by soft-mold reverse nanoimprint lithography

NASA Astrophysics Data System (ADS)

Song, Jingfeng; Lu, Haidong; Li, Shumin; Tan, Li; Gruverman, Alexei; Ducharme, Stephen

2016-01-01

Conventional nanoimprint lithography with expensive rigid molds is used to pattern ferroelectric polymer nanostructures on hard substrate for use in, e.g., organic electronics. The main innovation here is the use of inexpensive soft polycarbonate molds derived from recordable DVDs and reverse nanoimprint lithography at low pressure, which is compatible with flexible substrates. This approach was implemented to produce regular stripe arrays with a spacing of 700 nm from vinylidene fluoride co trifluoroethylene ferroelectric copolymer on flexible polyethylene terephthalate substrates. The nanostructures have very stable and switchable piezoelectric response and good crystallinity, and are highly promising for use in organic electronics enhanced or complemented by the unique properties of the ferroelectric polymer, such as bistable polarization, piezoelectric response, pyroelectric response, or electrocaloric function. The soft-mold reverse nanoimprint lithography also leaves little or no residual layer, affording good isolation of the nanostructures. This approach reduces the cost and facilitates large-area, high-throughput production of isolated functional polymer nanostructures on flexible substrates for the increasing application of ferroelectric polymers in flexible electronics.

Fabrication of ferroelectric polymer nanostructures on flexible substrates by soft-mold reverse nanoimprint lithography.

PubMed

Song, Jingfeng; Lu, Haidong; Li, Shumin; Tan, Li; Gruverman, Alexei; Ducharme, Stephen

2016-01-08

Conventional nanoimprint lithography with expensive rigid molds is used to pattern ferroelectric polymer nanostructures on hard substrate for use in, e.g., organic electronics. The main innovation here is the use of inexpensive soft polycarbonate molds derived from recordable DVDs and reverse nanoimprint lithography at low pressure, which is compatible with flexible substrates. This approach was implemented to produce regular stripe arrays with a spacing of 700 nm from vinylidene fluoride co trifluoroethylene ferroelectric copolymer on flexible polyethylene terephthalate substrates. The nanostructures have very stable and switchable piezoelectric response and good crystallinity, and are highly promising for use in organic electronics enhanced or complemented by the unique properties of the ferroelectric polymer, such as bistable polarization, piezoelectric response, pyroelectric response, or electrocaloric function. The soft-mold reverse nanoimprint lithography also leaves little or no residual layer, affording good isolation of the nanostructures. This approach reduces the cost and facilitates large-area, high-throughput production of isolated functional polymer nanostructures on flexible substrates for the increasing application of ferroelectric polymers in flexible electronics.

Achieving high efficiency laminated polymer solar cell with interfacial modified metallic electrode and pressure induced crystallization

NASA Astrophysics Data System (ADS)

Yuan, Yongbo; Bi, Yu; Huang, Jinsong

2011-02-01

We report efficient laminated organic photovoltaic device with efficiency approach the optimized device by regular method based on Poly(3-hexylthiophene-2,5-diyl) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The high efficiency is mainly attributed to the formation of a concrete polymer/metal interface mechanically and electrically by the use of electronic-glue, and using the highly conductive and flexible silver film as anode to reduce photovoltage loss and modifying its work function for efficiency hole extraction by ultraviolet/ozone treatment, and the pressure induced crystallization of PCBM.

Fabrication of amorphous silica nanowires via oxygen plasma treatment of polymers on silicon

NASA Astrophysics Data System (ADS)

Chen, Zhuojie; She, Didi; Chen, Qinghua; Li, Yanmei; Wu, Wengang

2018-02-01

We demonstrate a facile non-catalytic method of fabricating silica nanowires at room temperature. Different polymers including photoresists, parylene C and polystyrene are patterned into pedestals on the silicon substrates. The silica nanowires are obtained via the oxygen plasma treatment on those pedestals. Compared to traditional strategies of silica nanowire fabrication, this method is much simpler and low-cost. Through designing the proper initial patterns and plasma process parameters, the method can be used to fabricate various regiment nano-scale silica structure arrays in any laboratory with a regular oxygen-plasma-based cleaner or reactive-ion-etching equipment.

Effects of nanoscale aggregation on mechanical properties and local dynamics of precise acid- and ion-containing polymers

NASA Astrophysics Data System (ADS)

Middleton, Luri Robert

Acid- and ion-containing polymers have interchain interactions that alter polymer behavior at the nano, micro, and bulk length scales. Strong secondary-bonds act as thermo-reversible physical crosslinks between chains which drive self-assembly. Tuning theses interactions can modify bulk polymer properties including stiffness, toughness, melt viscosity, resilience, clarity, abrasion resistance and puncture resistance. Furthermore, understanding and improving the relevant factors that control transport properties would have vast implications on developing solid polymer electrolytes (SPEs) for technologically important applications including water desalination, ion exchange membranes and microelectronics. This thesis explores the structure - processing - morphology - property relationships of acid and ionic functionalized polymers. Improvements in synthetic techniques and advancements in characterization methods have enabled new studies of associating polymer systems. Synthesis of entangled, high molecular weight, linear polyethylene (PE) chains functionalized with interacting pendant groups (acidic or ionic) placed periodically along the polymer backbone represent a new class of associating polymers. These polymers with periodic distributions of acid groups are much more homogenous than the commercially available polymers. Previous studies of these polymers with greater structural homogeneity revealed great variety in morphologies of the nano-aggregated polar groups within the non-polar polymer matrix. This thesis correlated the morphologies with bulk properties through real-time X-ray scattering and tensile deformation at a range of temperatures and sample compositions. New, transient morphologies and hierarchical morphologies were observed which coincided with unusual tensile strain hardening. These results indicate that improvements in synthetic control of polymers can enhance physical properties such as tensile strain-hardening, through cooperative bonding between chains. The structural regularity of precise polyethylenes also enables robust comparisons between experiments and computer simulations. At pico- to nano-seconds time scales and length scales of polymer and aggregate dynamics, neutron scattering and molecular dynamics simulations were combined to extend the knowledge of the molecular-level aggregated polymer dynamics. These experiments provide a baseline for future studies of ion-conduction in associating polymer melts.

Polymers in the gut compress the colonic mucus hydrogel

PubMed Central

Datta, Sujit S.; Preska Steinberg, Asher

2016-01-01

Colonic mucus is a key biological hydrogel that protects the gut from infection and physical damage and mediates host–microbe interactions and drug delivery. However, little is known about how its structure is influenced by materials it comes into contact with regularly. For example, the gut abounds in polymers such as dietary fibers or administered therapeutics, yet whether such polymers interact with the mucus hydrogel, and if so, how, remains unclear. Although several biological processes have been identified as potential regulators of mucus structure, the polymeric composition of the gut environment has been ignored. Here, we demonstrate that gut polymers do in fact regulate mucus hydrogel structure, and that polymer–mucus interactions can be described using a thermodynamic model based on Flory–Huggins solution theory. We found that both dietary and therapeutic polymers dramatically compressed murine colonic mucus ex vivo and in vivo. This behavior depended strongly on both polymer concentration and molecular weight, in agreement with the predictions of our thermodynamic model. Moreover, exposure to polymer-rich luminal fluid from germ-free mice strongly compressed the mucus hydrogel, whereas exposure to luminal fluid from specific-pathogen-free mice—whose microbiota degrade gut polymers—did not; this suggests that gut microbes modulate mucus structure by degrading polymers. These findings highlight the role of mucus as a responsive biomaterial, and reveal a mechanism of mucus restructuring that must be integrated into the design and interpretation of studies involving therapeutic polymers, dietary fibers, and fiber-degrading gut microbes. PMID:27303035

Fluorescence biosensor for inorganic pyrophosphatase activity.

PubMed

Zhang, Ying; Guo, Yajuan; Zhao, Mengmeng; Lin, Cuiying; Lin, Zhenyu; Luo, Fang; Chen, Guonan

2017-02-01

A highly sensitive and selective fluorescence biosensor for inorganic pyrophosphatase (PPase) activity has been developed based on special click ligation trigger hyperbranched rolling circle amplification (CLT-HRCA). Pyrophosphate ion (PPi) can coordinate with Cu 2+ to form stable PPi/Cu 2+ complex and Cu 2+ in the complex cannot be reduced to Cu + . The addition of PPase causes the hydrolysis of PPi into orthophosphate (Pi) and therefore induces the releasing of Cu 2+ from the stable PPi/Cu 2+ complex, and the free Cu 2+ is easily reduced to Cu + by sodium ascorbate. Then Cu + catalyzes the cyclization reaction between the specially designed 5'-azide and 3'-alkyne tagged padlock probes through Cu + catalyzed azide-alkyne cycloaddition (CuAAC), which in turn initiates the hyperbranched rolling circle amplification (HRCA). Given that the CLT-HRCA products contain large amounts of double-stranded DNAs (dsDNAs), the addition of SYBR Green I resulted in the enhanced fluorescence signal. There was a linear relationship between the enhanced fluorescence intensity and the logarithm PPase activity ranging from 0.05 to 25 mU with a detection limit of 0.02 mU. Such proposed biosensor has been successfully applied to screen the potential PPase inhibitors and has accessed the related inhibit ability with high efficiency.

A novel 96-well gel-based assay for determining antifungal activity against filamentous fungi.

PubMed

Troskie, Anscha Mari; Vlok, Nicolas Maré; Rautenbach, Marina

2012-12-01

In recent years the global rise in antibiotic resistance and environmental consciousness lead to a renewed fervour to find and develop novel antibiotics, including antifungals. However, the influence of the environment on antifungal activity is often disregarded and many in vitro assays may cause the activity of certain antifungals to be overestimated or underestimated. The general antifungal test assays that are economically accessible to the majority of scientists primarily rely on visual examination or on spectrophotometric analysis. The effect of certain morphogenic antifungals, which may lead to hyperbranching of filamentous fungi, unfortunately renders these methods unreliable. To minimise the difficulties experienced as a result of hyperbranching, we developed a straightforward, economical 96-well gel-based method, independent of spectrophotometric analysis, for highly repeatable determination of antifungal activity. For the calculation of inhibition parameters, this method relies on the visualisation of assay results by digitisation. The antifungal activity results from our novel micro-gel dilution assay are comparable to that of the micro-broth dilution assay used as standard reference test of The Clinical and Laboratory Standard Institute. Furthermore, our economical assay is multifunctional as it permits microscopic analysis of the preserved assay results, as well as rendering highly reliable data. Copyright © 2012 Elsevier B.V. All rights reserved.

Rational Design of Hyperbranched Nanowire Systems for Tunable Superomniphobic Surfaces Enabled by Atomic Layer Deposition

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

Bielinski, Ashley R.; Boban, Mathew; He, Yang

2017-01-24

A method for tunable control of geometry in hyperbranched ZnO nanowire (NW) systems is reported, which enables the rational design and fabrication of superomniphobic surfaces. Branched NWs with tunable density and orientation were grown via a sequential hydrothermal process, in which atomic layer deposition (ALD) was used for NW seeding, disruption of epitaxy, and selective blocking of NW nucleation. This approach allows for the rational design and optimization of three-level hierarchical structures, in which the geometric parameters of each level of hierarchy can be individually controlled. We demonstrate the coupled relationships between geometry and contact angle for a variety ofmore » liquids, which is supported by mathematical models of structural superomniphobicity. The highest performing superomniphobic surface was designed with three levels of hierarchy and achieved the following advancing/receding contact angles, water: 172°/170°, hexadecane: 166°/156°, octane: 162°/145°, and heptane: 160°/130°. Low surface tension liquids were shown to bounce off the surface from a height of 7 cm without breaking through and wetting. This approach demonstrates the power of ALD as an enabling technique for hierarchical materials by design, spanning the macro, micro, and nano length scales.« less

Injectable hyperbranched poly(β-amino ester) hydrogels with on-demand degradation profiles to match wound healing processes† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc03913a

PubMed Central

Xu, Qian; Guo, Linru; A, Sigen; Gao, Yongsheng; Zhou, Dezhong; Greiser, Udo; Creagh-Flynn, Jack; Zhang, Hong; Dong, Yixiao; Cutlar, Lara; Wang, Fagang; Liu, Wenguang

2018-01-01

Adjusting biomaterial degradation profiles to match tissue regeneration is a challenging issue. Herein, biodegradable hyperbranched poly(β-amino ester)s (HP-PBAEs) were designed and synthesized via “A2 + B4” Michael addition polymerization, and displayed fast gelation with thiolated hyaluronic acid (HA-SH) via a “click” thiol–ene reaction. HP-PBAE/HA-SH hydrogels showed tunable degradation profiles both in vitro and in vivo using diamines with different alkyl chain lengths and poly(ethylene glycol) diacrylates with varied PEG spacers. The hydrogels with optimized degradation profiles encapsulating ADSCs were used as injectable hydrogels to treat two different types of humanized excisional wounds – acute wounds with faster healing rates and diabetic wounds with slower healing and neo-tissue formation. The fast-degrading hydrogel showed accelerated wound closure in acute wounds, while the slow-degrading hydrogel showed better wound healing for diabetic wounds. The results demonstrate that the new HP-PBAE-based hydrogel in combination with ADSCs can be used as a well-controlled biodegradable skin substitute, which demonstrates a promising approach in the treatment of various types of skin wounds. PMID:29719691

Dendrimer-based nanocarriers demonstrating a high efficiency for loading and releasing anticancer drugs against cancer cells in vitro and in vivo

NASA Astrophysics Data System (ADS)

Quyen Tran, Ngoc; Khoa Nguyen, Cuu; Phuong Nguyen, Thi

2013-12-01

Dendrimer, a new class of hyper-branched polymer with predetermined molecular weight and well-controlled size, has received much attention in nanobiomedical applications such as drug carrier, gene therapy, disease diagnosis, etc. In this study, pegylated polyamidoamine (PAMAM) dendrimer at generation 3.0 (G 3.0) and carboxylated PAMAM dendrimer G 2.5 were prepared for loading anticancer drugs. For loading cisplatin, carboxylated dendrimer could carry 26.64 wt/wt% of cisplatin. The nanocomplexes have size ranging from 10 to 30 nm in diameter. The drug nanocarrier showed activity against NCI-H460 lung cancer cell line with half maximal inhibitory (IC50) of 23.11 ± 2.08 μg ml-1. Pegylated PAMAM dendrimers (G 3.0) were synthesized below 40 nm in diameter for carrying 5-fluorouracil (5-FU). For 5-FU encapsulation, pegylated dendrimer showed a high drug-loading efficiency of the drug and a slow release profile of 5-FU. The drug nanocarrier system exhibited an antiproliferative activity against MCF-7 cells (breast cancer cell) with a half maximal inhibitory (IC50) of 9.92 ± 0.19 μg ml-1. In vivo tumor xenograft study showed that the 5-FU encapsulated pegylation of dendrimer exhibited a significant decrement in volume of tumor which was generated by MCF-7 cancer cells. These positive results from our studies could pave the ways for further research of drugs dendrimer nanocarriers toward cancer chemotherapy.

Oxidatively-Stable Linear Poly(propylenimine)-Containing Adsorbents for CO2 Capture from Ultra-Dilute Streams.

PubMed

Pang, Simon H; Lively, Ryan P; Jones, Christopher W

2018-05-29

Aminopolymer-based solid sorbents have been widely investigated for CO2 capture from dilute streams such as flue gas or ambient air. However, the oxidative stability of the most well-studied aminopolymer, poly(ethylenimine) (PEI), is limited, causing it to lose its CO2 capture capacity after exposure to oxygen at elevated temperatures. Here we demonstrate the use of linear poly(propylenimine) (PPI), synthesized via a simple cationic ring-opening polymerization, as a more oxidatively-stable alternative to PEI with high CO2 capacity and amine efficiency. The performance of linear PPI/SBA-15 composites is investigated over a range of CO2 capture conditions (CO2 partial pressure, adsorption temperature) to examine the trade-off between adsorption capacity and sorption site accessibility, which may be expected to be more limited in linear polymers relative to the prototypical hyperbranched PEI. Linear PPI/SBA-15 composites are more efficient at CO2 capture and retain 65-83% of their CO2 capacity after exposure to a harsh oxidative treatment, compared to 20-40% retention for linear PEI. Additionally, we demonstrate long-term stability of linear PPI sorbents over 50 adsorption/desorption cycles with no loss in performance. Combined with other strategies for improving oxidative stability and adsorption kinetics, linear PPI may play a role as a component of stable, solid adsorbents in commercial applications for CO2 capture. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of microcapsules containing double-component lubricant and self-lubricating performance of polymer composites

NASA Astrophysics Data System (ADS)

Li, Haiyan; Shi, Nanqi; Ji, Jing; Wang, Huaiyuan

2018-05-01

Double-component microcapsules containing lubricant oil and SiO2 nanoparticles were prepared by solvent evaporation method. The synthesized microcapsules have the regular spherical structure with the mean diameter of 105 μm and wall thickness of 15 μm. The synthesized microcapsules have excellent thermal stability, and the lubricant oil content was 71.4 wt%. Self-lubricating polymer composites were fabricated by incorporating double-component microcapsules into epoxy matrix. When the SiO2 nanoparticles content was 3 wt% relative to the lubricant oil, 10 wt% microcapsules brought 60.8% and 93.3% decrease for epoxy composites in the friction coefficient and specific wear rate, respectively. The synergetic effect between lubricant oil and SiO2 nanoparticles play a positive role in improving the triboligical properties of polymer composites.

Regularities in the association of polymethacrylic acid with benzethonium chloride in aqueous solutions

NASA Astrophysics Data System (ADS)

Tugay, A. V.; Zakordonskiy, V. P.

2006-06-01

The association of cationogenic benzethonium chloride with polymethacrylic acid in aqueous solutions was studied by nephelometry, conductometry, tensiometry, viscometry, and pH-metry. The critical concentrations of aggregation and polymer saturation with the surface-active substance were determined. A model describing processes in such systems step by step was suggested.

Marginal turbulent state of viscoelastic fluids: A polymer drag reduction perspective.

PubMed

Xi, Li; Bai, Xue

2016-04-01

The laminar-turbulent (LT) transition of dilute polymer solutions is of great interest not only for the complex transition dynamics itself, but also for its potential link to the maximum drag reduction (MDR) phenomenon. We present an in-depth investigation of the edge state (ES), an asymptotic solution on the LT boundary, in viscoelastic channel flow. For given Re and simulation domain size, mean flow statistics of the ES do not vary with the introduction of polymers, proving that there is a region of turbulent states not susceptible to polymer drag reduction effects. The dynamics of the ES features low-frequency fluctuations and in the longer domains we studied it is nearly periodic with regular bursts of turbulent activities separated by extended quiescent periods. Its flow field is dominated by elongated vortices and streaks, with very weak extensional and rotational flow motions. Polymer stretching is almost exclusively contributed by the mean shear and polymer-turbulence interaction is minimal. Flow structures and the kinematics of the ES match hibernating turbulence, an MDR-like phase intermittently occurring in turbulent dynamics. Its observation now seems to result from recurrent visits to certain parts of the ES. The ES offers explanations for the existence and universality of MDR, the quantitative magnitude of which, however, still remains unsolved.

Marginal turbulent state of viscoelastic fluids: A polymer drag reduction perspective

NASA Astrophysics Data System (ADS)

Xi, Li; Bai, Xue

2016-04-01

The laminar-turbulent (LT) transition of dilute polymer solutions is of great interest not only for the complex transition dynamics itself, but also for its potential link to the maximum drag reduction (MDR) phenomenon. We present an in-depth investigation of the edge state (ES), an asymptotic solution on the LT boundary, in viscoelastic channel flow. For given Re and simulation domain size, mean flow statistics of the ES do not vary with the introduction of polymers, proving that there is a region of turbulent states not susceptible to polymer drag reduction effects. The dynamics of the ES features low-frequency fluctuations and in the longer domains we studied it is nearly periodic with regular bursts of turbulent activities separated by extended quiescent periods. Its flow field is dominated by elongated vortices and streaks, with very weak extensional and rotational flow motions. Polymer stretching is almost exclusively contributed by the mean shear and polymer-turbulence interaction is minimal. Flow structures and the kinematics of the ES match hibernating turbulence, an MDR-like phase intermittently occurring in turbulent dynamics. Its observation now seems to result from recurrent visits to certain parts of the ES. The ES offers explanations for the existence and universality of MDR, the quantitative magnitude of which, however, still remains unsolved.

Second harmonic generation and photochromic grating in polyurethane films containing diazo isoxazole chromophore

NASA Astrophysics Data System (ADS)

Marański, Krzysztof; Kucharski, Stanisław; Ortyl, Ewelina; Nunzi, Jean-Michel; Ahmadi-Kandjani, Sohrab; Dabos-Seignon, Sylvie; Chan, Siu-Wai; Barille, Regis

2008-08-01

The chromophoric intermediate: 2,2'-({4-[( E)-(5-methylisoxazol-3-yl)diazenyl]phenyl}-imino)diethanol was used in polyaddition reaction with di-isocyanate to obtain a new polyurethane polymeric material showing nonlinear optical and photochromic properties. The maximum absorption band of the polymer film was at 418 nm. The illumination of the film with crossed beams of the 488 nm Ar + laser yielded surface relief grating of regular structure. Measurement of the frequency doubling signal with 1064 nm laser indicated the polymer as interesting material for photooptical applications. The measured nonlinear optical coefficient, d33, reached 90.2 pm/V.

Laboratory measurements of shock propagation through spherical cavities in an optically accessible polymer.

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

Chojnicki, Kirsten; Cooper, Marcia A.; Guo, Shuyue

Pore-scale aperture effects on flow in pore networks was studied in the laboratory to provide a parameterization for use in transport models. Four cases were considered: regular and irregular pillar/pore alignment with and without an aperture. The velocity field of each case was measured and simulated, providing quantitatively comparable results. Two aperture effect parameterizations were considered: permeability and transmission. Permeability values varied by an order of magnitude between the cases with and without apertures. However, transmission did not correlate with permeability. Despite having much greater permeability the regular aperture case permitted less transmission than the regular case. Moreover, both irregularmore » cases had greater transmission than the regular cases, a difference not supported by the permeabilities. Overall, these findings suggest that pore-scale aperture effects on flow though a pore-network may not be adequately captured by properties such as permeability for applications that are interested in determining particle transport volume and timing.« less

Healable supramolecular polymers as organic metals.

PubMed

Armao, Joseph J; Maaloum, Mounir; Ellis, Thomas; Fuks, Gad; Rawiso, Michel; Moulin, Emilie; Giuseppone, Nicolas

2014-08-13

Organic materials exhibiting metallic behavior are promising for numerous applications ranging from printed nanocircuits to large area electronics. However, the optimization of electronic conduction in organic metals such as charge-transfer salts or doped conjugated polymers requires high crystallinity, which is detrimental to their processability. To overcome this problem, the combination of the electronic properties of metal-like materials with the mechanical properties of soft self-assembled systems is attractive but necessitates the absence of structural defects in a regular lattice. Here we describe a one-dimensional supramolecular polymer in which photoinduced through-space charge-transfer complexes lead to highly coherent domains with delocalized electronic states displaying metallic behavior. We also reveal that diffusion of supramolecular polarons in the nanowires repairs structural defects thereby improving their conduction. The ability to access metallic properties from mendable self-assemblies extends the current understanding of both fields and opens a wide range of processing techniques for applications in organic electronics.

Directed polymers on a disordered tree with a defect subtree

NASA Astrophysics Data System (ADS)

Madras, Neal; Yıldırım, Gökhan

2018-04-01

We study the question of how the competition between bulk disorder and a localized microscopic defect affects the macroscopic behavior of a system in the directed polymer context at the free energy level. We consider the directed polymer model on a disordered d-ary tree and represent the localized microscopic defect by modifying the disorder distribution at each vertex in a single path (branch), or in a subtree, of the tree. The polymer must choose between following the microscopic defect and finding the best branches through the bulk disorder. We describe three possible phases, called the fully pinned, partially pinned and depinned phases. When the microscopic defect is associated only with a single branch, we compute the free energy and the critical curve of the model, and show that the partially pinned phase does not occur. When the localized microscopic defect is associated with a non-disordered regular subtree of the disordered tree, the picture is more complicated. We prove that all three phases are non-empty below a critical temperature, and that the partially pinned phase disappears above the critical temperature.

Generation of conductivity through transfer charge properties, for polyesters and polyamides with characteristic functional groups

NASA Astrophysics Data System (ADS)

Gonzalez, Carmen; Tagle, Luis Hernan; Terraza, Claudio A.; Barriga, Andres; Cabrera, A. L.; Volkmann, Ulrich G.

2011-03-01

Electro-optic properties of σ -conjugated polymers, as polysilylene; are associated with electron conjugation in the silicon atom, which allows a significant delocalization of electrons along of the chain. Thus, the conductivity is intimately connected to the mobility of charge carriers, which in turn depends on the structure and morphology of the system. We report the characterization of polyesters (PEFs) and polyamides (PAFs). Film thicknesses were obtained by ellipsometry. The vibration frequencies of the groups were determined by FT-IR and corroborated by Raman spectroscopy. Structural information was obtained from X-Ray diffraction (XRD). The structural and surface morphology were studied by scanning electron microscope (SEM). Electrical conductivity of the polymers was measured before and after exposure to iodine vapor, for films of different thicknesses. Morphological differentiation was studied by energy dispersive microscopy (EDX), showing a regular distribution of iodine within the polymer. Preliminary conductivity measurements showed adverse effects when oxidation of the polymer films is induced These effects are related to a certain grade of disorder within the system

Succession of microbial communities and changes of incremental oil in a post-polymer flooded reservoir with nutrient stimulation.

PubMed

Gao, Peike; Li, Guoqiang; Le, Jianjun; Liu, Xiaobo; Liu, Fang; Ma, Ting

2018-02-01

Further exploitation of the residual oil underground in post-polymer flooded reservoirs is attractive and challengeable. In this study, indigenous microbial enhanced oil recovery (IMEOR) in a post-polymer flooded reservoir was performed. The succession of microbial communities was revealed by high-throughput sequencing of 16S rRNA genes and changes of incremental oil were analyzed. The results indicated that the abundances of reservoir microorganisms significantly increased, with alpha diversities decreased in the IMEOR process. With the intermittent nutrient injection, microbial communities showed a regular change and were alternately dominated by minority populations: Pseudomonas and Acinetobacter significantly increased when nutrients were injected; Thauera, Azovibrio, Arcobacter, Helicobacter, Desulfitobacterium, and Clostridium increased in the following water-flooding process. Accompanied by the stimulated populations, higher oil production was obtained. However, these populations did not contribute a persistent level of incremental oil in the reservoir. In summary, this study revealed the alternative succession of microbial communities and the changes of incremental oil in a post-polymer flooded reservoir with intermittent nutrient stimulation process.

Experimental studies of contact angle hysteresis phenomena on polymer surfaces – Toward the understanding and control of wettability for different applications.

PubMed

Grundke, K; Pöschel, K; Synytska, A; Frenzel, R; Drechsler, A; Nitschke, M; Cordeiro, A L; Uhlmann, P; Welzel, P B

2015-08-01

Contact angle hysteresis phenomena on polymer surfaces have been studied by contact angle measurements using sessile liquid droplets and captive air bubbles in conjunction with a drop shape method known as Axisymmetric Drop Shape Analysis - Profile (ADSA-P). In addition, commercially available sessile drop goniometer techniques were used. The polymer surfaces were characterized with respect to their surface structure (morphology, roughness, swelling) and surface chemistry (elemental surface composition, acid-base characteristics) by scanning electron microscopy (SEM), scanning force microscopy (SFM), ellipsometry, X-ray photoelectron spectroscopy (XPS) and streaming potential measurements. Heterogeneous polymer surfaces with controlled roughness and chemical composition were prepared by different routes using plasma etching and subsequent dip coating or grafting of polymer brushes, anodic oxidation of aluminium substrates coated with thin polymer films, deposition techniques to create regular patterned and rough fractal surfaces from core-shell particles, and block copolymers. To reveal the effects of swelling and reorientation at the solid/liquid interface contact angle hysteresis phenomena on polyimide surfaces, cellulose membranes, and thermo-responsive hydrogels have been studied. The effect of different solutes in the liquid (electrolytes, surfactants) and their impact on contact angle hysteresis were characterized for solid polymers without and with ionizable functional surface groups in aqueous electrolyte solutions of different ion concentrations and pH and for photoresist surfaces in cationic aqueous surfactant solutions. The work is an attempt toward the understanding of contact angle hysteresis phenomena on polymer surfaces aimed at the control of wettability for different applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Analysis physical properties of composites polymer from cocofiber and polypropylene plastic waste with maleic anhydrate as crosslinking agent

NASA Astrophysics Data System (ADS)

Pelita, E.; Hidayani, T. R.; Akbar, A.

2017-07-01

This research was conducted with the aim to produce composites polymer with polypropylene plastic waste materials and cocofiber which aims to produce wood replacement material in the home furnishings industry. This research was conducted with several stages. The first stage is the process of soaking coco fiber with detergent to remove oil and 2% NaOH. The second stage is to combine the polypropylene plastic waste with cocofiber is a chemical bond, modification by adding maleic anhydride as a crosslinking agent and benzoyl peroxide as an initiator each as much as 1%. Mixing materials done by reflux method using xylene solvent. In this study, carried out a wide range of weight variation of coco fiber are added to the 10, 20, 30, 40 and 50%. The third stage is a polymer composite molding process using hot press at a temperature of 158°C. The results of polymer composites Showed optimum condition on the addition of 40% cocofiber with supple tensile strength value of 90.800 kgf /cm2 and value of elongation break at 3.6726 x 104 (kgf/cm2), melting point at 160.02°C, burning point 463.43°C, residue of TGA is 19%, the density of 0.84 g/mL. From these data, conclude that the resulting polymer composites meet the SNI 03-2105-2006 about ordinary composite polymer and polymer composite structural type 8 regular types from 17.5 to 10.5.

One-pot exfoliation, functionalization, and size manipulation of graphene sheets: efficient system for biomedical applications.

PubMed

Bani, Farhad; Bodaghi, Ali; Dadkhah, Abbas; Movahedi, Soodabeh; Bodaghabadi, Narges; Sadeghizadeh, Majid; Adeli, Mohsen

2018-05-01

In this work, we reported a facile method to produce stable aqueous graphene dispersion through direct exfoliation of graphite by modified hyperbranched polyglycerol. Size of graphene sheets was manipulated by simultaneous exfoliation and sonication of graphite, and functionalized graphene sheets with narrow size distribution were obtained. The polyglycerol-functionalized graphene sheets exhibited highly efficient cellular uptake and photothermal conversion, enabling it to serve as a photothermal agent for cancer therapy.

cAMP Signaling Regulates Synchronised Growth of Symbiotic Epichloë Fungi with the Host Grass Lolium perenne

PubMed Central

Voisey, Christine R.; Christensen, Michael T.; Johnson, Linda J.; Forester, Natasha T.; Gagic, Milan; Bryan, Gregory T.; Simpson, Wayne R.; Fleetwood, Damien J.; Card, Stuart D.; Koolaard, John P.; Maclean, Paul H.; Johnson, Richard D.

2016-01-01

The seed-transmitted fungal symbiont, Epichloë festucae, colonizes grasses by infecting host tissues as they form on the shoot apical meristem (SAM) of the seedling. How this fungus accommodates the complexities of plant development to successfully colonize the leaves and inflorescences is unclear. Since adenosine 3′, 5′-cyclic monophosphate (cAMP)-dependent signaling is often essential for host colonization by fungal pathogens, we disrupted the cAMP cascade by insertional mutagenesis of the E. festucae adenylate cyclase gene (acyA). Consistent with deletions of this gene in other fungi, acyA mutants had a slow radial growth rate in culture, and hyphae were convoluted and hyper-branched suggesting that fungal apical dominance had been disrupted. Nitro blue tetrazolium (NBT) staining of hyphae showed that cAMP disruption mutants were impaired in their ability to synthesize superoxide, indicating that cAMP signaling regulates accumulation of reactive oxygen species (ROS). Despite significant defects in hyphal growth and ROS production, E. festucae ΔacyA mutants were infectious and capable of forming symbiotic associations with grasses. Plants infected with E. festucae ΔacyA were marginally less robust than the wild-type (WT), however hyphae were hyper-branched, and leaf tissues heavily colonized, indicating that the tight regulation of hyphal growth normally observed in maturing leaves requires functional cAMP signaling. PMID:27833620

The surface characteristics of hyperbranched polyamide modified corncob and its adsorption property for Cr(VI)

NASA Astrophysics Data System (ADS)

Lin, Hai; Han, Shaoke; Dong, Yingbo; He, Yinhai

2017-08-01

A low-cost anion adsorbent for Cr(VI) effectively removing was synthesized by hyperbranched polyamide modified corncob (HPMC). Samples were characterized by Brunauer-Emmett-Teller (BET) surface area analysis, field-emission scanning electron microscopy (FE-SEM) with energy-dispersive X-ray spectroscopy, Fourier transform infrared (FTIR) and zeta potential analysis. Kinetics, isotherms and thermodynamics studies of HPMC for Cr(VI) adsorption were investigated in batch static experiments, in the temperature range of 25-45 °C, pH = 2.0. Results showed that the adsorption was rapid and stable, with the uptake capacity higher than 80% after 30 min. Adsorption behavior and rate-controlling mechanisms were analyzed using three kinetic models (pseudo-first order, pseudo-second order, intra-particle kinetic model). Kinetic studies showed that the adsorption of HPMC to Cr(VI) relied the pseudo-second-order model, and controlled both by the intra-particle diffusion and film diffusion. Equilibrium data was tested by Langmuir and Freundlich adsorption isotherm models. Langmuir model was more suitable to indicate a homogeneous distribution of active sites on HPMC and monolayer adsorption. The maximum adsorption capacity from the Langmuir model, qmax, was 131.6 mg/g at pH 2.0 and 45 °C for HPMC. Thermodynamic parameters revealed spontaneous and endothermic nature of the Cr(VI) adsorption onto HPMC.

Homogeneous and label-free detection of microRNAs using bifunctional strand displacement amplification-mediated hyperbranched rolling circle amplification.

PubMed

Zhang, Li-rong; Zhu, Guichi; Zhang, Chun-yang

2014-07-01

MicroRNAs (miRNAs) are an emerging class of biomarkers and therapeutic targets for various diseases including cancers. Here, we develop a homogeneous and label-free method for sensitive detection of let-7a miRNA based on bifunctional strand displacement amplification (SDA)-mediated hyperbranched rolling circle amplification (HRCA). The binding of target miRNA with the linear template initiates the bifunctional SDA reaction, generating two different kinds of triggers which can hybridize with the linear template to initiate new rounds of SDA reaction for the production of more and more triggers. In the meantime, the released two different kinds of triggers can function as the first and the second primers, respectively, to initiate the HRCA reaction whose products can be simply monitored by a standard fluorometer with SYBR Green I as the fluorescent indicator. The proposed method exhibits high sensitivity with a detection limit of as low as 1.8 × 10(-13) M and a large dynamic range of 5 orders of magnitude from 0.1 pM to 10 nM, and it can even discriminate the single-base difference among the miRNA family members. Moreover, this method can be used to analyze the total RNA samples from the human lung tissues and might be further applied for sensitive detection of various proteins, small molecules, and metal ions in combination with specific aptamers.

Effect and origin of the structure of hyperbranched polysiloxane on the surface and integrated performances of grafted Kevlar fibers

NASA Astrophysics Data System (ADS)

Zhang, Hongrui; Yuan, Li; Liang, Guozheng; Gu, Aijuan

2014-11-01

Four hyperbranched polysiloxanes (HPSis) with different molecular weights and concentration ratios of double bonds to epoxy groups (1:6.5-1:0.7) were synthesized and characterized. Each HPSi was facilely grafted onto surfaces of Kevlar fibers (KFs) to develop novel modified fibers (HPSi-g-KFs). The structures and integrated properties of HPSi-g-KFs as well as the origin behind were systematically investigated. Results show that HPSi-g-KFs have much rougher surface morphologies, and their surface free energies are as high as about 1.7 times that of KFs, showing greatly improved wettability. Besides, HPSi-g-KFs have excellent UV resistance after 168 h UV irradiation, the retentions of tenacity, energy to break, modulus and break extension are as high as 92, 86, 95 and 96%, respectively, while those of KFs are 66-85%. In addition, compared with KFs, HPSi-g-KFs have higher tensile tenacity and energy to break with similar modulus and break extension, much better thermal stability and flame retardancy. The nature of HPSi has different influence on different property of fibers, the HPSi with smaller molecular weight and more epoxy groups is beneficial to prepare HPSi-g-KFs with better wettability, while that with larger molecular weight and more double bonds tends to prepare HPSi-g-KF with better flame retardancy and UV resistance.

Octreotide-functionalized and resveratrol-loaded unimolecular micelles for targeted neuroendocrine cancer therapy

NASA Astrophysics Data System (ADS)

Xu, Wenjin; Burke, Jocelyn F.; Pilla, Srikanth; Chen, Herbert; Jaskula-Sztul, Renata; Gong, Shaoqin

2013-09-01

Medullary thyroid cancer (MTC) is a neuroendocrine tumor (NET) that is often resistant to standard therapies. Resveratrol suppresses MTC growth in vitro, but it has low bioavailability in vivo due to its poor water solubility and rapid metabolic breakdown, as well as lack of tumor-targeting ability. A novel unimolecular micelle based on a hyperbranched amphiphilic block copolymer was designed, synthesized, and characterized for NET-targeted delivery. The hyperbranched amphiphilic block copolymer consisted of a dendritic Boltorn® H40 core, a hydrophobic poly(l-lactide) (PLA) inner shell, and a hydrophilic poly(ethylene glycol) (PEG) outer shell. Octreotide (OCT), a peptide that shows strong binding affinity to somatostatin receptors, which are overexpressed on NET cells, was used as the targeting ligand. Resveratrol was physically encapsulated by the micelle with a drug loading content of 12.1%. The unimolecular micelles exhibited a uniform size distribution and spherical morphology, which were determined by both transmission electron microscopy (TEM) and dynamic light scattering (DLS). Cellular uptake, cellular proliferation, and Western blot analyses demonstrated that the resveratrol-loaded OCT-targeted micelles suppressed growth more effectively than non-targeted micelles. Moreover, resveratrol-loaded NET-targeted micelles affected MTC cells similarly to free resveratrol in vitro, with equal growth suppression and reduction in NET marker production. These results suggest that the H40-based unimolecular micelle may offer a promising approach for targeted NET therapy.

Stimuli-responsive hybrid nanocarriers developed by controllable integration of hyperbranched PEI with mesoporous silica nanoparticles for sustained intracellular siRNA delivery

PubMed Central

Prabhakar, Neeraj; Zhang, Jixi; Desai, Diti; Casals, Eudald; Gulin-Sarfraz, Tina; Näreoja, Tuomas; Westermarck, Jukka; Rosenholm, Jessica M

2016-01-01

Small interfering RNA (siRNA) is a highly potent drug in gene-based therapy with the challenge being to deliver it in a sustained manner. The combination of mesoporous silica nanoparticles (MSNs) and polycations in the confined pore space allows for incorporation and controlled release of therapeutic siRNA payloads. We hereby constructed MSNs with expanded mesopores and pore-surface-hyperbranched poly(ethyleneimine) (PEI) tethered with redox-cleavable linkers that could carry a high payload of siRNA (120 mg·g−1). The developed nanocarriers were efficiently taken up by cancer cells and were subsequently able to escape to the cytoplasm from the endosomes, most likely owing to the integrated PEI. Triggered by the intracellular redox conditions, the siRNA was sustainably released inside the cells over a period of several days. Functionality of siRNAs was demonstrated by using cell-killing siRNA as cargo. Despite not being the aim of the developed system, in vitro experiments using cell-killing siRNAs showed that the efficacy of siRNA transfection was comparable to the commercial in vitro transfection agent Lipofectamine. Consequently, the developed MSN-based delivery system offers a potential approach to hybrid nanocarriers for more efficient and long-term siRNA delivery and, in a longer perspective, in vivo gene silencing for RNA interference (RNAi) therapy. PMID:27994460

Charge generation layers for solution processed tandem organic light emitting diodes with regular device architecture.

PubMed

Höfle, Stefan; Bernhard, Christoph; Bruns, Michael; Kübel, Christian; Scherer, Torsten; Lemmer, Uli; Colsmann, Alexander

2015-04-22

Tandem organic light emitting diodes (OLEDs) utilizing fluorescent polymers in both sub-OLEDs and a regular device architecture were fabricated from solution, and their structure and performance characterized. The charge carrier generation layer comprised a zinc oxide layer, modified by a polyethylenimine interface dipole, for electron injection and either MoO3, WO3, or VOx for hole injection into the adjacent sub-OLEDs. ToF-SIMS investigations and STEM-EDX mapping verified the distinct functional layers throughout the layer stack. At a given device current density, the current efficiencies of both sub-OLEDs add up to a maximum of 25 cd/A, indicating a properly working tandem OLED.

Combined X-ray and neutron fibre diffraction studies of biological and synthetic polymers

NASA Astrophysics Data System (ADS)

Parrot, I. M.; Urban, V.; Gardner, K. H.; Forsyth, V. T.

2005-08-01

The fibrous state is a natural one for polymer molecules which tend to assume regular helical conformations rather than the globular structures characteristic of many proteins. Fibre diffraction therefore has broad application to the study of a wide range of biological and synthetic polymers. The purpose of this paper is to illustrate the general scope of the method and in particular to demonstrate the impact of a combined approach involving both X-ray and neutron diffraction methods. While the flux of modern X-ray synchrotron radiation sources allows high quality datasets to be recorded with good resolution within a very short space of time, neutron studies can provide unique information through the ability to locate hydrogen or deuterium atoms that are often difficult or impossible to locate using X-ray methods. Furthermore, neutron fibre diffraction methods can, through the ability to selectively label specific parts of a structure, be used to highlight novel aspects of polymer structure that can not be studied using X-rays. Two examples are given. The first describes X-ray and neutron diffraction studies of conformational transitions in DNA. The second describes structural studies of the synthetic high-performance polymer poly(p-phenylene terephthalamide) (PPTA), known commercially as Kevlar® or Twaron®.

Sodium selective ion channel formation in living cell membranes by polyamidoamine dendrimer.

PubMed

Nyitrai, Gabriella; Keszthelyi, Tamás; Bóta, Attila; Simon, Agnes; Tőke, Orsolya; Horváth, Gergő; Pál, Ildikó; Kardos, Julianna; Héja, László

2013-08-01

Polyamidoamine (PAMAM) dendrimers are highly charged hyperbranched protein-like polymers that are known to interact with cell membranes. In order to disclose the mechanisms of dendrimer-membrane interaction, we monitored the effect of PAMAM generation five (G5) dendrimer on the membrane permeability of living neuronal cells followed by exploring the underlying structural changes with infrared-visible sum frequency vibrational spectroscopy (SVFS), small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). G5 dendrimers were demonstrated to irreversibly increase the membrane permeability of neurons that could be blocked in low-[Na(+)], but not in low-[Ca(2+)] media suggesting the formation of specific Na(+) permeable channels. SFVS measurements on silica supported DPPG-DPPC bilayers suggested G5-specific trans-polarization of the membrane. SAXS data and freeze-fracture TEM imaging of self-organized DPPC vesicle systems demonstrated disruption of DPPC vesicle layers by G5 through polar interactions between G5 terminal amino groups and the anionic head groups of DPPC. We propose a nanoscale mechanism by which G5 incorporates into the membrane through multiple polar interactions that disrupt proximate membrane bilayer and shape a unique hydrophilic Na(+) ion permeable channel around the dendrimer. In addition, we tested whether these artificial Na(+) channels can be exploited as antibiotic tools. We showed that G5 quickly arrest the growth of resistant bacterial strains below 10μg/ml concentration, while they show no detrimental effect on red blood cell viability, offering the chance for the development of new generation anti-resistant antibiotics. Copyright © 2013 Elsevier B.V. All rights reserved.

Molecular Dynamics Study of the Structure, Flexibility, and Hydrophilicity of PETIM Dendrimers: A Comparison with PAMAM Dendrimers.

PubMed

Kanchi, Subbarao; Suresh, Gorle; Priyakumar, U Deva; Ayappa, K G; Maiti, Prabal K

2015-10-15

A new class of dendrimers, the poly(propyl ether imine) (PETIM) dendrimer, has been shown to be a novel hyperbranched polymer having potential applications as a drug delivery vehicle. Structure and dynamics of the amine terminated PETIM dendrimer and their changes with respect to the dendrimer generation are poorly understood. Since most drugs are hydrophobic in nature, the extent of hydrophobicity of the dendrimer core is related to its drug encapsulation and retention efficacy. In this study, we carry out fully atomistic molecular dynamics (MD) simulations to characterize the structure of PETIM (G2-G6) dendrimers in salt solution as a function of dendrimer generation at different protonation levels. Structural properties such as radius of gyration (Rg), radial density distribution, aspect ratio, and asphericity are calculated. In order to assess the hydrophilicity of the dendrimer, we compute the number of bound water molecules in the interior of dendrimer as well as the number of dendrimer-water hydrogen bonds. We conclude that PETIM dendrimers have relatively greater hydrophobicity and flexibility when compared with their extensively investigated PAMAM counterparts. Hence PETIM dendrimers are expected to have stronger interactions with lipid membranes as well as improved drug encapsulation and retention properties when compared with PAMAM dendrimers. We compute the root-mean-square fluctuation of dendrimers as well as their entropy to quantify the flexibility of the dendrimer. Finally we note that structural and solvation properties computed using force field parameters derived based on the CHARMM general purpose force field were in good quantitative agreement with those obtained using the generalized Amber force field (GAFF).

Au nanorice assemble electrolytically into mesostars.

PubMed

Bardhan, Rizia; Neumann, Oara; Mirin, Nikolay; Wang, Hui; Halas, Naomi J

2009-02-24

Star-shaped mesotructures are formed when an aqueous suspension of Au nanorice particles, which consist of prolate hematite cores and a thin Au shell, is subjected to an electric current. The nanorice particles assemble to form hyperbranched micrometer-scale mesostars. To our knowledge, this is the first reported observation of nanoparticle assembly into larger ordered structures under the influence of an electrochemical process (H(2)O electrolysis). The assembly is accompanied by significant modifications in the morphology, dimensions, chemical composition, crystallographic structure, and optical properties of the constituent nanoparticles.

Development of dye-sensitized solar cells composed of liquid crystal embedded, electrospun poly(vinylidene fluoride-co-hexafluoropropylene) nanofibers as polymer gel electrolytes.

PubMed

Ahn, Sung Kwang; Ban, Taewon; Sakthivel, P; Lee, Jae Wook; Gal, Yeong-Soon; Lee, Jin-Kook; Kim, Mi-Ra; Jin, Sung-Ho

2012-04-01

In order to overcome the problems associated with the use of liquid electrolytes in dye-sensitized solar cells (DSSCs), a new system composed of liquid crystal embedded, polymer electrolytes has been developed. For this purpose, three types of DSSCs have been fabricated. The cells contain electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (e-PVdF-co-HFP) polymer gel electrolyte, with and without doping with the liquid crystal E7 and with a liquid electrolyte. The morphologies of the newly prepared DSSCs were explored using field emission scanning electron microscopy (FE-SEM). Analysis of the FE-SEM images indicate that the DSSC composed of E7 embedded on e-PVdF-co-HFP polymer gel electrolyte has a greatly regular morphology with an average diameter. The ionic conductivity of E7 embedded on e-PVdF-co-HFP polymer gel electrolyte was found to be 2.9 × 10(-3) S/cm at room temperature, a value that is 37% higher than that of e-PVdF-co-HFP polymer gel electrolyte. The DCCS containing the E7 embedded, e-PVdF-co-HFP polymer gel electrolyte was observed to possess a much higher power conversion efficiency (PCE = 6.82%) than that of an e-PVdF-co-HFP nanofiber (6.35%). In addition, DSSCs parameters of the E7 embedded, e-PVdF-co-HFP polymer gel electrolyte (V(oc) = 0.72 V, J(sc) = 14.62 mA/cm(2), FF = 64.8%, and PCE = 6.82% at 1 sun intensity) are comparable to those of a liquid electrolyte (V(oc) = 0.75 V, J(sc) = 14.71 mA/cm(2), FF = 64.9%, and PCE = 7.17%, both at a 1 sun intensity).

Investigation of the interfacial properties of polyurethane/carbon nanotube hybrid composites: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Goclon, Jakub; Panczyk, Tomasz; Winkler, Krzysztof

2018-03-01

Considering the varied applications of hybrid polymer/carbon nanotube composites and the constant progress in the synthesis methods of such materials, we report a theoretical study of interfacial layer formation between pristine single-wall carbon nanotubes (SWCNTs) and polyurethane (PU) using molecular dynamic simulations. We vary the SWCNT diameter and the number of PU chains to examine various PU-SWCNT interaction patterns. Our simulations indicate the important role of intra-chain forces in PU. No regular polymeric structures could be identified on the carbon nanotube surface during the simulations. We find that increasing the SWCNT diameter results in stronger polymer binding. However, higher surface loadings of PU lead to stronger interpenetration by the polymeric segments; this effect is more apparent for SWCNTs with small diameters. Our core finding is that the attached PU binds most strongly to the carbon nanotubes with the largest diameters. Polymer dynamics reveal the loose distribution of PU chains in these systems.

Competition for hydrogen-bond formation in the helix-coil transition and protein folding

NASA Astrophysics Data System (ADS)

Badasyan, A. V.; Tonoyan, Sh. A.; Mamasakhlisov, Y. Sh.; Giacometti, Achille; Benight, A. S.; Morozov, V. F.

2011-05-01

The problem of the helix-coil transition of biopolymers in explicit solvents, such as water, with the ability for hydrogen bonding with a solvent is addressed analytically using a suitably modified version of the Generalized Model of Polypeptide Chains. Besides the regular helix-coil transition, an additional coil-helix or reentrant transition is also found at lower temperatures. The reentrant transition arises due to competition between polymer-polymer and polymer-water hydrogen bonds. The balance between the two types of hydrogen bonding can be shifted to either direction through changes not only in temperature, but also by pressure, mechanical force, osmotic stress, or other external influences. Both polypeptides and polynucleotides are considered within a unified formalism. Our approach provides an explanation of the experimental difficulty of observing the reentrant transition with pressure and underscores the advantage of pulling experiments for studies of DNA. Results are discussed and compared with those reported in a number of recent publications with which a significant level of agreement is obtained.

Impact of Interfacial Roughness on the Sorption Properties of Nanocast Polymers

DOE PAGES

Sridhar, Manasa; Gunugunuri, Krishna R.; Hu, Naiping; ...

2016-03-16

Nanocasting is an emerging method to prepare organic polymers with regular, nanometer pores using inorganic templates. This report assesses the impact of imperfect template replication on the sorption properties of such polymer castings. Existing X-ray diffraction data show that substantial diffuse scattering exists in the small-angle region even though TEM images show near perfect lattices of uniform pores. To assess the origin of the diffuse scattering, the morphology of the phenol - formaldehyde foams (PFF) was investigated by small-angle X-ray scattering (SAXS). The observed diffuse scattering is attributed to interfacial roughness due to fractal structures. Such roughness has a profoundmore » impact on the sorption properties. Conventional pore- filling models, for example, overestimate protein sorption capacity. A mathematical framework is presented to calculate sorption properties based on observed morphological parameters. The formalism uses the surface fractal dimension determined by SAXS in conjunction with nitrogen adsorption isotherms to predict lysozyme sorption. The results are consistent with measured lysozyme loading.« less

Healable thermoset polymer composite embedded with stimuli-responsive fibres

PubMed Central

Li, Guoqiang; Meng, Harper; Hu, Jinlian

2012-01-01

Severe wounds in biological systems such as human skin cannot heal themselves, unless they are first stitched together. Healing of macroscopic damage in thermoset polymer composites faces a similar challenge. Stimuli-responsive shape-changing polymeric fibres with outstanding mechanical properties embedded in polymers may be able to close macro-cracks automatically upon stimulation such as heating. Here, a stimuli-responsive fibre (SRF) with outstanding mechanical properties and supercontraction capability was fabricated for the purpose of healing macroscopic damage. The SRFs and thermoplastic particles (TPs) were incorporated into regular thermosetting epoxy for repeatedly healing macroscopic damages. The system works by mimicking self-healing of biological systems such as human skin, close (stitch) then heal, i.e. close the macroscopic crack through the thermal-induced supercontraction of the SRFs, and bond the closed crack through melting and diffusing of TPs at the crack interface. The healing efficiency determined using tapered double-cantilever beam specimens was 94 per cent. The self-healing process was reasonably repeatable. PMID:22896563

From microporous regular frameworks to mesoporous materials with ultrahigh surface area: dynamic reorganization of porous polymer networks.

PubMed

Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng; Thomas, Arne; Antonietti, Markus

2008-10-08

High surface area organic materials featuring both micro- and mesopores were synthesized under ionothermal conditions via the formation of polyaryltriazine networks. While the polytrimerization of nitriles in zinc chloride at 400 degrees C produces microporous polymers, higher reaction temperatures induce the formation of additional spherical mesopores with a narrow dispersity. The nitrogen-rich carbonaceous polymer materials thus obtained present surface areas and porosities up to 3300 m(2) g(-1) and 2.4 cm(3) g(-1), respectively. The key point of this synthesis relies on the occurrence of several high temperature polymerization reactions, where irreversible carbonization reactions coupled with the reversible trimerization of nitriles allow the reorganization of the dynamic triazine network. The ZnCl2 molten salt fulfills the requirement of a high temperature solvent, but is also required as catalyst. Thus, this dynamic polymerization system provides not only highly micro- and mesoporous materials, but also allows controlling the pore structure in amorphous organic materials.

Simulation of size-exclusion chromatography distribution coefficients of comb-shaped molecules in spherical pores comparison of simulation and experiment.

PubMed

Radke, Wolfgang

2004-03-05

Simulations of the distribution coefficients of linear polymers and regular combs with various spacings between the arms have been performed. The distribution coefficients were plotted as a function of the number of segments in order to compare the size exclusion chromatography (SEC)-elution behavior of combs relative to linear molecules. By comparing the simulated SEC-calibration curves it is possible to predict the elution behavior of comb-shaped polymers relative to linear ones. In order to compare the results obtained by computer simulations with experimental data, a variety of comb-shaped polymers varying in side chain length, spacing between the side chains and molecular weights of the backbone were analyzed by SEC with light-scattering detection. It was found that the computer simulations could predict the molecular weights of linear molecules having the same retention volume with an accuracy of about 10%, i.e. the error in the molecular weight obtained by calculating the molecular weight of the comb-polymer based on a calibration curve constructed using linear standards and the results of the computer simulations are of the same magnitude as the experimental error of absolute molecular weight determination.

Charge properties and bacterial contact-killing of hyperbranched polyurea-polyethyleneimine coatings with various degrees of alkylation

NASA Astrophysics Data System (ADS)

Roest, Steven; van der Mei, Henny C.; Loontjens, Ton J. A.; Busscher, Henk J.

2015-11-01

Coatings of immobilized-quaternary-ammonium-ions (QUAT) uniquely kill adhering bacteria upon contact. QUAT-coatings require a minimal cationic-charge surface density for effective contact-killing of adhering bacteria of around 1014 cm-2. Quaternization of nitrogen is generally achieved through alkylation. Here, we investigate the contribution of additional alkylation with methyl-iodide to the cationic-charge density of hexyl-bromide alkylated, hyperbranched polyurea-polyethyleneimine coatings measuring charge density with fluorescein staining. X-ray-photoelectron-spectroscopy was used to determine the at.% alkylated-nitrogen. Also streaming potentials, water contact-angles and bacterial contact-killing were measured. Cationic-charge density increased with methyl-iodide alkylation times up to 18 h, accompanied by an increase in the at.% alkylated-nitrogen. Zeta-potentials became more negative upon alkylation as a result of shielding of cationiccharges by hydrophobic alkyl-chains. Contact-killing of Gram-positive Staphylococci only occurred when the cationic-charge density exceeded 1016 cm-2 and was carried by alkylated-nitrogen (electron-binding energy 401.3 eV). Gram-negative Escherichia coli was not killed upon contact with the coatings. There with this study reveals that cationic-charge density is neither appropriate nor sufficient to determine the ability of QUAT-coatings to kill adhering bacteria. Alternatively, the at.% of alkylated-nitrogen at 401.3 eV is proposed, as it reflects both cationic-charge and its carrier. The at.% N401.3 eV should be above 0.45 at.% for Gram-positive bacterial contact-killing.

Breakdown Voltage of Thermoplastics with Clay Nanometer-Sized Fillers (Postprint)

DTIC Science & Technology

2008-12-01

of clay nanofillers. Low density polyethylene ( LDPE ) is a mechanically tough, inexpensive polymer used heavily in industry. Numerous studies have...A blend of LDPE grafted with maleic anhydride ( LDPE -g- MA) is tested in this work for improved electrical properties with clay addition. The...LLDPE) copolymer with octene. LLDPE improves over regular LDPE in a number of mechanical properties, though it has a higher production cost. A

Synthesis and Reactivity of 1-Methyl-e-Ethynylpyridinium Triflate

DTIC Science & Technology

1992-05-15

Approved for public release, distribution unlimited 13. ABSTRACT (Maximum 200 words) 1- Methyl -4-ethynylpyridiniurn triflate has been prepared by treatment of... treatment of 4-ethynylpyrdine with methyl tinflase in methylene chloride. I his new native acetylenic monomer timerized to tris. 1.3.5-( I...described their conversion to polymers with regular structure.8.9 Using the analogy to vinylpyridine, we examined reactions of 1 with triflic acid and methyl

Thin Films of Novel Linear-Dendritic Diblock Copolymers

NASA Astrophysics Data System (ADS)

Iyer, Jyotsna; Hammond, Paula

1998-03-01

A series of diblock copolymers with one linear block and one dendrimeric block have been synthesized with the objective of forming ultrathin film nanoporous membranes. Polyethyleneoxide serves as the linear hydrophilic portion of the diblock copolymer. The hyperbranched dendrimeric block consists of polyamidoamine with functional end groups. Thin films of these materials made by spin casting and the Langmuir-Blodgett techniques are being studied. The effect of the polyethylene oxide block size and the number and chemical nature of the dendrimer end group on the nature and stability of the films formed willbe discussed.

Incoherent light-induced self-organization of molecules.

PubMed

Kandjani, S Ahmadi; Barille, R; Dabos-Seignon, S; Nunzi, J M; Ortyl, E; Kucharski, S

2005-12-01

Although coherent light is usually required for the self-organization of regular spatial patterns from optical beams, we show that peculiar light-matter interaction can break this evidence. In the traditional method of recording laser-induced periodic surface structures, a light intensity distribution is produced at the surface of a polymer film by an interference between two coherent optical beams. We report on the self-organization followed by propagation of a surface relief pattern. It is induced in a polymer film by using a low-power and small-size coherent beam assisted by a high-power and large-size incoherent and unpolarized beam. We demonstrate that we can obtain large size and well-organized patterns starting from a dissipative interaction. Our experiments open new directions to improving optical processing systems.

Rational design of novel, fluorescent, tagged glutamic acid dendrimers with different terminal groups and in silico analysis of their properties

PubMed Central

Martinho, Nuno; Silva, Liana C; Florindo, Helena F; Brocchini, Steve; Zloh, Mire; Barata, Teresa S

2017-01-01

Dendrimers are hyperbranched polymers with a multifunctional architecture that can be tailored for the use in various biomedical applications. Peptide dendrimers are particularly relevant for drug delivery applications due to their versatility and safety profile. The overall lack of knowledge of their three-dimensional structure, conformational behavior and structure–activity relationship has slowed down their development. Fluorophores are often conjugated to dendrimers to study their interaction with biomolecules and provide information about their mechanism of action at the molecular level. However, these probes can change dendrimer surface properties and have a direct impact on their interactions with biomolecules and with lipid membranes. In this study, we have used computer-aided molecular design and molecular dynamics simulations to identify optimal topology of a poly(l-glutamic acid) (PG) backbone dendrimer that allows incorporation of fluorophores in the core with minimal availability for undesired interactions. Extensive all-atom molecular dynamic simulations with the CHARMM force field were carried out for different generations of PG dendrimers with the core modified with a fluorophore (nitrobenzoxadiazole and Oregon Green 488) and various surface groups (glutamic acid, lysine and tryptophan). Analysis of structural and topological features of all designed dendrimers provided information about their size, shape, internal distribution and dynamic behavior. We have found that four generations of a PG dendrimer are needed to ensure minimal exposure of a core-conjugated fluorophore to external environment and absence of undesired interactions regardless of the surface terminal groups. Our findings suggest that NBD-PG-G4 can provide a suitable scaffold to be used for biophysical studies of surface-modified dendrimers to provide a deeper understanding of their intermolecular interactions, mechanisms of action and trafficking in a biological system. PMID:29026301

Rational design of novel, fluorescent, tagged glutamic acid dendrimers with different terminal groups and in silico analysis of their properties.

PubMed

Martinho, Nuno; Silva, Liana C; Florindo, Helena F; Brocchini, Steve; Zloh, Mire; Barata, Teresa S

2017-01-01

Dendrimers are hyperbranched polymers with a multifunctional architecture that can be tailored for the use in various biomedical applications. Peptide dendrimers are particularly relevant for drug delivery applications due to their versatility and safety profile. The overall lack of knowledge of their three-dimensional structure, conformational behavior and structure-activity relationship has slowed down their development. Fluorophores are often conjugated to dendrimers to study their interaction with biomolecules and provide information about their mechanism of action at the molecular level. However, these probes can change dendrimer surface properties and have a direct impact on their interactions with biomolecules and with lipid membranes. In this study, we have used computer-aided molecular design and molecular dynamics simulations to identify optimal topology of a poly(l-glutamic acid) (PG) backbone dendrimer that allows incorporation of fluorophores in the core with minimal availability for undesired interactions. Extensive all-atom molecular dynamic simulations with the CHARMM force field were carried out for different generations of PG dendrimers with the core modified with a fluorophore (nitrobenzoxadiazole and Oregon Green 488) and various surface groups (glutamic acid, lysine and tryptophan). Analysis of structural and topological features of all designed dendrimers provided information about their size, shape, internal distribution and dynamic behavior. We have found that four generations of a PG dendrimer are needed to ensure minimal exposure of a core-conjugated fluorophore to external environment and absence of undesired interactions regardless of the surface terminal groups. Our findings suggest that NBD-PG-G4 can provide a suitable scaffold to be used for biophysical studies of surface-modified dendrimers to provide a deeper understanding of their intermolecular interactions, mechanisms of action and trafficking in a biological system.

Nanoarchitectonics of molecular aggregates: science and technology.

PubMed

Ramanathan, Muruganathan; Hong, Kunlun; Ji, Qingmin; Yonamine, Yusuke; Hill, Jonathan P; Ariga, Katsuhiko

2014-01-01

The field of making, studying and using molecular aggregates, in which the individual molecules (monomers) are arranged in a regular fashion, has come a long way. Taking control over the aggregation of small molecules and polymers in bulk, on surfaces and at interfaces pose a considerable challenge for their utilization in modern high tech applications. In this review, we provide a detailed insight into recent trends in molecular aggregates from the perspectives of nanoarchitectonics.

Chemical modification of electrolytes for lithium batteries

NASA Astrophysics Data System (ADS)

Afanas'ev, Vladimir N.; Grechin, Aleksandr G.

2002-09-01

Modern approaches to modifying chemically electrolytes for lithium batteries are analysed with the aim of optimising the charge-transfer processes in liquid-phase and solid (polymeric) media. The main regularities of transport properties of lithium electrolyte solutions containing complex (encapsulated) ions in aprotic solvents and polymers are discussed. The prospects for the development of electrolytic solvosystems with the chain (ionotropic) mechanism of conduction with respect to lithium ions are outlined. The bibliography includes 126 references.

Nanoarchitectonics of Molecular Aggregates: Science and Technology

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

Ramanathan, Nathan Muruganathan; Hong, Kunlun; Ji, Dr. Qingmin

2014-01-01

The field of making, studying and using molecular aggregates, in which the individual molecules (monomers) are arranged in a regular fashion, has come a long way. Taking control over the aggregation of small molecules and polymers in bulk, on surfaces and at interfaces pose a considerable challenge for their utilization in modern high tech applications. In this review we provide a detailed insight into recent trends in molecular aggregates from the perspectives of nanoarchitectonics.

Lessons learnt from early failure of a patient trial with a polymer-on-polymer resurfacing hip arthroplasty

PubMed Central

Van Susante, Job L C; Verdonschot, Nico; Bom, L Paul A; Tomaszewski, Pawel; Campbell, Pat; Ebramzadeh, Edward; Schreurs, B Wim

2018-01-01

Background and purpose Hip resurfacing (HR) is a treatment option promoted for hip arthritis in young and active patients. However, adverse reactions to metal are a concern and the search for non-metallic bearing options proceeds. We present the first clinical study performed in patients using a newly developed hydrophilic polymer-on-polymer hip resurfacing device. Patients and methods After performing extensive hip simulator tests, biocompatibility testing and animal tests (ISO 14242-1,3; 10993-3,4,5,10,11), approval was obtained from the IRB committee to enroll 15 patients in the first clinical study in humans using this experimental polymer-on-polymer hip resurfacing device. All surgeries were done by 2 experienced hip resurfacing surgeons. Clinical scores and standard radiographs as well as routine MRIs were obtained at regular intervals. Results The surgical technique proved feasible with successful implantation of the new device using PMMA cement fixation on both sides without complications. Postoperative imaging revealed a well-positioned and well-fixed polymer resurfacing hip arthroplasty in all 4 initial cases. All 4 patients were free of pain and had good function for the first 2 months. However, in all 4 cases early cup loosening occurred between 8 and 11 weeks after surgery, necessitating immediate closure of the study. All 4 patients had a reoperation and were revised to a conventional THA. Retrieval analyses confirmed early cup loosening at the implant–cement interface in all 4 cases. The femoral components remained well attached to the cement. The periprosthetic tissues showed only small amounts of polymeric wear debris and there was only a very mild inflammatory reaction to this. Interpretation Early cup loosening mandated a premature arrest of this study. After additional laboratory testing this failure mode was found to be the result of a small, yet measurable contraction in the cup size after exposing these implants to biological fluid divalent ion fluctuations in vivo. Currently used preclinical tests had failed to detect this failure mechanism. Modification of the polymer is essential to overcome these problems and before the potential of a polymer-on-polymer resurfacing arthroplasty may be further evaluated in patients. PMID:28931340

Lessons learnt from early failure of a patient trial with a polymer-on-polymer resurfacing hip arthroplasty.

PubMed

Van Susante, Job L C; Verdonschot, Nico; Bom, L Paul A; Tomaszewski, Pawel; Campbell, Pat; Ebramzadeh, Edward; Schreurs, B Wim

2018-02-01

Background and purpose - Hip resurfacing (HR) is a treatment option promoted for hip arthritis in young and active patients. However, adverse reactions to metal are a concern and the search for non-metallic bearing options proceeds. We present the first clinical study performed in patients using a newly developed hydrophilic polymer-on-polymer hip resurfacing device. Patients and methods - After performing extensive hip simulator tests, biocompatibility testing and animal tests (ISO 14242-1,3; 10993-3,4,5,10,11), approval was obtained from the IRB committee to enroll 15 patients in the first clinical study in humans using this experimental polymer-on-polymer hip resurfacing device. All surgeries were done by 2 experienced hip resurfacing surgeons. Clinical scores and standard radiographs as well as routine MRIs were obtained at regular intervals. Results - The surgical technique proved feasible with successful implantation of the new device using PMMA cement fixation on both sides without complications. Postoperative imaging revealed a well-positioned and well-fixed polymer resurfacing hip arthroplasty in all 4 initial cases. All 4 patients were free of pain and had good function for the first 2 months. However, in all 4 cases early cup loosening occurred between 8 and 11 weeks after surgery, necessitating immediate closure of the study. All 4 patients had a reoperation and were revised to a conventional THA. Retrieval analyses confirmed early cup loosening at the implant-cement interface in all 4 cases. The femoral components remained well attached to the cement. The periprosthetic tissues showed only small amounts of polymeric wear debris and there was only a very mild inflammatory reaction to this. Interpretation - Early cup loosening mandated a premature arrest of this study. After additional laboratory testing this failure mode was found to be the result of a small, yet measurable contraction in the cup size after exposing these implants to biological fluid divalent ion fluctuations in vivo. Currently used preclinical tests had failed to detect this failure mechanism. Modification of the polymer is essential to overcome these problems and before the potential of a polymer-on-polymer resurfacing arthroplasty may be further evaluated in patients.

Combined collapse by bridging and self-adhesion in a prototypical polymer model inspired by the bacterial nucleoid

NASA Astrophysics Data System (ADS)

Scolari, Vittore F.; Cosentino Lagomarsino, Marco

Recent experimental results suggest that the E. coli chromosome feels a self-attracting interaction of osmotic origin, and is condensed in foci by bridging interactions. Motivated by these findings, we explore a generic modeling framework combining solely these two ingredients, in order to characterize their joint effects. Specifically, we study a simple polymer physics computational model with weak ubiquitous short-ranged self attraction and stronger sparse bridging interactions. Combining theoretical arguments and simulations, we study the general phenomenology of polymer collapse induced by these dual contributions, in the case of regularly-spaced bridging. Our results distinguish a regime of classical Flory-like coil-globule collapse dictated by the interplay of excluded volume and attractive energy and a switch-like collapse where bridging interaction compete with entropy loss terms from the looped arms of a star-like rosette. Additionally, we show that bridging can induce stable compartmentalized domains. In these configurations, different "cores" of bridging proteins are kept separated by star-like polymer loops in an entropically favorable multi-domain configuration, with a mechanism that parallels micellar polysoaps. Such compartmentalized domains are stable, and do not need any intra-specific interactions driving their segregation. Domains can be stable also in presence of uniform attraction, as long as the uniform collapse is above its theta point.

Synthesis of heparin-like oligosaccharides on polymer supports.

PubMed

Ojeda, Rafael; Terentí, Olimpia; de Paz, José-Luis; Martín-Lomas, Manuel

2004-01-01

The biological functions of a variety of proteins are regulated by heparan sulfate glycosaminoglycans. In order to facilitate the elucidation of the molecular basis of glycosaminoglycan-protein interactions we have developed syntheses of heparin-like oligosaccharides on polymer supports. A completely stereoselective strategy previously developed by us for the synthesis of these oligosaccharides in solution has been extended to the solid phase using an acceptor-bound approach. Both a soluble polymer support and a polyethylene glycol-grafted polystyrene resin have been used and different strategies for the attachment of the acceptor to the support have been explored. The attachment of fully protected disaccharide building blocks to a soluble support through the carboxylic group of the uronic acid unit by a succinic ester linkage, the use of trichloroacetimidates as glycosylating agents and of a functionalized Merryfield type resin for the capping process allowed for the construction of hexasaccharide and octasaccharide fragments containing the structural motif of the regular region of heparin. This strategy may facilitate the synthesis of glycosaminoglycan oligosaccharides by using the required building blocks in the glycosylation sequence.

Tension-induced binding of semiflexible biopolymers

NASA Astrophysics Data System (ADS)

Benetatos, Panayotis; von der Heydt, Alice; Zippelius, Annette

2015-03-01

We investigate theoretically the effect of polymer tension on the collective behaviour of reversible cross-links. We use a model of two parallel-aligned, weakly-bending wormlike chains with a regularly spaced sequence of binding sites subjected to a tensile force. Reversible cross-links attach and detach at the binding sites with an affinity controlled by a chemical potential. In a mean-field approach, we calculate the free energy of the system and we show the emergence of a free energy barrier which controls the reversible (un)binding. The tension affects the conformational entropy of the chains which competes with the binding energy of the cross-links. This competition gives rise to a sudden increase in the fraction of bound sites as the polymer tension increases. The force-induced first-order transition in the number of cross-links implies a sudden force-induced stiffening of the effective stretching modulus of the polymers. This mechanism may be relevant to the formation and stress-induced strengthening of stress fibers in the cytoskeleton. We acknowledge support by the Deutsche Forschungsgemeinschaft (DFG) via grant SFB-937/A1.

Entanglements in Conjugated Polymers

NASA Astrophysics Data System (ADS)

Xie, Renxuan; Lee, Youngmin; Aplan, Melissa; Caggiano, Nick; Gomez, Enrique; Colby, Ralph

Conjugated polymers, such as poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly-((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT), are widely used as hole and electron transport materials in a variety of electronic devices. However, fundamental knowledge regarding chain entanglements and nematic-to-isotropic transition is still lacking and are crucial to maximize charge transport properties. A systematic melt rheology study on P3HT with various molecular weights and regio regularities was performed. We find that the entanglement molecular weight Me is 5.0 kg/mol for regiorandom P3HT, but the apparent Me for regioregular P3HT is significantly higher. The difference is postulated to arise from the presence of a nematic phase only in regioregular P3HT. Analogously, PFTBT shows a clear rheological signature of the nematic-to-isotropic transition as a reversible sharp transition at 278 C. Shearing of this nematic phase leads to anisotropic crystalline order in PFTBT. We postulate that aligning the microstructure will impact charge transport and thereby advance the field of conducting polymers. National Science Foundation.

Cold preservation with hyperbranched polyglycerol-based solution improves kidney functional recovery with less injury at reperfusion in rats

PubMed Central

Li, Shadan; Liu, Bin; Guan, Qiunong; Chafeeva, Irina; Brooks, Donald E; Nguan, Christopher YC; Kizhakkedathu, Jayachandran N; Du, Caigan

2017-01-01

Minimizing donor organ injury during cold preservation (including cold perfusion and storage) is the first step to prevent transplant failure. We recently reported the advantages of hyperbranched polyglycerol (HPG) as a novel substitute for hydroxyethyl starch in UW solution for both cold heart preservation and cold kidney perfusion. This study evaluated the functional recovery of the kidney at reperfusion after cold preservation with HPG solution. The impact of HPG solution compared to conventional UW and HTK solutions on tissue weight and cell survival at 4°C was examined using rat kidney tissues and cultured human umbilical vein endothelial cells (HUVECs), respectively. The kidney protection by HPG solution was tested in a rat model of cold kidney ischemia-reperfusion injury, and was evaluated by histology and kidney function. Here, we showed that preservation with HPG solution prevented cell death in cultured HUVECs and edema formation in kidney tissues at 4°C similar to UW solution, whereas HTK solution was less effective. In rat model of cold ischemia-reperfusion injury, the kidneys perfused and subsequently stored 1-hour with cold HPG solution showed less leukocyte infiltration, less tubular damage and better kidney function (lower levels of serum creatinine and blood urea nitrogen) at 48 h of reperfusion than those treated with UW or HTK solution. In conclusion, our data show the superiority of HPG solution to UW or HTK solution in the cold perfusion and storage of rat kidneys, suggesting that the HPG solution may be a promising candidate for improved donor kidney preservation prior to transplantation. PMID:28337272

Development of a fast curing tissue adhesive for meniscus tear repair.

PubMed

Bochyńska, Agnieszka Izabela; Hannink, Gerjon; Janssen, Dennis; Buma, Pieter; Grijpma, Dirk W

2017-01-01

Isocyanate-terminated adhesive amphiphilic block copolymers are attractive materials to treat meniscus tears due to their tuneable mechanical properties and good adhesive characteristics. However, a drawback of this class of materials is their relatively long curing time. In this study, we evaluate the use of an amine cross-linker and addition of catalysts as two strategies to accelerate the curing rates of a recently developed biodegradable reactive isocyanate-terminated hyper-branched adhesive block copolymer prepared from polyethylene glycol (PEG), trimethylene carbonate, citric acid and hexamethylene diisocyanate. The curing kinetics of the hyper-branched adhesive alone and in combination with different concentrations of spermidine solutions, and after addition of 2,2-dimorpholinodiethylether (DMDEE) or 1,4-diazabicyclo [2.2.2] octane (DABCO) were determined using FTIR. Additionally, lap-shear adhesion tests using all compositions at various time points were performed. The two most promising compositions of the fast curing adhesives were evaluated in a meniscus bucket handle lesion model and their performance was compared with that of fibrin glue. The results showed that addition of both spermidine and catalysts to the adhesive copolymer can accelerate the curing rate and that firm adhesion can already be achieved after 2 h. The adhesive strength to meniscus tissue of 3.2-3.7 N was considerably higher for the newly developed compositions than for fibrin glue (0.3 N). The proposed combination of an adhesive component and a cross-linking component or catalyst is a promising way to accelerate curing rates of isocyanate-terminated tissue adhesives.

Dendritic Growth Morphologies in Al-Zn Alloys—Part II: Phase-Field Computations

NASA Astrophysics Data System (ADS)

Dantzig, J. A.; Di Napoli, Paolo; Friedli, J.; Rappaz, M.

2013-12-01

In Part I of this article, the role of the Zn content in the development of solidification microstructures in Al-Zn alloys was investigated experimentally using X-ray tomographic microscopy. The transition region between dendrites found at low Zn content and dendrites found at high Zn content was characterized by textured seaweed-type structures. This Dendrite Orientation Transition (DOT) was explained by the effect of the Zn content on the weak anisotropy of the solid-liquid interfacial energy of Al. In order to further support this interpretation and to elucidate the growth mechanisms of the complex structures that form in the DOT region, a detailed phase-field study exploring anisotropy parameters' space is presented in this paper. For equiaxed growth, our results essentially recapitulate those of Haxhimali et al.[1] in simulations for pure materials. We find distinct regions of the parameter space associated with and dendrites, separated by a region where hyperbranched dendrites are observed. In simulations of directional solidification, we find similar behavior at the extrema, but in this case, the anisotropy parameters corresponding to the hyperbranched region produce textured seaweeds. As noted in the experimental work reported in Part I, these structures are actually dendrites that prefer to grow misaligned with respect to the thermal gradient direction. We also show that in this region, the dendrites grow with a blunted tip that oscillates and splits, resulting in an oriented trunk that continuously emits side branches in other directions. We conclude by making a correlation between the alloy composition and surface energy anisotropy parameters.

Molecular imprinted polymers for separation science: a review of reviews.

PubMed

Cheong, Won Jo; Yang, Song Hee; Ali, Faiz

2013-02-01

Molecular imprinted polymer is an artificial receptor made by imprinting molecules of a template in a polymer matrix followed by removing the template molecules via thorough washing to give the permanent template grooves. They show favored affinity to the template molecule compared to other molecules, and this property is the basic driving force for such diverse application of this techniques. Such techniques have been increasingly employed in a wide scope of applications such as chromatography, sample pretreatment, purification, catalysts, sensors, and drug delivery, etc., mostly in bioanalytical areas. A major part of them is related to development of new stationary phases and their application in chromatography and sample pretreatment. Embodiments of molecular imprinted polymer materials have been carried out in a variety of forms such as irregularly ground particles, regular spherical particles, nanoparticles, monoliths in a stainless steel or capillary column, open tubular layers in capillaries, surface attached thin layers, membranes, and composites, etc. There have been numerous review articles on molecular imprinted polymer issues. In this special review, the reviews in recent ca. 10 years will be categorized into several subgroups according to specified topics in separation science, and each review in each subgroup will be introduced in the order of date with brief summaries and comments on new developments and different scopes of prospects. Brief summaries of each categories and conclusive future perspectives are also given. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemistry and technology of radiation processed composite materials

NASA Astrophysics Data System (ADS)

Czvikovszky, T.

Composite materials of synthetics (based on monomers, oligomers and thermoplastics) and of natural polymers (wood and other fibrous cellulosics) prepared by radiation processing, offer valuable structural materials with enhanced coupling forces between the components. The applied polymer chemistry of such composites shows several common features with that of radiation grafting. E.g. the polymerization rate of oligomer-monomer mixtures in wood remains in most cases proportional to the square-root of the initiating dose-rate, just as in the simultaneous grafting, demonstrating that the chain termination kinetics remain regularly bimolecular in the corresponding dose-rate ranges. In the processing experiences of such composites, low dose requirement, easy process-control, and good technical feasibility have been found for composites of wood with oligomer-monomer mixtures, for coconut fibres with unsaturated polyesters and for pretreated wood fibre with polypropylene.

Biomimetic nanocoatings with exceptional mechanical, barrier, and flame-retardant properties from large-scale one-step coassembly

PubMed Central

Ding, Fuchuan; Liu, Jingjing; Zeng, Songshan; Xia, Yan; Wells, Kacie M.; Nieh, Mu-Ping; Sun, Luyi

2017-01-01

Large-scale biomimetic organic/inorganic hybrid nanocoatings with a nacre-like microstructure were prepared via a facile coassembly process. Different from conventional polymer nanocomposites, these nanocoatings contain a high concentration of nanosheets, which can be well aligned along the substrate surface. Moreover, the nanosheets and polymer matrix can be chemically co–cross-linked. As a result, the nanocoatings exhibit exceptional mechanical properties (high stiffness and strength), barrier properties (to both oxygen and water vapor), and flame retardancy, but they are also highly transparent (maintaining more than 85% of their original transmittance to visible light). The nanocoatings can be applied to various substrates and regular or irregular surfaces (for example, films and foams). Because of their excellent performance and high versatility, these nanocoatings are expected to find widespread application. PMID:28776038

Syntheses, crystal structures, and water adsorption behaviors of jungle-gym-type porous coordination polymers containing nitro moieties

NASA Astrophysics Data System (ADS)

Uemura, Kazuhiro; Onishi, Fumiaki; Yamasaki, Yukari; Kita, Hidetoshi

2009-10-01

NO 2 containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO 2) and 2,5-dinitroterephthalate (bdc-(NO 2) 2), afford porous coordination polymers, {[Zn 2(bdc-NO 2) 2(dabco)]· solvents} n ( 2⊃ solvents) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]· solvents} n ( 3⊃ solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn 2 units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2⊃ solvents and 3⊃ solvents, a rectangle pore surrounded by eight Zn 2 corners contains two and four NO 2 moieties, respectively. Thermal gravimetry (TG) and X-ray powder diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me 2CO. Adsorption measurements reveal that dried 2 and 3 adsorb H 2O molecules to be {[Zn 2(bdc-NO 2) 2(dabco)]·4H 2O} n ( 2⊃4H 2O) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]·6H 2O} n ( 3⊃6H 2O), showing the pore hydrophilicity enhancement caused by NO 2 group introduction.

Laser-induced periodic surface structures of thin, complex multi-component films

NASA Astrophysics Data System (ADS)

Reif, Juergen; Varlamova, Olga; Ratzke, Markus; Uhlig, Sebastian

2016-04-01

Femtosecond laser-induced regular nanostructures are generated on a complex multilayer target, namely a piece of a commercial, used hard disk memory. It is shown that after single-shot 800-nm irradiation at 0.26 J/cm2 only the polymer cover layer and—in the center—a portion of the magnetic multilayer are ablated. A regular array of linearly aligned spherical 450-nm features at the uncovered interface between cover and magnetic layers appears not to be produced by the irradiation. Only after about 10 pulses on one spot, classical ripples perpendicular to the laser polarization with a period of ≈700 nm are observed, with a modulation between 40 nm above and 40 nm below the pristine surface and an ablation depth only slightly larger than the thickness of the multilayer magnetic film. Further increase of the pulse number does not result in deeper ablation. However, 770-nm ripples become parallel to the polarization and are swelling to more than 120 nm above zero, much more than the full multilayer film thickness. In the spot periphery, much shallower 300-nm ripples are perpendicular to the strong modulation and the laser polarization. Irradiation with 0.49-J/cm2 pulses from an ultrafast white-light continuum results—in the spot periphery—in the formation of 200-nm ripples, only swelling above zero after removal of the polymer cover, without digging into the magnetic film.

Hollow microgels squeezed in overcrowded environments

NASA Astrophysics Data System (ADS)

Scotti, A.; Brugnoni, M.; Rudov, A. A.; Houston, J. E.; Potemkin, I. I.; Richtering, W.

2018-05-01

We study how a cavity changes the response of hollow microgels with respect to regular ones in overcrowded environments. The structural changes of hollow poly(N-isopropylacrylamide) microgels embedded within a matrix of regular ones are probed by small-angle neutron scattering with contrast variation. The form factors of the microgels at increasing compressions are directly measured. The decrease of the cavity size with increasing concentration shows that the hollow microgels have an alternative way with respect to regular cross-linked ones to respond to the squeezing due to their neighbors. The structural changes under compression are supported by the radial density profiles obtained with computer simulations. The presence of the cavity offers to the polymer network the possibility to expand toward the center of the microgels in response to the overcrowded environment. Furthermore, upon increasing compression, a two step transition occurs: First the microgels are compressed but the internal structure is unchanged; then, further compression causes the fuzzy shell to collapse completely and reduce the size of the cavity. Computer simulations also allow studying higher compression degrees than in the experiments leading to the microgel's faceting.

Distinct Tensile Response of Model Semi-flexible Elastomer Networks

NASA Astrophysics Data System (ADS)

Aguilera-Mercado, Bernardo M.; Cohen, Claude; Escobedo, Fernando A.

2011-03-01

Through coarse-grained molecular modeling, we study how the elastic response strongly depends upon nanostructural heterogeneities in model networks made of semi-flexible chains exhibiting both regular and realistic connectivity. Idealized regular polymer networks have been shown to display a peculiar elastic response similar to that of super-tough natural materials (e.g., organic adhesives inside abalone shells). We investigate the impact of chain stiffness, and the effect of including tri-block copolymer chains, on the network's topology and elastic response. We find in some systems a dual tensile response: a liquid-like behavior at small deformations, and a distinct saw-tooth shaped stress-strain curve at moderate to large deformations. Additionally, stiffer regular networks exhibit a marked hysteresis over loading-unloading cycles that can be deleted by heating-cooling cycles or by performing deformations along different axes. Furthermore, small variations of chain stiffness may entirely change the nature of the network's tensile response from an entropic to an enthalpic elastic regime, and micro-phase separation of different blocks within elastomer networks may significantly enhance their mechanical strength. This work was supported by the American Chemical Society.

Self-Controlled Synthesis of Hyperbranched Polyetherketones From A3 + B2 Approach Via Different Solubilities of Monomers in the Reaction Medium (Preprint)

DTIC Science & Technology

2006-10-01

higher yields than 1a and 2a after the similar work-up procedure, which involved Soxhlet extraction with water for 2 days and methanol for 2 days to get...the co-monomers. One such reaction medium, optimized PPA/P2O5 mixture, has been established for the electrophilic substitution reaction to yield high... Soxhlet -extracted with water for 2 days, methanol for 2 days, and finally dried under reduced pressure (0.05 mmHg) at 100°C for 150 h to give 3.30 g (76

The role of regioregularity, crystallinity, and chain orientation on electron transport in a high-mobility n-type copolymer.

PubMed

Steyrleuthner, Robert; Di Pietro, Riccardo; Collins, Brian A; Polzer, Frank; Himmelberger, Scott; Schubert, Marcel; Chen, Zhihua; Zhang, Shiming; Salleo, Alberto; Ade, Harald; Facchetti, Antonio; Neher, Dieter

2014-03-19

We investigated the correlation between the polymer backbone structural regularity and the charge transport properties of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T2)], a widely studied semiconducting polymer exhibiting high electron mobility and an unconventional micromorphology. To understand the influence of the chemical structure and crystal packing of conventional regioregular P(NDI2OD-T2) [RR-P(NDI2OD-T2)] on the charge transport, the corresponding regioirregular polymer RI-P(NDI2OD-T2) was synthesized. By combining optical, X-ray, and transmission electron microscopy data, we quantitatively characterized the aggregation, crystallization, and backbone orientation of all of the polymer films, which were then correlated to the electron mobilities in electron-only diodes. By carefully selecting the preparation conditions, we were able to obtain RR-P(NDI2OD-T2) films with similar crystalline structure along the three crystallographic axes but with different orientations of the polymer chains with respect to the substrate surface. RI-P(NDI2OD-T2), though exhibiting a rather similar LUMO structure and energy compared with the regioregular counterpart, displayed a very different packing structure characterized by the formation of ordered stacks along the lamellar direction without detectible π-stacking. Vertical electron mobilities were extracted from the space-charge-limited currents in unipolar devices. We demonstrate the anisotropy of the charge transport along the different crystallographic directions and how the mobility depends on π-stacking but is insensitive to the degree or coherence of lamellar stacking. The comparison between the regioregular and regioirregular polymers also shows how the use of large planar functional groups leads to improved charge transport, with mobilities that are less affected by chemical and structural disorder with respect to classic semicrystalline polymers such as poly(3-hexylthiophene).

Flexible packaging for PV modules

NASA Astrophysics Data System (ADS)

Dhere, Neelkanth G.

2008-08-01

Economic, flexible packages that provide needed level of protection to organic and some other PV cells over >25-years have not yet been developed. However, flexible packaging is essential in niche large-scale applications. Typical configuration used in flexible photovoltaic (PV) module packaging is transparent frontsheet/encapsulant/PV cells/flexible substrate. Besides flexibility of various components, the solder bonds should also be flexible and resistant to fatigue due to cyclic loading. Flexible front sheets should provide optical transparency, mechanical protection, scratch resistance, dielectric isolation, water resistance, UV stability and adhesion to encapsulant. Examples are Tefzel, Tedlar and Silicone. Dirt can get embedded in soft layers such as silicone and obscure light. Water vapor transmittance rate (WVTR) of polymer films used in the food packaging industry as moisture barriers are ~0.05 g/(m2.day) under ambient conditions. In comparison, light emitting diodes employ packaging components that have WVTR of ~10-6 g/(m2.day). WVTR of polymer sheets can be improved by coating them with dense inorganic/organic multilayers. Ethylene vinyl acetate, an amorphous copolymer used predominantly by the PV industry has very high O2 and H2O diffusivity. Quaternary carbon chains (such as acetate) in a polymer lead to cleavage and loss of adhesional strength at relatively low exposures. Reactivity of PV module components increases in presence of O2 and H2O. Adhesional strength degrades due to the breakdown of structure of polymer by reactive, free radicals formed by high-energy radiation. Free radical formation in polymers is reduced when the aromatic rings are attached at regular intervals. This paper will review flexible packaging for PV modules.

Lowest of AC-DC power output for electrostrictive polymers energy harvesting systems

NASA Astrophysics Data System (ADS)

Meddad, Mounir; Eddiai, Adil; Hajjaji, Abdelowahed; Guyomar, Daniel; Belkhiat, Saad; Boughaleb, Yahia; Chérif, Aida

2013-11-01

Advances in technology led to the development of electronic circuits and sensors with extremely low electricity consumption. At the same time, structural health monitoring, technology and intelligent integrated systems created a need for wireless sensors in hard to reach places in aerospace vehicles and large civil engineering structures. Powering sensors with energy harvesters eliminates the need to replace batteries on a regular basis. Scientists have been forced to search for new power source that are able to harvested energy from their surrounding environment (sunlight, temperature gradients etc.). Electrostrictive polymer belonging to the family of electro-active polymers, offer unique properties for the electromechanical transducer technology has been of particular interest over the last few years in order to replace conventional techniques such as those based on piezoelectric or electromagnetic, these materials are highly attractive for their low-density, with large strain capability that can be as high as two orders of magnitude greater than the striction-limited, rigid and fragile electroactive ceramics. Electrostrictive polymers sensors respond to vibration with an ac output signal, one of the most important objectives of the electronic interface is to realize the required AC-DC conversion. The goal of this paper is to design an active, high efficiency power doubler converter for electrostrictive polymers exclusively uses a fraction of the harvested energy to supply its active devices. The simulation results show that it is possible to obtain a maximum efficiency of the AC-DC converter equal to 80%. Premiliminary experimental measurements were performed and the results obtained are in good agreement with simulations.

Large-scale ordering of nanoparticles using viscoelastic shear processing.

PubMed

Zhao, Qibin; Finlayson, Chris E; Snoswell, David R E; Haines, Andrew; Schäfer, Christian; Spahn, Peter; Hellmann, Goetz P; Petukhov, Andrei V; Herrmann, Lars; Burdet, Pierre; Midgley, Paul A; Butler, Simon; Mackley, Malcolm; Guo, Qixin; Baumberg, Jeremy J

2016-06-03

Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong tunable structural colour. With oscillatory strain amplitudes of 300%, crystallization initiates at the wall and develops quickly across the bulk within only five oscillations. The resulting structure of random hexagonal close-packed layers is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonic materials, and forms a generic tool for ordering nanoparticles.

Pencil drawn strain gauges and chemiresistors on paper.

PubMed

Lin, Cheng-Wei; Zhao, Zhibo; Kim, Jaemyung; Huang, Jiaxing

2014-01-22

Pencil traces drawn on print papers are shown to function as strain gauges and chemiresistors. Regular graphite/clay pencils can leave traces composed of percolated networks of fine graphite powders, which exhibit reversible resistance changes upon compressive or tensile deflections. Flexible toy pencils can leave traces that are essentially thin films of graphite/polymer composites, which show reversible changes in resistance upon exposure to volatile organic compounds due to absorption/desorption induced swelling/recovery of the polymer binders. Pencil-on-paper devices are low-cost, extremely simple and rapid to fabricate. They are light, flexible, portable, disposable, and do not generate potentially negative environmental impact during processing and device fabrication. One can envision many other types of pencil drawn paper electronic devices that can take on a great variety of form factors. Hand drawn devices could be useful in resource-limited or emergency situations. They could also lead to new applications integrating art and electronics.

A generic interface to reduce the efficiency-stability-cost gap of perovskite solar cells

NASA Astrophysics Data System (ADS)

Hou, Yi; Du, Xiaoyan; Scheiner, Simon; McMeekin, David P.; Wang, Zhiping; Li, Ning; Killian, Manuela S.; Chen, Haiwei; Richter, Moses; Levchuk, Ievgen; Schrenker, Nadine; Spiecker, Erdmann; Stubhan, Tobias; Luechinger, Norman A.; Hirsch, Andreas; Schmuki, Patrik; Steinrück, Hans-Peter; Fink, Rainer H.; Halik, Marcus; Snaith, Henry J.; Brabec, Christoph J.

2017-12-01

A major bottleneck delaying the further commercialization of thin-film solar cells based on hybrid organohalide lead perovskites is interface loss in state-of-the-art devices. We present a generic interface architecture that combines solution-processed, reliable, and cost-efficient hole-transporting materials without compromising efficiency, stability, or scalability of perovskite solar cells. Tantalum-doped tungsten oxide (Ta-WOx)/conjugated polymer multilayers offer a surprisingly small interface barrier and form quasi-ohmic contacts universally with various scalable conjugated polymers. In a simple device with regular planar architecture and a self-assembled monolayer, Ta-WOx-doped interface-based perovskite solar cells achieve maximum efficiencies of 21.2% and offer more than 1000 hours of light stability. By eliminating additional ionic dopants, these findings open up the entire class of organics as scalable hole-transporting materials for perovskite solar cells.

Large-scale ordering of nanoparticles using viscoelastic shear processing

PubMed Central

Zhao, Qibin; Finlayson, Chris E.; Snoswell, David R. E.; Haines, Andrew; Schäfer, Christian; Spahn, Peter; Hellmann, Goetz P.; Petukhov, Andrei V.; Herrmann, Lars; Burdet, Pierre; Midgley, Paul A.; Butler, Simon; Mackley, Malcolm; Guo, Qixin; Baumberg, Jeremy J.

2016-01-01

Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong tunable structural colour. With oscillatory strain amplitudes of 300%, crystallization initiates at the wall and develops quickly across the bulk within only five oscillations. The resulting structure of random hexagonal close-packed layers is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonic materials, and forms a generic tool for ordering nanoparticles. PMID:27255808

Unknown Aspects of Self-Assembly of PbS Microscale Superstructures

PubMed Central

Querejeta-Fernández, Ana; Hernández-Garrido, Juan C.; Yang, Hengxi; Zhou, Yunlong; Varela, Aurea; Parras, Marina; Calvino-Gámez, José J.; González-Calbet, Jose M.; Green, Peter F.; Kotov, Nicholas A.

2012-01-01

A lot of interesting and sophisticated examples of nanoparticle (NP) self-assembly (SA) are known. From both fundamental and technological standpoints this field requires advancements in three principle directions: a) understanding the mechanism and driving forces of three-dimensional (3D) SA with both nano- and micro-levels of organization; b) understanding of disassembly/deconstruction processes; and c) finding synthetic methods of assembly into continuous superstructures without insulating barriers. From this perspective, we investigated the formation of well-known star-like PbS superstructures and found a number of previously unknown or overlooked aspects that can advance the knowledge of NP self-assembly in these three directions. The primary one is that the formation of large seemingly monocrystalline PbS superstructures with multiple levels of octahedral symmetry can be explained only by SA of small octahedral NPs. We found five distinct periods in the formation PbS hyperbranched stars: 1) nucleation of early PbS NPs with an average diameter of 31 nm; 2) assembly into 100–500 nm octahedral mesocrystals; 3) assembly into 1000–2500 nm hyperbranched stars; 4) assembly and ionic recrystallization into six-arm rods accompanied by disappearance of fine nanoscale structure; 5) deconstruction into rods and cubooctahedral NPs. The switches in assembly patterns between the periods occur due to variable dominance of pattern–determining forces that include vander Waals and electrostatic (charge-charge, dipole-dipole, and polarization) interactions. The superstructure deconstruction is triggered by chemical changes in the deep eutectic solvent (DES) used as the media. PbS superstructures can be excellent models for fundamental studies of nanoscale organization and SA manufacturing of (opto)electronics and energy harvesting devices which require organization of PbS components at multiple scales. PMID:22515512

Unknown aspects of self-assembly of PbS microscale superstructures.

PubMed

Querejeta-Fernández, Ana; Hernández-Garrido, Juan C; Yang, Hengxi; Zhou, Yunlong; Varela, Aurea; Parras, Marina; Calvino-Gámez, José J; González-Calbet, Jose M; Green, Peter F; Kotov, Nicholas A

2012-05-22

A lot of interesting and sophisticated examples of nanoparticle (NP) self-assembly (SA) are known. From both fundamental and technological standpoints, this field requires advancements in three principle directions: (a) understanding the mechanism and driving forces of three-dimensional (3D) SA with both nano- and microlevels of organization; (b) understanding disassembly/deconstruction processes; and (c) finding synthetic methods of assembly into continuous superstructures without insulating barriers. From this perspective, we investigated the formation of well-known star-like PbS superstructures and found a number of previously unknown or overlooked aspects that can advance the knowledge of NP self-assembly in these three directions. The primary one is that the formation of large seemingly monocrystalline PbS superstructures with multiple levels of octahedral symmetry can be explained only by SA of small octahedral NPs. We found five distinct periods in the formation PbS hyperbranched stars: (1) nucleation of early PbS NPs with an average diameter of 31 nm; (2) assembly into 100-500 nm octahedral mesocrystals; (3) assembly into 1000-2500 nm hyperbranched stars; (4) assembly and ionic recrystallization into six-arm rods accompanied by disappearance of fine nanoscale structure; (5) deconstruction into rods and cuboctahedral NPs. The switches in assembly patterns between the periods occur due to variable dominance of pattern-determining forces that include van der Waals and electrostatic (charge-charge, dipole-dipole, and polarization) interactions. The superstructure deconstruction is triggered by chemical changes in the deep eutectic solvent (DES) used as the media. PbS superstructures can be excellent models for fundamental studies of nanoscale organization and SA manufacturing of (opto)electronics and energy-harvesting devices which require organization of PbS components at multiple scales.

Construction of Hierarchical Fouling Resistance Surfaces onto Poly(vinylidene fluoride) Membranes for Combating Membrane Biofouling.

PubMed

Li, Xue; Hu, Xuefeng; Cai, Tao

2017-05-09

Owing to the highly hydrophobic nature, fluoropolymer membranes usually suffer from serious fouling problem, and therefore largely limited their practical applications. Also, the development of environmentally benign and nonreleasing antifouling coatings onto the inert fluoropolymer membranes remains a great challenge and is of prime importance for various scientific interests and industrial applications. In the present work, a facile and effective approach for the construction of hierarchical fouling resistance surfaces onto the poly(vinylidene fluoride) (PVDF) membranes was developed. Graft copolymers of PVDF with poly(hyperbranched polyglycerol methacrylamide) side chains (PVDF-g-PHPGMA copolymers) were synthesized via reversible addition-fragmentation chain transfer (RAFT) graft copolymerization of pentafluorophenyl methacrylate (PFMA) with the ozone-preactivated PVDF, followed by activated ester-amine reaction of PPFMA chains with amino-terminated hyperbranched polyglycerol (HPG-NH 2 ). The copolymers could be simply processed into microfiltration (MF) membranes with surface-tethered PHPGMA side chains on the membrane and pore surfaces by nonsolvent induced phase inversion. Furthermore, the PVDF-g-PHPGMA-g-PSBMA membrane was prepared via surface-initiated atom transfer radical polymerization (SI-ATRP) of zwitterionic monomer, N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (SBMA) from the PVDF-g-PHPGMA membrane and pore surfaces. Arise from a synergistic effect of the dendritic architecture of PHPGMA branches and "superhydrophilic" nature of PSBMA brushes, the PVDF-g-PHPGMA-g-PSBMA membranes exhibit superior resistance to protein and bacteria adhesion with insignificant cytotoxicity effects, making the membranes potentially useful for water treatment and biomedical applications. One may find the present study a general and effective method for the fabrication of antifouling fluoropolymer membranes in a controllable and green manner.

Multi-modal magnetic resonance imaging and histology of vascular function in xenografts using macromolecular contrast agent hyperbranched polyglycerol (HPG-GdF).

PubMed

Baker, Jennifer H E; McPhee, Kelly C; Moosvi, Firas; Saatchi, Katayoun; Häfeli, Urs O; Minchinton, Andrew I; Reinsberg, Stefan A

2016-01-01

Macromolecular gadolinium (Gd)-based contrast agents are in development as blood pool markers for MRI. HPG-GdF is a 583 kDa hyperbranched polyglycerol doubly tagged with Gd and Alexa 647 nm dye, making it both MR and histologically visible. In this study we examined the location of HPG-GdF in whole-tumor xenograft sections matched to in vivo DCE-MR images of both HPG-GdF and Gadovist. Despite its large size, we have shown that HPG-GdF extravasates from some tumor vessels and accumulates over time, but does not distribute beyond a few cell diameters from vessels. Fractional plasma volume (fPV) and apparent permeability-surface area product (aPS) parameters were derived from the MR concentration-time curves of HPG-GdF. Non-viable necrotic tumor tissue was excluded from the analysis by applying a novel bolus arrival time (BAT) algorithm to all voxels. aPS derived from HPG-GdF was the only MR parameter to identify a difference in vascular function between HCT116 and HT29 colorectal tumors. This study is the first to relate low and high molecular weight contrast agents with matched whole-tumor histological sections. These detailed comparisons identified tumor regions that appear distinct from each other using the HPG-GdF biomarkers related to perfusion and vessel leakiness, while Gadovist-imaged parameter measures in the same regions were unable to detect variation in vascular function. We have established HPG-GdF as a biocompatible multi-modal high molecular weight contrast agent with application for examining vascular function in both MR and histological modalities. Copyright © 2015 John Wiley & Sons, Ltd.

A tunable pH-sensing system based on Ag nanoclusters capped by hyperbranched polyethyleneimine with different molecular weights.

PubMed

Qu, Fei; Zou, Xuan; Kong, Rongmei; You, Jinmao

2016-01-01

In this assay, a tunable pH sensing system was developed based on Ag nanoclusters (Ag NCs) capped by hyperbranched polyethyleneimine (PEI) with different molecular weights (abbreviated as Ag NC-PEIs). For instance, when the molecular weight of PEI was 600 or 1800, the fluorescence intensities of Ag NCs exhibited a linear fashion over the pH range 4.10-7.96; when the molecular weight of PEI was 25,000, the pH linear range was from 4.78 to 7.96; when the molecular weight of PEI was 70,000, the pH linear range was 6.09-8.95. According to the molecular weight of PEI 600/1800, 25,000, and 70,000, the color change point was pH 4.10-4.78, 5.33-6.09, and 6.09-6.80, respectively. Therefore, Ag NC-PEI 600 and 1800 were proper to acid conditions; Ag NC-PEI 25,000 was sensitive to weak acid media; while Ag NC-PEI 70,000 was adapted to neutral solution. The tunable and selective color change points brought an excellent feature of Ag NC-PEIs as visual pH indicators, which was flexible and applicable to a variety of environments. Besides, the ratios of absorbance at 415 nm and 268 nm of Ag NCs also showed linear relationships with pH variations. Therefore, there were three ways of this system for sensing pH values, including fluorescence assay, ultraviolet-visible measurement, and visual detection, suggesting that this tunable pH-sensing platform was more feasible, reliable, and accurate. Copyright © 2015 Elsevier B.V. All rights reserved.

Peritoneal and Systemic Responses of Obese Type II Diabetic Rats to Chronic Exposure to a Hyperbranched Polyglycerol-based Dialysis Solution.

PubMed

Han, Bo La; Guan, Qiunong; Chafeeva, Irina; Mendelson, Asher A; Roza, Gerald da; Liggins, Richard; Kizhakkedathu, Jayachandran N; Du, Caigan

2018-05-12

Metabolic syndrome (MetS) is commonly observed among peritoneal dialysis (PD) patients, and hyperbranched polyglycerol (HPG) is a promising glucose-sparing osmotic agent for PD. However, the biocompatibility of a HPG-based PD solution (HPG) in subjects with MetS has not been investigated. This study compared the local and systemic effects of a HPG solution with conventional Physioneal (PYS) and Icodextrin (ICO) PD solutions in rats with MetS. Obese type 2 diabetic ZSF1 rats received a daily intraperitoneal injection of PD solutions (10 mL) for 3 months. The peritoneal membrane (PM) function was determined by ultrafiltration, and the systemic responses were determined by profiling blood metabolic substances, cytokines and oxidative status. Tissue damage was assessed by histology. At the end of the 3-month treatment with PD solutions, PM damage and ultrafiltration loss in both the PYS and ICO groups were greater than those in the HPG group. Blood analyses showed that compared to the baseline control, the rats in the HPG group exhibited a significant decrease only in serum albumin and IL-6 and a minor glomerular injury, whereas in both the PYS and ICO groups, there were more significant decreases in serum albumin, antioxidant activity, IL-6, KC/GRO (CXCL1) and TNF-α (in ICO only) as well as a mores substantial glomerular injury compared to the HPG group. Furthermore, PYS increased serum creatinine, serum glucose and urine production. In conclusion, compared to PYS or ICO solutions, the HPG solution had less adverse effects locally on the PM and systemically on distant organs (e.g., kidneys) and the plasma oxidative status in rats with MetS. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Grafting the surface of carbon nanotubes and carbon black with the chemical properties of hyperbranched polyamines

NASA Astrophysics Data System (ADS)

Morales-Lara, Francisco; Domingo-García, María; López-Garzón, Rafael; Luz Godino-Salido, María; Peñas-Sanjuán, Antonio; López-Garzón, F. Javier; Pérez-Mendoza, Manuel; Melguizo, Manuel

2016-01-01

Controlling the chemistry on the surface of new carbon materials is a key factor to widen the range of their applicability. In this paper we show a grafting methodology of polyalkylamines to the surface of carbon nanomaterials, in particular, carbon nanotubes and a carbon black. The aim of this work is to reach large degrees of covalent functionalization with hyperbranched polyethyleneimines (HBPEIs) and to efficiently preserve the strong chelating properties of the HBPEIs when they are fixed to the surface of these carbon materials. This functionalization opens new possibilities of using these carbon nanotubes-based hybrids. The results show that the HBPEIs are covalently attached to the carbon materials, forming hybrids. These hybrids emerge from the reaction of amine functions of the HBPEIs with carbonyls and carboxylic anhydrides of the carbon surface which become imine and imide bonds. Thus, due to the nature of these bonds, the pre-oxidized samples with relevant number of C=O groups showed an increase in the degree of functionalization with the HBPEIs. Furthermore, both the acid-base properties and the coordination capacity for metal ions of the hybrids are equivalent to that of the free HBPEIs in solution. This means that the chemical characteristics of the HBPEIs have been efficiently transferred to the hybrids. To reach this conclusion we have developed a novel procedure to assess the acid-base and the coordination properties of the hybrids (solids) by means of potentiometric titration. The good agreement of the values obtained for the hybrids and for the free HBPEIs in aqueous solution supports the reliability of the procedure. Moreover, the high capacity of the hybrids to capture Ni2+ by complexation opens new possibilities of using these hybrids to capture high-value metal ions such as Pd2+ and Pt2+.

Effects of Coating and Diametric Load on Fiber Bragg Gratings as Cryogenic Temperature Sensors

NASA Technical Reports Server (NTRS)

Wu, meng-Chou; Pater, Ruth H.; DeHaven, Stanton L.

2008-01-01

Cryogenic temperature sensing was demonstrated using pressurized fiber Bragg gratings (PFBGs) with polymer coating of various thicknesses. The PFBG was obtained by applying a small diametric load to a regular fiber Bragg grating (FBG). The Bragg wavelengths of FBGs and PFBG were measured at temperatures from 295 K to 4.2 K. The temperature sensitivities of the FBGs were increased by the polymer coating. A physical model was developed to relate the Bragg wavelength shifts to the thermal expansion coefficients, Young's moduli, and thicknesses of the coating polymers. When a diametric load of no more than 15 N was applied to a FBG, a pressure-induced transition occurred at 200 K during the cooling cycle. The pressure induced transition yielded PFBG temperature sensitivities three times greater than conventional FBGs for temperatures ranging from 80 to 200 K, and ten times greater than conventional fibers for temperatures below 80 K. PFBGs were found to produce an increased Bragg wavelength shift of 2.2 nm compared to conventional FBGs over the temperature range of 4.2 to 300 K. This effect was independent of coating thickness and attributed to the change of the fiber thermo-optic coefficient.

A mathematical model for interpreting in vitro rhGH release from laminar implants.

PubMed

Santoveña, A; García, J T; Oliva, A; Llabrés, M; Fariña, J B

2006-02-17

Recombinant human growth hormone (rhGH), used mainly for the treatment of growth hormone deficiency in children, requires daily subcutaneous injections. The use of controlled release formulations with appropriate rhGH release kinetics reduces the frequency of medication, improving patient compliance and quality of life. Biodegradable implants are a valid alternative, offering the feasibility of a regular release rate after administering a single dose, though it exists the slight disadvantage of a very minor surgical operation. Three laminar implant formulations (F(1), F(2) and F(3)) were produced by different manufacture procedures using solvent-casting techniques with the same copoly(D,L-lactic) glycolic acid (PLGA) polymer (Mw=48 kDa). A correlation in vitro between polymer matrix degradation and drug release rate from these formulations was found and a mathematical model was developed to interpret this. This model was applied to each formulation. The obtained results where explained in terms of manufacture parameters with the aim of elucidate whether drug release only occurs by diffusion or erosion, or by a combination of both mechanisms. Controlling the manufacture method and the resultant changes in polymer structure facilitates a suitable rhGH release profile for different rhGH deficiency treatments.

Exciton confinement in organic dendrimer quantum wells for opto-electronic applications

NASA Astrophysics Data System (ADS)

Lupton, J. M.; Samuel, I. D. W.; Burn, P. L.; Mukamel, S.

2002-01-01

Organic dendrimers are a fascinating new class of materials for opto-electronic applications. We present coupled electronic oscillator calculations on novel nanoscale conjugated dendrimers for use in organic light-emitting diodes. Strong confinement of excitations at the center of the dendrimers is observed, which accounts for the dependence of intermolecular interactions and charge transport on the degree of branching of the dendrimer. The calculated absorption spectra are in excellent agreement with the measured data and show that benzene rings are shared between excitations on the linear segments of the hyperbranched molecules. The coupled electronic oscillator approach is ideally suited to treat large dendritic molecules.

Covalent immobilization of invertase on PAMAM-dendrimer modified superparamagnetic iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Uzun, K.; Çevik, E.; Şenel, M.; Sözeri, H.; Baykal, A.; Abasıyanık, M. F.; Toprak, M. S.

2010-10-01

In this study, polyamidoamine (PAMAM) dendrimer was synthesized on the surface of superparamagnetite nanoparticles to enhance invertase immobilization. The amount of immobilized enzyme on the surface-hyperbranched magnetite nanoparticle was up to 2.5 times (i.e., 250%) as much as that of magnetite nanoparticle modified with only amino silane. Maximum reaction rate ( V max) and Michaelis-Menten constant ( K m) were determined for the free and immobilized enzymes. Various characteristics of immobilized invertase such as; the temperature activity, thermal stability, operational stability, and storage stability were evaluated and results revealed that stability of the enzyme is improved upon immobilization.

Polymer Nanocomposite Films: Dispersion of Polymer Grafted Nanorods and Optical Properties

NASA Astrophysics Data System (ADS)

Composto, Russell

2013-03-01

The thermodynamic factors that affect the dispersion of polymer-brush grafted gold nanorods (NR) in polymer matrix films have been studied by experiment and theory. When brush and matrix have a favorable interaction, such as poly(ethylene oxide) (PEO)-NR/ poly(methyl methacrylate) (PMMA) and polystyrene (PS)-NR / poly(2,6-dimethyl-p-phenylene oxide) (PPO), nanorods are uniformly dispersed. For PEO-NRs in PMMA, the NRs are regularly spaced and well dispersed, independent of the ratio of the degree of polymerization of the matrix (P) to that of the brush (N), namely P/N. As the NR volume fraction increases, the local orientation of the nanorods increases, whereas the macroscopic orientation remains isotropic. When the brush and matrix are similar (i.e., PS-NR / PS and PEO-NR / PEO), the nanorods randomly disperse for P/N < 2 (i.e., wet brush), but align side-by-side in aggregates for P/N > 2. UV-visible spectroscopy and discrete dipole approximation (DDA) calculations demonstrate that surface plasmon coupling leads to a blue shift in the longitudinal surface plasmon resonance (LSPR) as P/N increases. For P/N > 2, self-consistent field theory (SCFT) calculations and Monte Carlo (MC) simulations indicate that nanorod aggregation is caused by depletion-attraction forces. Starting with a dry brush system, namely, a PS matrix where P/N = 30, these attractive forces can be mediated by adding a compatibilizing agent (e.g., PPO) that drives the NRs to disperse. Finally, dry and wet brush behavior is observed for NR aspect ratios varying from 2.5 to 7. However, compared at the same volume fraction, long rods for the dry case exhibit much better local order than lower aspect ratio nanorods, suggesting that long rods may exhibit nematic-like ordering at higher loadings. NSF Polymer and CEMRI Programs.

Porphyrin-based Photocatalytic Nanolithography

PubMed Central

Bearinger, Jane P.; Stone, Gary; Dugan, Lawrence C.; El Dasher, Bassem; Stockton, Cheryl; Conway, James W.; Kuenzler, Tobias; Hubbell, Jeffrey A.

2009-01-01

Nanoarray fabrication is a multidisciplinary endeavor encompassing materials science, chemical engineering, and biology. We formed nanoarrays via a new technique, porphyrin-based photocatalytic nanolithography. The nanoarrays, with controlled features as small as 200 nm, exhibited regularly ordered patterns and may be appropriate for (a) rapid and parallel proteomics screening of immobilized biomolecules, (b) protein-protein interactions, and/or (c) biophysical and molecular biology studies involving spatially dictated ligand placement. We demonstrated protein immobilization utilizing nanoarrays fabricated via photocatalytic nanolithography on silicon substrates where the immobilized proteins are surrounded by a non-fouling polymer background. PMID:19406753

The Construction and Validation of All-Atom Bulk-Phase Models of Amorphous Polymers Using the TIGER2/TIGER3 Empirical Sampling Method

PubMed Central

Li, Xianfeng; Murthy, Sanjeeva; Latour, Robert A.

2011-01-01

A new empirical sampling method termed “temperature intervals with global exchange of replicas and reduced radii” (TIGER3) is presented and demonstrated to efficiently equilibrate entangled long-chain molecular systems such as amorphous polymers. The TIGER3 algorithm is a replica exchange method in which simulations are run in parallel over a range of temperature levels at and above a designated baseline temperature. The replicas sampled at temperature levels above the baseline are run through a series of cycles with each cycle containing four stages – heating, sampling, quenching, and temperature level reassignment. The method allows chain segments to pass through one another at elevated temperature levels during the sampling stage by reducing the van der Waals radii of the atoms, thus eliminating chain entanglement problems. Atomic radii are then returned to their regular values and re-equilibrated at elevated temperature prior to quenching to the baseline temperature. Following quenching, replicas are compared using a Metropolis Monte Carlo exchange process for the construction of an approximate Boltzmann-weighted ensemble of states and then reassigned to the elevated temperature levels for additional sampling. Further system equilibration is performed by periodic implementation of the previously developed TIGER2 algorithm between cycles of TIGER3, which applies thermal cycling without radii reduction. When coupled with a coarse-grained modeling approach, the combined TIGER2/TIGER3 algorithm yields fast equilibration of bulk-phase models of amorphous polymer, even for polymers with complex, highly branched structures. The developed method was tested by modeling the polyethylene melt. The calculated properties of chain conformation and chain segment packing agreed well with published data. The method was also applied to generate equilibrated structural models of three increasingly complex amorphous polymer systems: poly(methyl methacrylate), poly(butyl methacrylate), and DTB-succinate copolymer. Calculated glass transition temperature (Tg) and structural parameter profile (S(q)) for each resulting polymer model were found to be in close agreement with experimental Tg values and structural measurements obtained by x-ray diffraction, thus validating that the developed methods provide realistic models of amorphous polymer structure. PMID:21769156

Analytical Modeling Tool for Design of Hydrocarbon Sensitive Optical Fibers

PubMed Central

Vahdati, Nader; Lawand, Lydia

2017-01-01

Pipelines are the main transportation means for oil and gas products across large distances. Due to the severe conditions they operate in, they are regularly inspected using conventional Pipeline Inspection Gages (PIGs) for corrosion damage. The motivation for researching a real-time distributed monitoring solution arose to mitigate costs and provide a proactive indication of potential failures. Fiber optic sensors with polymer claddings provide a means of detecting contact with hydrocarbons. By coating the fibers with a layer of metal similar in composition to that of the parent pipeline, corrosion of this coating may be detected when the polymer cladding underneath is exposed to the surrounding hydrocarbons contained within the pipeline. A Refractive Index (RI) change occurs in the polymer cladding causing a loss in intensity of a traveling light pulse due to a reduction in the fiber’s modal capacity. Intensity losses may be detected using Optical Time Domain Reflectometry (OTDR) while pinpointing the spatial location of the contact via time delay calculations of the back-scattered pulses. This work presents a theoretical model for the above sensing solution to provide a design tool for the fiber optic cable in the context of hydrocarbon sensing following corrosion of an external metal coating. Results are verified against the experimental data published in the literature. PMID:28956847

Searching for low percolation thresholds within amphiphilic polymer membranes: The effect of side chain branching

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

Dorenbos, G., E-mail: dorenbos@ny.thn.ne.jp

Percolation thresholds for solvent diffusion within hydrated model polymeric membranes are derived from dissipative particle dynamics in combination with Monte Carlo (MC) tracer diffusion calculations. The polymer backbones are composed of hydrophobic A beads to which at regular intervals Y-shaped side chains are attached. Each side chain is composed of eight A beads and contains two identical branches that are each terminated with a pendant hydrophilic C bead. Four types of side chains are considered for which the two branches (each represented as [C], [AC], [AAC], or [AAAC]) are splitting off from the 8th, 6th, 4th, or 2nd A bead,more » respectively. Water diffusion through the phase separated water containing pore networks is deduced from MC tracer diffusion calculations. The percolation threshold for the architectures containing the [C] and [AC] branches is at a water volume fraction of ∼0.07 and 0.08, respectively. These are much lower than those derived earlier for linear architectures of various side chain length and side chain distributions. Control of side chain architecture is thus a very interesting design parameter to decrease the percolation threshold for solvent and proton transports within flexible amphiphilic polymer membranes.« less

Analytical Modeling Tool for Design of Hydrocarbon Sensitive Optical Fibers.

PubMed

Al Handawi, Khalil; Vahdati, Nader; Shiryayev, Oleg; Lawand, Lydia

2017-09-28

Pipelines are the main transportation means for oil and gas products across large distances. Due to the severe conditions they operate in, they are regularly inspected using conventional Pipeline Inspection Gages (PIGs) for corrosion damage. The motivation for researching a real-time distributed monitoring solution arose to mitigate costs and provide a proactive indication of potential failures. Fiber optic sensors with polymer claddings provide a means of detecting contact with hydrocarbons. By coating the fibers with a layer of metal similar in composition to that of the parent pipeline, corrosion of this coating may be detected when the polymer cladding underneath is exposed to the surrounding hydrocarbons contained within the pipeline. A Refractive Index (RI) change occurs in the polymer cladding causing a loss in intensity of a traveling light pulse due to a reduction in the fiber's modal capacity. Intensity losses may be detected using Optical Time Domain Reflectometry (OTDR) while pinpointing the spatial location of the contact via time delay calculations of the back-scattered pulses. This work presents a theoretical model for the above sensing solution to provide a design tool for the fiber optic cable in the context of hydrocarbon sensing following corrosion of an external metal coating. Results are verified against the experimental data published in the literature.

Fabrication and Characterization of Hybrid Organic-Inorganic Electron Extraction Layers for Polymer Solar Cells toward Improved Processing Robustness and Air Stability.

PubMed

Fredj, Donia; Pourcin, Florent; Alkarsifi, Riva; Kilinc, Volkan; Liu, Xianjie; Ben Dkhil, Sadok; Boudjada, Nassira Chniba; Fahlman, Mats; Videlot-Ackermann, Christine; Margeat, Olivier; Ackermann, Jörg; Boujelbene, Mohamed

2018-05-23

Organic-inorganic hybrid materials composed of bismuth and diaminopyridine are studied as novel materials for electron extraction layers in polymer solar cells using regular device structures. The hybrid materials are solution processed on top of two different low band gap polymers (PTB7 or PTB7-Th) as donor materials mixed with fullerene PC 70 BM as the acceptor. The intercalation of the hybrid layer between the photoactive layer and the aluminum cathode leads to solar cells with a power conversion efficiency of 7.8% because of significant improvements in all photovoltaic parameters, that is, short-circuit current density, fill factor, and open-circuit voltage, similar to the reference devices using ZnO as the interfacial layer. However when using thick layers of such hybrid materials for electron extraction, only small losses in photocurrent density are observed in contrast to the reference material ZnO of pronounced losses because of optical spacer effects. Importantly, these hybrid electron extraction layers also strongly improve the device stability in air compared with solar cells processed with ZnO interlayers. Both results underline the high potential of this new class of hybrid materials as electron extraction materials toward robust processing of air stable organic solar cells.

Peptoid nanosheets exhibit a new secondary-structure motif.

PubMed

Mannige, Ranjan V; Haxton, Thomas K; Proulx, Caroline; Robertson, Ellen J; Battigelli, Alessia; Butterfoss, Glenn L; Zuckermann, Ronald N; Whitelam, Stephen

2015-10-15

A promising route to the synthesis of protein-mimetic materials that are capable of complex functions, such as molecular recognition and catalysis, is provided by sequence-defined peptoid polymers--structural relatives of biologically occurring polypeptides. Peptoids, which are relatively non-toxic and resistant to degradation, can fold into defined structures through a combination of sequence-dependent interactions. However, the range of possible structures that are accessible to peptoids and other biological mimetics is unknown, and our ability to design protein-like architectures from these polymer classes is limited. Here we use molecular-dynamics simulations, together with scattering and microscopy data, to determine the atomic-resolution structure of the recently discovered peptoid nanosheet, an ordered supramolecular assembly that extends macroscopically in only two dimensions. Our simulations show that nanosheets are structurally and dynamically heterogeneous, can be formed only from peptoids of certain lengths, and are potentially porous to water and ions. Moreover, their formation is enabled by the peptoids' adoption of a secondary structure that is not seen in the natural world. This structure, a zigzag pattern that we call a Σ('sigma')-strand, results from the ability of adjacent backbone monomers to adopt opposed rotational states, thereby allowing the backbone to remain linear and untwisted. Linear backbones tiled in a brick-like way form an extended two-dimensional nanostructure, the Σ-sheet. The binary rotational-state motif of the Σ-strand is not seen in regular protein structures, which are usually built from one type of rotational state. We also show that the concept of building regular structures from multiple rotational states can be generalized beyond the peptoid nanosheet system.

Collection-limited theory interprets the extraordinary response of single semiconductor organic solar cells

PubMed Central

Ray, Biswajit; Baradwaj, Aditya G.; Khan, Mohammad Ryyan; Boudouris, Bryan W.; Alam, Muhammad Ashraful

2015-01-01

The bulk heterojunction (BHJ) organic photovoltaic (OPV) architecture has dominated the literature due to its ability to be implemented in devices with relatively high efficiency values. However, a simpler device architecture based on a single organic semiconductor (SS-OPV) offers several advantages: it obviates the need to control the highly system-dependent nanoscale BHJ morphology, and therefore, would allow the use of broader range of organic semiconductors. Unfortunately, the photocurrent in standard SS-OPV devices is typically very low, which generally is attributed to inefficient charge separation of the photogenerated excitons. Here we show that the short-circuit current density from SS-OPV devices can be enhanced significantly (∼100-fold) through the use of inverted device configurations, relative to a standard OPV device architecture. This result suggests that charge generation may not be the performance bottleneck in OPV device operation. Instead, poor charge collection, caused by defect-induced electric field screening, is most likely the primary performance bottleneck in regular-geometry SS-OPV cells. We justify this hypothesis by: (i) detailed numerical simulations, (ii) electrical characterization experiments of functional SS-OPV devices using multiple polymers as active layer materials, and (iii) impedance spectroscopy measurements. Furthermore, we show that the collection-limited photocurrent theory consistently interprets typical characteristics of regular SS-OPV devices. These insights should encourage the design and OPV implementation of high-purity, high-mobility polymers, and other soft materials that have shown promise in organic field-effect transistor applications, but have not performed well in BHJ OPV devices, wherein they adopt less-than-ideal nanostructures when blended with electron-accepting materials. PMID:26290582

Collection-limited theory interprets the extraordinary response of single semiconductor organic solar cells.

PubMed

Ray, Biswajit; Baradwaj, Aditya G; Khan, Mohammad Ryyan; Boudouris, Bryan W; Alam, Muhammad Ashraful

2015-09-08

The bulk heterojunction (BHJ) organic photovoltaic (OPV) architecture has dominated the literature due to its ability to be implemented in devices with relatively high efficiency values. However, a simpler device architecture based on a single organic semiconductor (SS-OPV) offers several advantages: it obviates the need to control the highly system-dependent nanoscale BHJ morphology, and therefore, would allow the use of broader range of organic semiconductors. Unfortunately, the photocurrent in standard SS-OPV devices is typically very low, which generally is attributed to inefficient charge separation of the photogenerated excitons. Here we show that the short-circuit current density from SS-OPV devices can be enhanced significantly (∼100-fold) through the use of inverted device configurations, relative to a standard OPV device architecture. This result suggests that charge generation may not be the performance bottleneck in OPV device operation. Instead, poor charge collection, caused by defect-induced electric field screening, is most likely the primary performance bottleneck in regular-geometry SS-OPV cells. We justify this hypothesis by: (i) detailed numerical simulations, (ii) electrical characterization experiments of functional SS-OPV devices using multiple polymers as active layer materials, and (iii) impedance spectroscopy measurements. Furthermore, we show that the collection-limited photocurrent theory consistently interprets typical characteristics of regular SS-OPV devices. These insights should encourage the design and OPV implementation of high-purity, high-mobility polymers, and other soft materials that have shown promise in organic field-effect transistor applications, but have not performed well in BHJ OPV devices, wherein they adopt less-than-ideal nanostructures when blended with electron-accepting materials.

Patterning of ultrathin polymethylmethacrylate films by in-situ photodirecting of the Marangoni flow

NASA Astrophysics Data System (ADS)

Elashnikov, Roman; Fitl, Premysl; Svorcik, Vaclav; Lyutakov, Oleksiy

2017-02-01

Laser heating and Marangoni flow result in the formation of surface structures with different geometries and shape on thin polymer films. By laser beam irradiation combined with a sample movement the solid polymethylmethacrylate (PMMA) films are heated and undergo phase transition which leads to a material flow. Since the laser beam has a non-linear distribution of energy, the PMMA film is heated inhomogeneously and a surface tension gradient in a lateral direction is introduced. During this procedure additional phenomena such as "reversible" or cyclic polymer flow also take place. The careful choice of experimental conditions enables the preparation of patterns with sophisticated geometries and with hierarchical pattern organization. Depending on initial PMMA film thickness and speed of the sample movement line arrays are created, which can subsequently be transformed into the crimped lines or system of circular holes. In addition, the introduction of a constant acceleration in the sample movement or a laser beam distortion enables the preparation of regularly crimped lines, ordered hexagonal holes or overlapped plates.

Nanocomposites Derived from Carbon Nanofibers and a Hyperbranched Poly(Ether-Ketone): In Situ Polymerization, Chain-End Modification, and Properties (Preprint)

DTIC Science & Technology

2007-05-01

and Soxhlet - extracted with water for three days and methanol for three more days. It was then dried over P2O5 under reduced pressure at 120 °C...for 72 h to give the product in quantitative yield . Anal. Calcd. for C16.39H8O4: C, 73.22%; 6 H, 2.98%; O, 23.81%. Found: C, 72.94%; H, 3.12%; O...HBP-PEK)-g-VGCNF, 3e, to afford 0.47 (94% yield based on initial amount) of a black solid. Found: C, 98.66%; H, 0.93%; N, ɘ.20%; O, ɘ.10

A Protocol for Measuring Pull-off Stress of Wound-Treatment Polymers

PubMed Central

Kheyfets, Vitaly O.; Thornton, Rita C.; Kowal, Mikala; Finol, Ender A.

2014-01-01

Skin wounds and burns compromise the body's natural barrier to bacteria and other pathogens. While many forms of wound dressings are available, polymeric films are advantageous for various reasons, ranging from the ease of application to durability. One common drawback of using polymeric films for a wound bandage is that the films tend to adhere to common inanimate objects. Patients spend hours in contact with soft and hard materials pressed against their skin, which, if the skin was dressed with a polymeric film, would inflict further wound damage upon body movement. In this work, we present a novel technique that allowed for measuring polymeric tackiness, after a long incubation period, with materials regularly encountered in a hospital or home setting, and soft fabrics. The polymers were exposed to an environment intended to simulate daily conditions and the technique is designed to perform multiple experiments simultaneously with ease. Four commercially available polymers (new-skin, no-sting skin-prep, skin shield, and Silesse) were tested as proof-of-concept to gather preliminary data for an overall assessment of wound treatment efficacy, resulting in the estimation of pull-off stress of the polymers from a specimen of porcine skin. Silesse did not reveal a measurable tackiness, no-sting skin-prep had the highest mean tackiness (13.8 kPa), while the mean tackiness between new-skin and skin shield was approximately equal (9.8 kPa vs. 10.1 kPa, respectively), p = 0.05. Future work on polymeric fluids for wound dressing applications should include tensile stress and dynamic viscosity estimations. PMID:24718322

Molecularly imprinted polymer microspheres prepared by Pickering emulsion polymerization for selective solid-phase extraction of eight bisphenols from human urine samples.

PubMed

Yang, Jiajia; Li, Yun; Wang, Jincheng; Sun, Xiaoli; Cao, Rong; Sun, Hao; Huang, Chaonan; Chen, Jiping

2015-05-04

The bisphenol A (BPA) imprinted polymer microspheres were prepared by simple Pickering emulsion polymerization. Compared to traditional bulk polymerization, both high yields of polymer and good control of particle sizes were achieved. The characterization results of scanning electron microscopy and nitrogen adsorption-desorption measurements showed that the obtained molecularly imprinted polymer microsphere (MIPMS) particles possessed regular spherical shape, narrow diameter distribution (30-60 μm), a specific surface area (S(BET)) of 281.26 m(2) g(-1) and a total pore volume (V(t)) of 0.459 cm(3) g(-1). Good specific adsorption capacity for BPA was obtained in the sorption experiment and good class selectivity for BPA and its seven structural analogs (bisphenol F, bisphenol B, bisphenol E, bisphenol AF, bisphenol S, bisphenol AP and bisphenol Z) was demonstrated by the chromatographic evaluation experiment. The MIPMS as solid-phase extraction (SPE) packing material was then evaluated for extraction and clean-up of these bisphenols (BPs) from human urine samples. An accurate and sensitive analytical method based on the MIPMS-SPE coupled with HPLC-DAD has been successfully established for simultaneous determination of eight BPs from human urine samples with detection limits of 1.2-2.2 ng mL(-1). The recoveries of BPs for urine samples at two spiking levels (100 and 500 ng mL(-1) for each BP) were in the range of 81.3-106.7% with RSD values below 8.3%. Copyright © 2015 Elsevier B.V. All rights reserved.

From the solution processing of hydrophilic molecules to polymer-phthalocyanine hybrid materials for ammonia sensing in high humidity atmospheres.

PubMed

Gaudillat, Pierre; Jurin, Florian; Lakard, Boris; Buron, Cédric; Suisse, Jean-Moïse; Bouvet, Marcel

2014-07-24

We have prepared different hybrid polymer-phthalocyanine materials by solution processing, starting from two sulfonated phthalocyanines, s-CoPc and CuTsPc, and polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), poly(acrylic acid-co-acrylamide) (PAA-AM), poly(diallyldimethylammonium chloride) (PDDA) and polyaniline (PANI) as polymers. We also studied the response to ammonia (NH3) of resistors prepared from these sensing materials. The solvent casted films, prepared from s-CoPc and PVP, PEG and PAA-AM, were highly insulating and very sensitive to the relative humidity (RH) variation. The incorporation of s-CoPc in PDDA by means of layer-by-layer (LBL) technique allowed to stabilize the film, but was too insulating to be interesting. We also prepared PANI-CuTsPc hybrid films by LBL technique. It allowed a regular deposition as evidenced by the linear increase of the absorbance at 688 nm as a function of the number of bilayers. The sensitivity to ammonia (NH3) of PANi-CuTsPc resistors was very high compared to that of individual materials, giving up to 80% of current decrease when exposed to 30 ppm NH3. Contrarily to what happens with neutral polymers, in PANI, CuTsPc was stabilized by strong electrostatic interactions, leading to a stable response to NH3, whatever the relative humidity in the range 10%-70%. Thus, the synergy of PANI with ionic macrocycles used as counteranions combined with their simple aqueous solution processing opens the way to the development of new gas sensors capable of operating in real world conditions.

Size-distribution analysis of macromolecules by sedimentation velocity ultracentrifugation and lamm equation modeling.

PubMed

Schuck, P

2000-03-01

A new method for the size-distribution analysis of polymers by sedimentation velocity analytical ultracentrifugation is described. It exploits the ability of Lamm equation modeling to discriminate between the spreading of the sedimentation boundary arising from sample heterogeneity and from diffusion. Finite element solutions of the Lamm equation for a large number of discrete noninteracting species are combined with maximum entropy regularization to represent a continuous size-distribution. As in the program CONTIN, the parameter governing the regularization constraint is adjusted by variance analysis to a predefined confidence level. Estimates of the partial specific volume and the frictional ratio of the macromolecules are used to calculate the diffusion coefficients, resulting in relatively high-resolution sedimentation coefficient distributions c(s) or molar mass distributions c(M). It can be applied to interference optical data that exhibit systematic noise components, and it does not require solution or solvent plateaus to be established. More details on the size-distribution can be obtained than from van Holde-Weischet analysis. The sensitivity to the values of the regularization parameter and to the shape parameters is explored with the help of simulated sedimentation data of discrete and continuous model size distributions, and by applications to experimental data of continuous and discrete protein mixtures.

Fem Simulation of Triple Diffusive Natural Convection Along Inclined Plate in Porous Medium: Prescribed Surface Heat, Solute and Nanoparticles Flux

NASA Astrophysics Data System (ADS)

Goyal, M.; Goyal, R.; Bhargava, R.

2017-12-01

In this paper, triple diffusive natural convection under Darcy flow over an inclined plate embedded in a porous medium saturated with a binary base fluid containing nanoparticles and two salts is studied. The model used for the nanofluid is the one which incorporates the effects of Brownian motion and thermophoresis. In addition, the thermal energy equations include regular diffusion and cross-diffusion terms. The vertical surface has the heat, mass and nanoparticle fluxes each prescribed as a power law function of the distance along the wall. The boundary layer equations are transformed into a set of ordinary differential equations with the help of group theory transformations. A wide range of parameter values are chosen to bring out the effect of buoyancy ratio, regular Lewis number and modified Dufour parameters of both salts and nanofluid parameters with varying angle of inclinations. The effects of parameters on the velocity, temperature, solutal and nanoparticles volume fraction profiles, as well as on the important parameters of heat and mass transfer, i.e., the reduced Nusselt, regular and nanofluid Sherwood numbers, are discussed. Such problems find application in extrusion of metals, polymers and ceramics, production of plastic films, insulation of wires and liquid packaging.

Hyperbranched polyglycerol is superior to glucose for long-term preservation of peritoneal membrane in a rat model of chronic peritoneal dialysis.

PubMed

Du, Caigan; Mendelson, Asher A; Guan, Qiunong; Dairi, Ghida; Chafeeva, Irina; da Roza, Gerald; Kizhakkedathu, Jayachandran N

2016-12-13

Replacing glucose with a better biocompatible osmotic agent in peritoneal dialysis (PD) solutions is needed in PD clinic. We previously demonstrated the potential of hyperbranched polyglycerol (HPG) as a replacement for glucose. This study further investigated the long-term effects of chronic exposure to HPG as compared to a glucose-based conventional PD solution on peritoneal membrane (PM) structure and function in rats. Adult male Wistar rats received once-daily intraperitoneal injection of 10 mL of HPG solution (1 kDa, HPG 6%) compared to Physioneal™ 40 (PYS, glucose 2.27%) or electrolyte solution (Control) for 3 months. The overall health conditions were determined by blood chemistry analysis. The PM function was determined by ultrafiltration, and its injury by histological and transcriptome-based pathway analyses. Here, we showed that there was no difference in the blood chemistry between rats receiving the HPG and the Control, while PYS increased serum alkaline phosphatase, globulin and creatinine and decreased serum albumin. Unlike PYS, HPG did not significantly attenuate PM function, which was associated with smaller change in both the structure and the angiogenesis of the PM and less cells expressing vascular endothelial growth factor, α-smooth muscle actin and MAC387 (macrophage marker). The pathway analysis revealed that there were more inflammatory signaling pathways functioning in the PM of PYS group than those of HPG or Control, which included the signaling for cytokine production in both macrophages and T cells, interleukin (IL)-6, IL-10, Toll-like receptors, triggering receptor expressed on myeloid cells 1 and high mobility group box 1. The results from this experimental study indicate the superiority of HPG to glucose in the preservation of the peritoneum function and structure during the long-term PD treatment, suggesting the potential of HPG as a novel osmotic agent for PD.

Pharmaceutical and biomedical potential of surface engineered dendrimers.

PubMed

Satija, Jitendra; Gupta, Umesh; Jain, Narendra Kumar

2007-01-01

Dendrimers are hyperbranched, globular, monodisperse, nanometric polymeric architecture, having definite molecular weight, shape, and size (which make these an inimitable and optimum carrier molecule in pharmaceutical field). Dendritic architecture is having immense potential over the other carrier systems, particularly in the field of drug delivery because of their unique properties, such as structural uniformity, high purity, efficient membrane transport, high drug pay load, targeting potential, and good colloidal, biological, and shelf stability. Despite their enormous applicability in different areas, the inherent cytotoxicity, reticuloendothelial system (RES) uptake, drug leakage, immunogenicity, and hemolytic toxicity restricted their use in clinical applications, which is primarily associated with cationic charge present on the periphery due to amine groups. To overcome this toxic nature of dendrimers, some new types of nontoxic, biocompatible, and biodegradable dendrimers have been developed (e.g., polyester dendrimer, citric acid dendrimer, arginine dendrimer, carbohydrate dendrimers, etc.). The surface engineering of parent dendrimers is graceful and convenient strategy, which not only shields the positive charge to make this carrier more biomimetic but also improves the physicochemical and biological behavior of parent dendrimers. Thus, surface modification chemistry of parent dendrimers holds promise in pharmaceutical applications (such as solubilization, improved drug encapsulation, enhanced gene transfection, sustained and controlled drug release, intracellular targeting) and in the diagnostic field. Development of multifunctional dendrimer holds greater promise toward the biomedical applications because a number of targeting ligands determine specificity in the same manner as another type of group would secure stability in biological milieu and prolonged circulation, whereas others facilitate their transport through cell membranes. Therefore, as a consequence of ideal hyperbranched architecture and the biocompatible nature of engineered dendrimers, their utilization has been included in the scope of this review, which focuses on current surface alteration strategies of dendrimers for their potential use in drug delivery and explains the possible beneficial applications of these engineered dendrimers in the biomedical field.

Grafting the surface of carbon nanotubes and carbon black with the chemical properties of hyperbranched polyamines

PubMed Central

Morales-Lara, Francisco; Domingo-García, María; López-Garzón, Rafael; Luz Godino-Salido, María; Peñas-Sanjuán, Antonio; López-Garzón, F. Javier; Pérez-Mendoza, Manuel; Melguizo, Manuel

2016-01-01

Abstract Controlling the chemistry on the surface of new carbon materials is a key factor to widen the range of their applicability. In this paper we show a grafting methodology of polyalkylamines to the surface of carbon nanomaterials, in particular, carbon nanotubes and a carbon black. The aim of this work is to reach large degrees of covalent functionalization with hyperbranched polyethyleneimines (HBPEIs) and to efficiently preserve the strong chelating properties of the HBPEIs when they are fixed to the surface of these carbon materials. This functionalization opens new possibilities of using these carbon nanotubes-based hybrids. The results show that the HBPEIs are covalently attached to the carbon materials, forming hybrids. These hybrids emerge from the reaction of amine functions of the HBPEIs with carbonyls and carboxylic anhydrides of the carbon surface which become imine and imide bonds. Thus, due to the nature of these bonds, the pre-oxidized samples with relevant number of C=O groups showed an increase in the degree of functionalization with the HBPEIs. Furthermore, both the acid-base properties and the coordination capacity for metal ions of the hybrids are equivalent to that of the free HBPEIs in solution. This means that the chemical characteristics of the HBPEIs have been efficiently transferred to the hybrids. To reach this conclusion we have developed a novel procedure to assess the acid-base and the coordination properties of the hybrids (solids) by means of potentiometric titration. The good agreement of the values obtained for the hybrids and for the free HBPEIs in aqueous solution supports the reliability of the procedure. Moreover, the high capacity of the hybrids to capture Ni2+ by complexation opens new possibilities of using these hybrids to capture high-value metal ions such as Pd2+ and Pt2+. PMID:27877902

Sensitive detection of T4 polynucleotide kinase activity based on multifunctional magnetic probes and polymerization nicking reactions mediated hyperbranched rolling circle amplification.

PubMed

Li, Xia; Xu, Xiaowen; Song, Juan; Xue, Qingwang; Li, Chenzhong; Jiang, Wei

2017-05-15

T4 polynucleotide kinase (PNK) plays critical roles in regulating DNA phosphorylation modes during the repair of DNA lesions. The aberrant activity of T4 PNK has been proven to be associated with a variety of human pathologies. Sensitive detection of T4 PNK activity is critical to both clinical diagnosis and therapeutics. Herein, a background-eliminated fluorescence assay for sensitive detection of T4 PNK activity has been developed by multifunctional magnetic probes and polymerization nicking reactions mediated hyperbranched rolling circle amplification (HRCA). First, the streptavidin-magnetic nanobeads (MBs) were functionalized with the biotin modified hairpin probe (HP) with 3'-phosphoryl, forming multifunctional magnetic probes (HP-MBs). Then, in the presence of T4 PNK, the 3'-phosphoryl of HP-MBs was hydrolyzed to 3'-hydroxyl, thus serving as primers to initiate the polymerization extension and nicking endonuclease cleavage reaction. Next, the primers released from above "polymerization-nicking" cycles were separated out to trigger the subsequently HRCA process, producing plenty of dsDNA. Finally, the intercalating dye SYBR Green I (SG) was inserted into the dsDNA, generating enhanced fluorescence signals. In our design, the HP-MBs here serve together as the T4 PNK, DNA polymerase, and endonuclease recognition probe, and thus avoid the demands of utilizing multiple probes design. Moreover, it performed primary "polymerization-nicking" amplification and mediate secondary HRCA. In addition to, performing the separation function, the binding of HP-MBs and SG could be avoided while a low background was acquired. This method showed excellent sensitivity with a detection limit of 0.0436 mU/mL, and accomplished exceptional characterization T4 PNK activity in cell extracts, offering a powerful tool for biomedical research and clinical diagnosis. Copyright © 2017 Elsevier B.V. All rights reserved.

Nanoscale Structure-Property Relationships of Polyacrylonitrile/CNT Composites as a Function of Polymer Crystallinity and CNT Diameter.

PubMed

Gissinger, Jacob R; Pramanik, Chandrani; Newcomb, Bradley; Kumar, Satish; Heinz, Hendrik

2018-01-10

Polyacrylonitrile (PAN)/carbon nanotube (CNT) composites are used as precursors for ultrastrong and lightweight carbon fibers. However, insights into the structure at the nanoscale and the relationships to mechanical and thermal properties have remained difficult to obtain. In this study, molecular dynamics simulation with accurate potentials and available experimental data were used to describe the influence of different degrees of PAN preorientation and CNT diameter on the atomic-scale structure and properties of the composites. The inclusion of CNTs in the polymer matrix is favored for an intermediate degree of PAN orientation and small CNT diameter whereas high PAN crystallinity and larger CNT diameter disfavor CNT inclusion. The glass transition at the CNT/PAN interface involves the release of rotational degrees of freedom of the polymer backbone and increased mobility of the protruding nitrile side groups in contact with the carbon nanotubes. The glass-transition temperature of the composite increases in correlation with the amount of CNT/polymer interfacial area per unit volume, i.e., in the presence of CNTs, for higher CNT volume fraction,  and inversely with CNT diameter. The increase in glass-transition temperature upon CNT addition is larger for PAN of lower crystallinity than for PAN of higher crystallinity. Interfacial shear strengths of the composites are higher for CNTs of smaller diameter and for PAN with preorientation, in correlation with more favorable CNT inclusion energies. The lowest interfacial shear strength was observed in amorphous PAN for the same CNT diameter. PAN with ∼75% crystallinity exhibited hexagonal patterns of nitrile groups near and far from the CNT interface which could influence carbonization into regular graphitic structures. The results illustrate the feasibility of near-quantitative insights into macroscale properties of polymer/CNT composites from simulations of nanometer-scale composite domains. Guidance is most effective when key assumptions in experiment and simulation are closely aligned, such as exfoliation versus bundling of CNTs, size, type, potential defects of CNTs, and precise measures for polymer crystallinity.

Achieving high performance polymer optoelectronic devices for high efficiency, long lifetime and low fabrication cost

NASA Astrophysics Data System (ADS)

Huang, Jinsong

This thesis described three types of organic optoelectronic devices: polymer light emitting diodes (PLED), polymer photovoltaic solar cell, and organic photo detector. The research in this work focuses improving their performance including device efficiency, operation lifetime simplifying fabrication process. With further understanding in PLED device physics, we come up new device operation model and improved device architecture design. This new method is closely related to understanding of the science and physics at organic/metal oxide and metal oxide/metal interface. In our new device design, both material and interface are considered in order to confine and balance all injected carriers, which has been demonstrated very be successful in increasing device efficiency. We created two world records in device efficiency: 18 lm/W for white emission fluorescence PLED, 22 lm/W for red emission phosphorescence PLED. Slow solvent drying process has been demonstrated to significantly increase device efficiency in poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C 61-butyric acid methyl ester (PCBM) mixture polymer solar cell. From the mobility study by time of flight, the increase of efficiency can be well correlated to the improved carrier transport property due to P3HT crystallization during slow solvent drying. And it is found that, similar to PLED, balanced carrier mobility is essential in high efficient polymer solar cell. There is also a revolution in our device fabrication method. A unique device fabrication method is presented by an electronic glue based lamination process combined with interface modification as a one-step polymer solar cell fabrication process. It can completely skip the thermal evaporation process, and benefit device lifetime by several merits: no air reactive. The device obtained is metal free, semi-transparent, flexible, self-encapsulated, and comparable efficiency with that by regular method. We found the photomultiplication (PM) phenomenon in C60 based device accidentally. The high PM factor makes it good candidate for photo detector. The high gain was assigned to the trapped-charge induced enhanced-injection at C60/PEDOT:PSS interface.

Surface morphology control of cross-linked polymer particles via dispersion polymerization.

PubMed

Peng, Bo; Imhof, Arnout

2015-05-14

Cross-linked polymer colloids (poly(methyl methacrylate) and polystyrene) with diverse shapes were prepared in polar solvents (ethanol, methanol and water) via dispersion polymerization, in which a linear addition of the cross-linker was used during reaction. Apart from spherical particles we found dented spheres or particles covered with nodules, or a combination of both. A comprehensive investigation was carried out, mainly concentrating on the effect of the experimental conditions (e.g., the addition start time and total addition time, cross-linker density and the solvency of the solvents) on particle morphologies. Consequently, we suggest a number of effective ways for the synthesis of regular (spherical) colloidal particles through maintaining a relatively low concentration of the cross-linker during the entire reaction, or forcing the co-polymerization (of monomer and cross-linker) locus to the continuous medium, or using a high quality or quantity of the stabilizer. Moreover, the size of the particles was also precisely manipulated by varying the polarity of the solvents, the concentration of the cross-linker, and the amount and average molecular weight of the stabilizer. In addition, the formation of the heavily dented particles with a very rough surface prepared under a pure or oxygen-'contaminated' nitrogen environment was monitored over time. The results accumulated in this article are of use for a better understanding of the mechanism of the polymerization and control over the structure and property of polymer particles.

Modeling the tetraphenylalanine-PEG hybrid amphiphile: from DFT calculations on the peptide to molecular dynamics simulations on the conjugate.

PubMed

Zanuy, David; Hamley, Ian W; Alemán, Carlos

2011-07-21

The conformational properties of the hybrid amphiphile formed by the conjugation of a hydrophobic peptide with four phenylalanine (Phe) residues and hydrophilic poly(ethylene glycol), have been investigated using quantum mechanical calculations and atomistic molecular dynamics simulations. The intrinsic conformational preferences of the peptide were examined using the building-up search procedure combined with B3LYP/6-31G(d) geometry optimizations, which led to the identification of 78, 78, and 92 minimum energy structures for the peptides containing one, two, and four Phe residues. These peptides tend to adopt regular organizations involving turn-like motifs that define ribbon or helical-like arrangements. Furthermore, calculations indicate that backbone···side chain interactions involving the N-H of the amide groups and the π clouds of the aromatic rings play a crucial role in Phe-containing peptides. On the other hand, MD simulations on the complete amphiphile in aqueous solution showed that the polymer fragment rapidly unfolds maximizing the contacts with the polar solvent, even though the hydrophobic peptide reduce the number of waters of hydration with respect to an individual polymer chain of equivalent molecular weight. In spite of the small effect of the peptide in the hydrodynamic properties of the polymer, we conclude that the two counterparts of the amphiphile tend to organize as independent modules.

A high performance ceramic-polymer separator for lithium batteries

NASA Astrophysics Data System (ADS)

Kumar, Jitendra; Kichambare, Padmakar; Rai, Amarendra K.; Bhattacharya, Rabi; Rodrigues, Stanley; Subramanyam, Guru

2016-01-01

A three-layered (ceramic-polymer-ceramic) hybrid separator was prepared by coating ceramic electrolyte [lithium aluminum germanium phosphate (LAGP)] over both sides of polyethylene (PE) polymer membrane using electron beam physical vapor deposition (EB-PVD) technique. Ionic conductivities of membranes were evaluated after soaking PE and LAGP/PE/LAGP membranes in a 1 Molar (1M) lithium hexafluroarsenate (LiAsF6) electrolyte in ethylene carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC) in volume ratio (1:1:1). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques were employed to evaluate morphology and structure of the separators before and after cycling performance tests to better understand structure-property correlation. As compared to regular PE separator, LAGP/PE/LAGP hybrid separator showed: (i) higher liquid electrolyte uptake, (ii) higher ionic conductivity, (iii) lower interfacial resistance with lithium and (iv) lower cell voltage polarization during lithium cycling at high current density of 1.3 mA cm-2 at room temperature. The enhanced performance is attributed to higher liquid uptake, LAGP-assisted faster ion conduction and dendrite prevention. Optimization of density and thickness of LAGP layer on PE or other membranes through manipulation of PVD deposition parameters will enable practical applications of this novel hybrid separator in rechargeable lithium batteries with high energy, high power, longer cycle life, and higher safety level.

Chemical Interactions and Their Role in the Microphase Separation of Block Copolymer Thin Films

PubMed Central

Farrell, Richard A.; Fitzgerald, Thomas G.; Borah, Dipu; Holmes, Justin D.; Morris, Michael A.

2009-01-01

The thermodynamics of self-assembling systems are discussed in terms of the chemical interactions and the intermolecular forces between species. It is clear that there are both theoretical and practical limitations on the dimensions and the structural regularity of these systems. These considerations are made with reference to the microphase separation that occurs in block copolymer (BCP) systems. BCP systems self-assemble via a thermodynamic driven process where chemical dis-affinity between the blocks driving them part is balanced by a restorative force deriving from the chemical bond between the blocks. These systems are attracting much interest because of their possible role in nanoelectronic fabrication. This form of self-assembly can obtain highly regular nanopatterns in certain circumstances where the orientation and alignment of chemically distinct blocks can be guided through molecular interactions between the polymer and the surrounding interfaces. However, for this to be possible, great care must be taken to properly engineer the interactions between the surfaces and the polymer blocks. The optimum methods of structure directing are chemical pre-patterning (defining regions on the substrate of different chemistry) and graphoepitaxy (topographical alignment) but both centre on generating alignment through favourable chemical interactions. As in all self-assembling systems, the problems of defect formation must be considered and the origin of defects in these systems is explored. It is argued that in these nanostructures equilibrium defects are relatively few and largely originate from kinetic effects arising during film growth. Many defects also arise from the confinement of the systems when they are ‘directed’ by topography. The potential applications of these materials in electronics are discussed. PMID:19865513

Collection-limited theory interprets the extraordinary response of single semiconductor organic solar cells

DOE PAGES

Ray, Biswajit; Baradwaj, Aditya G.; Khan, Mohammad Ryyan; ...

2015-08-19

The bulk heterojunction (BHJ) organic photovoltaic (OPV) architecture has dominated the literature due to its ability to be implemented in devices with relatively high efficiency values. However, a simpler device architecture based on a single organic semiconductor (SS-OPV) offers several advantages: it obviates the need to control the highly system-dependent nanoscale BHJ morphology, and therefore, would allow the use of broader range of organic semiconductors. Unfortunately, the photocurrent in standard SS-OPV devices is typically very low, which generally is attributed to inefficient charge separation of the photogenerated excitons. In this paper, we show that the short-circuit current density from SS-OPVmore » devices can be enhanced significantly (~100-fold) through the use of inverted device configurations, relative to a standard OPV device architecture. This result suggests that charge generation may not be the performance bottleneck in OPV device operation. Instead, poor charge collection, caused by defect-induced electric field screening, is most likely the primary performance bottleneck in regular-geometry SS-OPV cells. We justify this hypothesis by: ( i) detailed numerical simulations, ( ii) electrical characterization experiments of functional SS-OPV devices using multiple polymers as active layer materials, and ( iii) impedance spectroscopy measurements. Furthermore, we show that the collection-limited photocurrent theory consistently interprets typical characteristics of regular SS-OPV devices. Finally, these insights should encourage the design and OPV implementation of high-purity, high-mobility polymers, and other soft materials that have shown promise in organic field-effect transistor applications, but have not performed well in BHJ OPV devices, wherein they adopt less-than-ideal nanostructures when blended with electron-accepting materials.« less

Hyperbranched polyglycerol-grafted titanium oxide nanoparticles: synthesis, derivatization, characterization, size separation, and toxicology

NASA Astrophysics Data System (ADS)

Qin, Hongmei; Maruyama, Kyouhei; Amano, Tsukuru; Murakami, Takashi; Komatsu, Naoki

2016-10-01

We have been developing surface functionalization of various nanoparticles including nanodiamond and iron oxide nanoparticles in view of biomedical applications. In this context, TiO2 nanoparticles (TiO2 NP) are functionalized with polyglycerol (PG) to provide water-dispersible TiO2-PG, which is further derivatized through multi-step organic transformations. The resulting TiO2-PG and its derivatives are fully characterized by various analyses including solution-phase 1H and 13C NMR. TiO2-PG was size-tuned with centrifugation by changing the acceleration and duration. At last, no cytotoxicity of TiO2 NP, TiO2-PG, and TiO2-PG functionalized with RGD peptide was observed under dark conditions.

Novel multi-biotin grafted poly(lactic acid) and its self-assembling nanoparticles capable of binding to streptavidin

PubMed Central

Yan, Hao; Jiang, Weimin; Zhang, Yinxing; Liu, Ying; Wang, Bin; Yang, Li; Deng, Lihong; Singh, Gurinder K; Pan, Jun

2012-01-01

Targeted drug delivery requires novel biodegradable, specific binding systems with longer circulation time. The aim of this study was to prepare biotinylated poly(lactic acid) (PLA) nanoparticles (NPs) which can meet regular requirements as well conjugate more biotins in the polymer to provide better binding with streptavidin. A biotin-graft-PLA was synthesized based on previously published biodegradable poly(ethylene glycol) (PEG)-graft-PLA, with one polymer molecule containing three PEG molecules. Newly synthesized biotin-graft-PLA had three biotins per polymer molecule, higher than the previous biotinylated PLA (≤1 biotin per polymer molecule). A PEG with a much lower molecular weight (MW ~1900) than the previous biotinylated PLA (PEG MW ≥ 3800), and thus more biocompatible, was used which supplied good nonspecific protein-resistant property compatible to PEG-graft-PLA, suggesting its possible longer stay in the bloodstream. Biotin-graft-PLA specifically bound to streptavidin and self-assembled into NPs, during which naproxen, a model small molecule (MW 230 Da) and hydrophobic drug, was encapsulated (encapsulation efficiency 51.88%). The naproxen-loaded NPs with particle size and zeta potential of 175 nm and −27.35 mV realized controlled release within 170 hours, comparable to previous studies. The biotin-graft-PLA NPs adhered approximately two-fold more on streptavidin film and on biotin film via a streptavidin arm both in static and dynamic conditions compared with PEG-graft-PLA NPs, the proven nonspecific protein-resistant NPs. The specific binding of biotin-graft-PLA NPs with streptavidin and with biotin using streptavidin arm, as well as its entrapment and controlled release for naproxen, suggest potential applications in targeted drug delivery. PMID:22334778

Controlled evaporative self-assembly of confined microfluids: A route to complex ordered structures

NASA Astrophysics Data System (ADS)

Byun, Myunghwan

The evaporative self-assembly of nonvolatile solutes such as polymers, nanocrystals, and carbon nanotubes has been widely recognized as a non-lithographic means of producing a diverse range of intriguing complex structures. Due to the spatial variation of evaporative flux and possible convection, however, these non-equilibrium dissipative structures (e.g., fingering patterns and polygonal network structures) are often irregularly and stochastically organized. Yet for many applications in microelectronics, data storage devices, and biotechnology, it is highly desirable to achieve surface patterns having a well-controlled spatial arrangement. To date, only a few elegant studies have centered on precise control over the evaporation process to produce ordered structures. In a remarked comparison with conventional lithography techniques, surface patterning by controlled solvent evaporation is simple and cost-effective, offering a lithography- and external field-free means to organize nonvolatile materials into ordered microscopic structures over large surface areas. The ability to engineer an evaporative self-assembly process that yields a wide range of complex, self-organizing structures over large areas offers tremendous potential for applications in electronics, optoelectronics, and bio- or chemical sensors. We developed a facile, robust tool for evaporating polymer, nanoparticle, or DNA solutions in curve-on-flat geometries to create versatile, highly regular microstructures, including hierarchically structured polymer blend rings, conjugated polymer "snake-skins", block copolymer stripes, and punch-hole-like meshes, biomolecular microring arrays, etc. The mechanism of structure formation was elucidated both experimentally and theoretically. Our method further enhances current fabrication approaches to creating highly ordered structures in a simple and cost-effective manner, envisioning the potential to be tailored for use in photonics, optoelectronics, microfluidic devices, nanotechnology and biotechnology, etc.

From the Solution Processing of Hydrophilic Molecules to Polymer-Phthalocyanine Hybrid Materials for Ammonia Sensing in High Humidity Atmospheres

PubMed Central

Gaudillat, Pierre; Jurin, Florian; Lakard, Boris; Buron, Cédric; Suisse, Jean-Moïse; Bouvet, Marcel

2014-01-01

We have prepared different hybrid polymer-phthalocyanine materials by solution processing, starting from two sulfonated phthalocyanines, s-CoPc and CuTsPc, and polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), poly(acrylic acid-co-acrylamide) (PAA-AM), poly(diallyldimethylammonium chloride) (PDDA) and polyaniline (PANI) as polymers. We also studied the response to ammonia (NH3) of resistors prepared from these sensing materials. The solvent casted films, prepared from s-CoPc and PVP, PEG and PAA-AM, were highly insulating and very sensitive to the relative humidity (RH) variation. The incorporation of s-CoPc in PDDA by means of layer-by-layer (LBL) technique allowed to stabilize the film, but was too insulating to be interesting. We also prepared PANI-CuTsPc hybrid films by LBL technique. It allowed a regular deposition as evidenced by the linear increase of the absorbance at 688 nm as a function of the number of bilayers. The sensitivity to ammonia (NH3) of PANi-CuTsPc resistors was very high compared to that of individual materials, giving up to 80% of current decrease when exposed to 30 ppm NH3. Contrarily to what happens with neutral polymers, in PANI, CuTsPc was stabilized by strong electrostatic interactions, leading to a stable response to NH3, whatever the relative humidity in the range 10%–70%. Thus, the synergy of PANI with ionic macrocycles used as counteranions combined with their simple aqueous solution processing opens the way to the development of new gas sensors capable of operating in real world conditions. PMID:25061841

Surface characterization of LDEF materials

NASA Astrophysics Data System (ADS)

Wightman, J. P.; Grammer, Holly Little

1993-10-01

The NASA Long Duration Exposure Facility (LDEF), a passive experimental satellite, was placed into low-Earth orbit by the Shuttle Challenger in Apr. 1984. The LDEF spent an unprecedented 69 months in space. The flight and recovery of the LDEF provided a wealth of information on the longterm space environmental effects of a variety of materials exposed to the low-Earth orbit environment. Surface characterization of LDEF materials included polymers, composites, thermal control paints, and aluminum. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and contact angle analysis were used to document changes in both the surface composition and surface chemistry of these materials. Detailed XPS analysis of the polymer systems, such as Kapton, polyimide polysiloxane copolymers, and fluorinated ethylene propylene thermal blankets on the backside of the LDEF revealed significant changes in both the surface composition and surface chemistry as a result of exposure to the low-Earth orbit environment. Polymer systems such as Kapton, polyimide polysiloxane copolymers, and polysulfone showed a common trend of decreasing carbon content and increasing oxygen content with respect to the control sample. Carbon 1s curve fit XPS analysis of the composite samples, in conjunction with SEM photomicrographs, revealed significant ablation of the polymer matrix resin to expose the carbon fibers of the composite during exposure to the space environment. Surface characterization of anodized aluminum tray clamps, which were located at regular intervals over the entire LDEF frame, provided the first results to evaluate the extent of contamination with respect to position on the LDEF. The XPS results clearly showed that the amount and state of both silicon and fluorine contamination were directly dependent upon the position of the tray clamp on the LDEF.

Surface characterization of LDEF materials

NASA Technical Reports Server (NTRS)

Wightman, J. P.; Grammer, Holly Little

1993-01-01

The NASA Long Duration Exposure Facility (LDEF), a passive experimental satellite, was placed into low-Earth orbit by the Shuttle Challenger in Apr. 1984. The LDEF spent an unprecedented 69 months in space. The flight and recovery of the LDEF provided a wealth of information on the longterm space environmental effects of a variety of materials exposed to the low-Earth orbit environment. Surface characterization of LDEF materials included polymers, composites, thermal control paints, and aluminum. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and contact angle analysis were used to document changes in both the surface composition and surface chemistry of these materials. Detailed XPS analysis of the polymer systems, such as Kapton, polyimide polysiloxane copolymers, and fluorinated ethylene propylene thermal blankets on the backside of the LDEF revealed significant changes in both the surface composition and surface chemistry as a result of exposure to the low-Earth orbit environment. Polymer systems such as Kapton, polyimide polysiloxane copolymers, and polysulfone showed a common trend of decreasing carbon content and increasing oxygen content with respect to the control sample. Carbon 1s curve fit XPS analysis of the composite samples, in conjunction with SEM photomicrographs, revealed significant ablation of the polymer matrix resin to expose the carbon fibers of the composite during exposure to the space environment. Surface characterization of anodized aluminum tray clamps, which were located at regular intervals over the entire LDEF frame, provided the first results to evaluate the extent of contamination with respect to position on the LDEF. The XPS results clearly showed that the amount and state of both silicon and fluorine contamination were directly dependent upon the position of the tray clamp on the LDEF.

Analysis of mechanical properties anisotropy of nanomodified carbon fibre-reinforced woven composites

NASA Astrophysics Data System (ADS)

Ruslantsev, A. N.; Portnova, Ya M.; Tairova, L. P.; Dumansky, A. M.

2016-10-01

The polymer binder cracking problem arises while designing and maintaining polymer composite-based aircraft load-bearing members. Some technological methods are used to solve this problem. In particular the injection of nanoagents can block the initiation and growth of microscopic cracks. Crack propagation can also be blocked if the strain energy release is not related with fracturing. One of the possible ways for such energy release is creep. Testing of the anisotropy of the woven carbon fibre reinforced plastic elastic characteristics and creep have been conducted. The samples with different layouts have been made of woven carbon fibre laminate BMI-3/3692 with nanomodified bismaleimide matrix. This matrix has a higher glass transition temperature and improved mechanical properties. The deformation regularities have been analyzed, layer elastic characteristics have been determined. The constitutive equations describing composite material creep have been obtained and its parameters have been defined. Experimental and calculated creep curves have been plotted. It was found that the effects of rheology arise as the direction of load does not match the direction of reinforcing fibres of the material.

Pressure-induced cooperative spin transition in ironII 2D coordination polymers: room-temperature visible spectroscopic study.

PubMed

Levchenko, G; Bukin, G V; Terekhov, S A; Gaspar, A B; Martínez, V; Muñoz, M C; Real, J A

2011-06-30

For the 2D coordination polymers [Fe(3-Fpy)(2)M(II)(CN)(4)] (M(II) = Ni, Pd, Pt), the pressure-induced spin crossover behavior has been investigated at 298 K by monitoring the distinct optical properties associated with each spin state. Cooperative first-order spin transition characterized by a piezohysteresis loop ca. 0.1 GPa wide was observed for the three derivatives. Application of the mean field regular solution theory has enabled estimation of the cooperative parameter, Γ(p), and the enthalpy, ΔH(HL)(p), associated with the spin transition for each derivative. These values, found in the intervals 6.8-7.9 and 18.6-20.8 kJ mol(-1), respectively, are consistent with those previously reported for thermally induced spin transition at constant pressure for the title compounds (Chem.-Eur. J.2009, 15, 10960). Relevance of the elastic energy, Δ(elast), as a corrective parameter accounting for the pressure dependence of the critical temperature of thermally induced spin transitions (Clausius-Clapeiron equation) is also demonstrated and discussed.

Modeling the growth processes of polyelectrolyte multilayers using a quartz crystal resonator.

PubMed

Salomäki, Mikko; Kankare, Jouko

2007-07-26

The layer-by-layer buildup of chitosan/hyaluronan (CH/HA) and poly(l-lysine)/hyaluronan (PLL/HA) multilayers was followed on a quartz crystal resonator (QCR) in different ionic strengths and at different temperatures. These polyelectrolytes were chosen to demonstrate the method whereby useful information is retrieved from acoustically thick polymer layers during their buildup. Surface acoustic impedance recorded in these measurements gives a single or double spiral when plotted in the complex plane. The shape of this spiral depends on the viscoelasticity of the layer material and regularity of the growth process. The polymer layer is assumed to consist of one or two zones. A mathematical model was devised to represent the separation of the layer to two zones with different viscoelastic properties. Viscoelastic quantities of the layer material and the mode and parameters of the growth process were acquired by fitting a spiral to the experimental data. In all the cases the growth process was mainly exponential as a function of deposition cycles, the growth exponent being between 0.250 and 0.275.

Role of interfacial effects in carbon nanotube/epoxy nanocomposite behavior.

PubMed

Pécastaings, G; Delhaès, P; Derré, A; Saadaoui, H; Carmona, F; Cui, S

2004-09-01

The interfacial effects are critical to understand the nanocomposite behavior based on polymer matrices. These effects are dependent upon the morphology of carbon nanotubes, the type of used polymer and the processing technique. Indeed, we show that the different parameters, as the eventual surfactant use, the ultrasonic treatment and shear mixing have to be carefully examined, in particular, for nanotube dispersion and their possible alignment. A series of multiwalled nanotubes (MWNT) have been mixed with a regular epoxy resin under a controlled way to prepare nanocomposites. The influence of nanotube content is examined through helium bulk density, glass transition temperature of the matrix and direct current electrical conductivity measurements. These results, including the value of the percolation threshold, are analyzed in relationship with the mesostructural organization of these nanotubes, which is observed by standard and conductive probe atomic force microscopy (AFM) measurements. The wrapping effect of the organic matrix along the nanotubes is evidenced and analyzed to get a better understanding of the final composite characteristics, in particular, for eventually reinforcing the matrix without covalent bonding.

Microfluidic Assisted Synthesis of Multipurpose Polymer Nanoassembly Particles for Fluorescence, LSPR, and SERS Activities.

PubMed

Visaveliya, Nikunjkumar; Köhler, J Michael

2015-12-22

Potential biomedical applications such as controlled delivery with sustained drug release profile demand for multifunctional polymeric particles of precise chemical composition and with welldefined physicochemical properties. The real challenge is to obtain the reproducible and homogeneous nanoparticles in a minimum number of preparation steps. Here, single-step nanoarchitectures of soft surface layered copolymer nanoparticles with a regular tuning in the size via micro flow-through assisted synthesis are reported. Interfacial copolymerization induces the controlled compartmentalization where a hydrophobic core adopts spherical shape in order to minimize the surface energy and simultaneously shelter in the hydrophilic shelllike surface layer. Surface layer can swell in the aqueous medium and allow controlled entrapping of functional hydrophobic nanoparticles in the hydrophilic interior via electrostatic interaction which can be particularly interesting for combined fluorescence activity. Furthermore, the nanoarchitecture of size and concentration controlled polymer-metal nanoassembly particles can be implemented as an ideal surface-enhanced Raman scattering substrate for detection of the trace amounts of various analytes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Block versus Random Amphiphilic Glycopolymer Nanopaticles as Glucose-Responsive Vehicles.

PubMed

Guo, Qianqian; Zhang, Tianqi; An, Jinxia; Wu, Zhongming; Zhao, Yu; Dai, Xiaomei; Zhang, Xinge; Li, Chaoxing

2015-10-12

To explore the effect of polymer structure on their self-assembled aggregates and their unique characteristics, this study was devoted to developing a series of amphiphilic block and random phenylboronic acid-based glycopolymers by RAFT polymerization. The amphiphilic glycopolymers were successfully self-assembled into spherically shaped nanoparticles with narrow size distribution in aqueous solution. For block and random copolymers with similar monomer compositions, block copolymer nanoparticles exhibited a more regular transmittance change with the increasing glucose level, while a more evident variation of size and quicker decreasing tendency in I/I0 behavior in different glucose media were observed for random copolymer nanoparticles. Cell viability of all the polymer nanoparticles investigated by MTT assay was higher than 80%, indicating that both block and random copolymers had good cytocompatibility. Insulin could be encapsulated into both nanoparticles, and insulin release rate for random glycopolymer was slightly quicker than that for the block ones. We speculate that different chain conformations between block and random glycopolymers play an important role in self-assembled nanoaggregates and underlying glucose-sensitive behavior.

Spontaneous beating and synchronization of extensile active filament

NASA Astrophysics Data System (ADS)

Sarkar, Debarati; Thakur, Snigdha

2017-04-01

We simulate a semi-flexible active filament that exhibits spontaneous oscillations on clamping and show self-propulsion when left free. The activity on the filament relies on the nano-dimers distributed at regular intervals along the chain. With an emphasis on the spontaneous beating of a clamped filament, we demonstrate that the two competing forces necessary for oscillation are the elastic forces due to polymer rigidity and the active forces due to chemical activity. In addition, we also study the synchronization of two extensile filaments and the role played by non-local hydrodynamic interactions. We observe a phase lock scenario between the filaments during their synchronous motion.

Polyelectrolyte complexes of hTERT siRNA and polyethyleneimine: Effect of degree of PEG grafting on biological and cellular activity.

PubMed

Safari, Fatemeh; Tamaddon, Ali M; Zarghami, Nosratollah; Abolmali, S; Akbarzadeh, Abolfazl

2016-09-01

Gene silencing by siRNA (short interfering RNA)-targeted human telomerase reverse transcriptase (hTERT) is considered a successful strategy for cancer gene therapy. Polyelectrolyte complexes (PEC) of siRNA and cationic polymers such as polyethyleneimine (PEI) have been widely used for cellular transfection; however, they demonstrate some disadvantages such as cytotoxicity and extracellular matrix restrictions. PEG grafting technology was used in an attempt to improve the biocompatibility of PECs. Considering that this technology may compromise the cellular uptake of PECs, we aimed to study the effect of degree of PEI PEGylation on the carrier cytotoxicity, cellular association, and transfection efficiency of hTERT siRNA in the lung cancer cell line A549. Activated NHS ester of methoxy PEG-COOH 5 KDa was grafted to hyperbranched PEI 25 KDa in the molar ratios of 0.2 and 1. The copolymers were characterized by (1)H-NMR spectroscopy. PECs of PEI or PEG-g-PEI with siRNA, alone or co-incubated with heparin sulfate, were studied by the ethidium bromide exclusion assay. Cytotoxicity of the polymers (PEG-g-PEI vs PEI), alone and upon formation of PEC nanoparticles with hTERT siRNA, was determined by a validated MTT assay, in comparison to a scrambled control sequence, in A549 human lung carcinoma cells. The cellular uptake of the PECs of FITC-labeled siRNA was investigated by flow cytometry at different N/P ratios, and the silencing effect of the transfected siRNA was compared to that of the control sequence for different PECs by real time RT-PCR. The cytotoxicity of PEI decreased significantly by PEG grafting, even at a low degree of PEGylation. Moreover, the nonspecific cytotoxicity of PECs decreased by PEG grafting. PECs of PEG-g-PEI showed more biologic stability on incubation with heparin sulfate. Average particle size and zeta potential of PEC nanoparticles were diminished for those of PEG-g-PEI. The cellular association was more pronounced at an N/P ratio of 2.5 for PECs of PEI and PEG-g-PEI alike. The level of silencing of hTERT mRNA by PEC of PEG-g-PEI was sequence-dependent, and determined non-inferior when compared to the native PEI. Conclusively, the biocompatibility of PEI was improved by a low degree of PEGylation, with no adverse effect on the cellular uptake and the transfection activity. PEC nanoparticles of hTERT siRNA and PEG-g-PEI could act as a promising weapon against A549 cells, which has to be considered for an in vivo evaluation.

CuAAC-Based Click Chemistry in Self-Healing Polymers.

PubMed

Döhler, Diana; Michael, Philipp; Binder, Wolfgang H

2017-10-17

Click chemistry has emerged as a significant tool for materials science, organic chemistry, and bioscience. Based on the initial concept of Barry Sharpless in 2001, the copper(I)-catalyzed azide/alkyne cycloaddition (CuAAC) reaction has triggered a plethora of chemical concepts for linking molecules and building blocks under ambient conditions, forming the basis for applications in autonomous cross-linking materials. Self-healing systems on the other hand are often based on mild cross-linking chemistries that are able to react either autonomously or upon an external trigger. In the ideal case, self-healing takes place efficiently at low temperatures, independent of the substrate(s) used, by forming strong and stable networks, binding to the newly generated (cracked) interfaces to restore the original material properties. The use of the CuAAC in self-healing systems, most of all the careful design of copper-based catalysts linked to additives as well as the chemical diversity of substrates, has led to an enormous potential of applications of this singular reaction. The implementation of click-based strategies in self-healing systems therefore is highly attractive, as here chemical (and physical) concepts of molecular reactivity, molecular design, and even metal catalysis are connected to aspects of materials science. In this Account, we will show how CuAAC reactions of multivalent components can be used as a tool for self-healing materials, achieving cross-linking at low temperatures (exploiting concepts of autocatalysis or internal chelation within the bulk CuAAC and systematic optimization of the efficiency of the used Cu(I) catalysts). Encapsulation strategies to separate the click components by micro- and nanoencapsulation are required in this context. Consequently, the examples reported here describe chemical concepts to realize more efficient and faster click reactions in self-healing polymeric materials. Thus, enhanced chain diffusion in (hyper)branched polymers, autocatalysis, or internal chelation concepts enable efficient click cross-linking already at 5 °C with a simultaneously reduced amount of Cu(I) catalyst and increased reaction rates, culminating in the first reported self-healing system based on click cycloaddition reactions. Via tailor-made nanocarbon/Cu(I) catalysts we can further improve the click cross-linking reaction in view of efficiency and kinetics, leading to the generation of self-healing graphene-based epoxy nanocomposites. Additionally, we have designed special CuAAC click methods for chemical reporting and visualization systems based on the detection of ruptured capsules via a fluorogenic click reaction, which can be combined with CuAAC cross-linking reactions to obtain simultaneous stress detection and self-healing within polymeric materials. In a similar concept, we have prepared polymeric Cu(I)-biscarbene complexes to detect (mechanical) stress within self-healing polymeric materials via a triggered fluorogenic reaction, thus using a destructive force for a constructive chemical response.

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

Tong Dongge; Han Xue; Chu Wei

Co-B flowers with mesoporous structure were first prepared via reduction of cobalt acetate by potassium borohydride in the presence of complexing agent ethylenediamine. The as-prepared Co-B flowers were characterized by Fourier transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, N{sub 2} adsorption-desorption, and magnetic performance test. The Co-B flowers exhibited enhanced coercivity, and weakened saturation magnetization and remanet magnetization as compared with the regular Co-B. During the hydrolysis of KBH{sub 4}, the Co-B flowers exhibited higher catalytic activity than the regular Co-B. It is attributed to themore » larger specific surface area and mesoporous channels. During the successive reactions, the conversion of KBH{sub 4} over Co-B flowers was about 97%. The average H{sub 2} generation rate of Co-B flowers was 4620 mL/min/g-catalyst in 1.5 wt% NaOH + 15 wt% KBH{sub 4} solution, which may give a successive H{sub 2} supply for a 748 W polymer electrolyte membrane fuel cell (PEMFC) at 100% H{sub 2} utilization.« less

Ultrafast photophysics of pi-conjugated polymers for organic light emitting diode applications

NASA Astrophysics Data System (ADS)

Olejnik, Ella

In this work we used the pump-probe photomodulation (PM) spectroscopy technique to measure the transient PM spectrum and decay kinetics in various pi -- conjugated polymers (PCPs) films and blends. Using two ultrafast laser systems, we covered a broad spectral range from 0.25 -- 2.5 eV in the time domain from 200 fs to 1 ns with 150 fs time resolution. We also used continuous wave (CW) photomodulation spectroscopy, photoluminescence (PL), electro-absorption and doping-induced absorption to study the photoexcitations and other optical properties of PCPs and guest/ host blends. In particular we studied two different types of Poly(thienylenevinylene) polymer derivatives. One polymer type is the ordered regio-regular (RR) and regio-random (RRa) -- PTV in which the dark exciton, 2Ag is the lowest excited state. In these polymers the photoexcited exciton shows very fast decay kinetics due to the internal conversion to the dark exciton, which results in weak PL emission; thus these two polymers are non-luminescent. The other PTV derivative is the imide -- PTV which is more luminescent due to the proximity of 1Bu and 2Ag states, that results in longer decay kinetics and a difference between the calculated value of the QEPL (9%) and the measured one (1%). We also demonstrate transient strain spectroscopy in RR -- PTV thin films, where the ultrafast energy release associated with the exciton decay gives rise to substantial static and dynamic strains in the film that dramatically influences the film's transient PM response. We also study the photophysics of poly(dioctyloxy) phenylenevinylene polymer with different isotopes, where we substituted hydrogen (H-polymer) by deuterium (D-polymer), and 12C by 13C isotopes. From the transient decay kinetics measurements we found that the exciton recombination in DOO -- PPV consists of two processes. These are: intrinsic monomolecular, and exciton-exciton annihilation (bimolecular). In the D -- polymer, different probe frequencies of the main exciton photoinduced absorption band (PA1) show a variety of decay kinetics that result from various photoexcitations that contribute to the spectrum. Comparing the transient PM spectrum at 1 ns time delay to the CW PM shows the formation of triplet excitons, which is possible due to singlet fission of mAg (at 2.9 eV) into two triplets (2 X 1.4 eV). In the last part of this thesis we summarize our studies of organic light emitting diodes (OLED) devices based on a host/guest blend of Polyfluorene polymer that is mixed with various percentages of Ir(btp)2acac molecules. In this mixture the PFO (host) shows blue fluorescence, whereas the Ir-complex (guest) has red phosphorescence emission; thus OLED based on this mixture can serve as a `white OLED'. Since the PFO emission spectrum perfectly matches the absorption band of the Ir-complex, it induces an efficient energy transfer from the PFO host to the Ir-complex guest molecules, which we tried to time resolve by the transient PM method.

1D hetero-bimetallic regularly alternated 4f-3d coordination polymers based on N-oxide-4,4'-bipyridine (bipyMO) as a linker: photoluminescence and magnetic properties.

PubMed

Armelao, Lidia; Belli Dell'Amico, Daniela; Bottaro, Gregorio; Bellucci, Luca; Labella, Luca; Marchetti, Fabio; Mattei, Carlo Andrea; Mian, Federica; Pineider, Francesco; Poneti, Giordano; Samaritani, Simona

2018-06-13

Heterotopic divergent ligand N-oxide-4,4'-bipyridine (bipyMO) has been herein exploited for the preparation of hetero-bimetallic coordination polymers where Ln(hfac)3 and M(hfac)2 nodes regularly alternate (Hhfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), bipyMO being able to selectively use its two potential coordination sites to discriminate the metal ions. The synthesis of three coordination polymers, [Ln(hfac)3M(hfac)2(bipyMO)2]n (Ln = Eu, M = Zn, 1; Ln = Eu, M = Cu, 2, Ln = Dy, M = Co, 3), was carried out by reacting the appropriate [M(hfac)2(bipyMO)]n and [Ln(hfac)3] precursors in toluene in the presence of a given stoichiometric amount of bipyMO. The products were characterized by elemental analysis, X-ray powder diffraction, and FTIR spectroscopy. Single crystal X-ray diffraction studies carried out on 2 showed that it was formed by chains containing the hexa-coordinated 3d metal (Cu(hfac)2[N]2) and the octa-coordinated lanthanide (Eu(hfac)3[O]2) nodes, where [N] and [O] stand for the donor atom of the bridging divergent ligand. The X-ray powder diffraction patterns of the three compounds and the comparison of their cell constant values allowed establishing that the derivatives were isotypic. Photoluminescence (PL) studies on microcrystalline sample powders evidenced a bright red emission for 1 with an absolute PL quantum yield of 0.24. The sensitized emission of Eu3+ can be excited in a wide wavelength range, from UV to visible, up to ≈450 nm. Conversely, europium emissions are not detectable in 2 due to the presence of Cu(hfac)2(bipyMO) moieties whose strong absorption overlaps Eu3+ transitions. Magnetic measurements conducted on 3 revealed the presence of a weak ferromagnetic interaction below 2.1 K. An ac susceptibility study highlighted a slow relaxation of the magnetization of 3 with an applied static magnetic field of 0.1 T, which could be equally fitted with a Orbach-direct or a Raman-direct mechanism. No relaxation dynamics was detected without the application of a static magnetic field.

Chemical modification, antioxidant and α-amylase inhibitory activities of corn silk polysaccharides.

PubMed

Chen, Shuhan; Chen, Haixia; Tian, Jingge; Wang, Yanwei; Xing, Lisha; Wang, Jia

2013-10-15

Water-soluble corn silk polysaccharides (CSPS) were chemically modified to obtain their sulfated, acetylated and carboxymethylated derivatives. Chemical characterization and bioactivities of CSPS and its derivatives were comparatively investigated by chemical methods, gas chromatography, gel filtration chromatography, scanning electron microscope, infrared spectroscopy and circular dichroism spectroscopy, scavenging DPPH free radical assay, scavenging hydroxyl radical assay, ferric reducing power assay, lipid peroxidation inhibition assay and α-amylase activity inhibitory assay, respectively. Among the three derivatives, carboxylmethylated polysaccharide (C-CSPS) demonstrated higher solubility, narrower molecular weight distribution, lower intrinsic viscosity, a hyperbranched conformation, significantly higher antioxidant and α-amylase inhibitory abilities compared with the native polysaccharide and other derivatives. C-CSPS might be used as a novel nutraceutical agent for human consumption. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hydrothermal synthesis for new multifunctional materials: A few examples of phosphates and phosphonate-based hybrid materials

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

Rueff, Jean-Michel, E-mail: jean-michel.rueff@ensicaen.fr; Poienar, Maria; Guesdon, Anne

Novel physical or chemical properties are expected in a great variety of materials, in connection with the dimensionality of their structures and/or with their nanostructures, hierarchical superstructures etc. In the search of new advanced materials, the hydrothermal technique plays a crucial role, mimicking the nature able to produce fractal, hyperbranched, urchin-like or snow flake structures. In this short review including new results, this will be illustrated by examples selected in two types of materials, phosphates and phosphonates, prepared by this method. The importance of the synthesis parameters will be highlighted for a magnetic iron based phosphates and for hybrids containingmore » phosphonates organic building units crystallizing in different structural types. - Graphical abstract: Phosphate dendrite like and phosphonate platelet crystals.« less

Recent advances in dendrimer-based nanovectors for tumor-targeted drug and gene delivery

PubMed Central

Kesharwani, Prashant; Iyer, Arun K.

2015-01-01

Advances in the application of nanotechnology in medicine have given rise to multifunctional smart nanocarriers that can be engineered with tunable physicochemical characteristics to deliver one or more therapeutic agent(s) safely and selectively to cancer cells, including intracellular organelle-specific targeting. Dendrimers having properties resembling biomolecules, with well-defined 3D nanopolymeric architectures, are emerging as a highly attractive class of drug and gene delivery vector. The presence of numerous peripheral functional groups on hyperbranched dendrimers affords efficient conjugation of targeting ligands and biomarkers that can recognize and bind to receptors overexpressed on cancer cells for tumor-cell-specific delivery. The present review compiles the recent advances in dendrimer-mediated drug and gene delivery to tumors by passive and active targeting principles with illustrative examples. PMID:25555748

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.

Deep X-ray lithography for the fabrication of microstructures at ELSA

NASA Astrophysics Data System (ADS)

Pantenburg, F. J.; Mohr, J.

2001-07-01

Two beamlines at the Electron Stretcher Accelerator (ELSA) of Bonn University are dedicated for the production of microstructures by deep X-ray lithography with synchrotron radiation. They are equipped with state-of-the-art X-ray scanners, maintained and used by Forschungszentrum Karlsruhe. Polymer microstructure heights between 30 and 3000 μm are manufactured regularly for research and industrial projects. This requires different characteristic energies. Therefore, ELSA operates routinely at 1.6, 2.3 and 2.7 GeV, for high-resolution X-ray mask fabrication, deep and ultra-deep X-ray lithography, respectively. The experimental setup, as well as the structure quality of deep and ultra deep X-ray lithographic microstructures are described.

Use of organic precursors and graphenes in the controlled synthesis of carbon-containing nanomaterials for energy storage and conversion.

PubMed

Yang, Shubin; Bachman, Robert E; Feng, Xinliang; Müllen, Klaus

2013-01-15

The development of high-performance electrochemical energy storage and conversion devices, including supercapacitors, lithium-ion batteries, and fuel cells, is an important step on the road to alternative energy technologies. Carbon-containing nanomaterials (CCNMs), defined here as pure carbon materials and carbon/metal (oxide, hydroxide) hybrids with structural features on the nanometer scale, show potential application in such devices. Because of their pronounced electrochemical activity, high chemical and thermal stability and low cost, researchers are interested in CCNMs to serve as electrodes in energy-related devices. Various all-carbon materials are candidates for electrochemical energy storage and conversion devices. Furthermore, carbon-based hybrid materials, which consist of a carbon component with metal oxide- or metal hydroxide-based nanostructures, offer the opportunity to combine the attractive properties of these two components and tune the behavior of the resulting materials. As such, the design and synthesis of CCNMs provide an attractive route for the construction of high-performance electrode materials. Studies in these areas have revealed that both the composition and the fabrication protocol employed in preparing CCNMs influence the morphology and microstructure of the resulting material and its electrochemical performance. Consequently, researchers have developed several synthesis strategies, including hard-templated, soft-templated, and template-free synthesis of CCNMs. In this Account, we focus on recent advances in the controlled synthesis of such CCNMs and the potential of the resulting materials for energy storage or conversion applications. The Account is divided into four major categories based on the carbon precursor employed in the synthesis: low molecular weight organic or organometallic molecules, hyperbranched or cross-linked polymers consisting of aromatic subunits, self-assembling discotic molecules, and graphenes. In each case, we highlight representative examples of CCNMs with both new nanostructures and electrochemical performance suitable for energy storage or conversion applications. In addition, this Account provides an overall perspective on the current state of efforts aimed at the controlled synthesis of CCNMs and identifies some of the remaining challenges.

Design and construction of multifunctional hyperbranched polymers coated magnetite nanoparticles for both targeting magnetic resonance imaging and cancer therapy.

PubMed

Mashhadi Malekzadeh, Asemeh; Ramazani, Ali; Tabatabaei Rezaei, Seyed Jamal; Niknejad, Hassan

2017-03-15

Magnetic drug targeting is a drug delivery strategy that can be used to improve the therapeutic efficiency on tumor cells and reduce the side effects on normal cells and tissues. The aim in this study is designing a novel multifunctional drug delivery system based on superparamagnetic nanoparticles for cancer therapy. Magnetic nanoparticles were synthesized by coprecipitation of iron oxide followed by coating with poly citric acid (PCA) dendritic macromolecules via bulk polymerization strategy. It was further surface-functionalized with poly(ethylene glycol) (PEG) and then to achieve tumor cell targeting property, folic acid was further incorporated to the surface of prepared carriers via a facile coupling reaction between the hydroxyl end group of the PEG and the carboxyl group of folic acid. The so prepared nanocarriers (Fe 3 O 4 @PCA-PEG-FA) were characterized by X-ray diffraction, TEM, TGA, FT-IR, DLS and VSM techniques. The room temperature VSM measurements showed that magnetic particles were superparamagnetic. Transmission electron microscopy and dynamic light scattering were also performed which revealed that size of nanocarriers was lying in the range of 10-49nm. Quercetin loading and release profiles of prepared nanocarriers showed that up to 83% of loaded drug was released in 250h. Fluorescent microscopy showed that the cellular uptake by folate receptor-overexpressing HeLa cells of the quercetin-loaded Fe 3 O 4 @PCA-PEG-FA nanoparticles was higher than that of non-folate conjugated nanoparticles. Thus, folate conjugation significantly increased nanoparticle cytotoxicity. Also, T 2 -weighted MRI images of Fe 3 O 4 @PCA-PEG-FA nanoparticles showed that the magnetic resonance signal is enhanced significantly with increasing nanoparticle concentration in water and they also served as MRI contrast agents with relaxivities of 3.4mM -1 s -1 (r 1 ) and 99.8mM -1 s -1 (r 2 ). The results indicate that this multifunctional nanocarrier is a significant breakthrough in developing a drug delivery vehicle that combines drug targeting as well as sensing and therapy at the same time. Copyright © 2016 Elsevier Inc. All rights reserved.

Onset of the sharkskin phenomenon in polymer extrusion

NASA Astrophysics Data System (ADS)

Molenaar, J.; Koopmans, R. J.; den Doelder, C. F. J.

1998-10-01

A specific form of melt flow instabilities associated with surface defects for polymer extrudates, and commonly referred to as the ``sharkskin effect'', is modeled. When this effect occurs, a more or less regular pattern of ridges on the surface is observed resembling the skin of a shark if bent. It is shown that the relaxation oscillation model of Molenaar and Koopmans [J. Rheol. 38, 99 (1994)] developed to describe ``spurt'' defects - in this perturbation not only the surface but the extrudate as a whole shows distortions - can be expanded to include a description for the dynamics of surface defect appearance. By introducing a nonlinear viscoelastic constitutive equation (Kaye-Bernstein-Kearsly-Zapas model) into the relaxation oscillation model a boundary layer can develop which shows oscillating behavior. Explicit criteria for the onset of this behavior are derived. The relations between these criteria and experimental parameters are pointed out. This allows for an experimental verification of the supposition that this kind of solution is the origin of the sharkskin effect. The current macroscopic approach may form the basis for the reconciliation of the debate on the origin of melt flow instabilities as either a ``slip at the wall'' or a nonmonotone ``constitutive equation'' phenomenon.

Correlation between polymer architecture, mesoscale structure and photovoltaic performance in side-chain-modified PAE-PAV:fullerene bulk-heterojunction solar cells

NASA Astrophysics Data System (ADS)

Rathgeber, S.; Kuehnlenz, F.; Hoppe, H.; Egbe, D. A. M.; Tuerk, S.; Perlich, J.; Gehrke, R.

2012-02-01

A poly(arylene-ethynylene)-alt-poly(arylene-vinylene) statistical copolymer carrying linear and branched alkoxy side chains along the conjugated backbone in a random manner, yields, compared to its regular substituted counterparts, an improved performance in polymer:fullerene bulk-heterojunction solar cells. Results obtained from GiWAXS experiments show that the improved performance of the statistical copolymer may be attributed to the following structural characteristics: 1) Well, ordered stacked domains that promote backbone planarization and thus improve the ππ-overlap. 2) Partly face-on alignment of domains relative to the electrodes for an improved active layer electrode charge transfer. Branched side chains seem to promote face-on domain orientation. Most likely they can minimize their unfavorable contact with the interface by just bringing the CH3 groups of the branches into direct contact with the surface so that favorable phenylene-substrate interaction can promote face-on orientation. 3) A more isotropic domain orientation throughout the active layer to ensure that the backbone alignment direction has components perpendicular and parallel to the electrodes in order to compromise between light absorption and efficient intra-chain charge transport.

ESCA Study of Poly (Vinylidene Fluoride) Tetrafluoroethylene - Ethylene Copolymer and Polyethylene Exposed to Atomic Oxygen

NASA Technical Reports Server (NTRS)

Golub, Morton A.; Cormia, Robert D.

1989-01-01

The ESCA (electron spectroscopy for chemical analysis) spectra of films of poly(vinylidene fluoride) (PVDF), tetrafluoroethylene-ethylene copolymer (TFE/ET) and polyethylene (PE) exposed to atomic oxygen (O(P-3)), in or out of the glow of a radio-frequency O2 plasma, were compared. ESCA spectra of PE films exposed to (O(P-3)) in low Earth orbit (LEO) on the STS-8 Space Shuttle were also examined. Apart from O(P-3)-induced surface recession (etching), the various polymer films exhibited surface oxidation, which proceeded towards equilibrium saturation oxygen levels. The maximum surface oxygen uptakes for in-glow or out-of-glow exposures were in the order: PE greater than TFE/ET greater than PVDF; for PE itself, the oxygen uptakes were in the order: in glow greater than out of glow greater than LEO. Given prior ESCA data on poly(vinyl fluoride) and polytetrafluoroethylene films exposed to O(P-3), the extent of surface oxidation is seen to decrease regularly with increase in fluorine substitution in a family of ethylene-type polymers. (Keywords: ESCA; poly(vinylidene fluoride); tetrafluoroethylene ethylene copolymer; polyethylene; atomic oxygen; radio-frequency oxygen plasma; low Earth orbit)

Coupling crystal plasticity and phase-field damage to simulate β-HMX-based polymer-bonded explosive under shock load

NASA Astrophysics Data System (ADS)

Grilli, Nicolo; Dandekar, Akshay; Koslowski, Marisol

2017-06-01

The development of high explosive materials requires constitutive models that are able to predict the influence of microstructure and loading conditions on shock sensitivity. In this work a model at the continuum-scale for the polymer-bonded explosive constituted of β-HMX particles embedded in a Sylgard matrix is developed. It includes a Murnaghan equation of state, a crystal plasticity model, based on power-law slip rate and hardening, and a phase field damage model based on crack regularization. The temperature increase due to chemical reactions is introduced by a heat source term, which is validated using results from reactive molecular dynamics simulations. An initial damage field representing pre-existing voids and cracks is used in the simulations to understand the effect of these inhomogeneities on the damage propagation and shock sensitivity. We show the predictions of the crystal plasticity model and the effect of the HMX crystal orientation on the shock initiation and on the dissipated plastic work and damage propagation. The simulation results are validated with ultra-fast dynamic transmission electron microscopy experiments and x-ray experiments carried out at Purdue University. Membership Pending.

An analysis of degradation phenomena in polymer electrolyte membrane water electrolysis

NASA Astrophysics Data System (ADS)

Rakousky, Christoph; Reimer, Uwe; Wippermann, Klaus; Carmo, Marcelo; Lueke, Wiebke; Stolten, Detlef

2016-09-01

The durability of a polymer electrolyte membrane (PEM) water electrolysis single cell, assembled with regular porous transport layers (PTLs) is investigated for just over 1000 h. We observe a significant degradation rate of 194 μV h-1 and conclude that 78% of the detectable degradation can be explained by an increase in ohmic resistance, arising from the anodic Ti-PTL. Analysis of the polarization curves also indicates a decrease in the anodic exchange current density, j0, that results from the over-time contamination of the anode with Ti species. Furthermore, the average Pt-cathode particle size increases during the test, but we do not believe this phenomenon makes a significant contribution to increased cell voltages. To validate the anode Ti-PTL as a crucial source of increasing resistance, a second cell is assembled using Pt-coated Ti-PTLs. This yields a substantially reduced degradation rate of only 12 μV h-1, indicating that a non-corroding anode PTL is vital for PEM electrolyzers. It is our hope that forthcoming tailored PTLs will not only contribute to fast progress on cost-efficient stacks, but also to its long-term application of PEM electrolyzers involved in industrial processes.

A bifractal nature of reticular patterns induced by oxygen plasma on polymer films

NASA Astrophysics Data System (ADS)

Bae, Junwan; Lee, I. J.

2015-05-01

Plasma etching was demonstrated to be a promising tool for generating self-organized nano-patterns on various commercial films. Unfortunately, dynamic scaling approach toward fundamental understanding of the formation and growth of the plasma-induced nano-structure has not always been straightforward. The temporal evolution of self-aligned nano-patterns may often evolve with an additional scale-invariance, which leads to breakdown of the well-established dynamic scaling law. The concept of a bifractal interface is successfully applied to reticular patterns induced by oxygen plasma on the surface of polymer films. The reticular pattern, composed of nano-size self-aligned protuberances and underlying structure, develops two types of anomalous dynamic scaling characterized by super-roughening and intrinsic anomalous scaling, respectively. The diffusion and aggregation of short-cleaved chains under the plasma environment are responsible for the regular distribution of the nano-size protuberances. Remarkably, it is uncovered that the dynamic roughening of the underlying structure is governed by a relaxation mechanism described by the Edwards-Wilkinson universality class with a conservative noise. The evidence for the basic phase, characterized by the negative roughness and growth exponents, has been elusive since its first theoretical consideration more than two decades ago.

Bipartite design of a self-fibrillating protein copolymer with nanopatterned peptide display capabilities.

PubMed

Bruning, Marc; Kreplak, Laurent; Leopoldseder, Sonja; Müller, Shirley A; Ringler, Philippe; Duchesne, Laurence; Fernig, David G; Engel, Andreas; Ucurum-Fotiadis, Zöhre; Mayans, Olga

2010-11-10

The development of biomatrices for technological and biomedical applications employs self-assembled scaffolds built from short peptidic motifs. However, biopolymers composed of protein domains would offer more varied molecular frames to introduce finer and more complex functionalities in bioreactive scaffolds using bottom-up approaches. Yet, the rules governing the three-dimensional organization of protein architectures in nature are complex and poorly understood. As a result, the synthetic fabrication of ordered protein association into polymers poses major challenges to bioengineering. We have now fabricated a self-assembling protein nanofiber with predictable morphologies and amenable to bottom-up customization, where features supporting function and assembly are spatially segregated. The design was inspired by the cross-linking of titin filaments by telethonin in the muscle sarcomere. The resulting fiber is a two-protein system that has nanopatterned peptide display capabilities as shown by the recruitment of functionalized gold nanoparticles at regular intervals of ∼ 5 nm, yielding a semiregular linear array over micrometers. This polymer promises the uncomplicated display of biologically active motifs to selectively bind and organize matter in the fine nanoscale. Further, its conceptual design has high potential for controlled plurifunctionalization.

Unusual concentration-dependent microscopic dynamics of dendrimers in aqueous solution

NASA Astrophysics Data System (ADS)

Wong, Kaikin; Wu, Chin Ming; Lam, Hak Fai; Chathoth, Suresh M.

2016-05-01

Dendrimers are novel three-dimensional, hyperbranched globular nanopolymeric macromolecules. The nanoscopic size, narrow polydispersity index, excellent control over molecular structure, availability of multiple functional groups at the periphery, and cavities in the interior made them very attractive candidate for drug delivery. In this communication, we have studied the microscopic dynamics of tetra-acid and pentaerythritol glycidyl ether dendrimers dissolved in aqueous solution with different concentrations. The effects of concentration and temperature to their long-range diffusion process are investigated by dynamic light scattering. Experimental results show a huge variation in the translational diffusion coefficient for the two dendrimers samples. Besides, the dependence of diffusion coefficients on concentration is unusually different in these dendrimer samples. Although the diffusion process follows Arrhenius relation with the temperature in both systems, the activation energy for the diffusion process has a distinct concentration dependence.

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

Uemura, Kazuhiro, E-mail: k_uemura@gifu-u.ac.j; Onishi, Fumiaki; Yamasaki, Yukari

NO{sub 2} containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO{sub 2}) and 2,5-dinitroterephthalate (bdc-(NO{sub 2}){sub 2}), afford porous coordination polymers, {l_brace}[Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)].solvents{r_brace}{sub n} (2 contains solvents) and {l_brace}[Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)].solvents{r_brace}{sub n} (3 contains solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn{sub 2} units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2 contains solvents and 3 contains solvents, a rectangle pore surrounded by eight Zn{sub 2} corners contains two and four NO{sub 2} moieties, respectively. Thermal gravimetry (TG) and X-ray powdermore » diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me{sub 2}CO. Adsorption measurements reveal that dried 2 and 3 adsorb H{sub 2}O molecules to be {l_brace}[Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)].4H{sub 2}O{r_brace}{sub n} (2 contains 4H{sub 2}O) and {l_brace}[Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)].6H{sub 2}O{r_brace}{sub n} (3 contains 6H{sub 2}O), showing the pore hydrophilicity enhancement caused by NO{sub 2} group introduction. - Graphical abstract: Two hydrophilic porous coordination polymers, [Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)]{sub n} (2, bdc-NO{sub 2}=nitroterephthalate, dabco=1,4-diazabicyclo[2.2.2]octane) and [Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)]{sub n} (3, bdc-(NO{sub 2}){sub 2}=2,5-dinitroterephthalate), have been synthesized and characterized by single X-ray analyses, thermal gravimetry, and adsorption measurements.« less

Solvent-vapor-assisted dewetting of prepatterned thin polymer films: control of morphology, order, and pattern miniaturization.

PubMed

Bhandaru, Nandini; Goohpattader, Partho Sarathi; Faruqui, Danish; Mukherjee, Rabibrata; Sharma, Ashutosh

2015-03-17

Ultrathin (<100 nm) unstable polymer films exposed to a solvent vapor dewet by the growth of surface instability, the wavelength (λ) of which depends on the film thickness (h(f)). While the dewetting of a flat polymer thin film results in random structures, we show that the dewetting of a prepatterned film results in myriad ordered mesoscale morphologies under specific conditions. Such a film undergoes rupture over the thinnest parts when the initial local thickness of these zones (h(rm)) is lower than a limiting thickness h(lim) ≈ 10 nm. Additionally, the width of the pattern grooves (l(s)) must be wider than λ(s) corresponding to a flat film having a thickness of h(rm) for pattern-directed dewetting to take place over surface-tension-induced flattening. We first present an experimentally obtained morphology phase diagram that captures the conditions where a transition from surface-tension-induced flattening to pattern-directed-rupture takes place. Subsequently, we show the versatility of this technique in achieving a variety of aligned mesopatterns starting from a prepatterned film with simple grating geometry. The morphology of the evolving patterns depends on several parameters such as the initial film thickness (h(f)), prepattern amplitude (h(st)), duration of solvent vapor exposure (SVE), and wettability of the stamp used for patterning. Periodic rupture of the film at regular intervals imposes directionality on the evolving patterns, resulting in isolated long threads/cylindrical ridges of polymers, which subsequently disintegrate into an aligned array of droplets due to Rayleigh-Plateau instability under specific conditions. Other patterns such as a double periodic array of droplets and an array of holes are also possible to obtain. The evolution can be interrupted at any intermediate stage by terminating the solvent vapor annealing, allowing the creation of pattern morphology on demand. The created patterns are significantly miniaturized in size as compared to features obtained from dewetting a flat film with the same hf.

Engineering of the E. coli outer membrane protein FhuA to overcome the hydrophobic mismatch in thick polymeric membranes.

PubMed

Muhammad, Noor; Dworeck, Tamara; Fioroni, Marco; Schwaneberg, Ulrich

2011-03-17

Channel proteins like the engineered FhuA Δ1-159 often cannot insert into thick polymeric membranes due to a mismatch between the hydrophobic surface of the protein and the hydrophobic surface of the polymer membrane. To address this problem usually specific block copolymers are synthesized to facilitate protein insertion. Within this study in a reverse approach we match the protein to the polymer instead of matching the polymer to the protein. To increase the FhuA Δ1-159 hydrophobic surface by 1 nm, the last 5 amino acids of each of the 22 β-sheets, prior to the more regular periplasmatic β-turns, were doubled leading to an extended FhuA Δ1-159 (FhuA Δ1-159 Ext). The secondary structure prediction and CD spectroscopy indicate the β-barrel folding of FhuA Δ1-159 Ext. The FhuA Δ1-159 Ext insertion and functionality within a nanocontainer polymeric membrane based on the triblock copolymer PIB(1000)-PEG(6000)-PIB(1000) (PIB = polyisobutylene, PEG = polyethyleneglycol) has been proven by kinetic analysis using the HRP-TMB assay (HRP = Horse Radish Peroxidase, TMB = 3,3',5,5'-tetramethylbenzidine). Identical experiments with the unmodified FhuA Δ1-159 report no kinetics and presumably no insertion into the PIB(1000)-PEG(6000)-PIB(1000) membrane. Furthermore labeling of the Lys-NH(2) groups present in the FhuA Δ1-159 Ext channel, leads to controllability of in/out flux of substrates and products from the nanocontainer. Using a simple "semi rational" approach the protein's hydrophobic transmembrane region was increased by 1 nm, leading to a predicted lower hydrophobic mismatch between the protein and polymer membrane, minimizing the insertion energy penalty. The strategy of adding amino acids to the FhuA Δ1-159 Ext hydrophobic part can be further expanded to increase the protein's hydrophobicity, promoting the efficient embedding into thicker/more hydrophobic block copolymer membranes.

PEGylated PEI-based biodegradable polymers as non-viral gene vectors.

PubMed

Huang, Fu-Wei; Wang, Hui-Yuan; Li, Cao; Wang, Hua-Fen; Sun, Yun-Xia; Feng, Jun; Zhang, Xian-Zheng; Zhuo, Ren-Xi

2010-11-01

Novel functional biodegradable gene vectors, poly(L-succinimide)-g-polyethylenimines-g-poly(ethylene glycol) (PSI-g-PEI-g-PEGs) were synthesized by conjugating methoxy poly(ethylene glycol) (mPEG, M(w)=750 Da) to PEI segments (M(w)=800 Da) of PSI-g-PEI. The physicochemical properties of PSI-g-PEI-g-PEGs, including buffering capability, pDNA binding ability, cytotoxicity, zeta potential and the particle size of polymer/pDNA complexes, were explored. The influence of PEGylation was discussed based on a comparative study of PSI-g-PEI-g-PEGs, PSI-g-PEI and PEI25k (M(w)=25 kDa). SEM images revealed that PSI-g-PEI-g-PEG/pDNA particles have a regular shape with the diameter ranging from 70 to 170 nm. PEGylation could suppress the aggregation occurrence between complexes, resulting in a reduction of the polymer/pDNA complex size. PSI-g-PEI-g-PEGs exhibited remarkably lower cytotoxicity compared to PSI-g-PEI and PEI25k. In 293T and HeLa cells, the obtained PSI-g-PEI-g-PEGs showed very high transfection efficiency compared to PEI25k. Fluorescent confocal microscopy demonstrated that PSI-g-PEI-g-PEGs could effectively transport pGL-3 plasmids into the nuclei of HeLa cells. Taking into account the continued high transfection efficacy and decreased toxicity after PEG modification, PSI-g-PEI-g-PEGs show great potential as the non-viral vectors for gene transfection. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Charge Mobility Enhancement for Conjugated DPP-Selenophene Polymer by Simply Replacing One Bulky Branching Alkyl Chain with Linear One at Each DPP Unit

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

Wang, Zhijie; Liu, Zitong; Ning, Lu

Here, we demonstrate a simple, but efficient, approach for improving the semiconducting performances of DPP-based conjugated D-A polymers. This approach involves the replacement of one bulky branching alkyl chain with the linear one at each DPP unit in regular polymer PDPPSe-10 and PDPPSe-12. The UV–vis absorption, Raman spectra, PDS data, and theoretical calculations support that the replacement of bulky branching chains with linear ones can weaken the steric hindrance, and accordingly conjugated backbones become more planar and rigid. GIWAXS data show that the incorporation of linear alkyl chains as in PDPPSe-10 and PDPPSe-12 is beneficial for side-chain interdigitation and interchainmore » dense packing, leading to improvement of interchain packing order and thin film crystallinity by comparing with PDPPSe, which contains branching alkyl chains. On the basis of field-effect transistor (FET) studies, charge mobilities of PDPPSe-10 and PDPPSe-12 are remarkably enhanced. Hole mobilities of PDPPSe-10 and PDPPSe-12 in air are boosted to 8.1 and 9.4 cm 2 V –1 s –1, which are about 6 and 7 times, respectively, than that of PDPPSe (1.35 cm 2 V –1 s –1). Furthermore, both PDPPSe-10 and PDPPSe-12 behave as ambipolar semiconductors under a nitrogen atmosphere with increased hole/electron mobilities up to 6.5/0.48 cm 2 V –1 s –1 and 7.9/0.79 cm 2 V –1 s –1, respectively.« less

Charge Mobility Enhancement for Conjugated DPP-Selenophene Polymer by Simply Replacing One Bulky Branching Alkyl Chain with Linear One at Each DPP Unit

DOE PAGES

Wang, Zhijie; Liu, Zitong; Ning, Lu; ...

2018-04-17

Here, we demonstrate a simple, but efficient, approach for improving the semiconducting performances of DPP-based conjugated D-A polymers. This approach involves the replacement of one bulky branching alkyl chain with the linear one at each DPP unit in regular polymer PDPPSe-10 and PDPPSe-12. The UV–vis absorption, Raman spectra, PDS data, and theoretical calculations support that the replacement of bulky branching chains with linear ones can weaken the steric hindrance, and accordingly conjugated backbones become more planar and rigid. GIWAXS data show that the incorporation of linear alkyl chains as in PDPPSe-10 and PDPPSe-12 is beneficial for side-chain interdigitation and interchainmore » dense packing, leading to improvement of interchain packing order and thin film crystallinity by comparing with PDPPSe, which contains branching alkyl chains. On the basis of field-effect transistor (FET) studies, charge mobilities of PDPPSe-10 and PDPPSe-12 are remarkably enhanced. Hole mobilities of PDPPSe-10 and PDPPSe-12 in air are boosted to 8.1 and 9.4 cm 2 V –1 s –1, which are about 6 and 7 times, respectively, than that of PDPPSe (1.35 cm 2 V –1 s –1). Furthermore, both PDPPSe-10 and PDPPSe-12 behave as ambipolar semiconductors under a nitrogen atmosphere with increased hole/electron mobilities up to 6.5/0.48 cm 2 V –1 s –1 and 7.9/0.79 cm 2 V –1 s –1, respectively.« less

A Robust Damage-Reporting Strategy for Polymeric Materials Enabled by Aggregation-Induced Emission.

PubMed

Robb, Maxwell J; Li, Wenle; Gergely, Ryan C R; Matthews, Christopher C; White, Scott R; Sottos, Nancy R; Moore, Jeffrey S

2016-09-28

Microscopic damage inevitably leads to failure in polymers and composite materials, but it is difficult to detect without the aid of specialized equipment. The ability to enhance the detection of small-scale damage prior to catastrophic material failure is important for improving the safety and reliability of critical engineering components, while simultaneously reducing life cycle costs associated with regular maintenance and inspection. Here, we demonstrate a simple, robust, and sensitive fluorescence-based approach for autonomous detection of damage in polymeric materials and composites enabled by aggregation-induced emission (AIE). This simple, yet powerful system relies on a single active component, and the general mechanism delivers outstanding performance in a wide variety of materials with diverse chemical and mechanical properties.

Model-based traction force microscopy reveals differential tension in cellular actin bundles.

PubMed

Soiné, Jérôme R D; Brand, Christoph A; Stricker, Jonathan; Oakes, Patrick W; Gardel, Margaret L; Schwarz, Ulrich S

2015-03-01

Adherent cells use forces at the cell-substrate interface to sense and respond to the physical properties of their environment. These cell forces can be measured with traction force microscopy which inverts the equations of elasticity theory to calculate them from the deformations of soft polymer substrates. We introduce a new type of traction force microscopy that in contrast to traditional methods uses additional image data for cytoskeleton and adhesion structures and a biophysical model to improve the robustness of the inverse procedure and abolishes the need for regularization. We use this method to demonstrate that ventral stress fibers of U2OS-cells are typically under higher mechanical tension than dorsal stress fibers or transverse arcs.

Model-based Traction Force Microscopy Reveals Differential Tension in Cellular Actin Bundles

PubMed Central

Soiné, Jérôme R. D.; Brand, Christoph A.; Stricker, Jonathan; Oakes, Patrick W.; Gardel, Margaret L.; Schwarz, Ulrich S.

2015-01-01

Adherent cells use forces at the cell-substrate interface to sense and respond to the physical properties of their environment. These cell forces can be measured with traction force microscopy which inverts the equations of elasticity theory to calculate them from the deformations of soft polymer substrates. We introduce a new type of traction force microscopy that in contrast to traditional methods uses additional image data for cytoskeleton and adhesion structures and a biophysical model to improve the robustness of the inverse procedure and abolishes the need for regularization. We use this method to demonstrate that ventral stress fibers of U2OS-cells are typically under higher mechanical tension than dorsal stress fibers or transverse arcs. PMID:25748431

Finite element investigation of temperature dependence of elastic properties of carbon nanotube reinforced polypropylene

NASA Astrophysics Data System (ADS)

Ahmadi, Masoud; Ansari, Reza; Rouhi, Saeed

2017-11-01

This paper aims to investigate the elastic modulus of the polypropylene matrix reinforced by carbon nanotubes at different temperatures. To this end, the finite element approach is employed. The nanotubes with different volume fractions and aspect ratios (the ratio of length to diameter) are embedded in the polymer matrix. Besides, random and regular algorithms are utilized to disperse carbon nanotubes in the matrix. It is seen that as the pure polypropylene, the elastic modulus of carbon nanotube reinforced polypropylene decreases by increasing the temperature. It is also observed that when the carbon nanotubes are dispersed parallelly and the load is applied along the nanotube directions, the largest improvement in the elastic modulus of the nanotube/polypropylene nanocomposites is obtained.

Direct grafting of anti-fouling polyglycerol layers to steel and other technically relevant materials.

PubMed

Weber, Theresa; Bechthold, Maren; Winkler, Tobias; Dauselt, John; Terfort, Andreas

2013-11-01

Direct grafting of hyperbranched polyglycerol (PG) layers onto the oxide surfaces of steel, aluminum, and silicon has been achieved through surface-initiated polymerization of 2-hydroxymethyloxirane (glycidol). Optimization of the deposition conditions led to a protocol that employed N-methyl-2-pyrrolidone (NMP) as the solvent and temperatures of 100 and 140 °C, depending on the substrate material. In all cases, a linear growth of the PG layers could be attained, which allows for control of film thickness by altering the reaction time. At layer thicknesses >5 nm, the PG layers completely suppressed the adhesion of albumin, fibrinogen, and globulin. These layers were also at least 90% bio-repulsive for two bacteria strains, E. coli and Acinetobacter baylyi, with further improvement being observed when the PG film thickness was increased to 17 nm (up to 99.9% bio-repulsivity on silicon). Copyright © 2013 Elsevier B.V. All rights reserved.

Multifunctional, supramolecular, continuous artificial nacre fibres

NASA Astrophysics Data System (ADS)

Hu, Xiaozhen; Xu, Zhen; Gao, Chao

2012-10-01

Nature has created amazing materials during the process of evolution, inspiring scientists to studiously mimic them. Nacre is of particular interest, and it has been studied for more than half-century for its strong, stiff, and tough attributes resulting from the recognized ``brick-and-mortar'' (B&M) layered structure comprised of inorganic aragonite platelets and biomacromolecules. The past two decades have witnessed great advances in nacre-mimetic composites, but they are solely limited in films with finite size (centimetre-scale). To realize the adream target of continuous nacre-mimics with perfect structures is still a great challenge unresolved. Here, we present a simple and scalable strategy to produce bio-mimic continuous fibres with B&M structures of alternating graphene sheets and hyperbranched polyglycerol (HPG) binders via wet-spinning assembly technology. The resulting macroscopic supramolecular fibres exhibit excellent mechanical properties comparable or even superior to nacre and bone, and possess fine electrical conductivity and outstanding corrosion-resistance.

Architecture, Assembly, and Emerging Applications of Branched Functional Polyelectrolytes and Poly(ionic liquid)s.

PubMed

Xu, Weinan; Ledin, Petr A; Shevchenko, Valery V; Tsukruk, Vladimir V

2015-06-17

Branched polyelectrolytes with cylindrical brush, dendritic, hyperbranched, grafted, and star architectures bearing ionizable functional groups possess complex and unique assembly behavior in solution at surfaces and interfaces as compared to their linear counterparts. This review summarizes the recent developments in the introduction of various architectures and understanding of the assembly behavior of branched polyelectrolytes with a focus on functional polyelectrolytes and poly(ionic liquid)s with responsive properties. The branched polyelectrolytes and poly(ionic liquid)s interact electrostatically with small molecules, linear polyelectrolytes, or other branched polyelectrolytes to form assemblies of hybrid nanoparticles, multilayer thin films, responsive microcapsules, and ion-conductive membranes. The branched structures lead to unconventional assemblies and complex hierarchical structures with responsive properties as summarized in this review. Finally, we discuss prospectives for emerging applications of branched polyelectrolytes and poly(ionic liquid)s for energy harvesting and storage, controlled delivery, chemical microreactors, adaptive surfaces, and ion-exchange membranes.

Integrating DNA strand displacement circuitry to the nonlinear hybridization chain reaction.

PubMed

Zhang, Zhuo; Fan, Tsz Wing; Hsing, I-Ming

2017-02-23

Programmable and modular attributes of DNA molecules allow one to develop versatile sensing platforms that can be operated isothermally and enzyme-free. In this work, we present an approach to integrate upstream DNA strand displacement circuits that can be turned on by a sequence-specific microRNA analyte with a downstream nonlinear hybridization chain reaction for a cascading hyperbranched nucleic acid assembly. This system provides a two-step amplification strategy for highly sensitive detection of the miRNA analyte, conducive for multiplexed detection. Multiple miRNA analytes were tested with our integrated circuitry using the same downstream signal amplification setting, showing the decoupling of nonlinear self-assembly with the analyte sequence. Compared with the reported methods, our signal amplification approach provides an additional control module for higher-order DNA self-assembly and could be developed into a promising platform for the detection of critical nucleic-acid based biomarkers.

Polyglycerol-opioid conjugate produces analgesia devoid of side effects.

PubMed

González-Rodríguez, Sara; Quadir, Mohiuddin A; Gupta, Shilpi; Walker, Karolina A; Zhang, Xuejiao; Spahn, Viola; Labuz, Dominika; Rodriguez-Gaztelumendi, Antonio; Schmelz, Martin; Joseph, Jan; Parr, Maria K; Machelska, Halina; Haag, Rainer; Stein, Christoph

2017-07-04

Novel painkillers are urgently needed. The activation of opioid receptors in peripheral inflamed tissue can reduce pain without central adverse effects such as sedation, apnoea, or addiction. Here, we use an unprecedented strategy and report the synthesis and analgesic efficacy of the standard opioid morphine covalently attached to hyperbranched polyglycerol (PG-M) by a cleavable linker. With its high-molecular weight and hydrophilicity, this conjugate is designed to selectively release morphine in injured tissue and to prevent blood-brain barrier permeation. In contrast to conventional morphine, intravenous PG-M exclusively activated peripheral opioid receptors to produce analgesia in inflamed rat paws without major side effects such as sedation or constipation. Concentrations of morphine in the brain, blood, paw tissue, and in vitro confirmed the selective release of morphine in the inflamed milieu. Thus, PG-M may serve as prototype of a peripherally restricted opioid formulation designed to forego central and intestinal side effects.

On Topological Indices of Certain Families of Nanostar Dendrimers.

PubMed

Husin, Mohamad Nazri; Hasni, Roslan; Arif, Nabeel Ezzulddin; Imran, Muhammad

2016-06-24

A topological index of graph G is a numerical parameter related to G which characterizes its molecular topology and is usually graph invariant. In the field of quantitative structure-activity (QSAR)/quantitative structure-activity structure-property (QSPR) research, theoretical properties of the chemical compounds and their molecular topological indices such as the Randić connectivity index, atom-bond connectivity (ABC) index and geometric-arithmetic (GA) index are used to predict the bioactivity of different chemical compounds. A dendrimer is an artificially manufactured or synthesized molecule built up from the branched units called monomers. In this paper, the fourth version of ABC index and the fifth version of GA index of certain families of nanostar dendrimers are investigated. We derive the analytical closed formulas for these families of nanostar dendrimers. The obtained results can be of use in molecular data mining, particularly in researching the uniqueness of tested (hyper-branched) molecular graphs.

Superelastic and pH-Responsive Degradable Dendrimer Cryogels Prepared by Cryo-aza-Michael Addition Reaction.

PubMed

Wang, Juan; Yang, Hu

2018-05-08

Dendrimers exhibit super atomistic features by virtue of their well-defined discrete quantized nanoscale structures. Here, we show that hyperbranched amine-terminated polyamidoamine (PAMAM) dendrimer G4.0 reacts with linear polyethylene glycol (PEG) diacrylate (575 g/mol) via the aza-Michael addition reaction at a subzero temperature (-20 °C), namely cryo-aza-Michael addition, to form a macroporous superelastic network, i.e., dendrimer cryogel. Dendrimer cryogels exhibit biologically relevant Young's modulus, high compression elasticity and super resilience at ambient temperature. Furthermore, the dendrimer cryogels exhibit excellent rebound performance and do not show significant stress relaxation under cyclic deformation over a wide temperature range (-80 to 100 °C). The obtained dendrimer cryogels are stable at acidic pH but degrade quickly at physiological pH through self-triggered degradation. Taken together, dendrimer cryogels represent a new class of scaffolds with properties suitable for biomedical applications.

An Experimental Examination of Combustion of Isolated Liquid Fuel Droplets with Polymeric and Nanoparticle Additives

NASA Astrophysics Data System (ADS)

Ghamari, Mohsen

In spite of recent attention to renewable sources of energy, liquid hydrocarbon fuels are still the main source of energy for industrial and transportation systems. Manufactures and consumers are consistently looking for ways to optimize the efficiency of fuel combustion in terms of cost, emissions and consumer safety. In this regard, increasing burning rate of liquid fuels has been of special interest in both industrial and transportation systems. Recent studies have shown that adding combustible nano-particles could have promising effects on improving combustion performance of liquid fuels. Combustible nano-particles could enhance radiative and conductive heat transfer and also mixing within the droplet. Polymeric additive have also shown promising effect on improving fire safety by suppressing spreading behavior and splatter formation in case of crash scenario. Polymers are also known to have higher burning rate than regular hydrocarbon fuels. Therefore adding polymeric additive could have the potential to increase the burning rate. In this work, combustion dynamics of liquid fuel droplets with both polymeric and nanoparticle additives is studied in normal gravity. High speed photography is employed and the effect of additive concentration on droplet burning rate, burning time, extinction and soot morphology is investigated. Polymer added fuel was found to have a volatility controlled combustion with four distinct regimes. The first three zones are associated with combustion of base fuel while the polymer burns last and after a heating zone because of its higher boiling point. Polymer addition reduces the burning rate of the base fuel in the first zone by means of increasing viscosity and results in nucleate boiling and increased burning rates in the second and third stages. Overall, polymer addition resulted in a higher burning rate and shorter burning time in most of the scenarios. Colloidal suspensions of carbon-based nanomaterials in liquid fuels were also tested at different particle loadings. It was found that dispersing nanoparticles results in higher burning rate by means of enhanced radiative heat absorption and thermal conductivity. An optimum particle loading was found for each particle type at which the maximum burning rate was achieved. It was observed that the burning rate again starts to reduce after this optimum point most likely due to the formation of large aggregates that reduce thermal conductivity and suppress the diffusion of species.

Phase-breaking effect on polaron transport in organic conjugated polymers

DOE PAGES

Meng, Ruixuan; Yin, Sun; Zheng, Yujun; ...

2017-06-15

Despite intense investigations and many accepted viewpoints on theory and experiment, the coherent and incoherent carrier transport in organic semiconductors remains an unsettled topic due to the strong electron-phonon coupling. Based on the tight-binding Su-Schrieffer-Heeger (SSH) model combined with a non-adiabatic dynamics method, we study the effect of phase-breaking on polaron transport by introducing a group of phase-breaking factors into π-electron wave-functions in organic conjugated polymers. Two approaches are applied: the modification of the transfer integral and the phase-breaking addition to the wave-function. Within the former, it is found that a single site phase-breaking can trap a polaron. However, withmore » a larger regular phase-breaking a polaron becomes more delocalized and lighter. Additionally, a group of disordered phase-breaking factors can make the polaron disperse in transport process. Within the latter approach, we show that the phase-breaking can render the delocalized state in valence band discrete and the state in the gap more localized. Consequently, the phase-breaking frequency and intensity can reduce the stability of a polaron. Furthermore, the phase-breaking in organic systems is the main factor that degrades the coherent transport and destroys the carrier stability.« less

Cell wall peptidoglycan architecture in Bacillus subtilis

PubMed Central

Hayhurst, Emma J.; Kailas, Lekshmi; Hobbs, Jamie K.; Foster, Simon J.

2008-01-01

The bacterial cell wall is essential for viability and shape determination. Cell wall structural dynamics allowing growth and division, while maintaining integrity is a basic problem governing the life of bacteria. The polymer peptidoglycan is the main structural component for most bacteria and is made up of glycan strands that are cross-linked by peptide side chains. Despite study and speculation over many years, peptidoglycan architecture has remained largely elusive. Here, we show that the model rod-shaped bacterium Bacillus subtilis has glycan strands up to 5 μm, longer than the cell itself and 50 times longer than previously proposed. Atomic force microscopy revealed the glycan strands to be part of a peptidoglycan architecture allowing cell growth and division. The inner surface of the cell wall has a regular macrostructure with ≈50 nm-wide peptidoglycan cables [average 53 ± 12 nm (n = 91)] running basically across the short axis of the cell. Cross striations with an average periodicity of 25 ± 9 nm (n = 96) along each cable are also present. The fundamental cabling architecture is also maintained during septal development as part of cell division. We propose a coiled-coil model for peptidoglycan architecture encompassing our data and recent evidence concerning the biosynthetic machinery for this essential polymer. PMID:18784364

Selective separation of fluorinated compounds from complex organic mixtures by pyrolysis-comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry.

PubMed

Nakajima, Yoji; Arinami, Yuko; Yamamoto, Kiyoshi

2014-12-29

The usefulness of comprehensive two-dimensional gas chromatography (GC×GC) was demonstrated for the selective separation of fluorinated compounds from organic mixtures, such as kerosene/perfluorokerosene mixtures, pyrolysis products derived from polyethylene/ethylene-tetrafluoroethylene alternating copolymer mixture and poly[2-(perfluorohexyl)ethyl acrylate]. Perfluorocarbons were completely separated from hydrocarbons in the two-dimensional chromatogram. Fluorohydrocarbons in the pyrolysis products of polyethylene/ethylene-tetrafluoroethylene alternating copolymer mixture were selectively isolated from their hydrocarbon counterparts and regularly arranged according to their chain length and fluorine content in the two-dimensional chromatogram. A reliable structural analysis of the fluorohydrocarbons was achieved by combining effective GC×GC positional information with accurate mass spectral data obtained by high-resolution time-of-flight mass spectrometry (HRTOF-MS). 2-(Perfluorohexyl)ethyl acrylate monomer, dimer, and trimer as well as 2-(perfluorohexyl)ethyl alcohol in poly[2-(perfluorohexyl)ethyl acrylate] pyrolysis products were detected in the bottommost part of the two-dimensional chromatogram with separation from hydrocarbons possessing terminal structure information about the polymer, such as α-methylstyrene. Pyrolysis-GC×GC/HRTOF-MS appeared particularly suitable for the characterization of fluorinated polymer microstructures, such as monomer sequences and terminal groups. Copyright © 2014 Elsevier B.V. All rights reserved.

Gene silencing activity of siRNA polyplexes based on thiolated N,N,N-trimethylated chitosan.

PubMed

Varkouhi, Amir K; Verheul, Rolf J; Schiffelers, Raymond M; Lammers, Twan; Storm, Gert; Hennink, Wim E

2010-12-15

N,N,N-Trimethylated chitosan (TMC) is a biodegradable polymer emerging as a promising nonviral vector for nucleic acid and protein delivery. In the present study, we investigated whether the introduction of thiol groups in TMC enhances the extracellular stability of the complexes based on this polymer and promotes the intracellular release of siRNA. The gene silencing activity and the cellular cytotoxicity of polyplexes based on thiolated TMC were compared with those based on the nonthiolated counterpart and the regularly used lipidic transfection agent Lipofectamine. Incubation of H1299 human lung cancer cells expressing firefly luciferase with siRNA/thiolated TMC polyplexes resulted in 60-80% gene silencing activity, whereas complexes based on nonthiolated TMC showed less silencing (40%). The silencing activity of the complexes based on Lipofectamine 2000 was about 60-70%. Importantly, the TMC-SH polyplexes retained their silencing activity in the presence of hyaluronic acid, while nonthiolated TMC polyplexes hardly showed any silencing activity, demonstrating their stability against competing anionic macromolecules. Under the experimental conditions tested, the cytotoxicity of the thiolated and nonthiolated siRNA complexes was lower than those based on Lipofectamine. Given the good extracellular stability and good silencing activity, it is concluded that polyplexes based on TMC-SH are attractive systems for further in vivo evaluations.

Utilizing insulating nanoparticles as the spacer in laminated flexible polymer solar cells for improved mechanical stability.

PubMed

Lu, Yunzhang; Alexander, Clement; Xiao, Zhengguo; Yuan, Yongbo; Zhang, Runyu; Huang, Jinsong

2012-08-31

Roll-to-roll lamination is one promising technique to produce large-area organic electronic devices such as solar cells with a large through output. One challenge in this process is the frequent electric point shorting of the cathode and anode by the excess or concentrated applied stress from many possible sources. In this paper, we report a method to avoid electric point shorting by incorporating insulating and hard barium titanate (BaTiO(3)) nanoparticles (NPs) into the active layer to work as a spacer. It has been demonstrated that the incorporated BaTiO(3) NPs in poly(3-hexylthiophene):[6,6]-phenyl-c-61-butyric acid methyl ester (P3HT:PCBM) bulk heterojunction solar cells cause no deleterious effect to the power conversion process of this type of solar cell. The resulting laminated devices with NPs in the active layer display the same efficiency as the devices without NPs, while the laminated devices with NPs can sustain a ten times higher lamination stress of over 6 MPa. The flexible polymer solar cell device with incorporated NPs shows a much smaller survivable curvature radius of 4 mm, while a regular flexible device can only sustain a bending curvature radius of 8 mm before fracture.

Phase-breaking effect on polaron transport in organic conjugated polymers

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

Meng, Ruixuan; Yin, Sun; Zheng, Yujun

Despite intense investigations and many accepted viewpoints on theory and experiment, the coherent and incoherent carrier transport in organic semiconductors remains an unsettled topic due to the strong electron-phonon coupling. Based on the tight-binding Su-Schrieffer-Heeger (SSH) model combined with a non-adiabatic dynamics method, we study the effect of phase-breaking on polaron transport by introducing a group of phase-breaking factors into π-electron wave-functions in organic conjugated polymers. Two approaches are applied: the modification of the transfer integral and the phase-breaking addition to the wave-function. Within the former, it is found that a single site phase-breaking can trap a polaron. However, withmore » a larger regular phase-breaking a polaron becomes more delocalized and lighter. Additionally, a group of disordered phase-breaking factors can make the polaron disperse in transport process. Within the latter approach, we show that the phase-breaking can render the delocalized state in valence band discrete and the state in the gap more localized. Consequently, the phase-breaking frequency and intensity can reduce the stability of a polaron. Furthermore, the phase-breaking in organic systems is the main factor that degrades the coherent transport and destroys the carrier stability.« less

The future of metabolic syndrome and cardiovascular disease prevention: polyhype or polyhope? Tales from the polyera.

PubMed

Franco, O H; Karnik, K; Bonneux, L

2007-09-01

Recently society has been witnessing the rise of a new era in the prevention and treatment of the metabolic syndrome and cardiovascular disease: the Polyera. This new era started when a promising concept - the Polypill - was introduced by Wald et al. in 2003. The Polypill is a theoretical combination of six pharmacological compounds (a statin, three different antihypertensives, aspirin, and folic acid) that in combination could reduce cardiovascular disease by more than 80%. Although the Polypill could theoretically be a highly effective intervention, it is not yet available in the market and its effectiveness remains unproven. In the population at large, cheap prizes may come at prohibitive costs. With frail elderly and population prevalences of co-morbidity far higher than in drug trials, rare adverse effects may be frequent. In December 2004, a more natural, safer, and probably tastier alternative to the Polypill - the Polymeal - was introduced. Contrary to the Polypill, the Polymeal combined 6 different foods (fruits and vegetables, almonds, chocolate, wine, fish, and garlic) that taken together in a regular basis could cut cardiovascular disease risk by over 75%. Polyproducts from the polyera in true populations might hide unexpected polyinteractions. In the polyera, polytrials will need to establish benefits, harms, and costs.

2014 Global Conference on Polymer and Composite Materials (PCM 2014)

NASA Astrophysics Data System (ADS)

2014-08-01

The 2014 Global Conference on Polymer and Composite Materials (PCM 2014) sponsored by Ningbo Adhesives and Products Industry Association, Shanghai Bonding Technology Association, Zhejiang Bonding Technology Association, Wuhan Bonding Technology Association, Hebei Bonding and Coatings Association and Polyurethane Industry Association was held from May 27 to May 29 2014 in Ningbo, China. The technical program consisted of 8 international keynote speakers, oral presentations, and a poster session. The conference also included an industrial exhibition where more than 50 companies displayed in their booths their most recent advanced products and services. The present issue of IOP Conference Series: Materials Science and Engineering (MSE) records the proceedings of PCM 2014 and contains 37 specially selected manuscripts submitted to PCM2014 conference. The electronic submission and handling of manuscripts via the conference website, including the selection of reviewers and evaluation of manuscripts, were identical to the procedures applied to manuscripts submitted as regular contributions for publication. The organization of this conference and the preparation of proceedings volumes would have been impossible without the tremendous efforts and dedication of many individuals, especially from Ms. Yin Pan, who oversaw the organization of the conference and the program; and a large team of reviewers with their timely submission of quality reports. We express our sincere thanks to all authors and presenters for their contributions. We also thank very much our sponsors for their generous support. The 2015 Global Conference on Polymer and Composite Materials (PCM2015) will be held in Beijing, China on May 16-18, 2015. Beijing, the capital of the People's Republic of China and one of the most populous cities in the world, will welcome to all participants for a renewed and vibrant conference. Prof. Dr. Esteban Broitman Linköping University, Sweden Editor in Chief — PCM2014

Polymer scaffolds with no skin-effect for tissue engineering applications fabricated by thermally induced phase separation.

PubMed

Kasoju, Naresh; Kubies, Dana; Sedlačík, Tomáš; Janoušková, Olga; Koubková, Jana; Kumorek, Marta M; Rypáček, František

2016-01-11

Thermally induced phase separation (TIPS) based methods are widely used for the fabrication of porous scaffolds for tissue engineering and related applications. However, formation of a less-/non-porous layer at the scaffold's outer surface at the air-liquid interface, often known as the skin-effect, restricts the cell infiltration inside the scaffold and therefore limits its efficacy. To this end, we demonstrate a TIPS-based process involving the exposure of the just quenched poly(lactide-co-caprolactone):dioxane phases to the pure dioxane for a short time while still being under the quenching strength, herein after termed as the second quenching (2Q). Scanning electron microscopy, mercury intrusion porosimetry and contact angle analysis revealed a direct correlation between the time of 2Q and the gradual disappearance of the skin, followed by the widening of the outer pores and the formation of the fibrous filaments over the surface, with no effect on the internal pore architecture and the overall porosity of scaffolds. The experiments at various quenching temperatures and polymer concentrations revealed the versatility of 2Q in removing the skin. In addition, the in vitro cell culture studies with the human primary fibroblasts showed that the scaffolds prepared by the TIPS based 2Q process, with the optimal exposure time, resulted in a higher cell seeding and viability in contrast to the scaffolds prepared by the regular TIPS. Thus, TIPS including the 2Q step is a facile, versatile and innovative approach to fabricate the polymer scaffolds with a skin-free and fully open porous surface morphology for achieving a better cell response in tissue engineering and related applications.

Amphiphilic multiarm star block copolymer-based multifunctional unimolecular micelles for cancer targeted drug delivery and MR imaging.

PubMed

Li, Xiaojie; Qian, Yinfeng; Liu, Tao; Hu, Xianglong; Zhang, Guoying; You, Yezi; Liu, Shiyong

2011-09-01

We report on the fabrication of multifunctional polymeric unimolecular micelles as an integrated platform for cancer targeted drug delivery and magnetic resonance imaging (MRI) contrast enhancement under in vitro and in vivo conditions. Starting from a fractionated fourth-generation hyperbranched polyester (Boltorn H40), the ring-opening polymerization of ɛ-caprolactone (CL) from the periphery of H40 and subsequent terminal group esterification with 2-bromoisobutyryl bromide afforded star copolymer-based atom transfer radical polymerization (ATRP) macroinitiator, H40-PCL-Br. Well-defined multiarm star block copolymers, H40-PCL-b-P(OEGMA-co-AzPMA), were then synthesized by the ATRP of oligo(ethylene glycol) monomethyl ether methacrylate (OEGMA) and 3-azidopropyl methacrylate (AzPMA). This was followed by the click reaction of H40-PCL-b-P(OEGMA-co-AzPMA) with alkynyl-functionalized cancer cell-targeting moieties, alkynyl-folate, and T(1)-type MRI contrast agents, alkynyl-DOTA-Gd (DOTA is 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakisacetic acid), affording H40-PCL-b-P(OEGMA-Gd-FA). In aqueous solution, the amphiphilic multiarm star block copolymer exists as structurally stable unimolecular micelles possessing a hyperbranched polyester core, a hydrophobic PCL inner layer, and a hydrophilic P(OEGMA-Gd-FA) outer corona. H40-PCL-b-P(OEGMA-Gd-FA) unimolecular micelles are capable of encapsulating paclitaxel, a well-known hydrophobic anticancer drug, with a loading content of 6.67 w/w% and exhibiting controlled release of up to 80% loaded drug over a time period of ∼120 h. In vitro MRI experiments demonstrated considerably enhanced T(1) relaxivity (18.14 s(-1) mM(-1)) for unimolecular micelles compared to 3.12 s(-1) mM(-1) for that of the small molecule counterpart, alkynyl-DOTA-Gd. Further experiments of in vivo MR imaging in rats revealed good accumulation of unimolecular micelles within rat liver and kidney, prominent positive contrast enhancement, and relatively long duration of blood circulation. The reported unimolecular micelles-based structurally stable nanocarriers synergistically integrated with cancer targeted drug delivery and controlled release and MR imaging functions augur well for their potential applications as theranostic systems. Copyright © 2011 Elsevier Ltd. All rights reserved.

Hyperbranched Polyglycerol Is an Efficacious and Biocompatible Novel Osmotic Agent in a Rodent Model of Peritoneal Dialysis

PubMed Central

Mendelson, Asher A.; Guan, Qiunong; Chafeeva, Irina; da Roza, Gerald A.; Kizhakkedathu, Jayachandran N.; Du, Caigan

2013-01-01

♦ Objectives: To enhance the effectiveness of peritoneal dialysis (PD), new biocompatible PD solutions may be needed. The present study was designed to test the efficacy and biocompatibility of hyperbranched polyglycerol (HPG)—a nontoxic, nonimmunogenic water-soluble polyether polymer—in PD. ♦ Methods: Adult Sprague-Dawley rats were instilled with 30 mL HPG solution (molecular weight 3 kDa; 2.5% - 15%) or control glucose PD solution (2.5% Dianeal: Baxter Healthcare Corporation, Deerfield, IL, USA), and intraperitoneal fluid was recovered after 4 hours. Peritoneal injury and cellular infiltration were determined by histologic and flow cytometric analysis. Human peritoneal mesothelial cells were assessed for viability in vitro after 3 hours of PD fluid exposure. ♦ Results: The 15% HPG solution achieved a 4-hour dose-related ultrafiltration up to 43.33 ± 5.24 mL and a dose-related urea clearance up to 39.17 ± 5.21 mL, results that were superior to those with control PD solution (p < 0.05). The dialysate-to-plasma (D/P) ratios of urea with 7.5% and 15% HPG solution were not statistically different from those with control PD solution. Compared with fluid recovered from the control group, fluid recovered from the HPG group contained proportionally fewer neutrophils (3.63% ± 0.87% vs 9.31% ± 2.89%, p < 0.0001). Detachment of mesothelial cells positive for human bone marrow endothelial protein 1 did not increase in the HPG group compared with the stain control (p = 0.1832), but it was elevated in the control PD solution group (1.62% ± 0.68% vs 0.41% ± 0.31%, p = 0.0031). Peritoneal biopsies from animals in the HPG PD group, compared with those from control PD animals, demonstrated less neutrophilic infiltration and reduced thickness. Human peritoneal mesothelial cell survival after HPG exposure was superior in vitro (p < 0.0001, 7.5% HPG vs control; p < 0.01, 15% HPG vs control). Exposure to glucose PD solution induced cytoplasmic vacuolation and caspase 3-independent necrotic cell death that was not seen with HPG solution. ♦ Conclusions: Our novel HPG PD solution demonstrated effective ultrafiltration and waste removal with reduced peritoneal injury in a rodent model of PD. PMID:23349194

Brush-Like Polymers: New Design Platforms for Soft, Dry Materials with Unique Property Relations

NASA Astrophysics Data System (ADS)

Daniel, William Francis McKemie, Jr.

Elastomers represent a unique class of engineering materials due to their light weight, low cost, and desirable combination of softness (105 -107 Pa) and large extensibilities (up to 1000%). Despite these advantages, there exist applications that require many times softer modulus, greater extensibility, and stronger strain hardening for the purpose of mimicking the mechanical properties of systems such as biological tissues. Until recently, only liquid-filled gels were suitable materials for such applications, including soft robotics and implants. A considerable amount of work has been done to create gels with superior properties, but despite unique strengths they also suffer from unique weaknesses. This class of material displays fundamental limitations in the form of heterogeneous structures, solvent loss and phase transitions at extreme temperatures, and loss of liquid fraction upon high deformations. In gels the solvent fraction also introduces a large solvent/polymer interaction parameter which must be carefully considered when designing the final mechanical properties. These energetic considerations further exaggerate the capacity for inconstant mechanical properties caused by fluctuations of the solvent fraction. In order to overcome these weaknesses, a new platform for single component materials with low modulus (<105 Pa) must be developed. Single component systems do not suffer from compositional changes over time and display more stable performance in a wider variety of temperatures and humidity conditions. A solvent-free system also has the potential to be homogeneous which replaces the large energetic interactions with comparatively small architectural interaction parameters. If a solvent-free alternative to liquid-filled gels is to be created, we must first consider the fundamental barrier to softer elastomers, i.e. entanglements - intrinsic topological restrains which define a lower limit of modulus ( 105 Pa). These entanglements are determined by chemistry specific parameters (repeat unit volume and Kuhn segment size) in the polymer liquid (melt) prior to crosslinking. Previous solvent free replacements for gels include elastomers end-linked in semidilute conditions. These materials are generated through crosslinking telechelic polymer chains in semidilute solutions at the onset of chain overlap. At such low polymer concentrations entanglements are greatly diluted and once the resulting gel is dried it creates a supersoft and super-elastic network. Although such methods have successfully generated materials with moduli below the 105 Pa limit and high extensibilities ( 1000%) they present their own limitations. Firstly, the semidilute crosslinking methods uses an impractically large volume of solvent which is unattractive in industry. Second, producing and crosslinking large monodisperse telechelic chains is a nontrivial process leading to large uncertainties in the final network architecture and properties. Specifically, telechelics have a distribution of end-to-end distances and in semidilute solutions with extremely low fraction of chain ends the crosslink reaction is diffusion limited, very slow, and imprecise. In order to achieve a superior solvent-free platform, we propose alteration of mechanical properties through the architectural disentanglement of brush-like polymer structures. In recent year there has been an increase in the synthetic conditions and crosslinking schemes available for producing brush-like structures. This makes brush-like materials an attractive alternative to more restrictive methods such as end-linking. Standard networks have one major control factor outside of chemistry, the network stand length. Brush-like architectures are created from long strands with regularly grafted side chains creating three characteristic length scales which may be independently manipulated. In collaboration with M. Rubinstein, we have utilized bottlebrush polymer architectures (a densely grafted brush-like polymer) to experimentally verify theoretical predictions of disentangled bottlebrush melts. By attaching well-defined side chains onto long polymer backbones, individual polymer strands are separated in space (similar to dilution with solvent) accompanied by a comparatively small increase in the rigidity of the strands. The end result is an architectural disentangled melt with an entanglement plateau modulus as much as three orders of magnitude lower than typical linear polymers and a broadly expanded potential for extensibility once crosslinked.

Novel calibration tools and validation concepts for microarray-based platforms used in molecular diagnostics and food safety control.

PubMed

Brunner, C; Hoffmann, K; Thiele, T; Schedler, U; Jehle, H; Resch-Genger, U

2015-04-01

Commercial platforms consisting of ready-to-use microarrays printed with target-specific DNA probes, a microarray scanner, and software for data analysis are available for different applications in medical diagnostics and food analysis, detecting, e.g., viral and bacteriological DNA sequences. The transfer of these tools from basic research to routine analysis, their broad acceptance in regulated areas, and their use in medical practice requires suitable calibration tools for regular control of instrument performance in addition to internal assay controls. Here, we present the development of a novel assay-adapted calibration slide for a commercialized DNA-based assay platform, consisting of precisely arranged fluorescent areas of various intensities obtained by incorporating different concentrations of a "green" dye and a "red" dye in a polymer matrix. These dyes present "Cy3" and "Cy5" analogues with improved photostability, chosen based upon their spectroscopic properties closely matching those of common labels for the green and red channel of microarray scanners. This simple tool allows to efficiently and regularly assess and control the performance of the microarray scanner provided with the biochip platform and to compare different scanners. It will be eventually used as fluorescence intensity scale for referencing of assays results and to enhance the overall comparability of diagnostic tests.

Elastin: a representative ideal protein elastomer.

PubMed Central

Urry, D W; Hugel, T; Seitz, M; Gaub, H E; Sheiba, L; Dea, J; Xu, J; Parker, T

2002-01-01

During the last half century, identification of an ideal (predominantly entropic) protein elastomer was generally thought to require that the ideal protein elastomer be a random chain network. Here, we report two new sets of data and review previous data. The first set of new data utilizes atomic force microscopy to report single-chain force-extension curves for (GVGVP)(251) and (GVGIP)(260), and provides evidence for single-chain ideal elasticity. The second class of new data provides a direct contrast between low-frequency sound absorption (0.1-10 kHz) exhibited by random-chain network elastomers and by elastin protein-based polymers. Earlier composition, dielectric relaxation (1-1000 MHz), thermoelasticity, molecular mechanics and dynamics calculations and thermodynamic and statistical mechanical analyses are presented, that combine with the new data to contrast with random-chain network rubbers and to detail the presence of regular non-random structural elements of the elastin-based systems that lose entropic elastomeric force upon thermal denaturation. The data and analyses affirm an earlier contrary argument that components of elastin, the elastic protein of the mammalian elastic fibre, and purified elastin fibre itself contain dynamic, non-random, regularly repeating structures that exhibit dominantly entropic elasticity by means of a damping of internal chain dynamics on extension. PMID:11911774

Covariance in self-dual inhomogeneous models of effective quantum geometry: Spherical symmetry and Gowdy systems

NASA Astrophysics Data System (ADS)

Ben Achour, Jibril; Brahma, Suddhasattwa

2018-06-01

When applying the techniques of loop quantum gravity (LQG) to symmetry-reduced gravitational systems, one first regularizes the scalar constraint using holonomy corrections, prior to quantization. In inhomogeneous system, where a residual spatial diffeomorphism symmetry survives, such modification of the gauge generator generating time reparametrization can potentially lead to deformations or anomalies in the modified algebra of first-class constraints. When working with self-dual variables, it has already been shown that, for spherically symmetric geometry coupled to a scalar field, the holonomy-modified constraints do not generate any modifications to general covariance, as one faces in the real variables formulation, and can thus accommodate local degrees of freedom in such inhomogeneous models. In this paper, we extend this result to Gowdy cosmologies in the self-dual Ashtekar formulation. Furthermore, we show that the introduction of a μ ¯-scheme in midisuperspace models, as is required in the "improved dynamics" of LQG, is possible in the self-dual formalism while being out of reach in the current effective models using real-valued Ashtekar-Barbero variables. Our results indicate the advantages of using the self-dual variables to obtain a covariant loop regularization prior to quantization in inhomogeneous symmetry-reduced polymer models, additionally implementing the crucial μ ¯-scheme, and thus a consistent semiclassical limit.

Superabsorbent biphasic system based on poly(lactic acid) and poly(acrylic acid)

NASA Astrophysics Data System (ADS)

Sartore, Luciana; Pandini, Stefano; Baldi, Francesco; Bignotti, Fabio

2016-05-01

In this research work, biocomposites based on crosslinked particles of poly(acrylic acid), commonly used as superabsorbent polymer (SAP), and poly-L-lactic acid (PLLA) were developed to elucidate the role of the filler (i.e., polymeric crosslinked particles) on the overall physico-mechanical behavior and to obtain superabsorbent thermoplastic products. Samples prepared by melt-blending of components in different ratios showed a biphasic system with a regular distribution of particles, with diameter ranging from 5 to 10 μm, within the PLLA polymeric matrix. The polymeric biphasic system, coded PLASA i.e. superabsorbent poly(lactic acid), showed excellent swelling properties, demonstrating that cross-linked particles retain their superabsorbent ability, as in their free counterparts, even if distributed in a thermoplastic polymeric matrix. The thermal characteristics of the biocomposites evidence enhanced thermal stability in comparison with neat PLLA and also mechanical properties are markedly modified by addition of crosslinked particles which induce regular stiffening effect. Furthermore, in aqueous environments the particles swell and are leached from PLLA matrix generating very high porosity. These new open-pore PLLA foams, produced in absence of organic solvents and chemical foaming agents, with good physico-mechanical properties appear very promising for several applications, for instance in tissue engineering for scaffold production.

Sea urchin skeleton: Structure, composition, and application as a template for biomimetic materials

NASA Astrophysics Data System (ADS)

Shapkin, Nikolay P.; Khalchenko, Irina G.; Panasenko, Alexander E.; Drozdov, Anatoly L.

2017-07-01

SEM and optical microscopy, chemical and EDX analysis, XRD, and FT-IR spectroscopy of three sea urchins skeletons (tests) show that the test is a spongy stereom, consisting of calcite with high content of magnesium. The tests are composed of mineral-organic composite of calcite-magnesite crystals, coated with organic film, containing silicon in form of polyphenylsiloxane. In the test of sea urchin pore spaces are linked into united system of regular structure with structure motive period about 20 um. This developed three-dimensional structure was used as a template for polymer material based on polyferrofenilsiloxane [OSiC6H5OH]x[OSiC6H5O]y[OFeO]z, which is chemically similar to the native film, coating sea urchins skeleton.

Correlation between some technological parameters and properties of composite material based on recycled tires and polymer binder

NASA Astrophysics Data System (ADS)

Plesuma, Renate; Malers, Laimonis

2015-04-01

The present article is dedicated to the determination of a possible connection between the composition, specific properties of the composite material and molding pressure as an important technological parameter. Apparent density, Shore C hardness, compressive modulus of elasticity and compressive stress at 10% deformation was determined for composite material samples. Definite formation conditions - varying molding pressure conditions at ambient temperature and corresponding relative air humiditywere realized. The results obtained showed a significant effect of molding pressure on the apparent density, mechanical properties of composite material as well as on the compressive stress change at a cyclic mode of loading. Some general regularities were determined - mechanical properties of the composite material, as well as values of Shore C hardness increases with an increase of molding pressure.

Short communication: rearrangement of rumenic Acid in ruminant fats: a marker of thermal treatment.

PubMed

Destaillats, F; Japiot, C; Chouinard, P Y; Arul, J; Angers, P

2005-05-01

Rumenic (cis-9,trans-11 18:2) acid is the main conjugated linoleic acid (CLA) isomer in milk and other ruminant fats. Anhydrous regular and high-CLA butterfats were heated at 200 degrees C for 2, 4, and 6 h under atmospheric conditions. [1,5] Sigmatropic isomerization of rumenic acid occurred, resulting in the formation of trans-8,cis-10 18:2 acid, as determined by mass spectrometry of its 4,4-dimethyloxazoline derivative. Rate of isomerization was monitored by gas-liquid chromatography, using a 120-m capillary column coated with 70% equivalent cyanoalkylpolysiloxane polymer, and reaction was of first order. Furthermore, [1,5] sigmatropic rearrangement product analysis can be used as an indicator of heat treatment of natural fats and oils containing CLA.

On the theory of Carriers's Electrostatic Interaction near an Interface

NASA Astrophysics Data System (ADS)

Waters, Michael; Hashemi, Hossein; Kieffer, John

2015-03-01

Heterojunction interfaces are common in non-traditional photovoltaic device designs, such as those based small molecules, polymers, and perovskites. We have examined a number of the effects of the heterojunction interface region on carrier/exciton energetics using a mixture of both semi-classical and quantum electrostatic methods, ab initio methods, and statistical mechanics. Our theoretical analysis has yielded several useful relationships and numerical recipes that should be considered in device design regardless of the particular materials system. As a demonstration, we highlight these formalisms as applied to carriers and polaron pairs near a C60/subphthalocyanine interface. On the regularly ordered areas of the heterojunction, the effect of the interface is a significant set of corrections to the carrier energies, which in turn directly affects device performance.

Preparation and characterization of multi stimuli-responsive photoluminescent nanocomposites of graphene quantum dots with hyperbranched polyethylenimine derivatives

NASA Astrophysics Data System (ADS)

Liu, Xing; Liu, Hua-Ji; Cheng, Fa; Chen, Yu

2014-06-01

Oxidized graphene sheets (OGS) were treated with a hyperbranched polyethylenimine (PEI) under hydrothermal conditions to generate nanocomposites of graphene quantum dots (GQDs) functionalized with PEI (GQD-PEIs). The influence of the reaction temperature and the PEI/OGS feed ratio on the photoluminescence properties of the GQD-PEIs was studied. The obtained GQD-PEIs were characterized by TEM, dynamic light scattering, elemental analysis, FTIR, zeta potential measurements and 1H NMR spectroscopy, from which their structural information was inferred. Subsequently, isobutyric amide (IBAm) groups were attached to the GQD-PEIs through the amidation reaction of isobutyric anhydride with the PEI moieties, which resulted in GQD-PEI-IBAm nanocomposites. GQD-PEI-IBAm was not only thermoresponsive, but also responded to other stimuli, including inorganic salts, pH, and loaded organic guests. The cloud point temperature (Tcp) of aqueous solutions of GQD-PEI-IBAm could be modulated through changing the number of IBAm units in GQD-PEI-IBAm, by varying the type and concentration of the inorganic salts and loaded organic guests, or by varying the pH. All the obtained GQD-PEI-IBAm nanocomposites were photoluminescent, and their maximum emission wavelengths were not influenced by outside stimuli. Their emission intensities were influenced a little or negligibly by pH, traditional salting-out anions (Cl- and SO42-), and the relatively polar aspirin guest. However, the traditional salting-in I- anion and the more hydrophobic 1-pyrenebutyric acid (PBA) guest could effectively quench their fluorescence. 2D NOESY 1H NMR spectra verified that GQD-PEI-IBAm accommodated the relatively polar aspirin guest using the PEI-IBAm shell, but adsorbed the relatively hydrophobic PBA guest through the nanographene core. The release rate of the guest encapsulated by the thermoresponsive GQD is different below and above Tcp.Oxidized graphene sheets (OGS) were treated with a hyperbranched polyethylenimine (PEI) under hydrothermal conditions to generate nanocomposites of graphene quantum dots (GQDs) functionalized with PEI (GQD-PEIs). The influence of the reaction temperature and the PEI/OGS feed ratio on the photoluminescence properties of the GQD-PEIs was studied. The obtained GQD-PEIs were characterized by TEM, dynamic light scattering, elemental analysis, FTIR, zeta potential measurements and 1H NMR spectroscopy, from which their structural information was inferred. Subsequently, isobutyric amide (IBAm) groups were attached to the GQD-PEIs through the amidation reaction of isobutyric anhydride with the PEI moieties, which resulted in GQD-PEI-IBAm nanocomposites. GQD-PEI-IBAm was not only thermoresponsive, but also responded to other stimuli, including inorganic salts, pH, and loaded organic guests. The cloud point temperature (Tcp) of aqueous solutions of GQD-PEI-IBAm could be modulated through changing the number of IBAm units in GQD-PEI-IBAm, by varying the type and concentration of the inorganic salts and loaded organic guests, or by varying the pH. All the obtained GQD-PEI-IBAm nanocomposites were photoluminescent, and their maximum emission wavelengths were not influenced by outside stimuli. Their emission intensities were influenced a little or negligibly by pH, traditional salting-out anions (Cl- and SO42-), and the relatively polar aspirin guest. However, the traditional salting-in I- anion and the more hydrophobic 1-pyrenebutyric acid (PBA) guest could effectively quench their fluorescence. 2D NOESY 1H NMR spectra verified that GQD-PEI-IBAm accommodated the relatively polar aspirin guest using the PEI-IBAm shell, but adsorbed the relatively hydrophobic PBA guest through the nanographene core. The release rate of the guest encapsulated by the thermoresponsive GQD is different below and above Tcp. Electronic supplementary information (ESI) available: Elemental analysis data; typical FTIR spectra; typical photographs of the GQD solution before and after phase transition; typical luminescence photographs, and typical photoluminescence spectra. See DOI: 10.1039/c4nr00739e

Spectroscopic study of excitations in pi-conjugated polymers

NASA Astrophysics Data System (ADS)

Yang, Cungeng

This dissertation deals with spin-physics of photo excitations in pi-conjugated polymers. Optical and magneto-optical spectroscopies, including continuous wave and time-resolved photo-induced absorption, photoluminescence, electroluminescence, and their optically detected magnetic resonance, were used to study steady state and transient photogeneration, energy transfer, spin relaxation, and spin dependent recombination process in the time domain from tens of nanoseconds to tens of milliseconds in polymer materials including regio-random poly (3-hexyl-thiophene-2,5-diyl), regio-regular poly (3-hexyl-thiophene-2,5-diyl), poly (9,9-dioctyl-fluorenyl-2,7-diyl), poly (poly (2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene) of various morphologies, and transition metal complex poly (Pt-quinoxene). Our studies provided the tools to clarify the physical pictures regarding two types of long-lived photoexcitations, namely polarons (both germinate polaron-pairs, and unpaired polarons) and triplet excitons, which are the major excitations in these exotic semiconductors in electrical and optical related applications. From measurements of transient fluorescence and transient fluorescence detected magnetic resonance we show that photogenerated geminate polaron pairs live up to hundreds of microseconds following laser pulsed excitation. This conclusion is in agreement with the delayed formation of triplet excitons that we measured by transient photoinduced absorption. It also agrees with the weak spin-lattice relaxation rate in polymers that we measured using the optically detected magnetic resonance dynamic in thin films and organic light emitting devices. Randomly captured nongeminate polaron pairs were shown to be the major source of optically detected magnetic resonance signal at steady, state. We found that the dynamics and magnitude of the signal depend on the spin-relaxation rate, generation rate and decay rate of the geminate pairs and nongeminate pairs. Importantly we found that the spin-relaxation rate depends weakly on temperature and strongly on coupled heavy atom orbital and magnetic momentum dipole induced by dopants or high intensity excitation. Also the polaron generation rate is excitation energy and nano-morphology dependent; whereas the polaron decay rate is morphology and spin dependent.

IAEA programme in the field of radiation technology

NASA Astrophysics Data System (ADS)

Chmielewski, Andrzej G.; Haji-Saeid, Mohammad

2005-07-01

Radiation technologies applying gamma sources and electron accelerators for material modification are well-established processes. There are over 160 gamma industrial irradiators and 1300 electron industrial accelerators in operation worldwide. A new advancement in the field of radiation sources engineering is the development of high power direct e-/X conversion sources based on electron accelerators. Technologies to be developed beside environmental applications could be nanomaterials, structure engineered materials (sorbents, composites, ordered polymers, etc.) and natural polymers' processing. New products based on radiation-processed polysaccharides have already been commercialised in many countries of the East Asia and Pacific Region, especially in those being rich in natural polymers. Very important and promising applications concern environmental protection-radiation technology, being a clean and environment friendly process, helps to curb pollutants' emission as well. Industrial plants for flue gas treatment have been constructed in Poland and China. The pilot plant in Bulgaria using this technology has just started its operation. The Polish plant is equipped with accelerators of over 1 MW power, a breakthrough in radiation technology application. The industrial plant for wastewater treatment is under development in Korea and a pilot plant for sewage sludge irradiation has been in operation in India for many years. Due to recent developments, the Agency has restructured its programme and organized a Technical Meeting (TM) on "Emerging Applications of Radiation Technology for the 21st Century" at its Headquarters in Vienna, Austria, in April 2003, to review the present situation and possible developments of radiation technology to contribute to a sustainable development. This meeting provided the basic input to launch others in the most important fields of radiation technology applications: "Advances in Radiation Chemistry of Polymers" (Notre Dame, USA, September 2003), "Status of Industrial Scale Radiation Treatment of Wastewater" (Taejon, Republic of Korea, October 2003), "Radiation Processing of Polysaccharides" (Takasaki, Japan, November 2003), "Emerging Applications of Radiation in Nanotechnology" (Bologna, Italy, March 2004) and "Radiation Processing of Gaseous and Liquid Effluents" (Sofia, Bulgaria, September 2004). The Agency is presently supervising three Coordinated Research Projects on radiation wastewater treatment, radiation synthesis stimuli-responsive hydrogels for separation purposes and degradation effects of polymers. The role of this technology for a sustainable development is well illustrated by the fact that over 30 technical cooperation projects (including three regional ones) were accomplished in the years 2003-2004 and several new projects are being expected for the new cycle 2005-2006. Detailed analyses of the results of both, regular and TC programmes, laid the foundation for formulation of the new programme for the years 2006-2007. The emphasis will be put on nanotechnology, natural polymers, environment and health protection, including combat with hazardous bioagents.

Thermoplastic-based conductive composites containing multi-wall carbon nanotubes aligned under the application of external electric fields

NASA Astrophysics Data System (ADS)

Osazuwa, Osayuki

The objective of this thesis is to prepare thermoplastic/multi-wall carbon nanotubes (MWCNTs) and to apply external alternating current (AC) electric fields to achieve enhanced conductivity and dielectric properties. The first part of the thesis focuses on preparing polyolefin-based composites containing welldispersed MWCNTs. MWCNTs are functionalized with a hyperbranched polyethylene (HBPE) using a non-covalent, non-specific functionalization approach and melt compounded with an ethylene-octene copolymer (EOC) matrix. The improved filler dispersion in the functionalized EOC/MWCNT composite results in higher elongation at break compared to the non-functionalized composite. However, the electrical percolation threshold and the ultimate conductivity of the composites are not affected considerably, suggesting that this functionalization approach leaves the inherent properties of the nanotubes intact. EOC/HBPE-functionalized MWCNT composites are further subjected to external AC electric fields (35 -- 212 kV/m), which induce the formation of aligned columnar structures, as evidenced by Scanning Electron Microscopy. Experimentally acquired resistivity data are used to derive correlations between the characteristic insulator-to-conductor transition times of the composites and the electric field strength (E), polymer viscosity (eta) and MWCNT volume fraction (φ). A criterion for the selection of (eta, E, φ) conditions that enable MWCNT assembly under an electric field controlled regime (minimal Brownian motion-driven aggregation effects) is developed. The dielectric properties of the solidified aligned EOC/MWCNT composites are further studied using dielectric spectroscopy. Annealing of the composites at 160 °C results in the formation of interconnected structures, whereas electrification, using AC field of 71 and 212 kV/m induces the formation of aligned columnar structures. The electrified and annealed composites have increased real and imaginary permittivity compared to the as-compounded composite, resulting in improved conductivity and storage capacity. An equivalent circuit model is fitted to the experimentally obtained impedance data in order to correlate the effects of electric field and processing time to the dielectric characteristics of the treated composites. Finally poly(ethylene succinate) (PESu) composites containing well-dispersed MWCNT were prepared by an in-situ polymerization method. Composite electrification results in improvements in the electrical conductivity by up to 12 orders of magnitude, and a retention of high conductivity in the solidified state.

Interaction chromatography for characterization and large-scale fractionation of chemically heterogeneous copolymers

NASA Astrophysics Data System (ADS)

Han, Junwon

The remarkable development of polymer synthesis techniques to make complex polymers with controlled chain architectures has inevitably demanded the advancement of polymer characterization tools to analyze the molecular dispersity in polymeric materials beyond size exclusion chromatography (SEC). In particular, man-made synthetic copolymers that consist of more than one monomer type are disperse mixtures of polymer chains that have distributions in terms of both chemical heterogeneity and chain length (molar mass). While the molecular weight distribution has been quite reliably estimated by the SEC, it is still challenging to properly characterize the chemical composition distribution in the copolymers. Here, I have developed and applied adsorption-based interaction chromatography (IC) techniques as a promising tool to characterize and fractionate polystyrene-based block, random and branched copolymers in terms of their chemical heterogeneity. The first part of this thesis is focused on the adsorption-desorption based purification of PS-b-PMMA diblock copolymers using nanoporous silica. The liquid chromatography analysis and large scale purification are discussed for the PS-b-PMMA block copolymers that have been synthesized by sequential anionic polymerization. SEC and IC are compared to critically analyze the contents of PS homopolymers in the as-synthesized block copolymers. In addition, I have developed an IC technique to provide faster and more reliable information on the chemical heterogeneity in the as-synthesized block copolymers. Finally, a large scale (multi-gram) separation technique is developed to obtain "homopolymer-free" block copolymers via a simple chromatographic filtration technique. By taking advantage of the large specific surface area of nanoporous silica (≈300m 2/g), large scale purification of neat PS-b-PMMA has successfully been achieved by controlling adsorption and desorption of the block copolymers on the silica gel surface using a gravity column. The second part of this thesis is focused on the liquid chromatography analysis and fractionation of RAFT-polymerized PS-b -PMMA diblock copolymers and AFM studies. In this study, PS- b-PMMA block copolymers were synthesized by a RAFT free radical polymerization process---the PMMA block with a phenyldithiobenzoate end group was synthesized first. The contents of unreacted PS and PMMA homopolymers in as-synthesized PS-b-PMMA block copolymers were quantitatively analyzed by solvent gradient interaction chromatography (SGIC) technique employing bare silica and C18-bonded silica columns, respectively. In addition, by 2-dimensional large-scale IC fractionation method, atomic force microscopy (AFM) study of these fractionated samples revealed various morphologies with respect to the chemical composition of each fraction. The third part of this thesis is to analyze random copolymers with tunable monomer sequence distributions using interaction chromatography. Here, IC was used for characterizing the composition and monomer sequence distribution in statistical copolymers of poly(styrene-co-4-bromostyrene) (PBrxS). The PBrS copolymers were synthesized by the bromination of monodisperse polystyrenes; the degree of bromination (x) and the sequence distribution were adjusted by varying the bromination time and the solvent quality, respectively. Both normal-phase (bare silica) and reversed-phase (C18-bonded silica) columns were used at different combinations of solvents and non-solvents to monitor the content of the 4-bromostyrene units in the copolymer and their average monomer sequence distribution. The fourth part of this thesis is to analyze and fractionate highly branched polymers such as dendronized polymers and star-shaped homo and copolymers. I have developed an interaction chromatography technique to separate polymers with nonlinear chain architecture. Specifically, the IC technique has been used to separate dendronized polymers and PS-based highly branched copolymers and to ultimately obtain well-defined dendronized or branched copolymers with a low polydispersity. The effects of excess arm-polymers on (1) the micellar self-assembly of dendronized polymers and (2) the regularity of the pore morphology in the low-k applications by the sol-gel process have been studied.

Deconvolution of the relaxations associated with local and segmental motions in poly(methacrylate)s containing dichlorinated benzyl moieties in the ester residue.

PubMed

Dominguez-Espinosa, Gustavo; Díaz-Calleja, Ricardo; Riande, Evaristo; Gargallo, Ligia; Radic, Deodato

2005-09-15

The relaxation behavior of poly(2,3-dichlorobenzyl methacrylate) is studied by broadband dielectric spectroscopy in the frequency range of 10(-1)-10(9) Hz and temperature interval of 303-423 K. The isotherms representing the dielectric loss of the glassy polymer in the frequency domain present a single absorption, called beta process. At temperatures close to Tg, the dynamical alpha relaxation already overlaps with the beta process, the degree of overlapping increasing with temperature. The deconvolution of the alpha and beta relaxations is facilitated using the retardation spectra calculated from the isotherms utilizing linear programming regularization parameter techniques. The temperature dependence of the beta relaxation presents a crossover associated with a change in activation energy of the local processes. The distance between the alpha and beta peaks, expressed as log(fmax;beta/fmax;alpha) where fmax is the frequency at the peak maximum, follows Arrhenius behavior in the temperature range of 310-384 K. Above 384 K, the distance between the peaks remains nearly constant and, as a result, the a onset temperature exhibited for many polymers is not reached in this system. The fraction of relaxation carried out through the alpha process, without beta assistance, is larger than 60% in the temperature range of 310-384 K where the so-called Williams ansatz holds.

Microtubule organization in three-dimensional confined geometries: evaluating the role of elasticity through a combined in vitro and modeling approach.

PubMed

Cosentino Lagomarsino, Marco; Tanase, Catalin; Vos, Jan W; Emons, Anne Mie C; Mulder, Bela M; Dogterom, Marileen

2007-02-01

Microtubules or microtubule bundles in cells often grow longer than the size of the cell, which causes their shape and organization to adapt to constraints imposed by the cell geometry. We test the reciprocal role of elasticity and confinement in the organization of growing microtubules in a confining box-like geometry, in the absence of other (active) microtubule organizing processes. This is inspired, for example, by the cortical microtubule array of elongating plant cells, where microtubules are typically organized in an aligned array transverse to the cell elongation axis. The method we adopt is a combination of analytical calculations, in which the polymers are modeled as inextensible filaments with bending elasticity confined to a two-dimensional surface that defines the limits of a three-dimensional space, and in vitro experiments, in which microtubules are polymerized from nucleation seeds in microfabricated chambers. We show that these features are sufficient to organize the polymers in aligned, coiling configurations as for example observed in plant cells. Though elasticity can account for the regularity of these arrays, it cannot account for a transverse orientation of microtubules to the cell's long axis. We therefore conclude that an additional active, force-generating process is necessary to create a coiling configuration perpendicular to the long axis of the cell.

Laboratory and field evaluation of the impact of exercise on the performance of regular and polymer-based deet repellents.

PubMed

Schofield, Steven; Tepper, Martin; Gadawski, Randy

2007-11-01

Studies were done in Manitoba, Canada, to evaluate the impact of exercise on repellent performance against mosquitoes. Two products containing the active ingredient N,N-diethyl-3-methylbenzamide (deet) were tested; one product was a polymer-based cream (3M Ultrathon Insect Repellent) and the other product was an alcohol-based pump spray formulation (Muskol Insect Repellent). Assessments were done in the laboratory using Aedes aegypti (L.) and in the field with naturally occurring populations of mosquitoes. Repellent was applied to the forearms (laboratory) or a lower leg (field) of test subjects at 1.5 g of test product per 600 cm2 surface area (0.75 or 0.83 mg deet/cm2). For a given test day, subjects exercised or did not. Exposure to mosquito attack was for 1 min at 30-min intervals in laboratory procedures, and it was continuous in field tests. Performance was measured as complete protection time (CPT). Moderate levels of physical activity resulted in a >40% decline in mean CPT, from 468 to 267 min in the laboratory experiments and from 359 to 203 min in field tests. Repellent product did not affect the magnitude of the decline. Mean biting pressure during field trials was 21.3 bites per min, and mosquito collections were made up primarily of Ochlerotatus sticticus (Meigen) and Aedes vexans (Meigen).

Exploiting Photo-induced Reactions in Polymer Blends to Create Hierarchically Ordered, Defect-free Materials

ScienceCinema

Balazs, Anna [University of Pittsburgh, Pittsburgh, Pennsylvania, United States

2017-12-09

Computer simulations reveal how photo-induced chemical reactions can be exploited to create long-range order in binary and ternary polymeric materials. The process is initiated by shining a spatially uniform light over a photosensitive AB binary blend, which undergoes both a reversible chemical reaction and phase separation. We then introduce a well-collimated, higher-intensity light source. Rastering this secondary light over the sample locally increases the reaction rate and causes formation of defect-free, spatially periodic structures. These binary structures resemble either the lamellar or hexagonal phases of microphase-separated di-block copolymers. We measure the regularity of the ordered structures as a function of the relative reaction rates for different values of the rastering speed and determine the optimal conditions for creating defect-free structures in the binary systems. We then add a non-reactive homo-polymer C, which is immiscible with both A and B. We show that this component migrates to regions that are illuminated by the secondary, higher-intensity light, allowing us to effectively write a pattern of C onto the AB film. Rastering over the ternary blend with this collimated light now leads to hierarchically ordered patterns of A, B, and C. The findings point to a facile, non-intrusive process for manufacturing high-quality polymeric devices in a low-cost, efficient manner.

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

Jones, J.; Brown, J.; Robinson, C.

An industrial hygiene survey to assess personnel records and possible exposures to acrylonitrile (AN) (107131) in the Monsanto Plastics and Resins Company, Addyston, Ohio, for potential use in a retrospective cohort mortality/industrial hygiene survey is reported. The plant is involved in the production of AN polymers. Levels of exposure to AN vary with the process used. It is postulate that before 1974 levels of exposure to AN may have been greater than 100ppm during periods of peak exposure. Personal air samples taken by the company during 1977 are all below 20ppm with most below 10ppm. The company has an extensivemore » medical program including health maintenance, and individually designed annual physical examinations. Tests considered relevant to occupational exposure are conducted on a regular basis. It is maintained that the personnel records contain suitable data for use in a mortality study.« less

High-Performance Photovoltaic Behavior of Oriented Purple Membrane Polymer Composite Films

PubMed Central

Zhang, Liangmin; Zeng, Tingying; Cooper, Kristie; Claus, Richard O.

2003-01-01

The photovoltaic behavior of films in which bacteriorhodopsin molecules are embedded in a polyvinyl alcohol matrix has been investigated by using both pulsed laser excitation and regular light illumination. Response times as short as milliseconds, photocurrents as great as 120 μA/cm2, and photovoltages as large as 3.8 V have been obtained. A theoretical model has been developed and used to extract several physical parameters and fit the experimental results. Some important intrinsic parameters have been obtained. Theoretical results indicate that the average displacement of the excited protons is on the order of several tens of microns. Other curve fits show that photocurrent and photovoltage increase linearly with external field, but increase exponentially with flash power. These theoretical models and results can be extended to other kinds of photoactive polymeric materials. PMID:12668458

Mold-Based Application of Laser-Induced Periodic Surface Structures (LIPSS) on Biomaterials for Nanoscale Patterning.

PubMed

Hendrikson, Wim; Masman-Bakker, Wendy; van Bochove, Bas; Skolski, Johann; Eichstädt, Justus; Koopman, Bart; van Blitterswijk, Clemens; Grijpma, Dirk; Römer, Gert-Willem; Moroni, Lorenzo; Rouwkema, Jeroen

2016-01-01

Laser-induced periodic surface structures (LIPSS) are highly regular, but at the same time contain a certain level of disorder. The application of LIPSS is a promising method to functionalize biomaterials. However, the absorption of laser energy of most polymer biomaterials is insufficient for the direct application of LIPSS. Here, we report the application of LIPSS to relevant biomaterials using a two-step approach. First, LIPSS are fabricated on a stainless steel surface. Then, the structures are replicated onto biomaterials using the steel as a mold. Results show that LIPSS can be transferred successfully using this approach, and that human mesenchymal stromal cells respond to the transferred structures. With this approach, the range of biomaterials that can be supplied with LIPSS increases dramatically. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CHO-bearing organic compounds at the surface of 67P/Churyumov-Gerasimenko revealed by Ptolemy

NASA Astrophysics Data System (ADS)

Wright, I. P.; Sheridan, S.; Barber, S. J.; Morgan, G. H.; Andrews, D. J.; Morse, A. D.

2015-07-01

The surface and subsurface of comets preserve material from the formation of the solar system. The properties of cometary material thus provide insight into the physical and chemical conditions during their formation. We present mass spectra taken by the Ptolemy instrument 20 minutes after the initial touchdown of the Philae lander on the surface of comet 67P/Churyumov-Gerasimenko. Regular mass distributions indicate the presence of a sequence of compounds with additional -CH2- and -O- groups (mass/charge ratios 14 and 16, respectively). Similarities with the detected coma species of comet Halley suggest the presence of a radiation-induced polymer at the surface. Ptolemy measurements also indicate an apparent absence of aromatic compounds such as benzene, a lack of sulfur-bearing species, and very low concentrations of nitrogenous material.

Behaviors of printed circuit boards due to microwave supported curing process of coating materials.

PubMed

Bremerkamp, Felix; Nowottnick, Mathias; Seehase, Dirk; Bui, Trinh Dung

2012-01-01

The Application of a microwave supported curing process for coatings in the field of electronic industry poses a challenge. Here the implementation of this technology is represented. Within the scope of the investigation special PCB Test Layouts were designed and the polymer curing process examined by the method of dielectric analysis. Furthermore the coupling of microwave radiation with conductive PCB structures was analyzed experimentally by means of special test boards. The formation of standing waves and regular heating distribution along the conductive wires on the PCB could be observed. The experimental results were compared with numerical simulation. In this context the numerical analysis of microwave PCB interaction led to important findings concerning wave propagation on wired PCB. The final valuation demonstrated a substantial similarity between numerical simulations and experimental results.

Thermally responsive polymer systems for self-healing, reversible adhesion and shape memory applications

NASA Astrophysics Data System (ADS)

Luo, Xiaofan

Responsive polymers are "smart" materials that are capable of performing prescribed, dynamic functions under an applied stimulus. In this dissertation, we explore several novel design strategies to develop thermally responsive polymers and polymer composites for self-healing, reversible adhesion and shape memory applications. In the first case described in Chapters 2 and 3, a thermally triggered self-healing material was prepared by blending a high-temperature epoxy resin with a thermoplastic polymer, poly(epsilon-caprolactone) (PCL). The initially miscible system undergoes polymerization induced phase separation (PIPS) during the curing of epoxy and yields a variety of compositionally dependent morphologies. At a particular PCL loading, the cured blend displays a "bricks-and-mortar" morphology in which epoxy exists as interconnected spheres ("bricks") within a continuous PCL matrix ("mortar"). A heat induced "bleeding" phenomenon was observed in the form of spontaneous wetting of all free surfaces by the molten PCL, and is attributed to the volumetric thermal expansion of PCL above its melting point in excess of epoxy brick expansion, which we term differential expansive bleeding (DEB). This DEB is capable of healing damage such as cracks. In controlled self-healing experiments, heating of a cracked specimen led to PCL bleeding from the bulk that yields a liquid layer bridging the crack gap. Upon cooling, a "scar" composed of PCL crystals was formed at the site of the crack, restoring a significant portion of mechanical strength. We further utilized DEB to enable strong and thermally-reversible adhesion of the material to itself and to metallic substrates, without any requirement for macroscopic softening or flow. After that, Chapters 4--6 present a novel composite strategy for the design and fabrication of shape memory polymer composites. The basic approach involves physically combining two or more functional components into an interpenetrating fiber/matrix structure, allowing them to function in a synergistic fashion yet remain physically separated. This latter aspect is critical since it enables the control of overall composite properties and functions by separately tuning each component. Utilizing the intrinsic versatility of this approach, composites with novel properties and functions (in addition to "regular" shape memory) have been developed, including (1) shape memory elastomeric composites (SMECs; Chapter 4), (2) triple-shape polymeric composites (TSPCs; Chapter 5), and (3) electrically conductive nanocomposites (Chapter 6). Then in Chapter 7, by combining the success in both thermoplastic based self-healing and shape memory polymer composites, we demonstrate a thermally triggered self-healing coating. This coating features a unique "shape memory assisted self-healing" mechanism in which crack closure (via shape memory) and crack re-bonding (via melting and diffusion of the thermoplastic healing agent) are achieved simultaneously upon a single heating step, leading to both structural and functional (corrosion resistance) recovery. Finally, Chapter 8 presents for the first time the preparation of functionally graded shape memory polymers (SMPs) that, unlike conventional SMPs, have a range of glass transition temperatures that are spatially graded. This was achieved using a temperature gradient curing method that imposes different vitrification limits at different positions along the gradient. The resulting material is capable of responding to a wide range of thermal triggers and a good candidate for low-cost, material based temperature sensors. All the aforementioned materials and methods show great potential for practical applications due to their high performance, low cost and broad applicability. Some recommendations for future research and development are given in Chapter 9.

An in vitro and in vivo study of peptide-functionalized nanoparticles for brain targeting: The importance of selective blood-brain barrier uptake.

PubMed

Bode, Gerard H; Coué, Gregory; Freese, Christian; Pickl, Karin E; Sanchez-Purrà, Maria; Albaiges, Berta; Borrós, Salvador; van Winden, Ewoud C; Tziveleka, Leto-Aikaterini; Sideratou, Zili; Engbersen, Johan F J; Singh, Smriti; Albrecht, Krystyna; Groll, Jürgen; Möller, Martin; Pötgens, Andy J G; Schmitz, Christoph; Fröhlich, Eleonore; Grandfils, Christian; Sinner, Frank M; Kirkpatrick, C James; Steinbusch, Harry W M; Frank, Hans-Georg; Unger, Ronald E; Martinez-Martinez, Pilar

2017-04-01

Targeted delivery of drugs across endothelial barriers remains a formidable challenge, especially in the case of the brain, where the blood-brain barrier severely limits entry of drugs into the central nervous system. Nanoparticle-mediated transport of peptide/protein-based drugs across endothelial barriers shows great potential as a therapeutic strategy in a wide variety of diseases. Functionalizing nanoparticles with peptides allows for more efficient targeting to specific organs. We have evaluated the hemocompatibilty, cytotoxicity, endothelial uptake, efficacy of delivery and safety of liposome, hyperbranched polyester, poly(glycidol) and acrylamide-based nanoparticles functionalized with peptides targeting brain endothelial receptors, in vitro and in vivo. We used an ELISA-based method for the detection of nanoparticles in biological fluids, investigating the blood clearance rate and in vivo biodistribution of labeled nanoparticles in the brain after intravenous injection in Wistar rats. Herein, we provide a detailed report of in vitro and in vivo observations. Copyright © 2016 Elsevier Inc. All rights reserved.

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

Levin, Barnaby D. A.; Padgett, Elliot; Chen, Chien-Chun

Electron tomography in materials science has flourished with the demand to characterize nanoscale materials in three dimensions (3D). Access to experimental data is vital for developing and validating reconstruction methods that improve resolution and reduce radiation dose requirements. This work presents five high-quality scanning transmission electron microscope (STEM) tomography datasets in order to address the critical need for open access data in this field. The datasets represent the current limits of experimental technique, are of high quality, and contain materials with structural complexity. Included are tomographic series of a hyperbranched Co 2 P nanocrystal, platinum nanoparticles on a carbonmore » nanofibre imaged over the complete 180° tilt range, a platinum nanoparticle and a tungsten needle both imaged at atomic resolution by equal slope tomography, and a through-focal tilt series of PtCu nanoparticles. A volumetric reconstruction from every dataset is provided for comparison and development of post-processing and visualization techniques. Researchers interested in creating novel data processing and reconstruction algorithms will now have access to state of the art experimental test data.« less

Counterion adsorption theory of dilute polyelectrolyte solutions: Apparent molecular weight, second virial coefficient, and intermolecular structure factor

PubMed Central

Muthukumar, M.

2012-01-01

Polyelectrolyte chains are well known to be strongly correlated even in extremely dilute solutions in the absence of additional strong electrolytes. Such correlations result in severe difficulties in interpreting light scattering measurements in the determination of the molecular weight, radius of gyration, and the second virial coefficient of charged macromolecules at lower ionic strengths from added strong electrolytes. By accounting for charge-regularization of the polyelectrolyte by the counterions, we present a theory of the apparent molecular weight, second virial coefficient, and the intermolecular structure factor in dilute polyelectrolyte solutions in terms of concentrations of the polymer and the added strong electrolyte. The counterion adsorption of the polyelectrolyte chains to differing levels at different concentrations of the strong electrolyte can lead to even an order of magnitude discrepancy in the molecular weight inferred from light scattering measurements. Based on counterion-mediated charge regularization, the second virial coefficient of the polyelectrolyte and the interchain structure factor are derived self-consistently. The effect of the interchain correlations, dominating at lower salt concentrations, on the inference of the radius of gyration and on molecular weight is derived. Conditions for the onset of nonmonotonic scattering wave vector dependence of scattered intensity upon lowering the electrolyte concentration and interpretation of the apparent radius of gyration are derived in terms of the counterion adsorption mechanism. PMID:22830728

An order in Lewy body disorders: Retrograde degeneration in hyperbranching axons as a fundamental structural template accounting for focal/multifocal Lewy body disease.

PubMed

Uchihara, Toshiki

2017-04-01

Initial clinical recognition of "paralysis agitans" by James Parkinson was expanded by Jean-Martin Charcot, who recognized additional clinical findings of his own, such as slowness (distinct from paralysis), rigidity (distinct from spasticity) and characteristic countenance. Charcot assembled these findings under the umbrella of "Parkinson disease (PD)". This purely clinical concept was so prescient and penetrating that subsequent neuropathological and biochemical evidences were ordered along this axis to establish the nigra-central trinity of PD (dopamine depletion, nigral lesion with Lewy bodies: LBs). Although dramatic efficacy of levodopa boosted an enthusiasm for this nigra-centralism, extranigral lesions were identified, especially after identification of alpha-synuclein (αS) as a major constituent of LBs. Frequent αS lesions in the lower brainstem with their presumed upward spread were coupled with the self-propagating property of αS molecule, as a molecular template, to constitute the prion-Braak hypothesis. This hybrid concept might expectedly explain clinical, structural and biochemical features of PD/dementia with Lewy bodies (DLB) as if they were stereotypic. In spite of this ordered explanation, recent studies have demonstrated unexpectedly that αS lesions in the human brain, as well as their corresponding clinical manifestations, are much more disordered. Even with such a chaos of LB disorders, affected neuronal groups are uniformly characterized by hyperbranching axons, which may facilitate distal-dominant degeneration and retrograde progression of LB-related degeneration along axons as a fundamental structural order to template LB disorders. This "structural template" hypothesis may explain why: (i) some selective groups are prone to develop Lewy pathology; (ii) their clinical manifestations (especially non-motor components) are vague and generalized without somatotopic accentuation; (iii) distal axons and terminals are preferentially affected early, which is clinically detectable as reduced myocardial uptake of meta-iodobenzylguanidine in PD/DLB. Because each Lewy-prone system develops LBs independently, their isolated presentation as "focal LB disease" or their whatever combinations as "multifocal LB disease" are a more plausible framework to explain clinicopathological diversities of LB disorders. Clinical criteria are now being revised to integrate these clinicopathological disorders of PD/DLB. To gain closer access to the reality of the human brain, it is necessary to facilitate more interactions between clinicopathological and experimental fields so that both are mutually critical and complementary for improved diagnosis and treatment. © 2016 Japanese Society of Neuropathology.

Dendronized Polymers: Synthesis, Characterization, Assembly at Interfaces, and Manipulation.

PubMed

Schlüter; Rabe

2000-03-01

Dendrimers are presently one of the most intensely studied classes of compounds because of their unusual structure. They can be described as a jungle of entangled branches traversed by winding trails which lead to sweet fruits and bright blossoms. On these trails one can reach the thicket's interior as well as find a way out. Expressed less lyrically, this thicket stands for regularly branched, densely packed structures, and the trails represent voids and channels not filled by bent back branches but by solvent. The fruit and blossoms are photochemically, electrochemically, or synthetically addressable units, catalytically active sites, etc., and the back and forth on the trails stands for transport processes. In a mathematical sense dendrimers are enveloped by an interface, which defines what is either in or out. This interface is shaped like a sphere if the trails are filled to bursting. Otherwise dendrimers are more flattened like amoeba, especially if in contact with a surface. The high density of the functional groups, the expansion of these compounds to a range of several nanometers, the existence of usable "surface" and transport possibilities in and with them have made dendrimers interesting candidates for many applications. This review describes how dendrimer construction and polymer synthesis were combined and used to move from fully or flattened spherical shapes to cylindrical ones. The shape-inducing influence of dendritic substituents can be driven to create nanoobjects with a cylindrical shape, which not only considerably widens the range of applications for the dendrimer class but also opens up new perspectives for supramolecular and polymer chemistry. Because of the sheer size of the described objects and complexity of shape-related properties, research in this area must necessarily be interdisciplinary. This article tries to mirror this by giving special attention not only to synthesis but also the characterization and behavior of these compounds in bulk and at interfaces. Furthermore, potential application fields are described.

Influence of Size and Shape of Silica Supports on the Sol⁻Gel Surface Molecularly Imprinted Polymers for Selective Adsorption of Gossypol.

PubMed

Zhi, Keke; Wang, Lulu; Zhang, Yagang; Jiang, Yingfang; Zhang, Letao; Yasin, Akram

2018-05-11

The influence of various silica gel supports with different shapes and sizes on the recognition properties of surface molecular imprinted polymers (MIPs) was investigated. MIPs for selective recognition and adsorption of gossypol were synthesized via the sol⁻gel process with a surface imprinting technique on silica gel substrates. 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS) were chosen as the functional monomer and the cross-linker. The morphology and structure of the gossypol-MIPs were characterized using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and a standard Brunauer⁻Emett⁻Teller (BET) analysis. Results indicated that the surface imprinted polymer layer facilitated the removal and rebinding of the template, and thus, achieved fast binding kinetics. Compared with the MIPs prepared on irregularly shaped silica with a broad particle size distribution, the MIPs using regularly-shaped silica of uniform size showed higher imprinting factor (IF), and the MIP made with a relatively larger sized (60 μm) spherical silica, demonstrated higher adsorption capacity compared to the MIPs made with smaller sized, spherical silica. The MIP prepared with 60 μm spherically shaped silica, featured a fast adsorption kinetic of 10 min, and a saturated adsorption capacity of 204 mg·g −1 . The gossypol-MIP had higher selectivity (IF = 2.20) for gossypol over its structurally-similar analogs ellagic acid (IF = 1.13) and quercetin (IF = 1.20). The adsorption data of the MIP correlated well with the pseudo-second-order kinetic model and the Freundlich isotherm model, which implied that chemical adsorption dominated, and that multilayer adsorption occurred. Furthermore, the MIP exhibited an excellent regeneration performance, and the adsorption capacity of the MIP for gossypol only decreased by 6% after six reused cycles, indicating good application potential for selective adsorption of gossypol.

Charge-regularized swelling kinetics of polyelectrolyte gels

NASA Astrophysics Data System (ADS)

Sen, Swati; Kundagrami, Arindam

The swelling kinetics of polyelectrolyte gels with fixed and variable degrees of ionization in salt-free solvent is studied by solving the constitutive equation of motion of the spatially and temporally varying displacement variable. Two methods for the swelling kinetics - the Bulk Modulus Method (BMM), which uses a linear stress-strain relationship (and, hence a bulk modulus), and the Stress Relaxation Method (SRM), which uses a phenomenological expression of osmotic stress, are explored to provide the spatio-temporal profiles for polymer density, osmotic stress, and degree of ionization, along with the time evolution of the gel size. Further, we obtain an analytical expression for the elastic modulus for linearized stress in the limit of small deformations. We match our theoretical profiles with the experiments of swelling of PNIPAM (uncharged) and Imidazolium-based (charged) minigels available in the literature. Ministry of Human Resource Development (MHRD), Government of India.

The ``Swiss cheese'' instability of bacterial biofilms

NASA Astrophysics Data System (ADS)

Jang, Hongchul; Rusconi, Roberto; Stocker, Roman

2012-11-01

Bacteria often adhere to surfaces, where they develop polymer-encased communities (biofilms) that display dramatic resistance to antibiotic treatment. A better understanding of cell detachment from biofilms may lead to novel strategies for biofilm disruption. Here we describe a new detachment mode, whereby a biofilm develops a nearly regular array of ~50-100 μm holes. Using surface-treated microfluidic devices, we create biofilms of controlled shape and size. After the passage of an air plug, the break-up of the residual thin liquid film scrapes and rearranges bacteria on the surface, such that a ``Swiss cheese'' pattern is left in the residual biofilm. Fluorescent staining of the polymeric matrix (EPS) reveals that resistance to cell dislodgement correlates with local biofilm age, early settlers having had more time to hunker down. Because few survivors suffice to regrow a biofilm, these results point at the importance of considering microscale heterogeneity in assessing the effectiveness of biofilm removal strategies.

Molecular coordination of Staphylococcus aureus cell division

PubMed Central

Cotterell, Bryony E; Walther, Christa G; Fenn, Samuel J; Grein, Fabian; Wollman, Adam JM; Leake, Mark C; Olivier, Nicolas; Cadby, Ashley; Mesnage, Stéphane; Jones, Simon

2018-01-01

The bacterial cell wall is essential for viability, but despite its ability to withstand internal turgor must remain dynamic to permit growth and division. Peptidoglycan is the major cell wall structural polymer, whose synthesis requires multiple interacting components. The human pathogen Staphylococcus aureus is a prolate spheroid that divides in three orthogonal planes. Here, we have integrated cellular morphology during division with molecular level resolution imaging of peptidoglycan synthesis and the components responsible. Synthesis occurs across the developing septal surface in a diffuse pattern, a necessity of the observed septal geometry, that is matched by variegated division component distribution. Synthesis continues after septal annulus completion, where the core division component FtsZ remains. The novel molecular level information requires re-evaluation of the growth and division processes leading to a new conceptual model, whereby the cell cycle is expedited by a set of functionally connected but not regularly distributed components. PMID:29465397

A physical model describing the interaction of nuclear transport receptors with FG nucleoporin domain assemblies.

PubMed

Zahn, Raphael; Osmanović, Dino; Ehret, Severin; Araya Callis, Carolina; Frey, Steffen; Stewart, Murray; You, Changjiang; Görlich, Dirk; Hoogenboom, Bart W; Richter, Ralf P

2016-04-08

The permeability barrier of nuclear pore complexes (NPCs) controls bulk nucleocytoplasmic exchange. It consists of nucleoporin domains rich in phenylalanine-glycine motifs (FG domains). As a bottom-up nanoscale model for the permeability barrier, we have used planar films produced with three different end-grafted FG domains, and quantitatively analyzed the binding of two different nuclear transport receptors (NTRs), NTF2 and Importin β, together with the concomitant film thickness changes. NTR binding caused only moderate changes in film thickness; the binding isotherms showed negative cooperativity and could all be mapped onto a single master curve. This universal NTR binding behavior - a key element for the transport selectivity of the NPC - was quantitatively reproduced by a physical model that treats FG domains as regular, flexible polymers, and NTRs as spherical colloids with a homogeneous surface, ignoring the detailed arrangement of interaction sites along FG domains and on the NTR surface.

Monitoring eating habits using a piezoelectric sensor-based necklace.

PubMed

Kalantarian, Haik; Alshurafa, Nabil; Le, Tuan; Sarrafzadeh, Majid

2015-03-01

Maintaining appropriate levels of food intake and developing regularity in eating habits is crucial to weight loss and the preservation of a healthy lifestyle. Moreover, awareness of eating habits is an important step towards portion control and weight loss. In this paper, we introduce a novel food-intake monitoring system based around a wearable wireless-enabled necklace. The proposed necklace includes an embedded piezoelectric sensor, small Arduino-compatible microcontroller, Bluetooth LE transceiver, and Lithium-Polymer battery. Motion in the throat is captured and transmitted to a mobile application for processing and user guidance. Results from data collected from 30 subjects indicate that it is possible to detect solid and liquid foods, with an F-measure of 0.837 and 0.864, respectively, using a naive Bayes classifier. Furthermore, identification of extraneous motions such as head turns and walking are shown to significantly reduce the false positive rate of swallow detection. Copyright © 2015 Elsevier Ltd. All rights reserved.

Plasmonically amplified fluorescence bioassay with microarray format

NASA Astrophysics Data System (ADS)

Gogalic, S.; Hageneder, S.; Ctortecka, C.; Bauch, M.; Khan, I.; Preininger, Claudia; Sauer, U.; Dostalek, J.

2015-05-01

Plasmonic amplification of fluorescence signal in bioassays with microarray detection format is reported. A crossed relief diffraction grating was designed to couple an excitation laser beam to surface plasmons at the wavelength overlapping with the absorption and emission bands of fluorophore Dy647 that was used as a label. The surface of periodically corrugated sensor chip was coated with surface plasmon-supporting gold layer and a thin SU8 polymer film carrying epoxy groups. These groups were employed for the covalent immobilization of capture antibodies at arrays of spots. The plasmonic amplification of fluorescence signal on the developed microarray chip was tested by using interleukin 8 sandwich immunoassay. The readout was performed ex situ after drying the chip by using a commercial scanner with high numerical aperture collecting lens. Obtained results reveal the enhancement of fluorescence signal by a factor of 5 when compared to a regular glass chip.

Conversion of lanthanide glutarate chlorides with interstitial THF into lanthanide glutarates with unprecedented topologies

DOE PAGES

Zehnder, Ralph A.; Jenkins, James; Zeller, Matthias; ...

2017-11-26

Here, using slow diffusion methods at room temperature (RT), we obtained four isomorphous lanthanide glutarate chlorides, accommodating interstitial THF and water molecules, [Ln 2(Glut) 2Cl 2(H 2O) 8]·2H 2O·THF, with Ln = La , Ce, Pr, Nd. They assemble as 3-dimensional (3D) lanthanide (Ln) coordination polymers with LnO 10 coordination polyhedra. Their topology was elucidated to be a 4-coordinated sql net. slowly dissolve in water liberating the entrapped THF molecules and reassemble as regular Ln-glutarate hydrates when the solution is deprived of THF and water by slow evaporation. The new products crystallize as [Ln 2(Glut) 3(H 2O) 3]·5H 2O, withmore » Ln = La, Ce, Pr, and [Nd 2(Glut) 3(H 2O) 2]·3.5H 2O.« less

Nonsingular cosmology from evolutionary quantum gravity

NASA Astrophysics Data System (ADS)

Cianfrani, Francesco; Montani, Giovanni; Pittorino, Fabrizio

2014-11-01

We provide a cosmological implementation of the evolutionary quantum gravity, describing an isotropic Universe, in the presence of a negative cosmological constant and a massive (preinflationary) scalar field. We demonstrate that the considered Universe has a nonsingular quantum behavior, associated to a primordial bounce, whose ground state has a high occupation number. Furthermore, in such a vacuum state, the super-Hamiltonian eigenvalue is negative, corresponding to a positive emerging dust energy density. The regularization of the model is performed via a polymer quantum approach to the Universe scale factor and the proper classical limit is then recovered, in agreement with a preinflationary state of the Universe. Since the dust energy density is redshifted by the Universe de Sitter phase and the cosmological constant does not enter the ground state eigenvalue, we get a late-time cosmology, compatible with the present observations, endowed with a turning point in the far future.

Polyphenol oxidase activity and differential accumulation of polyphenolics in seed coats of pinto bean (Phaseolus vulgaris L.) characterize postharvest color changes.

PubMed

Marles, M A Susan; Vandenberg, Albert; Bett, Kirstin E

2008-08-27

Postharvest darkening of pinto bean (Phaseolus vulgaris L.) was evaluated in a population of recombinant inbred lines derived from a cross between CDC Pintium (a regular-darkening line) and 1533-15 (a slow-darkening line). Flavonoid metabolite concentrations, polyphenol oxidase activity, lignin concentration, and seed coat anatomy characteristics were assessed for cosegregation with the darkening phenotype. Significantly lower kaempferol concentrations (p = 0.00001) together with differences in polyphenol oxidase activity (p = 0.0045) were two of the key findings associated with these recombinant inbred lines. In addition, two different assays (thioglycolic acid and Klason lignin) to quantify lignin together with an assessment of extractable condensed tannin were used to estimate the contribution of these polymers to changes in the seed coat tissue. This is the first report of precise biochemical characterization of polyphenolics that associate with postharvest darkening in legumes.

Synthesis, characterization and AC conductivity studies of silver doped conducting polyaniline/graphene/SrTiO3 composites

NASA Astrophysics Data System (ADS)

Vinay, K.; Shivakumar, K.; Ravikiran, Y. T.; Revanasiddappa, M.

2018-05-01

The present work is an investigation of ac conduction behaviour and dielectric response of Polyaniline/Ag/Graphene/SrTiO3 (PAGS) composite prepared by in-situ chemical oxidative interfacial polymerization using (NH4)2S2O8 as an oxidising agent at 0-5°C. The structural characterization of the samples was examined using FT-IR and XRD techniques. The ac conductivity and dielectric response of synthesized polymer composites were investigated at room temperature in the frequency range varying from 5 × 101 - 5 × 106 Hz using HIOKI make 3532-50 LCR Hi-tester. The ac conductivity increases with increase in frequency and follows the regular trend, the real dielectric constant (ɛ') and imaginary dielectric constant (ɛ'') decreases with increase in frequency and exhibits almost zero dielectric loss at higher frequencies, which suggests that the composite is a lossless material at frequencies beyond 3Hz.

Conversion of lanthanide glutarate chlorides with interstitial THF into lanthanide glutarates with unprecedented topologies

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

Zehnder, Ralph A.; Jenkins, James; Zeller, Matthias

Here, using slow diffusion methods at room temperature (RT), we obtained four isomorphous lanthanide glutarate chlorides, accommodating interstitial THF and water molecules, [Ln 2(Glut) 2Cl 2(H 2O) 8]·2H 2O·THF, with Ln = La , Ce, Pr, Nd. They assemble as 3-dimensional (3D) lanthanide (Ln) coordination polymers with LnO 10 coordination polyhedra. Their topology was elucidated to be a 4-coordinated sql net. slowly dissolve in water liberating the entrapped THF molecules and reassemble as regular Ln-glutarate hydrates when the solution is deprived of THF and water by slow evaporation. The new products crystallize as [Ln 2(Glut) 3(H 2O) 3]·5H 2O, withmore » Ln = La, Ce, Pr, and [Nd 2(Glut) 3(H 2O) 2]·3.5H 2O.« less

Photoluminescence and solid state properties of rigid pi- conjugated polymers with applications to LED: Alkyl- substituted p-phenyleneethynylene polymers and triblock copolymers

NASA Astrophysics Data System (ADS)

Huang, Wen-Yao

A series of substituted poly(p-phenyleneethynylene)s, PPE, were synthesized by alkyne metathesis. The substituents dibutyl (a), dioctyl (b), ditetradecyl (c), di-2-ethylhexyl (d) and di-2-cyclohexylethyl; (e)were placed on the 2,5 positions of the phenyl rings. X-ray diffraction studies indicated that the main chains of each polymer were arranged in regular, layered arrays. Liquid crystalline structures were observed by polarized optical microscopy in PPE 4b, 4c and 4d. The temperatures of isotropization of the liquid crystalline structures coincided with the disordering temperatures determined by differential scanning calorimetry. The UV absorption spectra showed a gradual blue shift of the λmax for all these polymers, suggesting a decrease in the electronic delocalization along the chain as the size and geometry of the side group changed. The photoluminescence spectra in dilute toluene solutions are consistent with vibronic coupling and emission from localized excited states. The emission spectra of thin films show characteristics typical of excimer or aggregate formation in the solid state. Lastly, an improved method of molecular weight determination by end group analysis was devised. Molecular organization and orientation in thin films (~100 nm) of a triblock copolymer, PPEPEG, was studied. The morphology of the thin film can be visualized as consisting of PMMA as the major phase in which domains of vertically oriented triblock copolymers are dispersed with PEG groups facing the air-film interface. The molecular and supramolecular structure of a series of well-defined fully conjugated poly(2,5- diakyl-p-phenyleneethynylene)s, PPE, in toluene has been studied in the sol state and in the gel state by surface tension and photoluminescence measurements. Poly (2,6[4- phenyl quinoline]), I, and poly (2,6[p-phenylene] 4- phenyl quinoline), II, were synthesized by the self- condensation of 5-acetyl-2-aminobezophenone and 4-amino- 4 '-acetyl-3-benzoyl biphenyl, respectively. They were soluble in acidic solvents. The fluorescent properties of I and II were investigated as a function of concentration in HCOOH, CCl2HCOOH, and CH 3SO3H solutions. Silica sol was used as nanoscale glue to prepare composite gels. (Abstract shortened by UMI.)

Fabrication strategy for amphiphilic microcapsules with narrow size distribution by premix membrane emulsification.

PubMed

Wei, Yi; Wang, Yuxia; Wang, Lianyan; Hao, Dongxia; Ma, Guanghui

2011-10-15

Amphiphilic co-polymer, which can maintain the stability of proteins and increase the protein loading efficiency, is considered as an exploring-worthy biodegrade polymer for drug delivery. However, amphiphilic microcapsules prepared by conventional methods, such like mechanical stirring and spray-drying methods, exhibit broad size distributions due to its hydrophilic sequences, leading to poor reproducibility. In this study, we employed poly(monomethoxypoly ethylene glycol-co-D,L-lactide) (mPEG-PLA, PELA), one of common amphiphilic polymers, as model to focus on investigating the process parameters and mechanisms to prepare PELA microcapsules with narrow size distribution and regular sphericity by combining premix membrane emulsification and double emulsion technique. The coarse double emulsion with broad size distribution was repeatedly pressed through Shirasu Porous Glass (SPG) membrane with relatively high pressure to form the fine emulsion with narrow size distribution. Then, the microcapsules with narrow size distribution can be obtained by solvent extraction method. It was found that it was more difficult to obtain PELA microcapsules with narrow size distribution and smooth surface due to its amphiphilic property, compared with the cases of PLA and PLGA. The smooth surface morphology was found to be related to several factors including internal water phase with less volume, slower stirring rate during solidification and using ethyl acetate as oil phase. It was also found that mass ratio of hydrophilic mPEG, stabilizer PVA concentration in external water phase and transmembrane pressure played important role on the distribution of microcapsules size. The suitable preparation conditions were determined as follows: for the membrane with pore size of 2.8 μm, the mass ratio of PLA/mPEG was 19:1, volume ratio of W(1)/O was 1:10 and O/W(2) was 1:5, PVA concentration (w/v) was 1.0%, magnetic stirring rate during solidification was 60 rpm and 300 kPa was chosen as transmembrane pressure. There was a linear relationship between the diameter of microcapsules and the pore size of the membranes. Finally, by manipulating the process parameters, PELA microcapsules with narrow size distributions (coefficient of variation was less than 15%), smooth morphology and various sizes, were obtained. Most importantly, the key factors affecting fabrication have been revealed and mechanisms were illustrated in detail, which would shed light on the research of amphiphilic polymer formulation. Copyright © 2011 Elsevier B.V. All rights reserved.

Application effects of coated urea and urease and nitrification inhibitors on ammonia and greenhouse gas emissions from a subtropical cotton field of the Mississippi delta region.

PubMed

Tian, Zhou; Wang, Jim J; Liu, Shuai; Zhang, Zengqiang; Dodla, Syam K; Myers, Gerald

2015-11-15

Nitrogen (N) fertilization affects both ammonia (NH3) and greenhouse gas (GHG) emissions that have implications in air quality and global warming potential. Different cropping systems practice varying N fertilizations. The aim of this study was to investigate the effects of applications of polymer-coated urea and urea treated with N process inhibitors: NBPT [N-(n-butyl)thiophosphoric triamide], urease inhibitor, and DCD [Dicyandiamide], nitrification inhibitor, on NH3 and GHG emissions from a cotton production system in the Mississippi delta region. A two-year field experiment consisting of five treatments including the Check (unfertilized), urea, polymer-coated urea (ESN), urea+NBPT, and urea+DCD was conducted over 2013 and 2014 in a Cancienne loam (Fine-silty, mixed, superactive, nonacid, hyperthermic Fluvaquentic Epiaquepts). Ammonia and GHG samples were collected using active and passive chamber methods, respectively, and characterized. The results showed that the N loss to the atmosphere following urea-N application was dominated by a significantly higher emission of N2O-N than NH3-N and the most N2O-N and NH3-N emissions were during the first 30-50 days. Among different N treatments compared to regular urea, NBPT was the most effective in reducing NH3-N volatilization (by 58-63%), whereas DCD the most significant in mitigating N2O-N emissions (by 75%). Polymer-coated urea (ESN) and NBPT also significantly reduced N2O-N losses (both by 52%) over urea. The emission factors (EFs) for urea, ESN, urea-NBPT, urea+DCD were 1.9%, 1.0%, 0.2%, 0.8% for NH3-N, and 8.3%, 3.4%, 3.9%, 1.0% for N2O-N, respectively. There were no significant effects of different N treatments on CO2-C and CH4-C fluxes. Overall both of these N stabilizers and polymer-coated urea could be used as a mitigation strategy for reducing N2O emission while urease inhibitor NBPT for reducing NH3 emission in the subtropical cotton production system of the Mississippi delta region. Copyright © 2015 Elsevier B.V. All rights reserved.

Improved physicochemical characteristics of felodipine solid dispersion particles by supercritical anti-solvent precipitation process.

PubMed

Won, Dong-Han; Kim, Min-Soo; Lee, Sibeum; Park, Jeong-Sook; Hwang, Sung-Joo

2005-09-14

Solid dispersions of felodipine were formulated with HPMC and surfactants by the conventional solvent evaporation (CSE) and supercritical anti-solvent precipitation (SAS) methods. The solid dispersion particles were characterized by particle size, zeta potential, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), powder X-ray diffraction (XRD), solubility and dissolution studies. The effects of the drug/polymer ratio and surfactants on the solubility of felodipine were also studied. The mean particle size of the solid dispersions was 200-250 nm; these had a relatively regular spherical shape with a narrow size distribution. The particle size of the solid dispersions from the CSE method increased at 1 h after dispersed in distilled water. However, the particle sizes of solid dispersions from the SAS process were maintained for 6 h due to the increased solubility of felodipine. The physical state of felodipine changed from crystalline to amorphous during the CSE and SAS processes, confirmed by DSC/XRD data. The equilibrium solubility of the felodipine solid dispersion prepared by the SAS process was 1.5-20 microg/ml, while the maximum solubility was 35-110 microg/ml. Moreover, the solubility of felodipine increased with decreasing drug/polymer ratio or increasing HCO-60 content. The solid dispersions from the SAS process showed a high dissolution rate of over 90% within 2 h. The SAS process system may be used to enhance solubility or to produce oral dosage forms with high dissolution rate.

Nanomaterial datasets to advance tomography in scanning transmission electron microscopy

DOE PAGES

Levin, Barnaby D. A.; Padgett, Elliot; Chen, Chien-Chun; ...

2016-06-07

Electron tomography in materials science has flourished with the demand to characterize nanoscale materials in three dimensions (3D). Access to experimental data is vital for developing and validating reconstruction methods that improve resolution and reduce radiation dose requirements. This work presents five high-quality scanning transmission electron microscope (STEM) tomography datasets in order to address the critical need for open access data in this field. The datasets represent the current limits of experimental technique, are of high quality, and contain materials with structural complexity. Included are tomographic series of a hyperbranched Co 2 P nanocrystal, platinum nanoparticles on a carbonmore » nanofibre imaged over the complete 180° tilt range, a platinum nanoparticle and a tungsten needle both imaged at atomic resolution by equal slope tomography, and a through-focal tilt series of PtCu nanoparticles. A volumetric reconstruction from every dataset is provided for comparison and development of post-processing and visualization techniques. Researchers interested in creating novel data processing and reconstruction algorithms will now have access to state of the art experimental test data.« less

Phylogeny of fungal hemoglobins and expression analysis of the Aspergillus oryzae flavohemoglobin gene fhbA during hyphal growth.

PubMed

te Biesebeke, Rob; Levasseur, Anthony; Boussier, Amandine; Record, Eric; van den Hondel, Cees A M J J; Punt, Peter J

2010-01-01

The fhbA genes encoding putative flavohemoglobins (FHb) from Aspergillus niger and Aspergillus oryzae were isolated. Comparison of the deduced amino acid sequence of the A. niger fhbA gene and other putative filamentous fungal FHb-encoding genes to that of Ralstonia eutropha shows an overall conserved gene structure and completely conserved catalytic amino acids. Several yeasts and filamentous fungi, including both Aspergillus species have been found to contain a small FHb gene family mostly consisting of two family members. Based on these sequences the evolutionary history of the fungal FHb family was reconstructed. The isolated fhbA genes from A. oryzae and A. niger belong to a phylogenetic group, which exclusively contains Aspergillus genes. Different experimental approaches show that fhbA transcript levels appear during active hyphal growth. Moreover, in a pclA-disrupted strain with a hyperbranching growth phenotype, the transcript levels of the fhbA gene were 2–5 times higher compared to the wild-type. These results suggest that FHb from filamentous fungi have a function that is correlated to the hyphal growth phenotype.

Photocrosslinkable biodegradable elastomers based on cinnamate-functionalized polyesters.

PubMed

Zhu, Congcong; Kustra, Stephen R; Bettinger, Christopher J

2013-07-01

Synthetic biodegradable elastomers are an emerging class of materials that play a critical role in supporting innovations in bioabsorbable medical implants. This paper describes the synthesis and characterization of poly(glycerol-co-sebacate)-cinnamate (PGS-CinA), a biodegradable elastomer based on hyperbranched polyesters derivatized with pendant cinnamate groups. PGS-CinA can be prepared via photodimerization in the absence of photoinitiators using monomers that are found in common foods. The resulting network exhibits a Young's modulus of 50.5-152.1kPa and a projected in vitro degradation half-life time between 90 and 140days. PGS-CinA elastomers are intrinsically cell-adherent and support rapid proliferation of fibroblasts. Spreading and proliferation of fibroblasts are loosely governed by the substrate stiffness within the range of Young's moduli in PGS-CinA networks that were prepared. The thermo-mechanical properties, biodegradability and intrinsic support of cell attachment and proliferation suggest that PGS-CinA networks are broadly applicable for use in next generation bioabsorable materials including temporary medical devices and scaffolds for soft tissue engineering. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Functional characterization of the recombinant antimicrobial peptide Trx-Ace-AMP1 and its application on the control of tomato early blight disease.

PubMed

Wu, Yin; He, Yue; Ge, Xiaochun

2011-05-01

Ace-AMP1 is a potent antifungal peptide found in onion (Allium cepa) seeds with sequence similarity to plant lipid transfer proteins. Transgenic plants over-expressing Ace-AMP1 gene have enhanced disease resistance to some fungal pathogens. However, mass production in heterologous systems and in vitro application of this peptide have not been reported. In this study, Ace-AMP1 was highly expressed in a prokaryotic Escherichia coli system as a fusion protein. The purified protein inhibited the growth of many plant fungal pathogens, especially Alternaria solani, Fusarium oxysporum f. sp. vasinfectum, and Verticillium dahliae. The inhibitory effect was accompanied by hyphal hyperbranching for V. dahliae but not for F. oxysporum f. sp. vasinfectum and A. solani, suggesting that the mode of action of Ace-AMP1 on different fungi might be different. Application of Ace-AMP1 on tomato leaves showed that the recombinant protein conferred strong resistance to the tomato pathogen A. solani and could be used as an effective fungicide.

The small GTPase Rac and the p21-activated kinase Cla4 in Claviceps purpurea: interaction and impact on polarity, development and pathogenicity.

PubMed

Rolke, Yvonne; Tudzynski, Paul

2008-04-01

Claviceps purpurea, the ergot fungus, is a highly specialized pathogen of grasses; its colonization of host ovarian tissue requires an extended period of strictly polarized, oriented growth towards the vascular tissue. To understand this process, we study the role of signalling factors affecting polarity and differentiation. We showed that the small GTPase Cdc42 is involved in polarity, sporulation and in planta growth in C. purpurea. Here we present evidence that the GTPase Rac has an even stronger and, in some aspects, inverse impact on growth and development: Deltarac mutants form coralline-like colonies, show hyper-branching, loss of polarity, sporulation and ability to penetrate. Functional analyses and yeast two-hybrid studies prove that the p21-activated kinase Cla4 is a major downstream partner of Rac. Phosphorylation assays of MAP kinases and expression studies of genes encoding reactive oxygen species (ROS)-scavenging and -generating enzymes indicate a function of Rac and Cla4 in fungal ROS homoeostasis which could contribute to their drastic impact on differentiation.

Photocatalytic activity of CdS and Ag2S quantum dots deposited on poly(amidoamine) functionalized carbon nanotubes

PubMed Central

Neelgund, Gururaj M.; Oki, Aderemi

2011-01-01

Two novel ternary nanocatalysts, f-MWCNTs-CdS and f-MWCNTs-Ag2S were successfully constructed by covalent grafting of fourth generation (G4) hyperbranched, crosslinked poly(amidoamine) (PAMAM) to carboxylated multi-walled carbon nanotubes (MWCNTs-COOH) and subsequent deposition of CdS or Ag2S quantum dots (QDs). The structural transformation, surface potential, and morphology of functionalized MWCNTs (f-MWCNTs) and nanocatalysts were characterized by UV-vis spectrophotometer, Fourier transform infrared spectroscopy, powder X-ray diffraction, Raman spectroscopy, thermogravimetric analysis, scanning electron microscopy and energy dispersive spectroscopy. Transmission electron microscopy reveals the effective anchoring of QDs on f-MWCNTs. The catalytic activity of nanocatalysts was evaluated by photodegradation of methyl orange under illumination of UV light. The coupling of MWCNTs, PAMAM and CdS or Ag2S QDs significantly enhanced the catalytic efficiency of nanocatalysts. The rate constants for degradation of methyl orange in presence of nanocatalysts were calculated using the Langmuir-Hinshelwood model. Overall, the excellence in photodegradation was accomplished by hybridizing f-MWCNTs with CdS or Ag2S PMID:22267895

Nanomaterial datasets to advance tomography in scanning transmission electron microscopy.

PubMed

Levin, Barnaby D A; Padgett, Elliot; Chen, Chien-Chun; Scott, M C; Xu, Rui; Theis, Wolfgang; Jiang, Yi; Yang, Yongsoo; Ophus, Colin; Zhang, Haitao; Ha, Don-Hyung; Wang, Deli; Yu, Yingchao; Abruña, Hector D; Robinson, Richard D; Ercius, Peter; Kourkoutis, Lena F; Miao, Jianwei; Muller, David A; Hovden, Robert

2016-06-07

Electron tomography in materials science has flourished with the demand to characterize nanoscale materials in three dimensions (3D). Access to experimental data is vital for developing and validating reconstruction methods that improve resolution and reduce radiation dose requirements. This work presents five high-quality scanning transmission electron microscope (STEM) tomography datasets in order to address the critical need for open access data in this field. The datasets represent the current limits of experimental technique, are of high quality, and contain materials with structural complexity. Included are tomographic series of a hyperbranched Co2P nanocrystal, platinum nanoparticles on a carbon nanofibre imaged over the complete 180° tilt range, a platinum nanoparticle and a tungsten needle both imaged at atomic resolution by equal slope tomography, and a through-focal tilt series of PtCu nanoparticles. A volumetric reconstruction from every dataset is provided for comparison and development of post-processing and visualization techniques. Researchers interested in creating novel data processing and reconstruction algorithms will now have access to state of the art experimental test data.

Regulation of Neurospora crassa cell wall remodeling via the cot-1 pathway is mediated by gul-1.

PubMed

Herold, Inbal; Yarden, Oded

2017-02-01

Impairment of the Neurospora crassa Nuclear DBF2-related kinase-encoding gene cot-1 results in pleiotropic effects, including abnormally thick hyphal cell walls and septa. An increase in the transcript abundance of genes encoding chitin and glucan synthases and the chitinase gh18-5, but not the cell wall integrity pathway transcription factor rlm-1, accompany the phenotypic changes observed. Deletion of chs-5 or chs-7 in a cot-1 background results in a reduction of hyperbranching frequency characteristic of the cot-1 parent. gul-1 (a homologue of the yeast SSD1 gene) encodes a translational regulator and has been shown to partially suppress cot-1. We demonstrate that the high expression levels of the cell wall remodeling genes analyzed is curbed, and reaches near wild type levels, when gul-1 is inactivated. This is accompanied by morphological changes that include reduced cell wall thickness and restoration of normal chitin levels. We conclude that gul-1 is a mediator of cell wall remodeling within the cot-1 pathway.

Nanomaterial datasets to advance tomography in scanning transmission electron microscopy

PubMed Central

Levin, Barnaby D.A.; Padgett, Elliot; Chen, Chien-Chun; Scott, M.C.; Xu, Rui; Theis, Wolfgang; Jiang, Yi; Yang, Yongsoo; Ophus, Colin; Zhang, Haitao; Ha, Don-Hyung; Wang, Deli; Yu, Yingchao; Abruña, Hector D.; Robinson, Richard D.; Ercius, Peter; Kourkoutis, Lena F.; Miao, Jianwei; Muller, David A.; Hovden, Robert

2016-01-01

Electron tomography in materials science has flourished with the demand to characterize nanoscale materials in three dimensions (3D). Access to experimental data is vital for developing and validating reconstruction methods that improve resolution and reduce radiation dose requirements. This work presents five high-quality scanning transmission electron microscope (STEM) tomography datasets in order to address the critical need for open access data in this field. The datasets represent the current limits of experimental technique, are of high quality, and contain materials with structural complexity. Included are tomographic series of a hyperbranched Co2P nanocrystal, platinum nanoparticles on a carbon nanofibre imaged over the complete 180° tilt range, a platinum nanoparticle and a tungsten needle both imaged at atomic resolution by equal slope tomography, and a through-focal tilt series of PtCu nanoparticles. A volumetric reconstruction from every dataset is provided for comparison and development of post-processing and visualization techniques. Researchers interested in creating novel data processing and reconstruction algorithms will now have access to state of the art experimental test data. PMID:27272459

High selectivity of colorimetric detection of p-nitrophenol based on Ag nanoclusters

NASA Astrophysics Data System (ADS)

Qu, Fei; Chen, Ping; Zhu, Shuyun; You, Jinmao

2017-01-01

Ag nanoclusters (Ag NCs) templated by hyperbranched polyethyleneimine (PEI) with different terminal groups and molecular weights had been developed as a special optical sensor for detecting p-nitrophenol (p-NP). When adding p-NP into Ag NCs, an obvious color change from pale yellow to deep yellow could be observed by naked eyes, accompanying with an apparent red-shift of absorption peak, and the reason was attributed to the formation of oxygen anion of p-NP based on the transfer of H+ from p-NP to amine groups of PEI. The molecular weights of template would greatly affect the sensitivity of p-NP. Ag NCs capped by PEI terminated ethylenediamine (EDA) possessed better sensitivity than other Ag NCs, showing good linear range from 5 to 140 μM with the limit of detection as low as 1.28 μM. Most importantly, this present system displayed high selectivity toward p-NP even in the presence of other nitrophenols and nitrotoluenes. This reliable method had been successfully applied for the detection of p-NP in real water and soil samples.

Composites of multi-walled carbon nanotubes with polypropylene and thermoplastic olefin blends prepared by melt compounding

NASA Astrophysics Data System (ADS)

Petrie, Kyle G.

Composites of multi-walled carbon nanotubes (MWCNTs) with polypropylene (PP) and thermoplastic olefins (TPOs) were prepared by melt compounding. Two non-covalent functionalization methods were employed to improve nanotube dispersion and the resulting composite properties are reported. The first functionalization approach involved partial coating of the surface of the nanotubes with a hyperbranched polyethylene (HBPE). MWCNT functionalization with HBPE was only moderately successful in breaking up the large aggregates that formed upon melt mixing with PP. In spite of the formation of large aggregates, the samples were conductive above a percolation threshold of 7.3 wt%. MWCNT functionalization did not disrupt the electrical conductivity of the nanotubes. The composite strength was improved with addition of nanotubes, but ductility was severely compromised because of the existence of aggregates. The second method involved PP matrix functionalization with aromatic moieties capable of pi-pi interaction with MWCNT sidewalls. Various microscopy techniques revealed the addition of only 25 wt% of PP-g-pyridine (Py) to the neat PP was capable of drastically reducing nanotube aggregate size and amount. Raman spectroscopy confirmed improved polymer/nanotube interaction with the PP-g-Py matrix. Electrical percolation threshold was obtained at a MWCNT loading of approximately 1.2 wt%. Electrical conductivity on the order of 10 -2 S/m was achieved, suggesting possible use in semi-conducting applications. Composite strength was improved upon addition of MWCNTs. The matrix functionalization with Py resulted in a significant improvement in composite ductility when filled with MWCNTs in comparison to its maleic anhydride (MA) counterpart. Preliminary investigations suggest that the use of alternating current (AC) electric fields may be effective in aligning nanotubes in PP to reduce the filler loading required for electrical percolation. Composites containing MWCNT within PP/ethylene-octene copolymer (EOC) blends were prepared. Microscopy revealed that MWCNTs localized preferentially in the EOC phase. This was explained by the tendency of the system to minimize interfacial energy when the MWCNTs reside in the thermodynamically preferential phase. A kinetic approach, which involved pre-mixing the MWCNTs with PP and adding the EOC phase subsequently was attempted to monitor the migration of MWCNTs. MWCNTs began to migrate after two minutes of melt mixing with the EOC. The PP-g-Py matrix functionalization appears to slightly delay the migration. A reduction in electrical percolation threshold to 0.5 wt% MWCNTs was achieved with a co-continuous blend morphology, consisting of a 50/50 by weight ratio of PP and EOC.

Synthesis of arborescent model polymer structures by living carbocationic polymerization for structure-property studies

NASA Astrophysics Data System (ADS)

Dos Santos Freire, Lucas

Polyisobutylene is fully saturated, therefore exhibits outstanding chemical, oxidative and thermal stability,1 which makes it ideally suitable as a model to study mechanical and viscoelastic properties of elastomers, and to correlate properties with structure. The main objective of this dissertation was to develop a fundamental understanding of the mechanism of the synthesis of arborescent (hyperbranched) polyisobutylene (arbPIB) by inimer-type (initiator-monomer) living carbocationic polymerization. The strategy for the effective synthesis of arbPIBs consists of copolymerizing the 4-(2-methoxyisopropyl)styrene (IUPAC name: p-vinylcumyl methyl ether) (IB) via controlled/living carbocationic polymerization using TiCl4 coinitiator. In situ FTIR monitoring showed that the self-condensing vinyl polymerization (SCVP) of MeOIM is possible, and that when copolymerizing MeOIM and IB, a nearly alternating structure and multiple end groups are obtained. arbPIB was synthesized and the repeatability of the polymerization was demonstrated. It was found that higher branching was obtained with increasing [MeOIM] and that branching did not further increase if additional IB was added after the MeOIM had reacted completely. No evident changes were observed when switching solvents from Hx/MeCl to a MeCHx/MeCl mixture. Branching parameters showed that arbPIBs have a behavior between polydisperse stars and polycondensates with the number of branches increasing linearly with molecular weight. Novel arbPIB-based block copolymers (TPEs) were synthesized and it was found that copolymers with low Tg short end blocks and less than 5 mol% of a second monomer exhibit thermoplastic elastomeric properties. The materials were strongly reinforced when compounded with carbon black. arbPIB-b-PS are prospective biomaterials and the establishment of reliable methods for evaluating their short and long term properties is a subject of great importance. A dynamic fatigue testing methodology was developed for small, soft rubbery specimens that can be implanted into small animals and re-tested after explantation. Higher ultimate tensile strength and lower elongation at break were measured on microdumbbells than on standard dumbbells. Fatigue testing microdumbbells induced higher stresses at the same strain rate, thus presenting the worst case scenario and being appropriate for fatigue tests. The fatigue limit of linear polystyrene-b-polyisobutylene- b-polystyrene (SIBS) and analogous arbPIB- b-PS samples were determined by using stepwise increasing strain tests developed for fatigue analysis. The presence of branching and a broader molecular weight distribution arbPIB-b-PS led to better mechanical stability and higher fatigue limit than in analogous linear SIBS samples.

Four plant defensins from an indigenous South African Brassicaceae species display divergent activities against two test pathogens despite high sequence similarity in the encoding genes

PubMed Central

2011-01-01

Background Plant defensins are an important component of the innate defence system of plants where they form protective antimicrobial barriers between tissue types of plant organs as well as around seeds. These peptides also have other activities that are important for agricultural applications as well as the medical sector. Amongst the numerous plant peptides isolated from a variety of plant species, a significant number of promising defensins have been isolated from Brassicaceae species. Here we report on the isolation and characterization of four defensins from Heliophila coronopifolia, a native South African Brassicaceae species. Results Four defensin genes (Hc-AFP1-4) were isolated with a homology based PCR strategy. Analysis of the deduced amino acid sequences showed that the peptides were 72% similar and grouped closest to defensins isolated from other Brassicaceae species. The Hc-AFP1 and 3 peptides shared high homology (94%) and formed a unique grouping in the Brassicaceae defensins, whereas Hc-AFP2 and 4 formed a second homology grouping with defensins from Arabidopsis and Raphanus. Homology modelling showed that the few amino acids that differed between the four peptides had an effect on the surface properties of the defensins, specifically in the alpha-helix and the loop connecting the second and third beta-strands. These areas are implicated in determining differential activities of defensins. Comparing the activities after recombinant production of the peptides, Hc-AFP2 and 4 had IC50 values of 5-20 μg ml-1 against two test pathogens, whereas Hc-AFP1 and 3 were less active. The activity against Botrytis cinerea was associated with membrane permeabilization, hyper-branching, biomass reduction and even lytic activity. In contrast, only Hc-AFP2 and 4 caused membrane permeabilization and severe hyper-branching against the wilting pathogen Fusarium solani, while Hc-AFP1 and 3 had a mild morphogenetic effect on the fungus, without any indication of membrane activity. The peptides have a tissue-specific expression pattern since differential gene expression was observed in the native host. Hc-AFP1 and 3 expressed in mature leaves, stems and flowers, whereas Hc-AFP2 and 4 exclusively expressed in seedpods and seeds. Conclusions Two novel Brassicaceae defensin sequences were isolated amongst a group of four defensin encoding genes from the indigenous South African plant H. coronopifolia. All four peptides were active against two test pathogens, but displayed differential activities and modes of action. The expression patterns of the peptide encoding genes suggest a role in protecting either vegetative or reproductive structures in the native host against pathogen attack, or roles in unknown developmental and physiological processes in these tissues, as was shown with other defensins. PMID:22032337

Hardware/Software Data Acquisition System for Real Time Cell Temperature Monitoring in Air-Cooled Polymer Electrolyte Fuel Cells

PubMed Central

Bartolucci, Veronica

2017-01-01

This work presents a hardware/software data acquisition system developed for monitoring the temperature in real time of the cells in Air-Cooled Polymer Electrolyte Fuel Cells (AC-PEFC). These fuel cells are of great interest because they can carry out, in a single operation, the processes of oxidation and refrigeration. This allows reduction of weight, volume, cost and complexity of the control system in the AC-PEFC. In this type of PEFC (and in general in any PEFC), the reliable monitoring of temperature along the entire surface of the stack is fundamental, since a suitable temperature and a regular distribution thereof, are key for a better performance of the stack and a longer lifetime under the best operating conditions. The developed data acquisition (DAQ) system can perform non-intrusive temperature measurements of each individual cell of an AC-PEFC stack of any power (from watts to kilowatts). The stack power is related to the temperature gradient; i.e., a higher power corresponds to a higher stack surface, and consequently higher temperature difference between the coldest and the hottest point. The developed DAQ system has been implemented with the low-cost open-source platform Arduino, and it is completed with a modular virtual instrument that has been developed using NI LabVIEW. Temperature vs time evolution of all the cells of an AC-PEFC both together and individually can be registered and supervised. The paper explains comprehensively the developed DAQ system together with experimental results that demonstrate the suitability of the system. PMID:28698497