Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization

PubMed Central

2016-01-01

The need for polymers for high-end applications, coupled with the desire to mimic nature’s macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design. PMID:26795940

Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization.

PubMed

Olsén, Peter; Odelius, Karin; Albertsson, Ann-Christine

2016-03-14

The need for polymers for high-end applications, coupled with the desire to mimic nature's macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design.

Post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon lithography [A post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon polymerization

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

Oakdale, James S.; Ye, Jianchao; Smith, William L.

Here, two photon polymerization (TPP) is a precise, reliable, and increasingly popular technique for rapid prototyping of micro-scale parts with sub-micron resolution. The materials of choice underlying this process are predominately acrylic resins cross-linked via free-radical polymerization. Due to the nature of the printing process, the derived parts are only partially cured and the corresponding mechanical properties, i.e. modulus and ultimate strength, are lower than if the material were cross-linked to the maximum extent. Herein, post-print curing via UV-driven radical generation, is demonstrated to increase the overall degree of cross-linking of low density, TPP-derived structures.

Post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon lithography [A post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon polymerization

DOE PAGES

Oakdale, James S.; Ye, Jianchao; Smith, William L.; ...

2016-11-28

Here, two photon polymerization (TPP) is a precise, reliable, and increasingly popular technique for rapid prototyping of micro-scale parts with sub-micron resolution. The materials of choice underlying this process are predominately acrylic resins cross-linked via free-radical polymerization. Due to the nature of the printing process, the derived parts are only partially cured and the corresponding mechanical properties, i.e. modulus and ultimate strength, are lower than if the material were cross-linked to the maximum extent. Herein, post-print curing via UV-driven radical generation, is demonstrated to increase the overall degree of cross-linking of low density, TPP-derived structures.

Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons

PubMed Central

2017-01-01

The precise morphology of nanoscale gaps between noble-metal nanostructures controls their resonant wavelengths. Here we show photocatalytic plasmon-induced polymerization can locally enlarge the gap size and tune the plasmon resonances. We demonstrate light-directed programmable tuning of plasmons can be self-limiting. Selective control of polymer growth around individual plasmonic nanoparticles is achieved, with simultaneous real-time monitoring of the polymerization process in situ using dark-field spectroscopy. Even without initiators present, we show light-triggered chain growth of various monomers, implying plasmon initiation of free radicals via hot-electron transfer to monomers at the Au surface. This concept not only provides a programmable way to fine-tune plasmons for many applications but also provides a window on polymer chemistry at the sub-nanoscale. PMID:28670601

Bioactive Polymeric Materials for Tissue Repair

PubMed Central

Bienek, Diane R.; Tutak, Wojtek; Skrtic, Drago

2017-01-01

Bioactive polymeric materials based on calcium phosphates have tremendous appeal for hard tissue repair because of their well-documented biocompatibility. Amorphous calcium phosphate (ACP)-based ones additionally protect against unwanted demineralization and actively support regeneration of hard tissue minerals. Our group has been investigating the structure/composition/property relationships of ACP polymeric composites for the last two decades. Here, we present ACP’s dispersion in a polymer matrix and the fine-tuning of the resin affects the physicochemical, mechanical, and biological properties of ACP polymeric composites. These studies illustrate how the filler/resin interface and monomer/polymer molecular structure affect the material’s critical properties, such as ion release and mechanical strength. We also present evidence of the remineralization efficacy of ACP composites when exposed to accelerated acidic challenges representative of oral environment conditions. The utility of ACP has recently been extended to include airbrushing as a platform technology for fabrication of nanofiber scaffolds. These studies, focused on assessing the feasibility of incorporating ACP into various polymer fibers, also included the release kinetics of bioactive calcium and phosphate ions from nanofibers and evaluate the biorelevance of the polymeric ACP fiber networks. We also discuss the potential for future integration of the existing ACP scaffolds into therapeutic delivery systems used in the precision medicine field. PMID:28134776

Effect of shape on bone cement polymerization time in knee joint replacement surgery

PubMed Central

Yoon, Jung-Ro; Ko, Young-Rok; Shin, Young-Soo

2018-01-01

Abstract Background: Although many factors are known to influence the polymerization time of bone cement, it remains unclear which bone cement shape predicts the precise polymerization time. The purpose of this study was to investigate whether different cement shapes influenced polymerization time and to identify the relationship between cement shape and ambient operating theater temperature, relative humidity, and equilibration time. Methods: Samples were gathered prospectively from 237 patients undergoing primary total knee arthroplasty. The cement components were made into 2 different shapes: lump and pan. The time at which no macroscopic indentation of both cement models was possible was recorded as the polymerization time. Results: There was no significant difference between hand mixing (lump shape: 789.3 ± 128.4 seconds, P = .591; pan shape: 899.3 ± 152.2 seconds, P = .584) and vacuum mixing (lump shape: 780.2 ± 131.1 seconds, P = .591; pan shape: 909.9 ± 143.3 seconds, P = .584) in terms of polymerization time. Conversely, the polymerization time was significantly shorter for Antibiotic Simplex (lump shape: 757.4 ± 114.9 seconds, P = .001; pan shape: 879.5 ± 125.0 seconds, P < .001) when compared with Palacos R+G (lump shape: 829.0 ± 139.3 seconds, P = .001; pan shape: 942.9 ± 172.0 seconds, P < .001). Polymerization time was also significantly longer (P < .001) for the pan shape model (904 ± 148.0 seconds) when compared with the lump shape model (785.2 ± 129.4 seconds). In addition, the polymerization time decreased with increasing temperature (lump shape: R2 = 0.334, P < .001; pan shape: R2 = 0.375, P < .001), humidity (lump shape: R2 = 0.091, P < .001; pan shape: R2 = 0.106, P < .001), and equilibration time (lump shape: R2 = 0.073, P < .001; pan shape: R2 = 0.044, P < .001). Conclusions: The polymerization time was equally affected by temperature, relative humidity, and equilibration time regardless of bone cement shape. Furthermore, the pan shape model better reflected the cement polymerization time between implant and bone compared with the lump shape model. The current findings suggest that, clinically, constant pressure with the knee in <45° of flexion needs to be applied until remaining pan shaped cement is completely polymerized. PMID:29703041

Polymerization stresses in low-shrinkage dental resin composites measured by crack analysis.

PubMed

Yamamoto, Takatsugu; Kubota, Yu; Momoi, Yasuko; Ferracane, Jack L

2012-09-01

The objective of this study was to compare several dental restoratives currently advertised as low-shrinkage composites (Clearfil Majesty Posterior, Kalore, Reflexions XLS Dentin and Venus Diamond) with a microfill composite (Heliomolar) in terms of polymerization stress, polymerization shrinkage and elastic modulus. Cracks were made at several distances from the edge of a precision cavity in a soda-lime glass disk. The composites were placed into the cavity and lengths of the cracks were measured before and after light curing. Polymerization stresses generated in the glass at 2 and 10 min after the irradiation were calculated from the crack lengths and K(c) of the glass. Polymerization shrinkage and elastic modulus of the composites also were measured at 2 and 10 min after irradiation using a video-imaging device and a nanoindenter, respectively. The data were statistically analyzed by ANOVAs and Tukey's test (p<0.05). The stress was significantly affected by composite brand, distance and time. The stress was directly proportional to time and inversely proportional to distance from the edge of the cavity. Clearfil Majesty Posterior demonstrated the highest stress and it resulted in the fracture of the glass at 2 min. Venus Diamond and Heliomolar exhibited the greatest shrinkage at both times. The elastic moduli of Clearfil Majesty Posterior and Reflexions XLS Dentin were greatest at 2 and 10 min, respectively. Among the four low-shrinkage composites, two demonstrated significantly reduced polymerization stress compared to Heliomolar, which has previously been shown in in vitro tests to generate low curing stress. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Molecularly imprinted polymeric stir bar: Preparation and application for the determination of naftopidil in plasma and urine samples.

PubMed

Peng, Jun; Xiao, Deli; He, Hua; Zhao, Hongyan; Wang, Cuixia; Shi, Tian; Shi, Kexin

2016-01-01

In this study, molecularly imprinting technology and stir bar absorption technology were combined to develop a microextraction approach based on a molecularly imprinted polymeric stir bar. The molecularly imprinted polymer stir bar has a high performance, is specific, economical, and simple to prepare. The obtained naftopidil-imprinted polymer-coated bars could simultaneously agitate and adsorb naftopidil in the sample solution. The ratio of template/monomer/cross-linker and conditions of template removal were optimized to prepare a stir bar with highly efficient adsorption. Fourier transform infrared spectroscopy, scanning electron microscopy, selectivity, and extraction capacity experiments showed that the molecularly imprinted polymer stir bar was prepared successfully. To utilize the molecularly imprinted polymer stir bar for the determination of naftopidil in complex body fluid matrices, the extraction time, stirring speed, eluent, and elution time were optimized. The limits of detection of naftopidil in plasma and urine sample were 7.5 and 4.0 ng/mL, respectively, and the recoveries were in the range of 90-112%. The within-run precision and between-run precision were acceptable (relative standard deviation <7%). These data demonstrated that the molecularly imprinted polymeric stir bar based microextraction with high-performance liquid chromatography was a convenient, rapid, efficient, and specific method for the precise determination of trace naftopidil in clinical analysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing

DOEpatents

Anderson, Brian L.

2017-01-24

A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.

Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing

DOEpatents

Anderson, Brian L.

2015-05-26

A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.

Click polymerization for the synthesis of reduction-responsive polymeric prodrug

NASA Astrophysics Data System (ADS)

Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

2018-05-01

Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

3D mapping of polymerization shrinkage using X-ray micro-computed tomography to predict microleakage.

PubMed

Sun, Jirun; Eidelman, Naomi; Lin-Gibson, Sheng

2009-03-01

The objectives of this study were to (1) demonstrate X-ray micro-computed tomography (microCT) as a viable method for determining the polymerization shrinkage and microleakage on the same sample accurately and non-destructively, and (2) investigate the effect of sample geometry (e.g., C-factor and volume) on polymerization shrinkage and microleakage. Composites placed in a series of model cavities of controlled C-factors and volumes were imaged using microCT to determine their precise location and volume before and after photopolymerization. Shrinkage was calculated by comparing the volume of composites before and after polymerization and leakage was predicted based on gap formation between composites and cavity walls as a function of position. Dye penetration experiments were used to validate microCT results. The degree of conversion (DC) of composites measured using FTIR microspectroscopy in reflectance mode was nearly identical for composites filled in all model cavity geometries. The shrinkage of composites calculated based on microCT results was statistically identical regardless of sample geometry. Microleakage, on the other hand, was highly dependent on the C-factor as well as the composite volume, with higher C-factors and larger volumes leading to a greater probability of microleakage. Spatial distribution of microleakage determined by microCT agreed well with results determined by dye penetration. microCT has proven to be a powerful technique in quantifying polymerization shrinkage and corresponding microleakage for clinically relevant cavity geometries.

Synthesis and Characterization of Stimuli-Responsive Star-Like Polypept(o)ides: Introducing Biodegradable PeptoStars.

PubMed

Holm, Regina; Weber, Benjamin; Heller, Philipp; Klinker, Kristina; Westmeier, Dana; Docter, Dominic; Stauber, Roland H; Barz, Matthias

2017-06-01

Star-like polymers are one of the smallest systems in the class of core crosslinked polymeric nanoparticles. This article reports on a versatile, straightforward synthesis of three-arm star-like polypept(o)ide (polysarcosine-block-polylysine) polymers, which are designed to be either stable or degradable at elevated levels of glutathione. Polypept(o)ides are a recently introduced class of polymers combining the stealth-like properties of the polypeptoid polysarcosine with the functionality of polypeptides, thus enabling the synthesis of materials completely based on endogenous amino acids. The star-like homo and block copolymers are synthesized by living nucleophilic ring opening polymerization of the corresponding N-carboxyanhydrides (NCAs) yielding polymeric stars with precise control over the degree of polymerization (X n = 25, 50, 100), Poisson-like molecular weight distributions, and low dispersities (Đ = 1.06-1.15). Star-like polypept(o)ides display a hydrodynamic radius of 5 nm (μ 2 < 0.05) as determined by dynamic light scattering (DLS). While star-like polysarcosines and polypept(o)ides based on disulfide containing initiators are stable in solution, degradation occurs at 100 × 10 -3 m glutathione concentration. The disulfide cleavage yields the respective polymeric arms, which possess Poisson-like molecular weight distributions and low dispersities (Đ = 1.05-1.12). Initial cellular uptake and toxicity studies reveal that PeptoStars are well tolerated by HeLa, HEK 293, and DC 2.4 cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chain Reaction Polymerization.

ERIC Educational Resources Information Center

McGrath, James E.

1981-01-01

The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

From precision polymers to complex materials and systems

NASA Astrophysics Data System (ADS)

Lutz, Jean-François; Lehn, Jean-Marie; Meijer, E. W.; Matyjaszewski, Krzysztof

2016-05-01

Complex chemical systems, such as living biological matter, are highly organized structures based on discrete molecules in constant dynamic interactions. These natural materials can evolve and adapt to their environment. By contrast, man-made materials exhibit simpler properties. In this Review, we highlight that most of the necessary elements for the development of more complex synthetic matter are available today. Using modern strategies, such as controlled radical polymerizations, supramolecular polymerizations or stepwise synthesis, polymers with precisely controlled molecular structures can be synthesized. Moreover, such tailored polymers can be folded or self-assembled into defined nanoscale morphologies. These self-organized macromolecular objects can be at thermal equilibrium or can be driven out of equilibrium. Recently, in the latter case, interesting dynamic materials have been developed. However, this is just a start, and more complex adaptive materials are anticipated.

Multifunctional polymeric nanoconstructs for biomedical applications (Conference Presentation)

NASA Astrophysics Data System (ADS)

Decuzzi, Paolo

2016-09-01

Multifunctional nanoconstructs are particle-based nano-scale systems designed for the `smart' delivery of therapeutic and imaging agents. The Laboratory of Nanotechnology for Precision Medicine at the Italian Institute of Technology synthesizes polymeric nanoconstructs with different sizes, ranging from a few tens of nanometers to a few microns; shapes, including spherical, cubical and discoidal; surface properties, with positive, negative, neutral coatings; and mechanical stiffness, varying from that of cells to rigid, inorganic materials, such as iron oxide. These are the 4S parameters - size, shape, surface, stiffness - which can be precisely tuned in the synthesis process enabling disease- and patient-specific designs of multifunctional nanoconstructs. In this lecture, the application of these nanoconstructs to the detection and treatment of cancer lesions and cardiovascular diseases, such as thrombosis and atherosclerosis, is discussed. The contribution of the 4S parameters in modulating nanoconstruct sequestration by the mononuclear phagocyte system, organ specific accumulation, and blood longevity is also critically presented. These polymeric nanoconstructs can be loaded with a variety of therapeutic payloads - anti-cancer molecules (docetaxel, paclitaxel, doxorubicin), anti-inflammatory molecules (curcumin, diclofenac, celecoxib) and small biologicals (peptides, siRNAs, miRNAs); and imaging agents - optical probes; Gd and iron oxide nanoparticles for MR imaging; and radio-isotopes for Nuclear Imaging.

Radical-Mediated Enzymatic Polymerizations

PubMed Central

Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

2016-01-01

Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

21 CFR 177.2250 - Filters, microporous polymeric.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Filters, microporous polymeric. 177.2250 Section... Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in... liquid food. (a) Microporous polymeric filters consist of a suitably permeable, continuous, polymeric...

Photo-responsive polymeric micelles.

PubMed

Huang, Yu; Dong, Ruijiao; Zhu, Xinyuan; Yan, Deyue

2014-09-07

Photo-responsive polymeric micelles have received increasing attention in both academic and industrial fields due to their efficient photo-sensitive nature and unique nanostructure. In view of the photo-reaction mechanism, photo-responsive polymeric micelles can be divided into five major types: (1) photoisomerization polymeric micelles, (2) photo-induced rearrangement polymeric micelles, (3) photocleavage polymeric micelles, (4) photo-induced crosslinkable polymeric micelles, and (5) photo-induced energy conversion polymeric micelles. This review highlights the recent advances of photo-responsive polymeric micelles, including the design, synthesis and applications in various biomedical fields. Especially, the influence of different photo-reaction mechanisms on the morphology, structure and properties of the polymeric micelles is emphasized. Finally, the possible future directions and perspectives in this emerging area are briefly discussed.

Deterministic embedding of a single gold nanoparticle into polymeric microstructures by direct laser writing technique

NASA Astrophysics Data System (ADS)

Nguyen, Dam Thuy Trang; Pelissier, Aurélien; Montes, Kevin; Tong, Quang Cong; Ngo, Hoang Minh; Ledoux-Rak, Isabelle; Lai, Ngoc Diep

2016-04-01

We have precisely positioned and embedded a single gold nanoparticle (Au NP) into a desired polymeric photonic structure (PS) using a simple and low-cost technique called low one-photon absorption direct laser writing (LOPA DLW), with a two-step process: identification and fabrication. First, the position of the Au NP was identified with a precision of 20 nm by using DLW technique with ultralow excitation laser power (μW). This power did not induce the polymerization of the photoresist (SU8) due to its low absorption at the excitation wavelength (532 nm). Then, the structure containing the NP was fabricated by using the same DLW system with high excitation power (mW). Different 2D photonic structures have been fabricated, which contain a single Au NP at desired position. In particular, we obtained a microsphere instead of a micropillar at the position of the Au NP. The formation of such microsphere was explained by the thermal effect of the Au NP at the wavelength of 532 nm, which induced thermal polymerization of surrounding photoresist. The effect of the post-exposure bake on the quality of structures was taken into account, revealing a more efficient fabrication way by exploiting the local thermal effect of the laser. We studied further the influence of the NP size on the NP/PS coupling by investigating the fabrication and fluorescence measurement of Au NPs of different sizes: 10, 30, 50, 80, and 100 nm. The photon collection enhancements in each case were 12.9 +/- 2.5, 12.6 +/- 5.6, 3.9 +/- 2.7, 5.9 +/- 4.4, and 6.6 +/- 5.1 times, respectively. The gain in fluorescence could reach up to 36.6 times for 10-nm gold NPs.

MALDI MS-based Composition Analysis of the Polymerization Reaction of Toluene Diisocyanate (TDI) and Ethylene Glycol (EG).

PubMed

Ahn, Yeong Hee; Lee, Yeon Jung; Kim, Sung Ho

2015-01-01

This study describes an MS-based analysis method for monitoring changes in polymer composition during the polyaddition polymerization reaction of toluene diisocyanate (TDI) and ethylene glycol (EG). The polymerization was monitored as a function of reaction time using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF MS). The resulting series of polymer adducts terminated with various end-functional groups were precisely identified and the relative compositions of those series were estimated. A new MALDI MS data interpretation method was developed, consisting of a peak-resolving algorithm for overlapping peaks in MALDI MS spectra, a retrosynthetic analysis for the generation of reduced unit mass peaks, and a Gaussian fit-based selection of the most prominent polymer series among the reconstructed unit mass peaks. This method of data interpretation avoids errors originating from side reactions due to the presence of trace water in the reaction mixture or MALDI analysis. Quantitative changes in the relative compositions of the resulting polymer products were monitored as a function of reaction time. These results demonstrate that the mass data interpretation method described herein can be a powerful tool for estimating quantitative changes in the compositions of polymer products arising during a polymerization reaction.

Preparation of l-phenylalanine-imprinted solid-phase extraction sorbent by Pickering emulsion polymerization and the selective enrichment of l-phenylalanine from human urine.

PubMed

Li, Ji; Hu, Xiaoling; Guan, Ping; Zhang, Xiaoyan; Qian, Liwei; Zhang, Nan; Du, Chunbao; Song, Renyuan

2016-05-01

A novel l-phenylalanine molecularly imprinted solid-phase extraction sorbent was synthesized by the combination of Pickering emulsion polymerization and ion-pair dummy template imprinting. Compared to other polymerization methods, the molecularly imprinted polymers thus prepared exhibit a high specific surface, large pore diameter, and appropriate particle size. The key parameters for solid-phase extraction were optimized, and the result indicated that the molecularly imprinted polymer thus prepared exhibits a good recovery of 98.9% for l-phenylalanine. Under the optimized conditions of the procedure, an analytical method for l-phenylalanine was well established. By comparing the performance of the molecularly imprinted polymer and a commercial reverse-phase silica gel, the obtained molecularly imprinted polymer as an solid-phase extraction sorbent is more suitable, exhibiting high precision (relative standard deviation 3.2%, n = 4) and a low limit of detection (60.0 ± 1.9 nmol·L(-1) ) for the isolation of l-phenylalanine. Based on these results, the combination of the Pickering emulsion polymerization and ion-pair dummy template imprinting is effective for preparing selective solid-phase extraction sorbents for the separation of amino acids and organic acids from complex biological samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiation-induced polymerization of glass-forming systems. IV. Effect of the homogeneity of polymerization phase and polymer concentration on temperature dependence of initial polymerization rate

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

Kaetsu, I.; Ito, A.; Hayashi, K.

1973-06-01

The effect of homogeneity of polymerization phase and monomer concentration on the temperature dependence of initial polymerization rate was studied in the radiation-induced radical polymerization of binary systems consisting of glass-forming monomer and solvent. In the polymerization of a completely homogeneous system such as HEMA-propylene glycol, a maximum and a minimum in polymerization rates as a function of temperature, characteristic of the polymerization in glass-forming systems, were observed for all monomer concentrations. However, in the heterogeneous polymerization systems such as HEMA-triacetin and HEMAisoamyl acetate, maximum and minimum rates were observed in monomer-rich compositions but not at low monomer concentrations. Furthermore,more » in the HEMA-dioctyl phthalate polymerization system, which is extremely heterogeneous, no maximum and minimum rates were observed at any monomer concentration. The effect of conversion on the temperature dependence of polymerization rate in homogeneous bulk polymerization of HEMA and GMA was investigated. Maximum and minimum rates were observed clearly in conversions less than 10% in the case of HEMA and less than 50% in the case of GMA, but the maximum and minimum changed to a mere inflection in the curve at higher conversions. A similar effect of polymer concentration on the temperature dependence of polymerization rate in the GMA-poly(methyl methacrylate) system was also observed. It is deduced that the change in temperature dependence of polymerization rate is attributed to the decrease in contribution of mutual termination reaction of growing chain radicals to the polymerization rate. (auth)« less

Anionic polymerization of oxadiazole-containing 2-vinylpyridine by precisely tuning nucleophilicity and the polyelectrolyte characteristics of the resulting polymers

DOE PAGES

Goodwin, Andrew; Goodwin, Kimberly M.; Wang, Weiyu; ...

2016-09-01

Anionic polymerization is one of the most powerful techniques for preparation of well-defined polymers. However, this well-known and widely employed polymerization technique encounters major limitations for the polymerization of functional monomers containing heteroatoms. This work presents the anionic polymerization of 2-phenyl-5-(6-vinylpyridin-3-yl)-1,3,4-oxadiazole (VPyOzP), a heteroatom monomer that contains both oxadiazole and pyridine substituents within the same pendant group, using various initiating systems based on diphenylmethyl potassium (DPM-K) and triphenylmethyl potassium (TPM-K). Remarkably, well-defined poly(2-phenyl-5-(6-vinylpyridin-3-yl)-1,3,4-oxadiazole) (PVPyOzP) polymers having predicted molecular weights (MW) ranging from 2200 to 21 100 g/mol and polydispersity indices (PDI) ranging from 1.11 to 1.15 were prepared with TPM-K,more » without any additional additives, at –78 °C. The effect of temperature on the polymerization of PVPyOzP was also studied at –78, –45, 0, and 25 °C, and it was observed that increasing the polymerization temperature produced materials with unpredictable MW’s and broader molecular weight distributions. Furthermore, the nucleophilicity of PVPyOzP was investigated through copolymerization with methyl methacrylate and acrylonitrile, where only living poly(methyl methacrylate) (PMMA) prepared by DPM-K/VPPy and in the absence of additives such as lithium chloride (LiCl) and diethyl zinc (ZnEt 2) could be used to produce the well-defined block copolymer of PMMA-b-PVPyOzP. It was also demonstrated by sequential monomer addition that the nucleophilicity of living PVPyOzP is located between that of living PMMA and polyacrylonitrile (PAN). Here, the pyridine moiety of the pendant group also allowed for quaternization and produced PQVPyOzP homopolymer using methyl iodide (CH 3I) and bis(trifluoromethylsulfonyl)amide [Tf 2N –]. The resulting charged polymer and counterion complexes were manipulated and investigated for potential use as membranes for carbon dioxide (CO 2) capture.« less

Anionic polymerization of oxadiazole-containing 2-vinylpyridine by precisely tuning nucleophilicity and the polyelectrolyte characteristics of the resulting polymers

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

Goodwin, Andrew; Goodwin, Kimberly M.; Wang, Weiyu

Anionic polymerization is one of the most powerful techniques for preparation of well-defined polymers. However, this well-known and widely employed polymerization technique encounters major limitations for the polymerization of functional monomers containing heteroatoms. This work presents the anionic polymerization of 2-phenyl-5-(6-vinylpyridin-3-yl)-1,3,4-oxadiazole (VPyOzP), a heteroatom monomer that contains both oxadiazole and pyridine substituents within the same pendant group, using various initiating systems based on diphenylmethyl potassium (DPM-K) and triphenylmethyl potassium (TPM-K). Remarkably, well-defined poly(2-phenyl-5-(6-vinylpyridin-3-yl)-1,3,4-oxadiazole) (PVPyOzP) polymers having predicted molecular weights (MW) ranging from 2200 to 21 100 g/mol and polydispersity indices (PDI) ranging from 1.11 to 1.15 were prepared with TPM-K,more » without any additional additives, at –78 °C. The effect of temperature on the polymerization of PVPyOzP was also studied at –78, –45, 0, and 25 °C, and it was observed that increasing the polymerization temperature produced materials with unpredictable MW’s and broader molecular weight distributions. Furthermore, the nucleophilicity of PVPyOzP was investigated through copolymerization with methyl methacrylate and acrylonitrile, where only living poly(methyl methacrylate) (PMMA) prepared by DPM-K/VPPy and in the absence of additives such as lithium chloride (LiCl) and diethyl zinc (ZnEt 2) could be used to produce the well-defined block copolymer of PMMA-b-PVPyOzP. It was also demonstrated by sequential monomer addition that the nucleophilicity of living PVPyOzP is located between that of living PMMA and polyacrylonitrile (PAN). Here, the pyridine moiety of the pendant group also allowed for quaternization and produced PQVPyOzP homopolymer using methyl iodide (CH 3I) and bis(trifluoromethylsulfonyl)amide [Tf 2N –]. The resulting charged polymer and counterion complexes were manipulated and investigated for potential use as membranes for carbon dioxide (CO 2) capture.« less

PEG Molecular Net-Cloth Grafted on Polymeric Substrates and Its Bio-Merits

NASA Astrophysics Data System (ADS)

Zhao, Changwen; Lin, Zhifeng; Yin, Huabing; Ma, Yuhong; Xu, Fujian; Yang, Wantai

2014-05-01

Polymer brushes and hydrogels are sensitive to the environment, which can cause uncontrolled variations on their performance. Herein, for the first time, we report a non-swelling ``PEG molecular net-cloth'' on a solid surface, fabricated using a novel ``visible light induced surface controlled graft cross-linking polymerization'' (VSCGCP) technique. Via this method, we show that 1) the 3D-network structure of the net-cloth can be precisely modulated and its thickness controlled; 2) the PEG net-cloth has excellent resistance to non-specific protein adsorption and cell adhesion; 3) the mild polymerization conditions (i.e. visible light and room temperature) provided an ideal tool for in situ encapsulation of delicate biomolecules such as enzymes; 4) the successive grafting of reactive three-dimensional patterns on the PEG net-cloth enables the creation of protein microarrays with high signal to noise ratio. Importantly, this strategy is applicable to any C-H containing surface, and can be easily tailored for a broad range of applications.

Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High-Tg Polymeric Materials.

PubMed

Holmberg, Angela L; Reno, Kaleigh H; Nguyen, Ngoc A; Wool, Richard P; Epps, Thomas H

2016-05-17

As viable precursors to a diverse array of macromolecules, biomass-derived compounds must impart wide-ranging and precisely controllable properties to polymers. Herein, we report the synthesis and subsequent reversible addition-fragmentation chain-transfer polymerization of a new monomer, syringyl methacrylate (SM, 2,6-dimethoxyphenyl methacrylate), that can facilitate widespread property manipulations in macromolecules. Homopolymers and heteropolymers synthesized from SM and related monomers have broadly tunable and highly controllable glass transition temperatures ranging from 114 to 205 °C and zero-shear viscosities ranging from ∼0.2 kPa·s to ∼17,000 kPa·s at 220 °C, with consistent thermal stabilities. The tailorability of these properties is facilitated by the controlled polymerization kinetics of SM and the fact that one vs two o -methoxy groups negligibly affect monomer reactivity. Moreover, syringol, the precursor to SM, is an abundant component of depolymerized hardwood (e.g., oak) and graminaceous (e.g., switchgrass) lignins, making SM a potentially sustainable and low-cost candidate for tailoring macromolecular properties.

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.

Organocatalyzed atom transfer radical polymerization driven by visible light.

PubMed

Theriot, Jordan C; Lim, Chern-Hooi; Yang, Haishen; Ryan, Matthew D; Musgrave, Charles B; Miyake, Garret M

2016-05-27

Atom transfer radical polymerization (ATRP) has become one of the most implemented methods for polymer synthesis, owing to impressive control over polymer composition and associated properties. However, contamination of the polymer by the metal catalyst remains a major limitation. Organic ATRP photoredox catalysts have been sought to address this difficult challenge but have not achieved the precision performance of metal catalysts. Here, we introduce diaryl dihydrophenazines, identified through computationally directed discovery, as a class of strongly reducing photoredox catalysts. These catalysts achieve high initiator efficiencies through activation by visible light to synthesize polymers with tunable molecular weights and low dispersities. Copyright © 2016, American Association for the Advancement of Science.

Bifunctional Organic Polymeric Catalysts with a Tunable Acid-Base Distance and Framework Flexibility

PubMed Central

Chen, Huanhui; Wang, Yanan; Wang, Qunlong; Li, Junhui; Yang, Shiqi; Zhu, Zhirong

2014-01-01

Acid-base bifunctional organic polymeric catalysts were synthesized with tunable structures. we demonstrated two synthesis approaches for structural fine-tune. In the first case, the framework flexibility was tuned by changing the ratio of rigid blocks to flexible blocks within the polymer framework. In the second case, we precisely adjusted the acid-base distance by distributing basic monomers to be adjacent to acidic monomers, and by changing the chain length of acidic monomers. In a standard test reaction for the aldol condensation of 4-nitrobenzaldehyde with acetone, the catalysts showed good reusability upon recycling and maintained relatively high conversion percentage. PMID:25267260

An NMR relaxometry and gravimetric study of gelatin-free aqueous polyacrylamide dosimeters

NASA Astrophysics Data System (ADS)

Babic, Steven; Schreiner, L. John

2006-09-01

In conformal radiation therapy, a high dose of radiation is given to a target volume to increase the probability of cure, and care is taken to minimize the dose to surrounding healthy tissue. The techniques used to achieve this are very complicated and the precise verification of the resulting three-dimensional (3D) dose distribution is required. Polyacrylamide gelatin (PAG) dosimeters with magnetic resonance imaging and optical computed tomography scanning provide the required 3D dosimetry with high spatial resolution. Many basic studies have characterized these chemical dosimeters that polymerize under irradiation. However, the investigation of the fundamental properties of the radiation-induced polymerization in PAG dosimeters is complicated by the presence of the background gelatin matrix. In this work, a gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters has been developed. Experiments were performed on gelatin-free dosimeters, named aqueous polyacrylamide (APA) dosimeters, containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide. The APA dosimeters were prepared with four different total monomer concentrations (2, 4, 6 and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all four dosimeters, show a continuous degree of polymerization over the dose range of 0-25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of crosslinked polymer formed at each dose. This model can be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

An NMR relaxometry and gravimetric study of gelatin-free aqueous polyacrylamide dosimeters.

PubMed

Babic, Steven; Schreiner, L John

2006-09-07

In conformal radiation therapy, a high dose of radiation is given to a target volume to increase the probability of cure, and care is taken to minimize the dose to surrounding healthy tissue. The techniques used to achieve this are very complicated and the precise verification of the resulting three-dimensional (3D) dose distribution is required. Polyacrylamide gelatin (PAG) dosimeters with magnetic resonance imaging and optical computed tomography scanning provide the required 3D dosimetry with high spatial resolution. Many basic studies have characterized these chemical dosimeters that polymerize under irradiation. However, the investigation of the fundamental properties of the radiation-induced polymerization in PAG dosimeters is complicated by the presence of the background gelatin matrix. In this work, a gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters has been developed. Experiments were performed on gelatin-free dosimeters, named aqueous polyacrylamide (APA) dosimeters, containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide. The APA dosimeters were prepared with four different total monomer concentrations (2, 4, 6 and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all four dosimeters, show a continuous degree of polymerization over the dose range of 0-25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of crosslinked polymer formed at each dose. This model can be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

Simultaneous Enhancements of Conductivity and Stability for Anion Exchange Membranes (AEMs) through Precise Structure Design

PubMed Central

Ran, Jin; Wu, Liang; Wei, Bing; Chen, Yaoyao; Xu, Tongwen

2014-01-01

Polymeric materials as anion exchange membranes (AEMs) play an essential role in the field of energy and environment. The achievement of high performance AEMs by the precise manipulation of macromolecular architecture remains a daunting challenge. Herein, we firstly report a novel rod-coil graft copolymer AEM, possessing rigid hydrophobic main chains and soft hydrophilic graft chains. The low graft density, which can alleviate the adverse influences of ioinc graft chains on the main chains, was obtained by using the living polymerization technique. Consequently, the grafted ionic groups which result in the degradation of polymer backbone was decreased to a small degree. Moreover, the relatively long graft chains induced the nanophase separation between the hydrophobic polymer chains and hydrophilic graft chains, which creates a convinient pathway for high hydroxide ion mobility. Such an accurate molecular design simultaneously improves the hydroxide ion conductivity and alkaline stability as well as dimensional stability. PMID:25255843

Simultaneous Enhancements of Conductivity and Stability for Anion Exchange Membranes (AEMs) through Precise Structure Design

NASA Astrophysics Data System (ADS)

Ran, Jin; Wu, Liang; Wei, Bing; Chen, Yaoyao; Xu, Tongwen

2014-09-01

Polymeric materials as anion exchange membranes (AEMs) play an essential role in the field of energy and environment. The achievement of high performance AEMs by the precise manipulation of macromolecular architecture remains a daunting challenge. Herein, we firstly report a novel rod-coil graft copolymer AEM, possessing rigid hydrophobic main chains and soft hydrophilic graft chains. The low graft density, which can alleviate the adverse influences of ioinc graft chains on the main chains, was obtained by using the living polymerization technique. Consequently, the grafted ionic groups which result in the degradation of polymer backbone was decreased to a small degree. Moreover, the relatively long graft chains induced the nanophase separation between the hydrophobic polymer chains and hydrophilic graft chains, which creates a convinient pathway for high hydroxide ion mobility. Such an accurate molecular design simultaneously improves the hydroxide ion conductivity and alkaline stability as well as dimensional stability.

Sequence-controlled methacrylic multiblock copolymers via sulfur-free RAFT emulsion polymerization

NASA Astrophysics Data System (ADS)

Engelis, Nikolaos G.; Anastasaki, Athina; Nurumbetov, Gabit; Truong, Nghia P.; Nikolaou, Vasiliki; Shegiwal, Ataulla; Whittaker, Michael R.; Davis, Thomas P.; Haddleton, David M.

2017-02-01

Translating the precise monomer sequence control achieved in nature over macromolecular structure (for example, DNA) to whole synthetic systems has been limited due to the lack of efficient synthetic methodologies. So far, chemists have only been able to synthesize monomer sequence-controlled macromolecules by means of complex, time-consuming and iterative chemical strategies such as solid-state Merrifield-type approaches or molecularly dissolved solution-phase systems. Here, we report a rapid and quantitative synthesis of sequence-controlled multiblock polymers in discrete stable nanoscale compartments via an emulsion polymerization approach in which a vinyl-terminated macromolecule is used as an efficient chain-transfer agent. This approach is environmentally friendly, fully translatable to industry and thus represents a significant advance in the development of complex macromolecule synthesis, where a high level of molecular precision or monomer sequence control confers potential for molecular targeting, recognition and biocatalysis, as well as molecular information storage.

An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation.

PubMed

Huang, Feng; Lv, Yisheng; Wang, Liquan; Xu, Pengxiang; Lin, Jiaping; Lin, Shaoliang

2016-08-14

Polymerization-induced self-assembly is a one-pot route to produce concentrated dispersions of block copolymer nano-objects. Herein, dissipative particle dynamics simulations with a reaction model were employed to investigate the behaviors of polymerization-induced self-assembly. The polymerization kinetics in the polymerization-induced self-assembly were analyzed by comparing with solution polymerization. It was found that the polymerization rate enhances in the initial stage and decreases in the later stage. In addition, the effects of polymerization rate, length of macromolecular initiators, and concentration on the aggregate morphologies and formation pathway were studied. The polymerization rate and the length of the macromolecular initiators are found to have a marked influence on the pathway of the aggregate formations and the final structures. Morphology diagrams were mapped correspondingly. A comparison between simulation results and experimental findings is also made and an agreement is shown. This work can enrich our knowledge about polymerization-induced self-assembly.

Partially degradable fibers and microvascular materials formed from the fibers

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

Dong, Hefei; Pety, Stephen J.; Sottos, Nancy R.

A partially degradable polymeric fiber includes a thermally degradable polymeric core and a coating surrounding at least a portion of the core. The thermally degradable polymeric core includes a polymeric matrix including a poly(hydroxyalkanoate), and a metal selected from the group consisting of an alkali earth metal and a transition metal, in the core polymeric matrix. The concentration of the metal in the polymeric matrix is at least 0.1 wt %. The partially degradable polymeric fiber may be used to form a microvascular system containing one or more microfluidic channels.

Reinforced self-assembly of donor-acceptor π-conjugated molecules to DNA templates by dipole-dipole interactions together with complementary hydrogen bonding interactions for biomimetics.

PubMed

Yang, Wanggui; Chen, Yali; Wong, Man Shing; Lo, Pik Kwan

2012-10-08

One of the most important criteria for the successful DNA-templated polymerization to generate fully synthetic biomimetic polymers is to design the complementary structural monomers, which assemble to the templates strongly and precisely before carrying polymerization. In this study, water-soluble, laterally thymine-substituted donor-acceptor π-conjugated molecules were designed and synthesized to self-assemble with complementary oligoadenines templates, dA(20) and dA(40), into stable and tubular assemblies through noncovalent interactions including π-π stacking, dipole-dipole interactions, and the complementary adenine-thymine (A-T) hydrogen-bonding. UV-vis, fluorescence, circular dichroism (CD), atomic force microscopy (AFM), and transmission electron microscopy (TEM) techniques were used to investigate the formation of highly robust nanofibrous structures. Our results have demonstrated for the first time that the dipole-dipole interactions are stronger and useful to reinforce the assembly of donor-acceptor π-conjugated molecules to DNA templates and the formation of the stable and robust supramolecular nanofibrous complexes together with the complementary hydrogen bonding interactions. This provides an initial step toward DNA-templated polymerization to create fully synthetic DNA-mimetic polymers for biotechnological applications. This study also presents an opportunity to precisely position donor-acceptor type molecules in a controlled manner and tailor-make advanced materials for various biotechnological applications.

Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

DOEpatents

Kanatzidis, Mercouri G; Katsoulidis, Alexandros

2015-03-10

Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

DOEpatents

Kanatzidis, Mercouri G.; Katsoulidis, Alexandros

2016-10-18

Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

Solution Synthesis of Atomically Precise Graphene Nanoribbons

NASA Astrophysics Data System (ADS)

Shekhirev, Mikhail; Sinitskii, Alexander

2017-05-01

Bottom-up fabrication of narrow strips of graphene, also known as graphene nanoribbons or GNRs, is an attractive way to open a bandgap in semimetallic graphene. In this chapter, we review recent progress in solution-based synthesis of GNRs with atomically precise structures. We discuss a variety of atomically precise GNRs and highlight theoretical and practical aspects of their structural design and solution synthesis. These GNRs are typically synthesized through a polymerization of rationally designed molecular precursors followed by a planarization through a cyclodehydrogenation reaction. We discuss various synthetic techniques for polymerization and planarization steps, possible approaches for chemical modification of GNRs, and compare the properties of GNRs that could be achieved by different synthetic methods. We also discuss the importance of the rational design of molecular precursors to avoid isomerization during the synthesis and achieve GNRs that have only one possible structure. Significant attention in this chapter is paid to the methods of material characterization of solution-synthesized GNRs. The chapter is concluded with the discussion of the most significant challenges in the field and the future outlook.

Investigation of Solution Polymerizations in Microgravity and 1 G

NASA Technical Reports Server (NTRS)

Kennedy, Alvin P.

1998-01-01

The in-situ dielectric spectra for the solution polymerization of polydiacetylene has been successfully measured. The results show a distinct difference between the response for the bulk solution and surface polymerization. It also shows a low frequency peak in the dissipation factor which is present in both the bulk and surface polymerizations. These features may prove to be significant indicators for important polymerization processes. Future studies will investigate the mechanisms responsible for these dielectric responses. This technique will eventually be used to monitor microgravity polymerizations and provide in-situ data on how microgravity affects solution polymerization.

Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates and Method Relating Thereto

NASA Technical Reports Server (NTRS)

Simpson, Joycelyn O. (Inventor); St.Claire, Terry L. (Inventor)

2002-01-01

A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared, This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches. adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrates; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates

NASA Technical Reports Server (NTRS)

Simpson, Joycely O. (Inventor); St.Clair, Terry L. (Inventor)

1999-01-01

A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers. acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors, in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors. weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 1000 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

Method of Making Thermally Stable, Piezoelectric and Proelectric Polymeric Substrates

NASA Technical Reports Server (NTRS)

Simpson, Joycelyn O. (Inventor); St.Clair, Terry L. (Inventor)

1999-01-01

A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium: applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

Dynamics and Regulation of RecA Polymerization and De-Polymerization on Double-Stranded DNA

PubMed Central

Muniyappa, Kalappa; Yan, Jie

2013-01-01

The RecA filament formed on double-stranded (ds) DNA is proposed to be a functional state analogous to that generated during the process of DNA strand exchange. RecA polymerization and de-polymerization on dsDNA is governed by multiple physiological factors. However, a comprehensive understanding of how these factors regulate the processes of polymerization and de-polymerization of RecA filament on dsDNA is still evolving. Here, we investigate the effects of temperature, pH, tensile force, and DNA ends (in particular ssDNA overhang) on the polymerization and de-polymerization dynamics of the E. coli RecA filament at a single-molecule level. Our results identified the optimal conditions that permitted spontaneous RecA nucleation and polymerization, as well as conditions that could maintain the stability of a preformed RecA filament. Further examination at a nano-meter spatial resolution, by stretching short DNA constructs, revealed a striking dynamic RecA polymerization and de-polymerization induced saw-tooth pattern in DNA extension fluctuation. In addition, we show that RecA does not polymerize on S-DNA, a recently identified novel base-paired elongated DNA structure that was previously proposed to be a possible binding substrate for RecA. Overall, our studies have helped to resolve several previous single-molecule studies that reported contradictory and inconsistent results on RecA nucleation, polymerization and stability. Furthermore, our findings also provide insights into the regulatory mechanisms of RecA filament formation and stability in vivo. PMID:23825559

Validation protocol of analytical procedures for quantification of drugs in polymeric systems for parenteral administration: dexamethasone phosphate disodium microparticles.

PubMed

Martín-Sabroso, Cristina; Tavares-Fernandes, Daniel Filipe; Espada-García, Juan Ignacio; Torres-Suárez, Ana Isabel

2013-12-15

In this work a protocol to validate analytical procedures for the quantification of drug substances formulated in polymeric systems that comprise both drug entrapped into the polymeric matrix (assay:content test) and drug released from the systems (assay:dissolution test) is developed. This protocol is applied to the validation two isocratic HPLC analytical procedures for the analysis of dexamethasone phosphate disodium microparticles for parenteral administration. Preparation of authentic samples and artificially "spiked" and "unspiked" samples is described. Specificity (ability to quantify dexamethasone phosphate disodium in presence of constituents of the dissolution medium and other microparticle constituents), linearity, accuracy and precision are evaluated, in the range from 10 to 50 μg mL(-1) in the assay:content test procedure and from 0.25 to 10 μg mL(-1) in the assay:dissolution test procedure. The robustness of the analytical method to extract drug from microparticles is also assessed. The validation protocol developed allows us to conclude that both analytical methods are suitable for their intended purpose, but the lack of proportionality of the assay:dissolution analytical method should be taken into account. The validation protocol designed in this work could be applied to the validation of any analytical procedure for the quantification of drugs formulated in controlled release polymeric microparticles. Copyright © 2013 Elsevier B.V. All rights reserved.

A New Vertebral Body Replacement Strategy Using Expandable Polymeric Cages

PubMed Central

Liu, Xifeng; Paulsen, Alex; Giambini, Hugo; Guo, Ji; Miller, A. Lee; Lin, Po-Chun; Yaszemski, Michael J.

2017-01-01

We have developed a novel polymeric expandable cage that can be delivered via a posterior-only surgical approach for the treatment of noncontained vertebral defects. This approach is less invasive than an anterior-only or combined approach and much more cost-effective than currently used expandable metal cages. The polymeric expandable cage is composed of oligo poly(ethylene glycol) fumarate (OPF), a hydrogel that has been previously shown to have excellent nerve and bone tissue biocompatibility. OPF hydrogel cages can expand to twice their original diameter and length within a surgical time frame following hydration. Modulation of parameters such as polymeric network crosslink density or the introduction of charge to the network allowed for precise expansion kinetics. To meet specific requirements due to size variations in patient vertebral bodies, we fabricated a series of molds with varied diameters and explored the expansion kinetics of the OPF cages. Results showed a stable expansion ratio of approximately twofold to the original size within 20 min, regardless of the absolute value of the cage size. Following implantation of a dried OPF cage into a noncontained vertebral defect and its in situ expansion with normal saline, other augmentation biomaterials, such as poly(propylene fumarate) (PPF), can be injected to the lumen of the OPF cage and allowed to crosslink in situ. The OPF/PPF composite scaffold can provide the necessary rigidity and stability to the augmented spine. PMID:27835935

Functional nanocomposites prepared by self-assembly and polymerization of diacetylene surfactants and silicic acid

NASA Technical Reports Server (NTRS)

Yang, Yi; Lu, Yunfeng; Lu, Mengcheng; Huang, Jinman; Haddad, Raid; Xomeritakis, George; Liu, Nanguo; Malanoski, Anthony P.; Sturmayr, Dietmar; Fan, Hongyou;

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.

Preparation of magnetic molecularly imprinted polymers by atom transfer radical polymerization for the rapid extraction of avermectin from fish samples.

PubMed

You, Xiaoxiao; Gao, Lei; Qin, Dongli; Chen, Ligang

2017-01-01

A novel and highly efficient approach to obtain magnetic molecularly imprinted polymers is described to detect avermectin in fish samples. The magnetic molecularly imprinted polymers were synthesized by surface imprinting polymerization using magnetic multiwalled carbon nanotubes as the support materials, atom transfer radical polymerization as the polymerization method, avermectin as template, acrylamide as functional monomer, and ethylene glycol dimethacrylate as crosslinker. The characteristics of the magnetic molecularly imprinted polymers were assessed by using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, vibrating sample magnetometry, X-ray diffraction, and thermogravimetric analysis. The binding characteristics of magnetic molecularly imprinted polymers were researched through isothermal adsorption experiment, kinetics adsorption experiment, and the selectivity experiment. Coupled with ultra high performance liquid chromatography and tandem mass spectrometry, the extraction conditions of the magnetic molecularly imprinted polymers as adsorbents for avermectin were investigated in detail. The recovery of avermectin was 84.2-97.0%, and the limit of detection was 0.075 μg/kg. Relative standard deviations of intra- and inter-day precisions were in the range of 1.7-2.9% and 3.4-5.6%, respectively. The results demonstrated that the extraction method not only has high selectivity and accuracy, but also is convenient for the determination of avermectin in fish samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-healing elastomer system

NASA Technical Reports Server (NTRS)

Sottos, Nancy R. (Inventor); Keller, Michael W. (Inventor); White, Scott R. (Inventor)

2009-01-01

A composite material includes an elastomer matrix, a set of first capsules containing a polymerizer, and a set of second capsules containing a corresponding activator for the polymerizer. The polymerizer may be a polymerizer for an elastomer. The composite material may be prepared by combining a first set of capsules containing a polymerizer, a second set of capsules containing a corresponding activator for the polymerizer, and a matrix precursor, and then solidifying the matrix precursor to form an elastomeric matrix.

[Effect of techniques of composite resin insertion and polymerization on microleakage and microhardness].

PubMed

Amaral, Cristiane Mariote; Castro, Ana Karina Barbieri Bedran de; Pimenta, Luiz André Freire; Ambrosano, Glaucia Maria Boni

2002-01-01

The aim of this study was to evaluate the influence of techniques of composite resin polymerization and insertion on microleakage and microhardness. One hundred and eighty class II cavities were prepared in bovine teeth and assigned to six groups: G1 - bulk filling + conventional polymerization; G2 - bucco-lingual increments + conventional polymerization; G3 - bulk filling + soft-start polymerization; G4 - bucco-lingual increments + soft-start polymerization; G5 - bulk filling + progressive polymerization; G6 - bucco-lingual increments + progressive polymerization. All cavities were restored with the Z100/Single Bond system (3M). After thermocycling, the samples were immersed in 2% methylene blue dye solution for 4 hours. Half of the samples were embedded in polystyrene resin, and Knoop microhardness was measured. The Kruskal-Wallis test did not reveal statistical differences (p > 0.05) between the polymerization and insertion techniques as to microleakage. Regarding microhardness, the two-way ANOVA and the Tukey test did not reveal statistical differences between the restorative techniques (p > 0.05), but progressive polymerization (G5 and G6) was associated with smaller Knoop microhardness values (p < 0.05): G = 144.11; G2 = 143.89; G3 = 141.14; G4 = 142.79; G5 = 132.15; G6 = 131.67. It was concluded that the evaluated polymerization and insertion techniques did not affect marginal microleakage, but a decrease in microhardness occurred when progressive polymerization was carried out.

Synthesis and polymerization of vinyl triazolium ionic liquids

DOEpatents

Luebke, David; Nulwala, Hunaid; Matyjaszewski, Krzysztof; Adzima, Brian

2018-05-15

Herein, we describe polymerized ionic liquids, demonstrate the synthesis of polymerized ionic liquids, and demonstrate the polymerization of triazolium monomers. One embodiment shows the polymeriazation of the triazolium monomers with bis(trifluoromethanesulfonyl)imide anions. In another embodiment we show the feasibility of copolymerizing with commodity monomers such as styrene using free radical polymerization techniques.

Equilibrium polymerization on the equivalent-neighbor lattice

NASA Technical Reports Server (NTRS)

Kaufman, Miron

1989-01-01

The equilibrium polymerization problem is solved exactly on the equivalent-neighbor lattice. The Flory-Huggins (Flory, 1986) entropy of mixing is exact for this lattice. The discrete version of the n-vector model is verified when n approaches 0 is equivalent to the equal reactivity polymerization process in the whole parameter space, including the polymerized phase. The polymerization processes for polymers satisfying the Schulz (1939) distribution exhibit nonuniversal critical behavior. A close analogy is found between the polymerization problem of index the Schulz r and the Bose-Einstein ideal gas in d = -2r dimensions, with the critical polymerization corresponding to the Bose-Einstein condensation.

Process for impregnating a concrete or cement body with a polymeric material

DOEpatents

Mattus, A.J.; Spence, R.D.

1988-05-04

A process for impregnating cementitious solids with polymeric materials by blending polymeric materials in a grout, allowing the grout to cure, and contacting the resulting solidified grout containing the polymeric materials with an organic mixture containing a monomer, a cross-linking agent and a catalyst. The mixture dissolves the polymerized particles and forms a channel for distributing the monomer throughout the network formed by the polymeric particles. The organic components are then cured to form a substantially water-impermeable mass.

Polymerization of Conducting Polymers Confined to Free Surfaces: A comparison of the Langmuir-Blodgett Polymerization of 3-Alkyl Pyrroles and 2- Alkyl Anilines

DTIC Science & Technology

1992-05-19

Confined to Free Surfaces: A Comparison of the Langmuir-Blodgett Polymerization of 3- Alkyl Pyrroles and 2- Alkyl Anilines Submitted for Publication in...Surfaces: A Comparison of the Langmuir Blodgett Polymerizations of 3- alkyl pyrroles and 2- alkyl anilines R. S. Duran and H.C. Zhou Dept. of Chemistry...polymerization reactions in more detail and compare them. To do this, the polymerization reactions were run under two conditions. In the first case

Process for impregnating a concrete or cement body with a polymeric material

DOEpatents

Mattus, Alfred J.; Spence, Roger D.

1989-01-01

A process for impregnating cementitious solids with polymeric materials by blending polymeric materials in a grout, allowing the grout to cure, and contacting the resulting solidified grout containing the polymeric materials with an organic mixture containing a monomer, a cross-linking agent and a catalyst. The mixture dissolves the polymerized particles and forms a channel for distributing the monomer throughout the network formed by the polymeric particles. The organic components are then cured to form a substantially water-impermeable mass.

Olefin metathesis for effective polymer healing via dynamic exchange of strong carbon-carbon bonds

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

Guan, Zhibin; Lu, Yixuan

A method of preparing a malleable and/or self-healing polymeric or composite material is provided. The method includes providing a polymeric or composite material comprising at least one alkene-containing polymer, combining the polymer with at least one homogeneous or heterogeneous transition metal olefin metathesis catalyst to form a polymeric or composite material, and performing an olefin metathesis reaction on the polymer so as to form reversible carbon-carbon double bonds in the polymer. Also provided is a method of healing a fractured surface of a polymeric material. The method includes bringing a fractured surface of a first polymeric material into contact withmore » a second polymeric material, and performing an olefin metathesis reaction in the presence of a transition metal olefin metathesis catalyst such that the first polymeric material forms reversible carbon-carbon double bonds with the second polymeric material. Compositions comprising malleable and/or self-healing polymeric or composite material are also provided.« less

Polymeric hydrogels for novel contact lens-based ophthalmic drug delivery systems: a review.

PubMed

Xinming, Li; Yingde, Cui; Lloyd, Andrew W; Mikhalovsky, Sergey V; Sandeman, Susan R; Howel, Carol A; Liewen, Liao

2008-04-01

Only about 5% of drugs administrated by eye drops are bioavailable, and currently eye drops account for more than 90% of all ophthalmic formulations. The bioavailability of ophthalmic drugs can be improved by a soft contact lens-based ophthalmic drug delivery system. Several polymeric hydrogels have been investigated for soft contact lens-based ophthalmic drug delivery systems: (i) polymeric hydrogels for conventional contact lens to absorb and release ophthalmic drugs; (ii) polymeric hydrogels for piggyback contact lens combining with a drug plate or drug solution; (iii) surface-modified polymeric hydrogels to immobilize drugs on the surface of contact lenses; (iv) polymeric hydrogels for inclusion of drugs in a colloidal structure dispersed in the lens; (v) ion ligand-containing polymeric hydrogels; (vi) molecularly imprinted polymeric hydrogels which provide the contact lens with a high affinity and selectivity for a given drug. Polymeric hydrogels for these contact lens-based ophthalmic drug delivery systems, their advantages and drawbacks are critically analyzed in this review.

Magnetic Levitation To Characterize the Kinetics of Free-Radical Polymerization.

PubMed

Ge, Shencheng; Semenov, Sergey N; Nagarkar, Amit A; Milette, Jonathan; Christodouleas, Dionysios C; Yuan, Li; Whitesides, George M

2017-12-27

This work describes the development of magnetic levitation (MagLev) to characterize the kinetics of free-radical polymerization of water-insoluble, low-molecular-weight monomers that show a large change in density upon polymerization. Maglev measures density, and certain classes of monomers show a large change in density when monomers covalently join in polymer chains. MagLev characterized both the thermal polymerization of methacrylate-based monomers and the photopolymerization of methyl methacrylate and made it possible to determine the orders of reaction and the Arrhenius activation energy of polymerization. MagLev also made it possible to monitor polymerization in the presence of solids (aramid fibers, and carbon fibers, and glass fibers). MagLev offers a new analytical technique to materials and polymer scientists that complements other methods (even those based on density, such as dilatometry), and will be useful in investigating polymerizations, evaluating inhibition of polymerizations, and studying polymerization in the presence of included solid materials (e.g., for composite materials).

Development and validation of an HPLC method to quantify camptothecin in polymeric nanocapsule suspensions.

PubMed

Granada, Andréa; Murakami, Fabio S; Sartori, Tatiane; Lemos-Senna, Elenara; Silva, Marcos A S

2008-01-01

A simple, rapid, and sensitive reversed-phase column high-performance liquid chromatographic method was developed and validated to quantify camptothecin (CPT) in polymeric nanocapsule suspensions. The chromatographic separation was performed on a Supelcosil LC-18 column (15 cm x 4.6 mm id, 5 microm) using a mobile phase consisting of methanol-10 mM KH2PO4 (60 + 40, v/v; pH 2.8) at a flow rate of 1.0 mL/min and ultraviolet detection at 254 nm. The calibration graph was linear from 0.5 to 3.0 microg/mL with a correlation coefficient of 0.9979, and the limit of quantitation was 0.35 microg/mL. The assay recovery ranged from 97.3 to 105.0%. The intraday and interday relative standard deviation values were < 5.0%. The validation results confirmed that the developed method is specific, linear, accurate, and precise for its intended use. The current method was successfully applied to the evaluation of CPT entrapment efficiency and drug content in polymeric nanocapsule suspensions during the early stage of formulation development.

Polymeric check valve with an elevated pedestal for precise cracking pressure in a glaucoma drainage device.

PubMed

Park, Chang-Ju; Yang, Dong-Seong; Cha, Jung-Joon; Lee, Jong-Hyun

2016-02-01

This paper presents the design, fabrication, and characterization of a polymeric micro check valve for a glaucoma drainage device (GDD) featuring the precise regulation of intraocular pressure (IOP) and effective aqueous humor turnover (AHT). The pedestal, slightly elevated by selective coating of a parylene C film, induces pre-stress in the thin valve membrane, which enhances the predictability of the cracking pressure of the GDD. The proposed GDD comprises a cannula and a normally closed polymeric micro check valve, which are made of PDMS, a biocompatible polymer, with three layers: top (cover), intermediate (thin valve membrane), and bottom (base plate). A feedback channel, located between the top and intermediate layers, prevents reverse flow by feeding the pressure of the outlet channel back to the thin valve membrane. To achieve a precise cracking pressure and sufficient drainage of humor for humans, the thicknesses of the valve membrane and parylene C film are designed to be 58 μm and 1 μm, respectively, which are confirmed using a COMSOL simulation. The experimental results show that the cracking pressure of the fabricated GDD lies within the range of normal IOP (1.33-2.67 kPa). The forward flow rate (drainage rate), 4.3 ± 0.9 μL/min at 2.5 kPa, is adequate to accommodate the rate of AHT in a normal human eye (2.4 ± 0.6 μL/min). The reverse flow was not observed when a hydrostatic pressure of up to 4 kPa was applied to the outlet and the feedback channel.

Polymer-Polymer Bilayer Actuator

NASA Technical Reports Server (NTRS)

Su, Ji (Inventor); Harrison, Joycelyn S. (Inventor); St.Clair, Terry L. (Inventor)

2003-01-01

A device for providing an electromechanical response includes two polymeric webs bonded to each other along their lengths. At least one polymeric web is activated upon application thereto of an electric field and exhibits electrostriction by rotation of polar graft moieties within the polymeric web. In one embodiment, one of the two polymeric webs in an active web upon application thereto of the electric field, and the other polymeric web is a non-active web upon application thereto of the electric field. In another embodiment, both of the two polymeric webs are capable of being active webs upon application thereto of the electric field. However, these two polymeric webs are alternately activated and non-activated by the electric field.

Versatile Tandem Ring-Opening/Ring-Closing Metathesis Polymerization: Strategies for Successful Polymerization of Challenging Monomers and Their Mechanistic Studies.

PubMed

Park, Hyeon; Kang, Eun-Hye; Müller, Laura; Choi, Tae-Lim

2016-02-24

Tandem ring-opening/ring-closing metathesis (RO/RCM) results in extremely fast living polymerization; however, according to previous reports, only monomers containing certain combinations of cycloalkenes, terminal alkynes, and nitrogen linkers successfully underwent tandem polymerization. After examining the polymerization pathways, we proposed that the relatively slow intramolecular cyclization might lead to competing side reactions such as intermolecular cross metathesis reactions to form inactive propagating species. Thus, we developed two strategies to enhance tandem polymerization efficiency. First, we modified monomer structures to accelerate tandem RO/RCM cyclization by enhancing the Thorpe-Ingold effect. This strategy increased the polymerization rate and suppressed the chain transfer reaction to achieve controlled polymerization, even for challenging syntheses of dendronized polymers. Alternatively, reducing the reaction concentration facilitated tandem polymerization, suggesting that the slow tandem RO/RCM cyclization step was the main reason for the previous failure. To broaden the monomer scope, we used monomers containing internal alkynes and observed that two different polymer units with different ring sizes were produced as a result of nonselective α-addition and β-addition on the internal alkynes. Thorough experiments with various monomers with internal alkynes suggested that steric and electronic effects of the alkyne substituents influenced alkyne addition selectivity and the polymerization reactivity. Further polymerization kinetics studies revealed that the rate-determining step of monomers containing certain internal alkynes was the six-membered cyclization step via β-addition, whereas that for other monomers was the conventional intermolecular propagation step, as observed in other chain-growth polymerizations. This conclusion agrees well with all those polymerization results and thus validates our strategies.

Method of Preparing Polymers with Low Melt Viscosity

NASA Technical Reports Server (NTRS)

Jensen, Brian J. (Inventor)

2001-01-01

This invention is an improvement in standard polymerizations procedures, i.e., addition-type and step-growth type polymerizations, wherein monomers are reacted to form a growing polymer chain. The improvement includes employing an effective amount of a trifunctional monomer (such as a trifunctional amine anhydride, or phenol) in the polymerization procedure to form a mixture of polymeric materials consisting of branced polymers, star-shaped polymers, and linear polymers. This mixture of polymeric materials has a lower melt temperature and a lower melt viscosity than corresponding linear polymeric materials of equivalent molecular weight.

Comparative Effect of Different Polymerization Techniques on the Flexural and Surface Properties of Acrylic Denture Bases.

PubMed

Gad, Mohammed M; Fouda, Shaimaa M; ArRejaie, Aws S; Al-Thobity, Ahmad M

2017-05-22

Polymerization techniques have been modified to improve physical and mechanical properties of polymethylmethacrylate (PMMA) denture base, as have the laboratory procedures that facilitate denture construction techniques. The purpose of the present study was to investigate the effect of autoclave polymerization on flexural strength, elastic modulus, surface roughness, and the hardness of PMMA denture base resins. Major Base and Vertex Implacryl heat-polymerized acrylic resins were used to fabricate 180 specimens. According to the polymerization technique, tested groups were divided into: group I (water-bath polymerization), group II (short autoclave polymerization cycle, 60°C for 30 minutes, then 130°C for 10 minutes), and group III (long autoclave polymerization cycle, 60°C for 30 minutes, then 130°C for 20 minutes). Each group was divided into two subgroups based on the materials used. Flexural strength and elastic modulus were determined by a three-point bending test. Surface roughness and hardness were evaluated with a profilometer and Vickers hardness (VH) test, respectively. One-way ANOVA and the Tukey-Kramer multiple-comparison test were used for results analysis, which were statistically significant at p ≤ 0.05. Autoclave polymerization showed a significant increase in flexural strength and hardness of the two resins (p < 0.05). The elastic modulus showed a significant increase in the major base resin, while a significant decrease was seen for Vertex Implacryl in all groups (p < 0.05); however, there was no significant difference in surface roughness between autoclave polymerization and water-bath polymerization (p > 0.05). Autoclave polymerization significantly increased the flexural properties and hardness of PMMA denture bases, while the surface roughness was within acceptable clinical limits. For a long autoclave polymerization cycle, it could be used as an alternative to water-bath polymerization. © 2017 by the American College of Prosthodontists.

3-Acetyl-11-keto-beta-boswellic acid loaded-polymeric nanomicelles for topical anti-inflammatory and anti-arthritic activity.

PubMed

Goel, Amit; Ahmad, Farhan Jalees; Singh, Raman Mohan; Singh, Gyanendra Nath

2010-02-01

The aim of this study was to develop 3-acetyl-11-keto-beta-boswellic acid (AKBA)-loaded polymeric nanomicelles for topical anti-inflammatory and anti-arthritic activity. Polymeric nanomicelles of AKBA were developed by a radical polymerization method using N-isopropylacrylamide, vinylpyrrolidone and acrylic acid. The polymeric nanomicelles obtained were characterized by Fourier transform infrared (FTIR), transmission electron microscopy (TEM) and dynamic light scattering (DLS). In-vitro and in-vivo evaluations of AKBA polymeric nanomicelles gel were carried out for enhanced skin permeability and anti-inflammatory and anti-arthritic activity. TEM and DLS results demonstrated that polymeric nanomicelles were spherical with a mean diameter approximately 45 nm. FTIR data indicated a weak interaction between polymer and AKBA in the encapsulated system. The release of drug in aqueous buffer (pH 7.4) from the polymeric nanomicelles was 23 and 55% after 2 and 8 h, respectively, indicating sustained release. In-vitro skin permeation studies through excised abdominal skin indicated a threefold increase in skin permeability compared with AKBA gel containing the same amount of AKBA as the AKBA polymeric nanomicelles gel. The AKBA polymeric nanomicelle gel showed significantly enhanced anti-inflammatory and anti-arthritic activity compared with the AKBA gel. This study suggested that AKBA polymeric nanomicelle gel significantly enhanced skin permeability, and anti-inflammatory and anti-arthritic activity.

Integration of CuAAC Polymerization and Controlled Radical Polymerization into Electron Transfer Mediated "Click-Radical" Concurrent Polymerization.

PubMed

Xue, Wentao; Wang, Jie; Wen, Ming; Chen, Gaojian; Zhang, Weidong

2017-03-01

The successful chain-growth copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization employing Cu(0)/pentamethyldiethylenetriamine (PMDETA) and alkyl halide as catalyst is first investigated by a combination of nuclear magnetic resonance, gel-permeation chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In addition, the electron transfer mediated "click-radical" concurrent polymerization utilizing Cu(0)/PMDETA as catalyst is successfully employed to generate well-defined copolymers, where controlled CuAAC polymerization of clickable ester monomer is progressed in the main chain acting as the polymer backbone, the controlled radical polymerization (CRP) of acrylic monomer is carried out in the side chain. Furthermore, it is found that there is strong collaborative effect and compatibility between CRP and CuAAC polymerization to improve the controllability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonlinear optical and conductive polymeric material

DOEpatents

Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

1992-05-19

A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl.sub.5 or W(CO).sub.6 /hv.

Nonlinear optical and conductive polymeric material

DOEpatents

Barton, T.J.; Ijadi-Maghsooodi, S; Yi Pang.

1993-10-19

A polymeric material is described which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl[sub 5] or W(CO)[sub 6].

Nonlinear optical and conductive polymeric material

DOEpatents

Barton, T.J.; Ijadi-Maghsoodi, S.; Pang, Y.

1992-05-19

A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl[sub 5] or W(CO)[sub 6]/hv.

Nonlinear optical and conductive polymeric material

DOEpatents

Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

1993-10-19

A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl.sub.5 or W(CO).sub.6 /hv.

Method of preparing water purification membranes. [polymerization of allyl amine as thin films in plasma discharge

NASA Technical Reports Server (NTRS)

Hollahan, J. R.; Wydeven, T. J., Jr. (Inventor)

1974-01-01

Allyl amine and chemically related compounds are polymerized as thin films in the presence of a plasma discharge. The monomer compound can be polymerized by itself or in the presence of an additive gas to promote polymerization and act as a carrier. The polymerized films thus produced show outstanding advantages when used as reverse osmosis membranes.

Effect of heat polymerization conditions and microwave on the flexural strength of polymethyl methacrylate

PubMed Central

Ozkir, Serhat Emre; Yilmaz, Burak; Unal, Server Mutluay; Culhaoglu, Ahmet; Kurkcuoglu, Isin

2018-01-01

Objective: The objective of this study is the effect of different heat polymerization conditions on the strength of polymethyl methacrylate (PMMA) resin base is unknown. Distinguishing one method that provides improved mechanical properties may be beneficial to the clinical success of complete and partial dentures and overdentures. The purpose of this study was to evaluate the effect of different polymerization methods on the flexural strength of a dental PMMA resin. Materials and Methods: Forty PMMA specimens (64 mm × 10 mm × 4 mm) were prepared with 4 different polymerization methods (n = 10); heat polymerization at 74°C for 9 h, at 100°C for 40 min, and with 620 kPa pressure at 100°C for 20 min. The remaining group of specimens was microwave polymerized at 180 W for 6 min. All specimens were thermocycled at 5°C and 55°C for 5000 times. Three-point flexure test was used to measure the flexural strength of specimens. One-way ANOVA and Tukey Honestly Significant Difference were applied to analyze the differences in flexural strengths (α = 0.05). Results: The flexural strength of heat-polymerized groups was similar. The flexural strength of microwave polymerized group was significantly different and lower than the other groups (P < 0.05). Conclusion: Polymerizing conventional heat-polymerizing PMMA resin with microwave energy resulted in a significant decrease in flexural strength. The results of this study suggest that clinicians may benefit from using heat polymerization when processing PMMA denture bases instead of microvawe polymerization when tested brand is used. PMID:29657535

Polymerization Reactor Engineering.

ERIC Educational Resources Information Center

Skaates, J. Michael

1987-01-01

Describes a polymerization reactor engineering course offered at Michigan Technological University which focuses on the design and operation of industrial polymerization reactors to achieve a desired degree of polymerization and molecular weight distribution. Provides a list of the course topics and assigned readings. (TW)

Dimensional change in complete dentures fabricated by injection molding and microwave processing.

PubMed

Keenan, Phillip L J; Radford, David R; Clark, Robert K F

2003-01-01

Acrylic resin complete dentures undergo dimensional changes during polymerization. Techniques with injection molding and polymerization and microwave polymerization are reported to reduce these changes and thereby improve clinical fit. These dimensional changes need to be quantified. The purpose of this study was to compare differences in dimensional changes of simulated maxillary complete dentures during polymerization and storage in water after injection molding and conventional polymerization, or microwave polymerization against a control of conventionally packed and polymerized simulated maxillary complete dentures. Forty identical maxillary denture bases were prepared in dental wax with anatomic teeth. They were invested and the wax eliminated from the molds. Ten specimens each were randomly assigned to 1 of 4 groups. Group 1 was compression molded and conventionally polymerized; group 2 was injection molded and conventionally polymerized (Success); group 3 was injection molded and microwave polymerized (Acron MC); and group 4 was injection molded and microwave polymerized (Microbase). Intermolar width and changes in vertical dimension of occlusion, were determined after polymerization and after storage in water for 28 days. Measurements in triplicate were made between points scribed on the second molar teeth with a traveling microscope (accurate to 0.005 mm). Vertical dimension of occlusion was measured between points scribed on the upper and lower members of an articulator by use of an internal micrometer (accurate to 0.05 mm). Data were analyzed by use of a 1-way analysis of variance with Tukey post-hoc contrasts (P <.05). Polymerization contractions (intermolar widths) for each group were: group 1, -0.24%; group 2, -0.27%; group 3, -0.35%; and group 4, -0.37%. The Microbase specimens had greater shrinkage than conventionally polymerized specimens, but there were no significant differences between the groups. All injection methods had less postpolymerization increase in vertical dimension of occlusion (0.63 to 0.41 mm) than the conventional Trevalon control (0.74 mm), but only group 4 was significantly different (P<.004). After storage in water for 28 days, all specimens increased in vertical dimension of occlusion (0.10% to 0.16%) from polymerization techniques, but there were no significant differences between groups. Within the limitations of this study, injection molding resulted in a slightly less increase of vertical dimension of occlusion than conventional polymerization techniques, the difference being significant for Microbase compared with the conventional Trevalon control.

Heterofunctional Glycopolypeptides by Combination of Thiol-Ene Chemistry and NCA Polymerization.

PubMed

Krannig, Kai-Steffen; Schlaad, Helmut

2016-01-01

Glycopolypeptides are prepared either by the polymerization of glycosylated amino acid N-carboxyanhydrides (NCAs) or by the post-polymerization functionalization of polypeptides with suitable functional groups. Here we present a method for the in-situ functionalization and (co-) polymerization of allylglycine N-carboxyanhydride in a facile one-pot procedure, combining radical thiol-ene photochemistry and nucleophilic ring-opening polymerization techniques, to yield well-defined heterofunctional glycopolypeptides.

Reconstituted Polymeric Materials Derived From Post-Consumer Waste, Industrial Scrap And Virgin Resins Made By Solid State Shear Pulverizat

DOEpatents

Khait, Klementina

2005-02-01

A method of making polymeric particulates wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatibilizing agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product.

Reconstituted polymeric materials derived from post-consumer waste, industrial scrap and virgin resins made by solid state pulverization

DOEpatents

Khait, K.

1998-09-29

A method of making polymeric particulates is described wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatible agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product. 29 figs.

Reconstituted polymeric materials derived from post-consumer waste, industrial scrap and virgin resins made by solid state shear pulverization

DOEpatents

Khait, Klementina

2001-01-30

A method of making polymeric particulates wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatibilizing agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product.

Reconstituted polymeric materials derived from post-consumer waste, industrial scrap and virgin resins made by solid state pulverization

DOEpatents

Khait, Klementina

1998-09-29

A method of making polymeric particulates wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatibilizing agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product.

Photoinitiated polymerization of 1-vinylimidazole

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

Joshi, M.G.; Rodriguez, F.

1984-04-01

The photoinitiated polymerization of 1-vinylimidazole (VI) does not follow the classical kinetic scheme for free radical polymerization. Kinetic results for VI suggest a degradative addition reaction between the macroradical and the monomer to produce a relatively stable, unreactive radical, which does not reinitiate polymerization, is low, 1.5 kcal/mol. Among the 3 photoinitiators used, the highest quantum efficiency was demonstrated by 2,2'-diethoxyacetophenone followed by bezoin methyl ether and benzoin isopropyl ether. Under the experimental conditions used, the polymerization of VI does not proceed to complete conversion, and the phenomenon of dead-end polymerization is observed.

Architecture of Amylose Supramolecules in Form of Inclusion Complexes by Phosphorylase-Catalyzed Enzymatic Polymerization

PubMed Central

Kadokawa, Jun-ichi

2013-01-01

This paper reviews the architecture of amylose supramolecules in form of inclusion complexes with synthetic polymers by phosphorylase-catalyzed enzymatic polymerization. Amylose is known to be synthesized by enzymatic polymerization using α-d-glucose 1-phosphate as a monomer, by phosphorylase catalysis. When the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of various hydrophobic polymers, such as polyethers, polyesters, poly(ester-ether), and polycarbonates as a guest polymer, such inclusion supramolecules were formed by the hydrophobic interaction in the progress of polymerization. Because the representation of propagation in the polymerization is similar to the way that a vine of a plant grows, twining around a rod, this polymerization method for the formation of amylose-polymer inclusion complexes was proposed to be named “vine-twining polymerization”. To yield an inclusion complex from a strongly hydrophobic polyester, the parallel enzymatic polymerization system was extensively developed. The author found that amylose selectively included one side of the guest polymer from a mixture of two resemblant guest polymers, as well as a specific range in molecular weights of the guest polymers poly(tetrahydrofuran) (PTHF) in the vine-twining polymerization. Selective inclusion behavior of amylose toward stereoisomers of chiral polyesters, poly(lactide)s, also appeared in the vine-twining polymerization. PMID:24970172

Radiation-induced polymerization of glass-forming systems. V. Initial polymerization rate in binary glass-forming systems

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

Kaetsu, Isao; Okubo, Hiroshi; Ito, Akihiko

1973-06-01

The radiation-induced polymerization of binary systems consisting of glass-forming monomer and glass-forming solvent in supercooled phase was studied. The initial polymerization rates were markedly affected by T/sub g/ (glass transition temperature) and T/sub v/ of the system (30-50 deg C higher than T/sub g/), which are functions of the composition. The composition and temperature dependence of initial polymerization rate in binary glass-forming systems were much affected by homogeneity of the polymerization system and the T of the glass- forming solvent. The composition and temperature dependences in the glycidyl methacrylate --triacetin system as a typical homogeneous polymerization system were studied inmore » detail, and the polymerizations of hydroxyethyl methacrylate triacetln and hydroxyethyl methacrylate --isoamyl acetate systems were studied for the heterogeneous polymerization systems; the former illustrates the combination of lower T/sub g/ monomer and higher T/sub g/ solvent and the latter typifies a system consisting of higher T/sub g/ monomer and lower T/sub g/ solvent. All experimental results for the composition and temperature dependence of initial polymerization rate in binary glass-forming systems could be explained by considering the product of the effect of the physical effect relating to T/sub v/ and T/sub g/ of the system and the effect of composition in normal solution polymerization at higher temperature, which was also the product of a dilution effect and a chemical or physical acceleration effect. (auth)« less

Rapid energy-efficient manufacturing of polymers and composites via frontal polymerization.

PubMed

Robertson, Ian D; Yourdkhani, Mostafa; Centellas, Polette J; Aw, Jia En; Ivanoff, Douglas G; Goli, Elyas; Lloyd, Evan M; Dean, Leon M; Sottos, Nancy R; Geubelle, Philippe H; Moore, Jeffrey S; White, Scott R

2018-05-01

Thermoset polymers and composite materials are integral to today's aerospace, automotive, marine and energy industries and will be vital to the next generation of lightweight, energy-efficient structures in these enterprises, owing to their excellent specific stiffness and strength, thermal stability and chemical resistance 1-5 . The manufacture of high-performance thermoset components requires the monomer to be cured at high temperatures (around 180 °C) for several hours, under a combined external pressure and internal vacuum 6 . Curing is generally accomplished using large autoclaves or ovens that scale in size with the component. Hence this traditional curing approach is slow, requires a large amount of energy and involves substantial capital investment 6,7 . Frontal polymerization is a promising alternative curing strategy, in which a self-propagating exothermic reaction wave transforms liquid monomers to fully cured polymers. We report here the frontal polymerization of a high-performance thermoset polymer that allows the rapid fabrication of parts with microscale features, three-dimensional printed structures and carbon-fibre-reinforced polymer composites. Precise control of the polymerization kinetics at both ambient and elevated temperatures allows stable monomer solutions to transform into fully cured polymers within seconds, reducing energy requirements and cure times by several orders of magnitude compared with conventional oven or autoclave curing approaches. The resulting polymer and composite parts possess similar mechanical properties to those cured conventionally. This curing strategy greatly improves the efficiency of manufacturing of high-performance polymers and composites, and is widely applicable to many industries.

Measurement and Analysis of in vitro Actin Polymerization

PubMed Central

Doolittle, Lynda K.; Rosen, Michael K.; Padrick, Shae B.

2014-01-01

Summary The polymerization of actin underlies force generation in numerous cellular processes. While actin polymerization can occur spontaneously, cells maintain control over this important process by preventing actin filament nucleation and then allowing stimulated polymerization and elongation by several regulated factors. Actin polymerization, regulated nucleation and controlled elongation activities can be reconstituted in vitro, and used to probe the signaling cascades cells use to control when and where actin polymerization occurs. Introducing a pyrene fluorophore allows detection of filament formation by an increase in pyrene fluorescence. This method has been used for many years and continues to be broadly used, owing to its simplicity and flexibility. Here we describe how to perform and analyze these in vitro actin polymerization assays, with an emphasis on extracting useful descriptive parameters from kinetic data. PMID:23868594

Reactivity of polymeric proanthocyanidins toward salivary proteins and their contribution to young red wine astringency.

PubMed

Sun, Baoshan; de Sá, Marta; Leandro, Conceição; Caldeira, Ilda; Duarte, Filomena L; Spranger, Isabel

2013-01-30

Recent studies have indicated the presence of significant amount of highly polymerized and soluble proanthocyanidins in red wine and such compounds interacted readily with proteins, suggesting that they might be particularly astringent. Thus, the objective of this work was to verify the astringency of polymeric proanthocyanidins and their contribution to red wine astringency. The precipitation reactions of the purified oligomeric procyanidins (degree of polymerization ranging from 2 to 12-15) and polymeric procyanidins (degree of polymerization ranging from 12-15 to 32-34) with human salivary proteins were studied; salivary proteins composition changes before and after the reaction was verified by SDS-PAGE and procyanidins composition changes by spectrometric, direct HPLC and thiolysis-HPLC methods. The astringency intensity of these two procyanidin fractions was evaluated by a sensory analysis panel. For verifying the correlation between polymeric proanthocyanidins and young red wine astringency, the levels of total oligomeric and total polymeric proanthocyanidins and other phenolic composition in various young red wines were quantified and the astringency intensities of these wines were evaluated by a sensory panel. The results showed that polymeric proanthocyanidins had much higher reactivity toward human salivary proteins and higher astringency intensity than the oligomeric ones. Furthermore, young red wine astringency intensities were highly correlated to levels of polymeric proanthocyanidins, particularly at low concentration range (correlation coefficient r = 0.9840) but not significant correlated to total polyphenols (r = 0.2343) or other individual phenolic compounds (generally r < 0.3). These results indicate the important contribution of polymeric proanthocyanidins to red wine astringency and the levels of polymeric polyphenols in red wines may be used as an indicator for its astringency.

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

PubMed Central

HU, LIGANG; CAI, YONG; JIANG, GUIBIN

2016-01-01

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

The effect of photopolymerization on the degree of conversion, polymerization kinetic, biaxial flexure strength, and modulus of self-adhesive resin cements.

PubMed

Aguiar, Thaiane R; de Oliveira, Michele; Arrais, César A G; Ambrosano, Glaucia M B; Rueggeberg, Frederick; Giannini, Marcelo

2015-02-01

Understanding the effect of the degree of conversion on the mechanical properties of auto- and dual-polymerizing self-adhesive resin cements leads to a better estimation of their performance in different clinical scenarios. The purpose of this study was to evaluate the effect of photopolymerization on the degree of conversion (DC) and polymerization kinetic of 4 dual-polymerized resin cements, 20 minutes after mixing, and its effects on the mechanical properties (biaxial flexural strength [FS] and modulus [FM]) after short-term aging. Conventional (RelyX ARC and Clearfil Esthetic Cement) and self-adhesive resin cements (RelyX Unicem and Clearfil SA Cement) were applied to a Fourier infrared spectrometer to assess the DC (n=5) under the following 3 polymerization conditions: direct light exposure (dual-polymerizing mode), exposure through the prepolymerized disk, or autopolymerizing. The polymerization kinetic was recorded for 20 minutes. Then, disk-shaped specimens (n=11) were prepared to evaluate the effect of polymerization on the FS and FM in both extreme polymerization conditions (dual-polymerizing or autopolymerizing). Data were statistically analyzed by 2-way repeated measure ANOVA (DC) and by 2-way ANOVA (FS and FM), followed by the Tukey-Kramer post hoc test (α=.05). Autopolymerizing groups exhibited reduced DC means, whereas intermediate values were observed when resin cements were polymerized through the disk. All groups exhibited higher DC at the end of 20 minutes. The polymerization kinetic revealed a rising curve, and materials, when directly photopolymerized, reached a plateau immediately after light exposure. Regarding the flexural biaxial testing, most of the resin cements were affected by polymerization mode and differences among groups were product dependent. The resin cements achieved immediate higher DC and mechanical properties when photopolymerized. The total absence of photoactivation may still impair their mechanical properties even after short-term aging. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Chemoselective, Stereospecific, and Living Polymerization of Polar Divinyl Monomers by Chiral Zirconocenium Catalysts.

PubMed

Vidal, Fernando; Gowda, Ravikumar R; Chen, Eugene Y-X

2015-07-29

This contribution reports the first chemoselective, stereospecific, and living polymerization of polar divinyl monomers, enabled by chiral ansa-zirconocenium catalysts through an enantiomorphic-site controlled coordination-addition polymerization mechanism. Silyl-bridged-ansa-zirconocenium ester enolate 2 has been synthesized and structurally characterized, but it exhibits low to negligible activity and stereospecificity in the polymerization of polar divinyl monomers including vinyl methacrylate (VMA), allyl methacrylate (AMA), 4-vinylbenzyl methacrylate (VBMA), and N,N-diallyl acrylamide (DAA). In contrast, ethylene-bridged-ansa-zirconocenium ester enolate 1 is highly active and stereospecific in the polymerization of such monomers including AMA, VBMA, and DAA. The polymerization by 1 is perfectly chemoselective for all four polar divinyl monomers, proceeding exclusively through conjugate addition across the methacrylic C═C bond, while leaving the pendant C═C bonds intact. The polymerization of DAA is most stereospecific and controlled, producing essentially stereoperfect isotactic PDAA with [mmmm] > 99%, M(n) matching the theoretical value (thus a quantitative initiation efficiency), and a narrow molecular weight distribution (Đ = 1.06-1.16). The stereospecificity is slightly lower for the AMA polymerization but still leading to highly isotactic poly(allyl methacrylate) (PAMA) with 95-97% [mm]. The polymerization of VBMA is further less stereospecific, affording PVBMA with 90-94% [mm], while the polymerization VMA is least stereospecific. Several lines of evidence from both homo- and block copolymerization results have demonstrated living characteristics of the AMA polymerization by 1. Mechanistic studies of this polymerization have yielded a monometallic coordination-addition polymerization mechanism involving the eight-membered chelating intermediate. Post-functionalization of isotactic polymers bearing the pendant vinyl group on every repeating unit via the thiol-ene "click" reaction achieves a full conversion of all the pendant double bonds to the corresponding thioether bonds. Photocuring of such isotactic polymers is also successful, producing an elastic material readily characterizable by dynamic mechanical analysis.

Chimeric protein identification of dystrophic, Pierson and other laminin polymerization residues

PubMed Central

McKee, Karen K.; Aleksandrova, Maya; Yurchenco, Peter D.

2018-01-01

Laminin polymerization is a key step of basement membrane self-assembly that depends on the binding of the three different N-terminal globular LN domains. Several mutations in the LN domains cause LAMA2-deficient muscular dystrophy and LAMB2-deficient Pierson syndrome. These mutations may affect polymerization. A novel approach to identify the amino acid residues required for polymerization has been applied to an analysis of these and other laminin LN mutations. The approach utilizes laminin-nidogen chimeric fusion proteins that bind to recombinant non-polymerizing laminins to provide a missing functional LN domain. Single amino acid substitutions introduced into these chimeras were tested to determine if polymerization activity and the ability to assemble on cell surfaces were lost. Several laminin-deficient muscular dystrophy mutations, renal Pierson syndrome mutations, and Drosophila mutations causing defects of heart development were identified as ones causing loss of laminin polymerization. In addition, two novel residues required for polymerization were identified in the laminin γ1 LN domain. PMID:29408412

Polymeric micelles as a new drug carrier system and their required considerations for clinical trials.

PubMed

Yokoyama, Masayuki

2010-02-01

A polymeric micelle is a macromolecular assembly composed of an inner core and an outer shell, and most typically is formed from block copolymers. In the last two decades, polymeric micelles have been actively studied as a new type of drug carrier system, in particular for drug targeting of anticancer drugs to solid tumors. In this review, polymeric micelle drug carrier systems are discussed with a focus on toxicities of the polymeric micelle carrier systems and on pharmacological activities of the block copolymers. In the first section, the importance of the above-mentioned evaluation of these properties is explained, as this importance does not seem to be well recognized compared with the importance of targeting and enhanced pharmacological activity of drugs, particularly in the basic studies. Then, designs, types and classifications of the polymeric micelle system are briefly summarized and explained, followed by a detailed discussion regarding several examples of polymeric micelle carrier systems. Readers will gain a strategy of drug delivery with polymeric carriers as well as recent progress of the polymeric micelle carrier systems in their basic studies and clinical trials. The purpose of this review is to achieve tight connections between the basic studies and clinical trials.

21 CFR 872.6070 - Ultraviolet activator for polymerization.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ultraviolet activator for polymerization. 872.6070 Section 872.6070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... polymerization. (a) Identification. An ultraviolet activator for polymerization is a device that produces...

21 CFR 872.6070 - Ultraviolet activator for polymerization.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ultraviolet activator for polymerization. 872.6070 Section 872.6070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... polymerization. (a) Identification. An ultraviolet activator for polymerization is a device that produces...

Polymer-phyllosilicate nanocomposites and their preparation

DOEpatents

Chaiko, David J.

2007-01-09

Polymer-phyllosilicate nanocomposites that exhibit superior properties compared to the polymer alone, and methods-for producing these polymer-phyllosilicate nanocomposites, are provided. Polymeric surfactant compatabilizers are adsorbed onto the surface of hydrophilic or natural phyllosilicates to facilitate the dispersal and exfoliation of the phyllosilicate in a polymer matrix. Utilizing polymeric glycol based surfactants, polymeric dicarboxylic acids, polymeric diammonium surfactants, and polymeric diamine surfactants as compatabilizers facilitates natural phyllosilicate and hydrophilic organoclay dispersal in a polymer matrix to produce nanocomposites.

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

PubMed Central

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

2014-01-01

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

In vitro comparison of autoclave polymerization on the transverse strength of denture base resins.

PubMed

Durkan, Rukiye; Ozel, Mehmet Birol; Bağiş, Bora; Usanmaz, Ali

2008-07-01

The aim of this study was to determine the effect of autoclave polymerization on the transverse strength of denture base polymers. To this end, 30 rectangular test specimens were fabricated of two heat-polymerized denture base polymers. The test groups were: (I) control, i.e., conventional water bath to polymerize resins by heat at 100 degrees C for 30 minutes; (II) autoclave polymerization at 60 degrees C for 30 minutes followed by 130 degrees C for 10 minutes; and (III) autoclave polymerization at 60 degrees C for 30 minutes followed by 130 degrees C for 20 minutes. The specimens were tested with three-point bending test at a crosshead speed of 5 mm/min. It was revealed that the transverse strength of specimens increased with statistical significance when the autoclave was used for polymerization.

The influence of various cations on the catalytic properties of clays. [polymerization of alanine adenylate

NASA Technical Reports Server (NTRS)

Paecht-Horowitz, M.

1978-01-01

The polymerization of alanine adenylate in the presence of the sodium form of various clays was studied, and hectorite was found to cause more polymerization than nontronite and montmorillonite (in that order) although the differences were not great. The effect on polymerization of presaturating montmorillonite with different cations was determined. Hectorite, with increased basicity of the interspatial planes, allows polymerization of lysine, which montmorillonite does not. The general trend is that, for the same amino acid, higher degrees of polymerization are obtained when the cation in the octahedral lattice of the clay is divalent rather than trivalent. With the exchangeable cations the order is reversed, for a reason that is explained. The main role of clays in the polymerization mechanism of amino acids is concentration and neutralization of charges.

Imidazoline and imidazolidine nitroxides as controlling agents in nitroxide-mediated pseudoliving radical polymerization

NASA Astrophysics Data System (ADS)

Edeleva, M. V.; Marque, S. R. A.; Bagryanskaya, E. G.

2018-04-01

Controlled, or pseudoliving, radical polymerization provides unique opportunities for the synthesis of structurally diverse polymers with a narrow molecular-weight distribution. These reactions occur under relatively mild conditions with broad tolerance to functional groups in the monomers. The nitroxide-mediated pseudoliving radical polymerization is of particular interest for the synthesis of polymers for biomedical applications. This review briefly describes one of the mechanisms of controlled radical polymerization. The studies dealing with the use of imidazoline and imidazolidine nitroxides as controlling agents for nitroxide-mediated pseudoliving radical polymerization of various monomers are summarized and analyzed. The publications addressing the key steps of the controlled radical polymerization in the presence of imidazoline and imidazolidine nitroxides and new approaches to nitroxide-mediated polymerization based on protonation of both nitroxides and monomers are considered. The bibliography includes 154 references.

Interaction mechanisms of condensed tannins (proanthocyanidins) with wheat gluten proteins

USDA-ARS?s Scientific Manuscript database

Proanthocyanidins (PA) crosslink wheat gluten, increasing its polymer size and strength. However, precise mechanisms behind these interactions are unknown. This study used PA of different MW profiles (mDP 8.3 and 19.5) to investigate the interactions involved in PA polymerization of gluten. The high...

21 CFR 177.2250 - Filters, microporous polymeric.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Filters, microporous polymeric. 177.2250 Section... as Components of Articles Intended for Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in paragraph (a) of this section may be safely used, subject to the...

21 CFR 177.2250 - Filters, microporous polymeric.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Filters, microporous polymeric. 177.2250 Section... as Components of Articles Intended for Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in paragraph (a) of this section may be safely used, subject to the...

21 CFR 177.2250 - Filters, microporous polymeric.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Filters, microporous polymeric. 177.2250 Section... as Components of Articles Intended for Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in paragraph (a) of this section may be safely used, subject to the...

21 CFR 177.2250 - Filters, microporous polymeric.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Filters, microporous polymeric. 177.2250 Section... as Components of Articles Intended for Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in paragraph (a) of this section may be safely used, subject to the...

21 CFR 870.3650 - Pacemaker polymeric mesh bag.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

21 CFR 870.3650 - Pacemaker polymeric mesh bag.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

21 CFR 870.3650 - Pacemaker polymeric mesh bag.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

21 CFR 870.3650 - Pacemaker polymeric mesh bag.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

49 CFR 173.221 - Polymeric beads, expandable and Plastic molding compound.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 2 2011-10-01 2011-10-01 false Polymeric beads, expandable and Plastic molding... Than Class 1 and Class 7 § 173.221 Polymeric beads, expandable and Plastic molding compound. (a) Non-bulk shipments of Polymeric beads (or granules), expandable, evolving flammable vapor and Plastic...

49 CFR 173.221 - Polymeric beads, expandable and Plastic molding compound.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 2 2010-10-01 2010-10-01 false Polymeric beads, expandable and Plastic molding... Than Class 1 and Class 7 § 173.221 Polymeric beads, expandable and Plastic molding compound. (a) Non-bulk shipments of Polymeric beads (or granules), expandable, evolving flammable vapor and Plastic...

49 CFR 173.221 - Polymeric beads, expandable and Plastic molding compound.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 49 Transportation 2 2012-10-01 2012-10-01 false Polymeric beads, expandable and Plastic molding... Than Class 1 and Class 7 § 173.221 Polymeric beads, expandable and Plastic molding compound. (a) Non-bulk shipments of Polymeric beads (or granules), expandable, evolving flammable vapor and Plastic...

49 CFR 173.221 - Polymeric beads, expandable and Plastic molding compound.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 49 Transportation 2 2014-10-01 2014-10-01 false Polymeric beads, expandable and Plastic molding... Than Class 1 and Class 7 § 173.221 Polymeric beads, expandable and Plastic molding compound. (a) Non-bulk shipments of Polymeric beads (or granules), expandable evolving flammable vapor and Plastic...

49 CFR 173.221 - Polymeric beads, expandable and Plastic molding compound.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 49 Transportation 2 2013-10-01 2013-10-01 false Polymeric beads, expandable and Plastic molding... Than Class 1 and Class 7 § 173.221 Polymeric beads, expandable and Plastic molding compound. (a) Non-bulk shipments of Polymeric beads (or granules), expandable evolving flammable vapor and Plastic...

Lipase-catalyzed ring-opening polymerization of lactones to polyesters and its mechanistic aspects.

PubMed

Namekawa, S; Suda, S; Uyama, H; Kobayashi, S

1999-01-01

Lipase catalysis induced a ring-opening polymerization of lactones with different ring-sizes. Small-size (four-membered) and medium-size lactones (six- and seven-membered) as well as macrolides (12-, 13-, 16-, and 17-membered) were subjected to lipase-catalyzed polymerization. The polymerization behaviors depended primarily on the lipase origin and the monomer structure. The macrolides showing much lower anionic polymerizability were enzymatically polymerized faster than epsilon-caprolactone. The granular immobilized lipase derived from Candida antartica showed extremely efficient catalysis in the polymerization of epsilon-caprolactone. Single-step terminal functionalization of the polyester was achieved by initiator and terminator methods. The enzymatic polymerizability of lactones was quantitatively evaluated by Michaelis-Menten kinetics.

Spatial control of actin polymerization during neutrophil chemotaxis

PubMed Central

Weiner, Orion D.; Servant, Guy; Welch, Matthew D.; Mitchison, Timothy J.; Sedat, John W.; Bourne, Henry R.

2010-01-01

Neutrophils respond to chemotactic stimuli by increasing the nucleation and polymerization of actin filaments, but the location and regulation of these processes are not well understood. Here, using a permeabilized-cell assay, we show that chemotactic stimuli cause neutrophils to organize many discrete sites of actin polymerization, the distribution of which is biased by external chemotactic gradients. Furthermore, the Arp2/3 complex, which can nucleate actin polymerization, dynamically redistributes to the region of living neutrophils that receives maximal chemotactic stimulation, and the least-extractable pool of the Arp2/3 complex co-localizes with sites of actin polymerization. Our observations indicate that chemoattractant-stimulated neutrophils may establish discrete foci of actin polymerization that are similar to those generated at the posterior surface of the intracellular bacterium Listeria monocytogenes. We propose that asymmetrical establishment and/or maintenance of sites of actin polymerization produces directional migration of neutrophils in response to chemotactic gradients. PMID:10559877

Spatial control of actin polymerization during neutrophil chemotaxis.

PubMed

Weiner, O D; Servant, G; Welch, M D; Mitchison, T J; Sedat, J W; Bourne, H R

1999-06-01

Neutrophils respond to chemotactic stimuli by increasing the nucleation and polymerization of actin filaments, but the location and regulation of these processes are not well understood. Here, using a permeabilized-cell assay, we show that chemotactic stimuli cause neutrophils to organize many discrete sites of actin polymerization, the distribution of which is biased by external chemotactic gradients. Furthermore, the Arp2/3 complex, which can nucleate actin polymerization, dynamically redistributes to the region of living neutrophils that receives maximal chemotactic stimulation, and the least-extractable pool of the Arp2/3 complex co-localizes with sites of actin polymerization. Our observations indicate that chemoattractant-stimulated neutrophils may establish discrete foci of actin polymerization that are similar to those generated at the posterior surface of the intracellular bacterium Listeria monocytogenes. We propose that asymmetrical establishment and/or maintenance of sites of actin polymerization produces directional migration of neutrophils in response to chemotactic gradients.

Step Transfer-Addition and Radical-Termination (START) Polymerization of α,ω-Unconjugated Dienes under Irradiation of Blue LED Light.

PubMed

Xu, Tianchi; Yin, Hongnan; Li, Xiaohong; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2017-07-01

A new polymerization method, termed as step transfer-addition and radical-termination, is developed for the step-growth radical polymerization of α,ω-unconjugated dienes under irradiation of visible light at room temperature (25 °C) for the first time. α,ω-Diiodoperfluoroalkane monomers (signified as A) are added onto α,ω-unconjugated dienes (signified as B) alternatively and efficiently with the generation of perfluorocarbon-containing alternating copolymers (AB) n . Based on the combined analyses of polymerization kinetics and NMR spectra ( 1 H and 19 F), the mechanism of the novel polymerization method, including the side reaction, is proposed. This novel polymerization method provides a new strategy not only for the step-growth radical polymerization of α,ω-unconjugated dienes but also for the construction of high molecular weight perfluorocarbon-containing alternating copolymers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoinitiated Polymerization-Induced Self-Assembly of Glycidyl Methacrylate for the Synthesis of Epoxy-Functionalized Block Copolymer Nano-Objects.

PubMed

Tan, Jianbo; Liu, Dongdong; Huang, Chundong; Li, Xueliang; He, Jun; Xu, Qin; Zhang, Li

2017-08-01

Herein, a novel photoinitiated polymerization-induced self-assembly formulation via photoinitiated reversible addition-fragmentation chain transfer dispersion polymerization of glycidyl methacrylate (PGMA) in ethanol-water at room temperature is reported. It is demonstrated that conducting polymerization-induced self-assembly (PISA) at low temperatures is crucial for obtaining colloidal stable PGMA-based diblock copolymer nano-objects. Good control is maintained during the photo-PISA process with a high rate of polymerization. The polymerization can be switched between "ON" and "OFF" in response to visible light. A phase diagram is constructed by varying monomer concentration and degree of polymerization. The PGMA-based diblock copolymer nano-objects can be further cross-linked by using a bifunctional primary amine reagent. Finally, silver nanoparticles are loaded within cross-linked vesicles via in situ reduction, exhibiting good catalytic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Signal amplification strategies for DNA and protein detection based on polymeric nanocomposites and polymerization: A review.

PubMed

Zhou, Shaohong; Yuan, Liang; Hua, Xin; Xu, Lingling; Liu, Songqin

2015-06-02

Demand is increasing for ultrasensitive bioassays for disease diagnosis, environmental monitoring and other research areas. This requires novel signal amplification strategies to maximize the signal output. In this review, we focus on a series of significant signal amplification strategies based on polymeric nanocomposites and polymerization. Some common polymers are used as carriers to increase the local concentration of signal probes and/or biomolecules on their surfaces or in their interiors. Some polymers with special fluorescence and optical properties can efficiently transfer the excitation energy from a single site to the whole polymer backbone. This results in superior fluorescence signal amplification due to the resulting collective effort (integration of signal). Recent polymerization-based signal amplification strategies that employ atom transfer radical polymerization (ATRP) and photo-initiated polymerization are also summarized. Several distinctive applications of polymers in ultrasensitive bioanalysis are highlighted. Copyright © 2015 Elsevier B.V. All rights reserved.

75 FR 70254 - Typographical Error in Summary Notice of Filing in Docket for Polymerized Fatty Acid Esters With...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-17

... Notice of Filing in Docket for Polymerized Fatty Acid Esters With Aminoalcohol Alkoxylates; Correction... (NOF) for Pesticide Petition (PP) 0E7699 for polymerized fatty acid esters with aminoalcohol... Pesticide Petition (PP) 0E7699 for polymerized fatty acid esters with aminoalcohol alkoxylates submitted by...

Remarkable effect of halogenation of aromatic compounds on efficiency of nanowire formation through polymerization/crosslinking by high-energy single particle irradiation

NASA Astrophysics Data System (ADS)

Horio, Akifumi; Sakurai, Tsuneaki; Kayama, Kazuto; Lakshmi, G. B. V. S.; Kumar Avasthi, Devesh; Sugimoto, Masaki; Yamaki, Tetsuya; Chiba, Atsuya; Saito, Yuichi; Seki, Shu

2018-01-01

Irradiation of high-energy ion particles on organic films induced solid-state polymerization and crosslinking reactions of the materials along the ion trajectories, resulting in the formation of insoluble uniform nanowires with a precise diameter. The nanowires were isolated by the development process i.e. the irradiated film was immersed in organic solvents, and their morphology was visualized by atomic force microscopy. The target organic materials are 4-vinyltriphenylamine, poly(4-vinyltriphenylamine), and polystyrene derivatives with/without the partial substitutions by halogen atoms. It was found that 4-vinyltriphenylamines, in spite of their small molecular sizes, afforded nanowires more clearly than poly(4-vinyltriphenylamine)s. Moreover, the efficiency of demonstrated polymerization/crosslinking reactions obviously depends on the substituted halogen atom species. The averaged diameters of nanowires from bromo- or iodo- substituted 4-vinyltriphenylamine (9.3 and 9.4 nm, respectively) were larger than that obtained from simple 4-vinyltriphenylamine (6.8 nm). The remarkable effect of halogenation of aromatic compounds on the efficiency of the radiation-induced reactions was also observed for polystyrene derivatives. This contrast was considered to originate from the sum of the efficiency of elementary reactions including dissociative electron attachment.

Vapor-phase polymerization of poly(3, 4-ethylenedioxythiophene) nanofibers on carbon cloth as electrodes for flexible supercapacitors.

PubMed

Zhao, Xin; Dong, Mengyang; Zhang, Junxian; Li, Yingzhi; Zhang, Qinghua

2016-09-23

In this study, an evaporative vapor-phase polymerization approach was employed to fabricate vertically aligned poly(3, 4-ethylenedioxythiophene) (PEDOT) nanofibers on the surface of carbon cloth (CC). Optimized reaction conditions can obtain well distributed and uniform layers of high-aspect-ratio PEDOT nanofibers on CC. The hierarchical PEDOT/CC structure as a freestanding electrode exhibits good electrochemical properties. As a flexible symmetric supercapacitor, the PEDOT/CC hybrid electrode displays a specific areal capacitance of 201.4 mF cm(-2) at 1 mA cm(-2), good flexibility with a higher value (204.6 mF cm(-2)) in the bending state, and a good cycling stability of 92.4% after 1000 cycles. Moreover, the device shows a maximum energy density of 4.0 Wh kg(-1) (with a power density of 3.2 kW kg(-1)) and a maximum power density of 4.2 kW kg(-1) (with an energy density of 3.1 Wh kg(-1)). The results demonstrate that PEDOT may be a promising material for storage devices through a simple and efficient vapor-phase polymerization process with precisely controlled reaction conditions.

Vapor-phase polymerization of poly(3, 4-ethylenedioxythiophene) nanofibers on carbon cloth as electrodes for flexible supercapacitors

NASA Astrophysics Data System (ADS)

Zhao, Xin; Dong, Mengyang; Zhang, Junxian; Li, Yingzhi; Zhang, Qinghua

2016-09-01

In this study, an evaporative vapor-phase polymerization approach was employed to fabricate vertically aligned poly(3, 4-ethylenedioxythiophene) (PEDOT) nanofibers on the surface of carbon cloth (CC). Optimized reaction conditions can obtain well distributed and uniform layers of high-aspect-ratio PEDOT nanofibers on CC. The hierarchical PEDOT/CC structure as a freestanding electrode exhibits good electrochemical properties. As a flexible symmetric supercapacitor, the PEDOT/CC hybrid electrode displays a specific areal capacitance of 201.4 mF cm-2 at 1 mA cm-2, good flexibility with a higher value (204.6 mF cm-2) in the bending state, and a good cycling stability of 92.4% after 1000 cycles. Moreover, the device shows a maximum energy density of 4.0 Wh kg-1 (with a power density of 3.2 kW kg-1) and a maximum power density of 4.2 kW kg-1 (with an energy density of 3.1 Wh kg-1). The results demonstrate that PEDOT may be a promising material for storage devices through a simple and efficient vapor-phase polymerization process with precisely controlled reaction conditions.

Novel polymeric materials from vegetable oils and vinyl monomers: preparation, properties, and applications.

PubMed

Lu, Yongshang; Larock, Richard C

2009-01-01

Veggie-based products: Vegetable-oil-based polymeric materials, prepared by free radical, cationic, and olefin metathesis polymerizations, range from soft rubbers to ductile or rigid plastics, and to high-performance biocomposites and nanocomposites. They display a wide range of thermophysical and mechanical properties and may find promising applications as alternatives to petroleum-based polymers.Vegetable oils are considered to be among the most promising renewable raw materials for polymers, because of their ready availability, inherent biodegradability, and their many versatile applications. Research on and development of vegetable oil based polymeric materials, including thermosetting resins, biocomposites, and nanocomposites, have attracted increasing attention in recent years. This Minireview focuses on the latest developments in the preparation, properties, and applications of vegetable oil based polymeric materials obtained by free radical, cationic, and olefin metathesis polymerizations. The novel vegetable oil based polymeric materials obtained range from soft rubbery materials to ductile or rigid plastics and to high-performance biocomposites and nanocomposites. These vegetable oil based polymeric materials display a wide range of thermophysical and mechanical properties and should find useful applications as alternatives to their petroleum-based counterparts.

Effects of organic solvents on drug incorporation into polymeric carriers and morphological analyses of drug-incorporated polymeric micelles.

PubMed

Harada, Yoshiko; Yamamoto, Tatsuhiro; Sakai, Masaru; Saiki, Toshiharu; Kawano, Kumi; Maitani, Yoshie; Yokoyama, Masayuki

2011-02-14

We incorporated an anticancer agent, camptothecin (CPT), into polymeric micelle carriers by using two different solvents (TFE and chloroform) in the solvent-evaporation drug incorporation process. We observed significant differences in the drug-incorporation behaviors, in the morphologies of the incorporated drug and the polymeric micelles, and in the pharmacokinetic behaviors between the two solvents' cases. In particular, the CPT-incorporated polymeric micelles prepared with TFE as the incorporation solvent exhibited more stable circulation in blood than those prepared with chloroform. This contrast indicates a novel technological perspective regarding the drug incorporation into polymeric micelle carriers. Morphological analyses of the inner core have revealed the presence of the directed alignment of the CPT molecules and CPT crystals in the micelle inner core. This is the first report of the morphologies of the drug incorporated into the polymeric micelle inner cores. We believe these analyses are very important for further pharmaceutical developments of polymeric micelle drug-carrier systems. Copyright © 2010 Elsevier B.V. All rights reserved.

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

PubMed

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

1980-11-01

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

Modulation of interferon-γ synthesis by the effects of lignin-like enzymatically polymerized polyphenols on antigen-presenting cell activation and the subsequent cell-to-cell interactions.

PubMed

Yamanaka, Daisuke; Motoi, Masuro; Ishibashi, Ken-ichi; Miura, Noriko N; Adachi, Yoshiyuki; Ohno, Naohito

2013-12-15

Lignin-like polymerized polyphenols strongly activate lymphocytes and induce cytokine synthesis. We aimed to characterise the mechanisms of action of polymerized polyphenols on immunomodulating functions. We compared the reactivity of leukocytes from various organs to that of polymerized polyphenols. Splenocytes and resident peritoneal cavity cells (PCCs) responded to polymerized polyphenols and released several cytokines, whereas thymocytes and bone-marrow cells showed no response. Next, we eliminated antigen-presenting cells (APCs) from splenocytes to study their involvement in cytokine synthesis. We found that APC-negative splenocytes showed significantly reduced cytokine production induced by polymerized polyphenols. Additionally, adequate interferon-γ (IFN-γ) induction by polymerized polyphenols was mediated by the coexistence of APCs and T cells because the addition of T cells to PCCs increased IFN-γ production. Furthermore, inhibition of the T cell-APC interaction using neutralising antibodies significantly decreased cytokine production. Thus, cytokine induction by polymerized polyphenols was mediated by the interaction between APCs and T cells. Copyright © 2013 Elsevier Ltd. All rights reserved.

Polymeric ionic liquid coatings versus commercial solid-phase microextraction coatings for the determination of volatile compounds in cheeses.

PubMed

Trujillo-Rodríguez, María J; Yu, Honglian; Cole, William T S; Ho, Tien D; Pino, Verónica; Anderson, Jared L; Afonso, Ana M

2014-04-01

The extraction performance of four polymeric ionic liquid (PIL)-based solid-phase microextraction (SPME) coatings has been studied and compared to that of commercial SPME coatings for the extraction of 16 volatile compounds in cheeses. The analytes include 2 free fatty acids, 2 aldehydes, 2 ketones and 10 phenols and were determined by headspace (HS)-SPME coupled to gas chromatography (GC) with flame-ionization detection (FID). The PIL-based coatings produced by UV co-polymerization were more efficient than PIL-based coatings produced by thermal AIBN polymerization. Partition coefficients of analytes between the sample and the coating (Kfs) were estimated for all PIL-based coatings and the commercial SPME fiber showing the best performance among the commercial fibers tested: carboxen-polydimethylsyloxane (CAR-PDMS). For the PIL-based fibers, the highest K(fs) value (1.96 ± 0.03) was obtained for eugenol. The normalized calibration slope, which takes into account the SPME coating thickness, was also used as a simpler approximate tool to compare the nature of the coating within the determinations, with results entirely comparable to those obtained with estimated K(fs) values. The PIL-based materials obtained by UV co-polymerization containing the 1-vinyl-3-hexylimidazolium chloride IL monomer and 1,12-di(3-vinylimiazolium)dodecane dibromide IL crosslinker exhibited the best performance in the extraction of the select analytes from cheeses. Despite a coating thickness of only 7 µm, this copolymeric sorbent coating was capable of quantitating analytes in HS-SPME in a 30 to 2000 µg L(-1) concentration range, with correlation coefficient (R) values higher than 0.9938, inter-day precision values (as relative standard deviation in %) varying from 6.1 to 20%, and detection limits down to 1.6 µg L(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

Enhancement of dissolution and oral bioavailability of lacidipine via pluronic P123/F127 mixed polymeric micelles: formulation, optimization using central composite design and in vivo bioavailability study.

PubMed

Fares, Ahmed R; ElMeshad, Aliaa N; Kassem, Mohamed A A

2018-11-01

This study aims at preparing and optimizing lacidipine (LCDP) polymeric micelles using thin film hydration technique in order to overcome LCDP solubility-limited oral bioavailability. A two-factor three-level central composite face-centered design (CCFD) was employed to optimize the formulation variables to obtain LCDP polymeric micelles of high entrapment efficiency and small and uniform particle size (PS). Formulation variables were: Pluronic to drug ratio (A) and Pluronic P123 percentage (B). LCDP polymeric micelles were assessed for entrapment efficiency (EE%), PS and polydispersity index (PDI). The formula with the highest desirability (0.959) was chosen as the optimized formula. The values of the formulation variables (A and B) in the optimized polymeric micelles formula were 45% and 80%, respectively. Optimum LCDP polymeric micelles had entrapment efficiency of 99.23%, PS of 21.08 nm and PDI of 0.11. Optimum LCDP polymeric micelles formula was physically characterized using transmission electron microscopy. LCDP polymeric micelles showed saturation solubility approximately 450 times that of raw LCDP in addition to significantly enhanced dissolution rate. Bioavailability study of optimum LCDP polymeric micelles formula in rabbits revealed a 6.85-fold increase in LCDP bioavailability compared to LCDP oral suspension.

Photopolymerization of Dienoyl Lipids Creates Planar Supported Poly(lipid) Membranes with Retained Fluidity.

PubMed

Orosz, Kristina S; Jones, Ian W; Keogh, John P; Smith, Christopher M; Griffin, Kaitlyn R; Xu, Juhua; Comi, Troy J; Hall, H K; Saavedra, S Scott

2016-02-16

Polymerization of substrate-supported bilayers composed of dienoylphosphatidylcholine (PC) lipids is known to greatly enhance their chemical and mechanical stability; however, the effects of polymerization on membrane fluidity have not been investigated. Here planar supported lipid bilayers (PSLBs) composed of dienoyl PCs on glass substrates were examined to assess the degree to which UV-initiated polymerization affects lateral lipid mobility. Fluorescence recovery after photobleaching (FRAP) was used to measure the diffusion coefficients (D) and mobile fractions of rhodamine-DOPE in unpolymerized and polymerized PSLBs composed of bis-sorbyl phosphatidylcholine (bis-SorbPC), mono-sorbyl-phosphatidylcholine (mono-SorbPC), bis-dienoyl-phosphatidylcholine (bis-DenPC), and mono-dienoyl phosphatidylcholine (mono-DenPC). Polymerization was performed in both the Lα and Lβ phase for each lipid. In all cases, polymerization reduced membrane fluidity; however, measurable lateral diffusion was retained which is attributed to a low degree of polymerization. The D values for sorbyl lipids were less than those of the denoyl lipids; this may be a consequence of the distal location of polymerizable group in the sorbyl lipids which may facilitate interleaflet bonding. The D values measured after polymerization were 0.1-0.8 of those measured before polymerization, a range that corresponds to fluidity intermediate between that of a Lα phase and a Lβ phase. This D range is comparable to ratios of D values reported for liquid-disordered (Ld) and liquid-ordered (Lo) lipid phases and indicates that the effect of UV polymerization on lateral diffusion in a dienoyl PSLB is similar to the transition from a Ld phase to a Lo phase. The partial retention of fluidity in UV-polymerized PSLBs, their enhanced stability, and the activity of incorporated transmembrane proteins and peptides is discussed.

Photopolymerization of dienoyl lipids creates planar supported poly(lipid) membranes with retained fluidity

PubMed Central

Orosz, Kristina S.; Jones, Ian W.; Keogh, John P.; Smith, Christopher M.; Griffin, Kaitlyn R.; Xu, Juhua; Comi, Troy J.; Hall, H. K.

2016-01-01

Polymerization of substrate-supported bilayers composed of dienoyl phosphatidylcholine (PC) lipids is known to greatly enhance their chemical and mechanical stability, however the effects of polymerization on membrane fluidity have not been investigated. Here planar supported lipid bilayers (PSLBs) composed of dienoyl PCs on glass substrates were examined to assess the degree to which UV-initiated polymerization affects lateral lipid mobility. Fluorescence recovery after photobleaching (FRAP) was used to measure the diffusion coefficients (D) and mobile fractions of rhodamine-DOPE in unpolymerized and polymerized PSLBs composed of bis-sorbyl phosphatidylcholine (bis-SorbPC), mono-sorbyl phosphatidylcholine (mono-SorbPC), bis-dienoyl phosphatidylcholine (bis-DenPC) and mono-dienoyl phosphatidylcholine (mono-DenPC). Polymerization was performed in both the Lα and Lβ phase for each lipid. In all cases, polymerization reduced membrane fluidity, however measurable lateral diffusion was retained which is attributed to a low degree of polymerization. The D values for sorbyl lipids were less than those of the denoyl lipids; this may be a consequence of the distal location of polymerizable group in the sorbyl lipids which may facilitate inter-leaflet bonding. The D values measured after polymerization were 0.1 to 0.8 of those measured before polymerization, a range that corresponds to fluidity intermediate between that of a Lα phase and a Lβ phase. This D range is comparable to ratios of D values reported for liquid-disordered (Ld) and liquid-ordered (Lo) lipid phases, and indicates that the effect of UV polymerization on lateral diffusion in a dienoyl PSLB is similar to the transition from a Ld phase to a Lo phase. The partial retention of fluidity in UV polymerized PSLBs, their enhanced stability, and the activity of incorporated transmembrane proteins and peptides is discussed. PMID:26794208

Polymeric nanoparticles for targeted drug delivery system for cancer therapy.

PubMed

Masood, Farha

2016-03-01

A targeted delivery system based on the polymeric nanoparticles as a drug carrier represents a marvelous avenue for cancer therapy. The pivotal characteristics of this system include biodegradability, biocompatibility, non-toxicity, prolonged circulation and a wide payload spectrum of a therapeutic agent. Other outstanding features are their distinctive size and shape properties for tissue penetration via an active and passive targeting, specific cellular/subcellular trafficking pathways and facile control of cargo release by sophisticated material engineering. In this review, the current implications of encapsulation of anticancer agents within polyhydroxyalkanoates, poly-(lactic-co-glycolic acid) and cyclodextrin based nanoparticles to precisely target the tumor site, i.e., cell, tissue and organ are highlighted. Furthermore, the promising perspectives in this emerging field are discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

Polymeric microspheres

DOEpatents

Walt, David R.; Mandal, Tarun K.; Fleming, Michael S.

2004-04-13

The invention features core-shell microsphere compositions, hollow polymeric microspheres, and methods for making the microspheres. The microspheres are characterized as having a polymeric shell with consistent shell thickness.

Preparation of polymeric diacetylene thin films for nonlinear optical applications

NASA Technical Reports Server (NTRS)

Frazier, Donald O. (Inventor); Mcmanus, Samuel P. (Inventor); Paley, Mark S. (Inventor); Donovan, David N. (Inventor)

1995-01-01

A method for producing polymeric diacetylene thin films having desirable nonlinear optical characteristics has been achieved by producing amorphous diacetylene polymeric films by simultaneous polymerization of diacetylene monomers in solution and deposition of polymerized diacetylenes on to the surface of a transparent substrate through which ultraviolet light has been transmitted. These amorphous polydiacetylene films produced by photo-deposition from solution possess very high optical quality and exhibit large third order nonlinear optical susceptibilities, such properties being suitable for nonlinear optical devices such as waveguides and integrated optics.

Raman spectroscopy for the characterization of the polymerization rate in an acrylamide-based photopolymer

NASA Astrophysics Data System (ADS)

Jallapuram, Raghavendra; Naydenova, Izabela; Byrne, Hugh J.; Martin, Suzanne; Howard, Robert; Toal, Vincent

2008-01-01

Investigations of polymerization rates in an acrylamide-based photopolymer are presented. The polymerization rate for acrylamide and methylenebisacrylamide was determined by monitoring the changes in the characteristic vibrational peaks at 1284 and 1607 cm-1 corresponding to the bending mode of the CH bond and CC double bonds of acrylamide and in the characteristic peak at 1629 cm-1 corresponding to the carbon-carbon double bond of methylenebisacrylamide using Raman spectroscopy. To study the dependence of the polymerization rate on intensity and to find the dependence parameter, the polymerization rate constant is measured at different intensities. A comparison with a commercially available photopolymer shows that the polymerization rate in this photopolymer is much faster.

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

PubMed Central

Theriot, Jordan C.; Ryan, Matthew D.; French, Tracy A.; Pearson, Ryan M.; Miyake, Garret M.

2016-01-01

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism. PMID:27166728

Synthesis of nanosized (<20 nm) polymer particles by radical polymerization in miniemulsion employing in situ surfactant formation.

PubMed

Guo, Yi; Zetterlund, Per B

2011-10-18

A novel method for synthesis of ultrafine polymeric nanoparticles of diameters less than 20 nm has been developed. The method is based on miniemulsion polymerization exploiting combination of the in situ surfactant generation approach (whereby the surfactant is formed at the oil-water interface by reaction between an organic acid and a base) and ultrasonication. Conventional radical polymerization and nitroxide-mediated radical polymerization of styrene have been conducted in miniemulsion using oleic acid/potassium hydroxide, demonstrating that particles with diameters less than 20 nm can be obtained by this approach at surfactant contents much lower than traditionally required in microemulsion polymerizations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PREFACE: IUMRS-ICA 2008 Symposium, Sessions 'X. Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science' and 'Y. Frontier of Polymeric Nano-Soft-Materials - Precision Polymer Synthesis, Self-assembling and Their Functionalization'

NASA Astrophysics Data System (ADS)

Takahara, Atsushi; Kawahara, Seiichi

2009-09-01

Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science (Symposium X of IUMRS-ICA2008) Toshiji Kanaya, Kohji Tashiro, Kazuo Sakura Keiji Tanaka, Sono Sasaki, Naoya Torikai, Moonhor Ree, Kookheon Char, Charles C Han, Atsushi Takahara This volume contains peer-reviewed invited and contributed papers that were presented in Symposium X 'Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science' at the IUMRS International Conference in Asia 2008 (IUMRS-ICA 2008), which was held on 9-13 December 2008, at Nagoya Congress Center, Nagoya, Japan. Structure analyses of soft materials based on synchrotron radiation (SR) and neutron beam have been developed steadily. Small-angle scattering and wide-angle diffraction techniques clarified the higher-order structure as well as time dependence of structure development such as crystallization and microphase-separation. On the other hand, reflectivity, grazing-incidence scattering and diffraction techniques revealed the surface and interface structural features of soft materials. From the viewpoint of strong interests on the development of SR and neutron beam techniques for soft materials, the objective of this symposium is to provide an interdisciplinary forum for the discussion of recent advances in research, development, and applications of SR and neutron beams to soft matter science. In this symposium, 21 oral papers containing 16 invited papers and 14 poster papers from China, India, Korea, Taiwan, and Japan were presented during the three-day symposium. As a result of the review of poster and oral presentations of young scientists by symposium chairs, Dr Kummetha Raghunatha Reddy (Toyota Technological Institute) received the IUMRS-ICA 2008 Young Researcher Award. We are grateful to all invited speakers and many participants for valuable contributions and active discussions. Organizing committee of Symposium (IUMRS-ICA 2008) Professor Toshiji Kanaya (Kyoto University) Professor Kohji Tashiro (Toyota Technological Institute) Professor Kazuo Sakurai(Kitakyushu University) Professor Keiji Tanaka (Kyushu University) Dr Sono Sasaki (JASRI/Spring-8) Professor Naoya Torikai (KENS) Professor Moonhor Ree (POSTECH) Professor Kookheon Char (Seoul National University) Professor Charles C Han (CAS) Professor Atsushi Takahara(Kyushu University) Frontier of Polymeric Nano-Soft-Materials, Precision Polymer Synthesis, Self-assembling and Their Functionalization (Symposium Y of IUMRS-ICA2008) Seiichi Kawahara, Rong-Ming Ho, Hiroshi Jinnai, Masami Kamigaito, Takashi Miyata, Hiroshi Morita, Hideyuki Otsuka, Daewon Sohn, Keiji Tanaka It is our great pleasure and honor to publish peer-reviewed papers, presented in Symposium Y 'Frontier of Polymeric Nano-Soft-Materials Precision Polymer Synthesis, Self-assembling and Their Functionalization' at the International Union of Materials Research Societies International Conference in Asia 2008 (IUMRS-ICA2008), which was held on 9-13 December 2008, at Nagoya Congress Center, Nagoya, Japan. 'Polymeric nano-soft-materials' are novel outcomes based on a recent innovative evolution in polymer science, i.e. precision polymer synthesis, self-assembling and functionalization of multi-component systems. The materials are expected to exhibit specific functions and unique properties due to their hierarchic morphologies brought either by naturally-generated ordering or by artificial manipulation of the systems, e.g., crystallization and phase-separation. The emerging precision synthesis has brought out new types of polymers with well-controlled primary structures. Furthermore, the surface and interface of the material are recognized to play an important role in the outstanding mechanical, electrical and optical properties, which are required for medical and engineering applications. In order to understand structure-property relationships in the nano-soft-materials, it is indispensable to develop novel characterization techniques. Symposium Y aimed to provide recent advances in polymer synthesis, self-assembling processes and morphologies, and functionalization of nano-soft-materials in order to initiate mutual and collaborative research interest that is essential to develop revolutionarily new nano-soft-materials in the decades ahead. Four Keynote lectures, 15 invited talks and 30 posters presented important new discoveries in polymeric nano-soft-materials, precision polymer synthesis, self-assembling and their functionalization. As for the precision polymer synthesis, the latest results were provided for studies on synthesis of polyrotaxane with movable graft chains, organic-inorganic hybridization of polymers, supra-molecular coordination assembly of conjugated polymers, precision polymerization of adamantane-containing monomers, production of high density polymer brush and synthesis of rod coil type polymer. The state-of-the-art results were introduced for the formation of nano-helical-structure of block copolymer containing asymmetric carbon atoms, self-assembling of block copolymers under the electric field, self-assembling of liquid crystalline elastomers, preparation of nano cylinder template films and mesoscopic simulation of phase transition of polymers and so forth. Moreover, recent advantages of three-dimensional electron microtomography and scanning force microscopy were proposed for analyses of nano-structures and properties of polymeric multi-component systems. Syntheses, properties and functions of slide-ring-gel, organic-inorganic hybrid hydrogels, hydrogel nano-particles, liquid-crystalline gels, the self-oscillating gels, and double network gels attracted participants' attention. Modifications of naturally occurring polymeric materials with supercritical carbon dioxide were introduced as a novel technology. Some of the attractive topics are presented in this issue. We are grateful to all the speakers and participants for valuable contributions and active discussions. Organizing committee of Symposium Y (IUMRS-ICA 2008) Chair Seiichi Kawahara (Nagaoka University of Technology, Japan) Vice Chairs Rong-Ming Ho (National Tsing Hua University, Taiwan) Hiroshi Jinnai (Kyoto Institute of Technology, Japan) Masami Kamigaito (Nagoya University, Japan) Takashi Miyata (Kansai University, Japan) Hiroshi Morita (National Institute of Advanced Industrial Science and Technology, Japan) Hideyuki Otsuka (Kyushu University, Japan) Daewon Sohn (Hanyang University, Korea) Keiji Tanaka (Kyushu University, Japan)

Interfacial Stacks of Polymeric Nanofilms on Soft Biological Surfaces that Release Multiple Agents.

PubMed

Herron, Maggie; Schurr, Michael J; Murphy, Christopher J; McAnulty, Jonathan F; Czuprynski, Charles J; Abbott, Nicholas L

2016-10-03

We report a general and facile method that permits the transfer (stacking) of multiple independently fabricated and nanoscopically thin polymeric films, each containing a distinct bioactive agent, onto soft biomedically relevant surfaces (e.g., collagen-based wound dressings). By using polyelectrolyte multilayer films (PEMs) formed from poly(allyl amine hydrochloride) and poly(acrylic acid) as representative polymeric nanofilms and micrometer-thick water-soluble poly(vinyl alcohol) sacrificial films to stack the PEMs, we demonstrate that it is possible to create stacked polymeric constructs containing multiple bioactive agents (e.g., antimicrobial and antibiofilm agents) on soft and chemically complex surfaces onto which PEMs cannot be routinely transferred by stamping. We illustrate the characteristics and merits of the approach by fabricating stacks of Ga 3+ (antibiofilm agent)- and Ag + (antimicrobial agent)-loaded PEMs as prototypical examples of agent-containing PEMs and demonstrate that the stacked PEMs incorporate precise loadings of the agents and provide flexibility in terms of tuning release rates. Specifically, we show that simultaneous release of Ga 3+ and Ag + from the stacked PEMs on collagen-based wound dressings can lead to synergistic effects on bacteria, killing and dispersing biofilms formed by Pseudomonas aeruginosa (two strains: ATCC 27853 and MPAO1) at sufficiently low loadings of agents such that cytotoxic effects on mammalian cells are avoided. The approach is general (a wide range of bioactive agents other than Ga 3+ and Ag + can be incorporated into PEMs), and the modular nature of the approach potentially allows end-user functionalization of soft biological surfaces for programmed release of multiple bioactive agents.

Measuring the Acoustic Release of a Chemotherapeutic Agent from Folate-Targeted Polymeric Micelles.

PubMed

Abusara, Ayah; Abdel-Hafez, Mamoun; Husseini, Ghaleb

2018-08-01

In this paper, we compare the use of Bayesian filters for the estimation of release and re-encapsulation rates of a chemotherapeutic agent (namely Doxorubicin) from nanocarriers in an acoustically activated drug release system. The study is implemented using an advanced kinetic model that takes into account cavitation events causing the antineoplastic agent's release from polymeric micelles upon exposure to ultrasound. This model is an improvement over the previous representations of acoustic release that used simple zero-, first- and second-order release and re-encapsulation kinetics to study acoustically triggered drug release from polymeric micelles. The new model incorporates drug release and micellar reassembly events caused by cavitation allowing for the controlled release of chemotherapeutics specially and temporally. Different Bayesian estimators are tested for this purpose including Kalman filters (KF), Extended Kalman filters (EKF), Particle filters (PF), and multi-model KF and EKF. Simulated and experimental results are used to verify the performance of the above-mentioned estimators. The proposed methods demonstrate the utility and high-accuracy of using estimation methods in modeling this drug delivery technique. The results show that, in both cases (linear and non-linear dynamics), the modeling errors are expensive but can be minimized using a multi-model approach. In addition, particle filters are more flexible filters that perform reasonably well compared to the other two filters. The study improved the accuracy of the kinetic models used to capture acoustically activated drug release from polymeric micelles, which may in turn help in designing hardware and software capable of precisely controlling the delivered amount of chemotherapeutics to cancerous tissue.

Deposition of functionalized polymer layers in surface plasmon resonance immunosensors by in-situ polymerization in the evanescent wave field.

PubMed

Chegel, Vladimir; Whitcombe, Michael J; Turner, Nicholas W; Piletsky, Sergey A

2009-01-01

Traditionally, the integration of sensing gel layers in surface plasmon resonance (SPR) is achieved via "bulk" methods, such as precipitation, spin-coating or in-situ polymerization onto the total surface of the sensor chip, combined with covalent attachment of the antibody or receptor to the gel surface. This is wasteful in terms of materials as the sensing only occurs at the point of resonance interrogated by the laser. By isolating the sensing materials (antibodies, enzymes, aptamers, polymers, MIPs, etc.) to this exact spot a more efficient use of these recognition elements will be achieved. Here we present a method for the in-situ formation of polymers, using the energy of the evanescent wave field on the surface of an SPR device, specifically localized at the point of interrogation. Using the photo-initiator couple of methylene blue (sensitizing dye) and sodium p-toluenesulfinate (reducing agent) we polymerized a mixture of N,N-methylene-bis-acrylamide and methacrylic acid in water at the focal point of SPR. No polymerization was seen in solution or at any other sites on the sensor surface. Varying parameters such as monomer concentration and exposure time allowed precise control over the polymer thickness (from 20-200 nm). Standard coupling with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide was used for the immobilization of protein G which was used to bind IgG in a typical biosensor format. This model system demonstrated the characteristic performance for this type of immunosensor, validating our deposition method.

Delayed photo-activation and addition of thio-urethane: Impact on polymerization kinetics and stress of dual-cured resin cements.

PubMed

Faria-E-Silva, André L; Pfeifer, Carmem S

2017-10-01

1) to determine the moment during the redox polymerization reaction of dual cure cements at which to photo-activate the material in order to reduce the polymerization stress, and 2) to evaluate possible synergistic effects between adding chain transfer agents and delayed photo-activation. The two pastes of an experimental dual-cure material were mixed, and the polymerization kinetics of the redox phase was followed. The moment when the material reached its maximum rate of redox polymerization (MRRP) of cement was determined. The degree of conversion (DC) and maximum rates of polymerization (Rp max ) were assessed for materials where: the photoactivation immediately followed material mixing, at MRRP, 1min before and 1min after MRRP. Thio-urethane (TU) additives were synthesized and added to the cement (20% wt), which was then cured under the same conditions. The polymerization kinetics was evaluated for both cements photo-activated immediately or at MRRP, followed by measurements of polymerization stress, flexural strength (FS) and elastic modulus (EM). Knoop hardness was measured before and after ethanol storage. Photo-activating the cement at or after MRRP reduced the Rp max and the polymerization stress. Addition of TU promoted additional and more significant reduction, while not affecting the Rp max . Greater hardness loss was observed for cements with TU, but the final hardness was similar for all experimental conditions. Addition of TU slightly reduced the EM and did not affect the FS. Delayed photo-activation and addition of TU significantly reduce the polymerization stress of dual-cured cements. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed Central

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

2011-01-01

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

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

PubMed

Sancho, J; Egido, J; González, E

1983-06-10

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

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

PubMed

Naresh, S; Atreja, S K

2015-12-01

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

Thermoset molecular composites

DOEpatents

Benicewicz, Brian C.; Douglas, Elliot P.; Hjelm, Jr., Rex P.

1996-01-01

A polymeric composition including a liquid crystalline polymer and a thermosettable liquid crystalline monomer matrix, said polymeric composition characterized by a phase separation on the scale of less than about 500 Angstroms and a polymeric composition including a liquid crystalline polymer and a liquid crystalline thermoset matrix, said polymeric composition characterized by a phase separation on the scale of less than about 500 Angstroms are disclosed.

Ion-Molecule Association in Acrylonitrile

NASA Technical Reports Server (NTRS)

Wilson, Paul F.; Milligan, Daniel B.; McEwan, Murray J.

1997-01-01

Acrylonitrile (propernenitrile or vinyl cyanide) polymerizes readily via a radical mechanism in solution at room temparature. The propensity to polymerize is sufficiently strong that it is usual to add a radical scavenger to the solution to prevent polymerization when oxygen (an inhibitor) is removed. Polymerization of acrylonitrile is also know to occur via nucleophilic addition of an anion by a michael-type reaction.

Changes in chroma of two indirect composite materials polymerized with different polymerization systems.

PubMed

Ayano, Michiya

2012-01-01

This study evaluated chroma change in two composite materials (Sinfony and Pearleste) polymerized with two different systems. Disk specimens were prepared using a metal halide unit (Hyper LII) and an exposure time of 60 to 180 s. The proprietary polymerization systems (Visio and Pearlcure systems) were used as the reference polymerization modes. After storage at 37°C for 24 h, CIE 1976 L*a*b* values were measured by using a dental chroma meter (ShadeEye NCC) with a gray background. The specimens were then immersed in water or tea. Color change from baseline to 4 weeks was evaluated by measuring ΔL*, Δa*, and Δb*, after which ΔE*(ab) values were calculated. The brightness of Sinfony specimens was reduced by tea immersion. The color of both materials shifted to yellow after tea immersion, although color change in Sinfony specimens was greater than that in Pearleste specimens. For both materials, color change was less after polymerization with the metal halide unit. In conclusion, Sinfony polymerized with the Hyper LII unit, and Pearleste polymerized with either system, were stable against discoloration due to tea immersion.

[The influence of polymerization time on physicochemical properties of the acrylic resin Vertex RS].

PubMed

Fraczak, Bogumiła; Sobolewska, Ewa; Ey-Chmielewska, Halina; Skowronek, Maria; Błazewicz, Stanisław

2009-01-01

A good denture can only be produced through proper actions during the clinical and laboratory stages of the production process. The aim of this study was to determine if a change in polymerization time affects the physicochemical properties of polymethacrylate material used for dentures. We examined the acrylic resin Vertex R.S. polymerized for 15, 25, 40, or 60 minutes. Palapress Vario was taken as reference material. Static bending, microhardness, surface wettability, and susceptibility to abrasion were determined. The microhardness test showed that most of the samples had similar Vickers hardness (VS) values, except for the sample polymerized for 25 min. which demonstrated a significantly higher value. Grindability was affected by a change in polymerization time. Mass loss was greatest for samples polymerized for 15, 25, and 60 min. and smallest for Vertex 40 and Palapress Vario. We also observed differences in the wetting angle. Vertex 40 and 60 had a relatively low wetting angle signifying that longer polymerization time results in lower hydrophobicity of the material. The present study has demonstrated that polymerization time has a significant effect on the hardness and some mechanical properties of the acrylic resin.

Induction of HoxB Transcription by Retinoic Acid Requires Actin Polymerization

PubMed Central

Ferrai, Carmelo; Naum-Onganía, Gabriela; Longobardi, Elena; Palazzolo, Martina; Disanza, Andrea; Diaz, Victor M.; Crippa, Massimo P.; Scita, Giorgio

2009-01-01

We have analyzed the role of actin polymerization in retinoic acid (RA)-induced HoxB transcription, which is mediated by the HoxB regulator Prep1. RA induction of the HoxB genes can be prevented by the inhibition of actin polymerization. Importantly, inhibition of actin polymerization specifically affects the transcription of inducible Hox genes, but not that of their transcriptional regulators, the RARs, nor of constitutively expressed, nor of actively transcribed Hox genes. RA treatment induces the recruitment to the HoxB2 gene enhancer of a complex composed of “elongating” RNAPII, Prep1, β-actin, and N-WASP as well as the accessory splicing components p54Nrb and PSF. We show that inhibition of actin polymerization prevents such recruitment. We conclude that inducible Hox genes are selectively sensitive to the inhibition of actin polymerization and that actin polymerization is required for the assembly of a transcription complex on the regulatory region of the Hox genes. PMID:19477923

Induction of HoxB transcription by retinoic acid requires actin polymerization.

PubMed

Ferrai, Carmelo; Naum-Onganía, Gabriela; Longobardi, Elena; Palazzolo, Martina; Disanza, Andrea; Diaz, Victor M; Crippa, Massimo P; Scita, Giorgio; Blasi, Francesco

2009-08-01

We have analyzed the role of actin polymerization in retinoic acid (RA)-induced HoxB transcription, which is mediated by the HoxB regulator Prep1. RA induction of the HoxB genes can be prevented by the inhibition of actin polymerization. Importantly, inhibition of actin polymerization specifically affects the transcription of inducible Hox genes, but not that of their transcriptional regulators, the RARs, nor of constitutively expressed, nor of actively transcribed Hox genes. RA treatment induces the recruitment to the HoxB2 gene enhancer of a complex composed of "elongating" RNAPII, Prep1, beta-actin, and N-WASP as well as the accessory splicing components p54Nrb and PSF. We show that inhibition of actin polymerization prevents such recruitment. We conclude that inducible Hox genes are selectively sensitive to the inhibition of actin polymerization and that actin polymerization is required for the assembly of a transcription complex on the regulatory region of the Hox genes.

L-Lactide Ring-Opening Polymerization with Tris(acetylacetonate)Titanium(IV) for Renewable Material.

PubMed

Kim, Da Hee; Yoo, Ji Yun; Ko, Young Soo

2016-05-01

A new Ti-type of catalyst for L-lactide polymerization was synthesized by reaction of titanium(IV) isopropoxide (TTIP) with acetylacetone (AA). Moreover, PLA was prepared by the bulk ring-opening polymerization using synthesized Ti catalyst. Polymerization behaviors were examined depending on monomer/catalyst molar ratio, polymerization temperature and time. The structure of synthesized catalysts was verified with FT-IR and 1H NMR and the properties of poly(L-lactide) (PLLA) were examined by GPC, DSC and FT-IR. There existed about 30 minutes of induction time at the monomer/catalyst molar ratio of 300. The molecular weight (MW) increased as monomer/catalyst molar ratio increased. The MW increased almost linearly as polymerization progressed. Increasing polymerization temperature increased the molecular weight of PLLA as well as monomer/catalyst molar ratio. The melting point (T(m)) of polymers was in the range of 142 to 167 degrees C. Lower T(m) was expected to be resulted from relatively lower molecular weight.

Characteristics of low polymerization shrinkage flowable resin composites in newly-developed cavity base materials for bulk filling technique.

PubMed

Nitta, Keiko; Nomoto, Rie; Tsubota, Yuji; Tsuchikawa, Masuji; Hayakawa, Tohru

2017-11-29

The purpose of this study was to evaluate polymerization shrinkage and other physical properties of newly-developed cavity base materials for bulk filling technique, with the brand name BULK BASE (BBS). Polymerization shrinkage was measured according to ISO/FDIS 17304. BBS showed the significantly lowest polymerization shrinkage and significantly higher depth of cure than conventional flowable resin composites (p<0.05). The Knoop hardness, flexural strength and elastic modulus of that were significantly lower than conventional flowable resin composites (p<0.05). BBS had the significantly greatest filler content (p<0.05). SEM images of the surface showed failure of fillers. The lowest polymerization shrinkage was due to the incorporation of a new type of low shrinkage monomer, which has urethane moieties. There were no clear correlations between inorganic filler contents and polymerization shrinkage, flexural strength and elastic modulus. In conclusion, the low polymerization shrinkage of BBS will be useful for cavity treatment in dental clinics.

Polymeric Janus Nanoparticles: Recent Advances in Synthetic Strategies, Materials Properties, and Applications.

PubMed

Fan, Xiaoshan; Yang, Jing; Loh, Xian Jun; Li, Zibiao

2018-06-13

Polymeric Janus nanoparticles with two sides of incompatible chemistry have received increasing attention due to their tunable asymmetric structure and unique material characteristics. Recently, with the rapid progress in controlled polymerization combined with novel fabrication techniques, a large array of functional polymeric Janus particles are diversified with sophisticated architecture and applications. In this review, the most recently developed strategies for controlled synthesis of polymeric Janus nanoparticles with well-defined size and complex superstructures are summarized. In addition, the pros and cons of each approach in mediating the anisotropic shapes of polymeric Janus particles as well as their asymmetric spatial distribution of chemical compositions and functionalities are discussed and compared. Finally, these newly developed structural nanoparticles with specific shapes and surface functions orientated applications in different domains are also discussed, followed by the perspectives and challenges faced in the further advancement of polymeric Janus nanoparticles as high performance materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterogeneous chemical reactions: Preparation of monodisperse latexes

NASA Technical Reports Server (NTRS)

Vanderhoff, J. W.; Micale, F. J.; El-Aasser, M. S.; Sterk, A. A.; Bethke, G. W.

1977-01-01

It is demonstrated that a photoinitiated emulsion polymerization can be carried out to a significant conversion in a SPAR rocket prototype polymerization vessel within the six minutes allowed for the experiment. The percentage of conversion was determined by both dilatometry and gravimetric methods with good agreement. The experimental results lead to the following conclusions: (1) emulsion polymerizations can be carried out to conversions as high as 75%, using a stable micellized styrene-SLS system plus photoinitiator; (2) dilatometry can be used to accurately determine both the rate and conversion of polymerization; (3) thermal expansion due to the light source and heat of reaction is small and can be corrected for if necessary; (4) although seeded emulsion polymerizations are unfavorable in photoinitiation, as opposed to chemical initiation, polymerizations can be carried out to at least 15% conversion using 7940A seed particles, with 0.05% solids; and (5) photoinitiation should be used to initiate polymerization in the SPAR rocket experiments because of the mechanical simplicity of the experiment.

Noncovalent assembly. A rational strategy for the realization of chain-growth supramolecular polymerization.

PubMed

Kang, Jiheong; Miyajima, Daigo; Mori, Tadashi; Inoue, Yoshihisa; Itoh, Yoshimitsu; Aida, Takuzo

2015-02-06

Over the past decade, major progress in supramolecular polymerization has had a substantial effect on the design of functional soft materials. However, despite recent advances, most studies are still based on a preconceived notion that supramolecular polymerization follows a step-growth mechanism, which precludes control over chain length, sequence, and stereochemical structure. Here we report the realization of chain-growth polymerization by designing metastable monomers with a shape-promoted intramolecular hydrogen-bonding network. The monomers are conformationally restricted from spontaneous polymerization at ambient temperatures but begin to polymerize with characteristics typical of a living mechanism upon mixing with tailored initiators. The chain growth occurs stereoselectively and therefore enables optical resolution of a racemic monomer. Copyright © 2015, American Association for the Advancement of Science.

Amphiphilic graft polymer with reduction breakable main chain prepared via click polymerization and grafting onto

NASA Astrophysics Data System (ADS)

Zhang, Xiaojin; Dai, Yu

2018-06-01

Amphiphilic graft polymer PSS- g-Pal/PEG with reduction breakable main chain was synthesized via click polymerization of dialkynyl (containing disulfide bond) and diazide (containing pendant diol) and one-pot grafting onto of hydrophobic palmitate (Pal) and hydrophilic methoxy poly(ethylene glycol) (PEG). PSS- g-Pal/PEG is able to form polymeric micelles by self-assembly in water via dialysis. Polymeric micelles are nano-sized spheres and the particle size is approximately 70 nm. Of note, polymeric micelles are reduction-responsive owing to the disulfide bonds in main chain of PSS- g-Pal/PEG. Therefore, polymeric micelles prepared from amphiphilic graft polymer PSS- g-Pal/PEG are able to fast release the drugs in the presence of the reducing agents such as DL-dithiothreitol (DTT).

Anionic polymerization of p-(2,2'-diphenylethyl)styrene and applications to graft copolymers.

PubMed

Huang, Minglu; Han, Bingyong; Lu, Jianmin; Yang, Wantai; Fu, Zhifeng

2017-01-01

Well-controlled anionic polymerization of an initiator-functionalized monomer, p -(2,2'-diphenylethyl)styrene (DPES), was achieved for the first time. The polymerization was performed in a mixed solvent of cyclohexane and tetrahydrofuran (THF) at 40 °C with n -BuLi as initiator. When the volume ratio of cyclohexane to THF was 20, the anionic polymerization of DPES showed living polymerization characteristics, and well-defined block copolymer PDPES- b -PS was successfully synthesized. Furthermore, radical polymerization of methyl methacrylate in the presence of PDPES effectively afforded a graft copolymer composed of a polystyrene backbone and poly(methyl methacrylate) branches. The designation of analogous monomers and polymers was of great significance to synthesize a variety of sophisticated copolymer and functionalize polymer materials.

Monitoring technology

NASA Technical Reports Server (NTRS)

Stevenson, William A. (Inventor)

1989-01-01

A process for infrared spectroscopic monitoring of insitu compositional changes in a polymeric material comprises the steps of providing an elongated infrared radiation transmitting fiber that has a transmission portion and a sensor portion, embedding the sensor portion in the polymeric material to be monitored, subjecting the polymeric material to a processing sequence, applying a beam of infrared radiation to the fiber for transmission through the transmitting portion to the sensor portion for modification as a function of properties of the polymeric material, monitoring the modified infrared radiation spectra as the polymeric material is being subjected to the processing sequence to obtain kinetic data on changes in the polymeric material during the processing sequence, and adjusting the processing sequence as a function of the kinetic data provided by the modified infrared radiation spectra information.

Monitoring technology

NASA Technical Reports Server (NTRS)

Stevenson, William A. (Inventor)

1992-01-01

A process for infrared spectroscopic monitoring of insitu compositional changes in a polymeric material comprises the steps of providing an elongated infrared radiation transmitting fiber that has a transmission portion and a sensor portion, embedding the sensor portion in the polymeric material to be monitored, subjecting the polymeric material to a processing sequence, applying a beam of infrared radiation to the fiber for transmission through the transmitting portion to the sensor portion for modification as a function of properties of the polymeric material, monitoring the modified infrared radiation spectra as the polymeric material is being subjected to the processing sequence to obtain kinetic data on changes in the polymeric material during the processing sequence, and adjusting the processing sequence as a function of the kinetic data provided by the modified infrared radiation spectra information.

Polymerization of the tubulin-colchicine complex: relation to microtubule assembly.

PubMed

Andreu, J M; Wagenknecht, T; Timasheff, S N

1983-03-29

The polymerization of purified tubulin-colchicine complex, which results in polymers different from microtubules under microtubule-promoting conditions, has been characterized. It proceeds as a nucleated condensation polymerization, requires Mg2+, and is inhibited by small concentrations of Ca2+. Polymerization requires GTP binding, but GDP is inhibitory. The GTPase activity proceeds, but it is unlinked to polymerization. The thermodynamic characteristics of the growth reaction, namely, the apparent changes of free energy, enthalpy, entropy, heat capacity, and preferential interaction with H+ and Mg2+, are very similar to those of microtubule assembly. It is proposed that the interactions responsible for the two types of polymerization are very similar and that the molecular mechanism of microtubule inhibition by colchicine may consist in a drug-induced distortion of the normal protomer bonding geometry.

Polymeric membrane materials for artificial organs.

PubMed

Kawakami, Hiroyoshi

2008-01-01

Many polymeric materials have already been used in the field of artificial organs. However, the materials used in artificial organs are not necessarily created with the best material selectivity and materials design; therefore, the development of synthesized polymeric membrane materials for artificial organs based on well-defined designs is required. The approaches to the development of biocompatible polymeric materials fall into three categories: (1) control of physicochemical characteristics on material surfaces, (2) modification of material surfaces using biomolecules, and (3) construction of biomimetic membrane surfaces. This review will describe current issues regarding polymeric membrane materials for use in artificial organs.

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

PubMed

Liu, Lianying; Ren, Mingwei; Yang, Wantai

2009-09-15

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

In vivo polymerization of poly(3,4-ethylenedioxythiophene) in the living rat hippocampus does not cause a significant loss of performance in a delayed alternation task

NASA Astrophysics Data System (ADS)

Ouyang, Liangqi; Shaw, Crystal L.; Kuo, Chin-chen; Griffin, Amy L.; Martin, David C.

2014-04-01

After extended implantation times, traditional intracortical neural probes exhibit a foreign-body reaction characterized by a reactive glial sheath that has been associated with increased system impedance and signal deterioration. Previously, we have proposed that the local in vivo polymerization of an electronically and ionically conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), might help to rebuild charge transport pathways across the glial scar between the device and surrounding parenchyma (Richardson-Burns et al 2007 J. Neural Eng. 4 L6-13). The EDOT monomer can be delivered via a microcannula/electrode system into the brain tissue of living animals followed by direct electrochemical polymerization, using the electrode itself as a source of oxidative current. In this study, we investigated the long-term effect of local in vivo PEDOT deposition on hippocampal neural function and histology. Rodent subjects were trained on a hippocampus-dependent task, delayed alternation (DA), and implanted with the microcannula/electrode system in the hippocampus. The animals were divided into four groups with different delay times between the initial surgery and the electrochemical polymerization: (1) control (no polymerization), (2) immediate (polymerization within 5 min of device implantation), (3) early (polymerization within 3-4 weeks after implantation) and (4) late (polymerization 7-8 weeks after polymerization). System impedance at 1 kHz was recorded and the tissue reactions were evaluated by immunohistochemistry. We found that under our deposition conditions, PEDOT typically grew at the tip of the electrode, forming an ˜500 µm cloud in the tissue. This is much larger than the typical width of the glial scar (˜150 µm). After polymerization, the impedance amplitude near the neurologically important frequency of 1 kHz dropped for all the groups; however, there was a time window of 3-4 weeks for an optimal decrease in impedance. For all surgery-polymerization time intervals, the polymerization did not cause significant deficits in performance of the DA task, suggesting that hippocampal function was not impaired by PEDOT deposition. However, GFAP+ and ED-1+ cells were also found at the deposition two weeks after the polymerization, suggesting potential secondary scarring. Therefore, less extensive deposition or milder deposition conditions may be desirable to minimize this scarring while maintaining decreased system impedance.

In vivo polymerization of poly(3,4-ethylenedioxythiophene) (PEDOT) in living rat hippocampus does not cause a significant loss of performance in a delayed alternation (DA) task

PubMed Central

Ouyang, Liangqi; Shaw, Crystal L.; Kuo, Chin-chen; Griffin, Amy L.; Martin, David C.

2014-01-01

After extended implantation times, traditional intracortical neural probes exhibit a foreign body reaction characterized by a reactive glial sheath that has been associated with increased system impedance and signal deterioration. Previously, we have proposed that the local in vivo polymerization of an electronically and ionically conducting polymer, poly(3,4 ethylene dioxythiophene) (PEDOT), might help to rebuild charge transport pathways across the glial scar between the device and surrounding parenchyma (Richardson-Burns, Hendricks, & Martin, 2007). The EDOT monomer can be delivered via a microcannula/electrode system into the brain tissue of living animals followed by direct electrochemical polymerization, using the electrode itself as a source of oxidative current. In this study we investigated the long-term effect of local in vivo PEDOT deposition on hippocampal neural function and histology. Rodent subjects were trained on a hippocampus-dependent task, Delayed Alternation (DA), and implanted with the microcannula/electrode system in the hippocampus. The animals were divided into four groups with different delay times between the initial surgery and the electrochemical polymerization: (1) Control (no polymerization), (2) Immediate (polymerization within 5 minutes of device implantation), (3) Early (polymerization within 3–4 weeks after implantation), and (4) Late (polymerization 7–8 weeks after polymerization). System impedance at 1 kHz was recorded and the tissue reactions were evaluated by immunohistochemistry. We found that under our deposition conditions, PEDOT typically grew at the tip of the electrode, forming a ~500 μm cloud into the tissue. This is much larger than the typical width of the glial scar (~150 μm). After polymerization, the impedance amplitude near the neurologically important frequency of 1 kHz dropped for all the groups, however, there was a time window of 3–4 weeks for optimal decrease in impedance. For all surgery-polymerization time intervals, the polymerization did not cause significant deficits in performance of the DA task, suggesting that hippocampal function was not impaired by PEDOT deposition. However, GFAP+ and ED-1+ cells were also found at the deposition 2 weeks after the polymerization, suggesting potential secondary scarring. Therefore less extensive deposition or milder deposition conditions may be desirable to minimize this scarring while maintaining decreased system impedance. PMID:24503720

Low-melting elemental metal or fusible alloy encapsulated polymerization initiator for delayed initiation

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

Hermes, Robert E.

2017-08-15

An encapsulated composition for polymerization includes an initiator composition for initiating a polymerization reaction, and a capsule prepared from an elemental metal or fusible alloy having a melting temperature from about 20.degree. C. to about 200.degree. C. A fluid for polymerization includes the encapsulated composition and a monomer. When the capsule melts or breaks open, the initiator is released.

Acrylic esters in radiation polymerization

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

Fomina, N.V.; Khoromskaya, V.A.; Shiryaeva, G.V.

1988-03-01

The radiation behavior of (meth)acrylic esters of varying structure was studied. It was shown that in radiation polymerization, in contrast to thermal polymerization, the structure of the ester part can significantly affect the reaction rate and capacity for polymerization in the presence of oxygen. The experimental data are explained from the point of view of consideration of nonvalence effects of the substitutent on the reactivity of the double bond.

Sequence-Controlled Polymerization on Facially Amphiphilic Templates at Interfaces

DTIC Science & Technology

2016-06-14

controlled chain growth polymerization. We will synthesize a ?- conjugated “parent” polymer by iterative exponential growth (IEG), attach cyclic olefin...template that is programmed to direct sequence- controlled chain growth polymerization. We will synthesize a ?- conjugated “parent” polymer by iterative...polymerization. We will synthesize a π- conjugated “parent” polymer by organometallic iterative exponential growth (IEG),2 attach cyclic olefin “daughter

Two-Photon Polymerization of Defects in Photonic Crystals

DTIC Science & Technology

2006-01-01

technique employs two-photon polymerization (TPP) (for description, see Section 2.2) to fabricate high-resolution 3D embedded polymer features within... polymer , and therefore does not influence the polymerization . The image contrast is from the different reflectivities of the interfaces in the system due...Spectroscopy also confirmed for the first time the successful polymerization of a uniform, dense polymer feature throughout the thickness of the

EFFECT OF CONVENTIONAL AND EXPERIMENTAL GINGIVAL RETRACTION SOLUTIONS ON THE TENSILE STRENGTH AND INHIBITION OF POLYMERIZATION OF FOUR TYPES OF IMPRESSION MATERIALS

PubMed Central

Sábio, Sérgio; Franciscone, Paulo Afonso; Mondelli, José

2008-01-01

In the present study, two types of tests (tensile strength test and polymerization inhibition test) were performed to evaluate the physical and chemical properties of four impression materials [a polysulfide (Permlastic), a polyether (Impregum), a condensation silicone (Xantopren) and a polyvinylsiloxane (Aquasil)] when polymerized in contact with of one conventional (Hemostop) and two experimental (Vislin and Afrin) gingival retraction solutions. For the tensile strength test, the impression materials were mixed and packed into a steel plate with perforations that had residues of the gingival retraction solutions. After polymerization, the specimens were tested in tensile strength in a universal testing machine. For the polymerization inhibition test, specimens were obtained after taking impressions from a matrix with perforations that contained 1 drop of the gingival retraction solutions. Two independent examiners decided on whether or not impression material remnants remained unpolymerized, indicating interference of the chemical solutions. Based on the analysis of the results of both tests, the following conclusions were reached: 1. The tensile strength of the polysulfide decreased after contact with Hemostop and Afrin. 2. None of the chemical solutions inhibited the polymerization of the polysulfide; 3. The polyether presented lower tensile strength after polymerization in contact with the three gingival retraction agents; 4. The polyether had its polymerization inhibited only by Hemostop; 5. None of the chemical solutions affected the tensile strength of the condensation silicone; 6. Only Hemostop inhibited the polymerization of the condensation silicone; 7. The polyvinylsiloxane specimens polymerized in contact with Hemostop had significantly lower tensile strength; 8. Neither of the chemical solutions (Afrin and Vislin) affected the tensile strength of the polyvinylsiloxane and the condensation silicone; 9. Results of the tensile strength and polymerization inhibition tests suggest that Vislin can be used as substance of gingival retraction without affecting the tested properties of four impression materials. PMID:19089261

Effect of conventional and experimental gingival retraction solutions on the tensile strength and inhibition of polymerization of four types of impression materials.

PubMed

Sábio, Sérgio; Franciscone, Paulo Afonso; Mondelli, José

2008-01-01

In the present study, two types of tests (tensile strength test and polymerization inhibition test) were performed to evaluate the physical and chemical properties of four impression materials [a polysulfide (Permlastic), a polyether (Impregum), a condensation silicone (Xantopren) and a polyvinylsiloxane (Aquasil)] when polymerized in contact with of one conventional (Hemostop) and two experimental (Vislin and Afrin) gingival retraction solutions. For the tensile strength test, the impression materials were mixed and packed into a steel plate with perforations that had residues of the gingival retraction solutions. After polymerization, the specimens were tested in tensile strength in a universal testing machine. For the polymerization inhibition test, specimens were obtained after taking impressions from a matrix with perforations that contained 1 drop of the gingival retraction solutions. Two independent examiners decided on whether or not impression material remnants remained unpolymerized, indicating interference of the chemical solutions. Based on the analysis of the results of both tests, the following conclusions were reached: 1. The tensile strength of the polysulfide decreased after contact with Hemostop and Afrin. 2. None of the chemical solutions inhibited the polymerization of the polysulfide; 3. The polyether presented lower tensile strength after polymerization in contact with the three gingival retraction agents; 4. The polyether had its polymerization inhibited only by Hemostop; 5. None of the chemical solutions affected the tensile strength of the condensation silicone; 6. Only Hemostop inhibited the polymerization of the condensation silicone; 7. The polyvinylsiloxane specimens polymerized in contact with Hemostop had significantly lower tensile strength; 8. Neither of the chemical solutions (Afrin and Vislin) affected the tensile strength of the polyvinylsiloxane and the condensation silicone; 9. Results of the tensile strength and polymerization inhibition tests suggest that Vislin can be used as substance of gingival retraction without affecting the tested properties of four impression materials.

Polymerization of perfluorobutadiene

NASA Technical Reports Server (NTRS)

Newman, J.; Toy, M. S.

1970-01-01

Diisopropyl peroxydicarbonate dissolved in liquid perfluorobutadiene is conducted in a sealed vessel at the autogenous pressure of polymerization. Reaction temperature, ratio of catalyst to monomer, and amount of agitation determine degree of polymerization and product yield.

DNA-Templated Polymerization of Side-Chain-Functionalized Peptide Nucleic Acid Aldehydes

PubMed Central

Kleiner, Ralph E.; Brudno, Yevgeny; Birnbaum, Michael E.; Liu, David R.

2009-01-01

The DNA-templated polymerization of synthetic building blocks provides a potential route to the laboratory evolution of sequence-defined polymers with structures and properties not necessarily limited to those of natural biopolymers. We previously reported the efficient and sequence-specific DNA-templated polymerization of peptide nucleic acid (PNA) aldehydes. Here, we report the enzyme-free, DNA-templated polymerization of side-chain-functionalized PNA tetramer and pentamer aldehydes. We observed that the polymerization of tetramer and pentamer PNA building blocks with a single lysine-based side chain at various positions in the building block could proceed efficiently and sequence-specifically. In addition, DNA-templated polymerization also proceeded efficiently and in a sequence-specific manner with pentamer PNA aldehydes containing two or three lysine side chains in a single building block to generate more densely functionalized polymers. To further our understanding of side-chain compatibility and expand the capabilities of this system, we also examined the polymerization efficiencies of 20 pentamer building blocks each containing one of five different side-chain groups and four different side-chain regio- and stereochemistries. Polymerization reactions were efficient for all five different side-chain groups and for three of the four combinations of side-chain regio- and stereochemistries. Differences in the efficiency and initial rate of polymerization correlate with the apparent melting temperature of each building block, which is dependent on side-chain regio- and stereochemistry, but relatively insensitive to side-chain structure among the substrates tested. Our findings represent a significant step towards the evolution of sequence-defined synthetic polymers and also demonstrate that enzyme-free nucleic acid-templated polymerization can occur efficiently using substrates with a wide range of side-chain structures, functionalization positions within each building block, and functionalization densities. PMID:18341334

Laser-directed 3D assembly of carbon nanotubes using two-photon polymerization (Conference Presentation)

NASA Astrophysics Data System (ADS)

Liu, Ying; Xiong, Wei; Jiang, Li Jia; Zhou, Yunshen; Li, Dawei; Jiang, Lan; Silvain, Jean-Francois; Lu, Yongfeng

2017-02-01

Precise assembly of carbon nanotubes (CNTs) in arbitrary 3D space with proper alignment is critically important and desirable for CNT applications but still remains as a long-standing challenge. Using the two-photon polymerization (TPP) technique, it is possible to fabricate 3D micro/nanoscale CNT/polymer architectures with proper CNT alignments in desired directions, which is expected to enable a broad range of applications of CNTs in functional devices. To unleash the full potential of CNTs, it is strategically important to develop TPP-compatible resins with high CNT concentrations for precise assembly of CNTs into 3D micro/nanostructures for functional device applications. We investigated a thiol grafting method in functionalizing multiwalled carbon nanotubes (MWNTs) to develop TPP-compatible MWNT-thiol-acrylate (MTA) composite resins. The composite resins developed had high MWNT concentrations up to 0.2 wt%, over one order of magnitude higher than previously published work. Significantly enhanced electrical and mechanical properties of the 3D micro/nanostructures were achieved. Precisely controlled MWNT assembly and strong anisotropic effects were confirmed. Microelectronic devices made of the MTA composite polymer were demonstrated. The nanofabrication method can achieve controlled assembly of MWNTs in 3D micro/nanostructures, enabling a broad range of CNT applications, including 3D electronics, integrated photonics, and micro/nanoelectromechanical systems (MEMS/NEMS).

In Situ Monitoring of RAFT Polymerization by Tetraphenylethylene-Containing Agents with Aggregation-Induced Emission Characteristics.

PubMed

Liu, Shunjie; Cheng, Yanhua; Zhang, Haoke; Qiu, Zijie; Kwok, Ryan T K; Lam, Jacky W Y; Tang, Ben Zhong

2018-05-22

A facile and efficient approach is demonstrated to visualize the polymerization in situ. A group of tetraphenylethylene (TPE)-containing dithiocarbamates were synthesized and screened as agents for reversible addition fragmentation chain transfer (RAFT) polymerizations. The spatial-temporal control characteristics of photochemistry enabled the RAFT polymerizations to be ON and OFF on demand under alternating visible light irradiation. The emission of TPE is sensitive to the local viscosity change owing to its aggregation-induced emission characteristic. Quantitative information could be easily acquired by the naked eye without destroying the reaction system. Furthermore, the versatility of such a technique was well demonstrated by 12 different polymerization systems. The present approach thus demonstrated a powerful platform for understanding the controlled living radical polymerization process. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymerized-type I collagen downregulates inflammation and improves clinical outcomes in patients with symptomatic knee osteoarthritis following arthroscopic lavage: a randomized, double-blind, and placebo-controlled clinical trial.

PubMed

Furuzawa-Carballeda, Janette; Lima, Guadalupe; Llorente, Luis; Nuñez-Álvarez, Carlos; Ruiz-Ordaz, Blanca H; Echevarría-Zuno, Santiago; Hernández-Cuevas, Virgilio

2012-01-01

Polymerized-type I collagen (polymerized collagen) is a downmodulator of inflammation and cartilage regenerator biodrug. To evaluate the effect of intraarticular injections of polymerized collagen after arthroscopic lavage on inflammation and clinical improvement in patients with knee osteoarthritis (OA). Patients (n = 19) were treated with 6 intraarticular injections of 2 mL of polymerized collagen (n = 10) or 2 mL of placebo (n = 9) during 3 months. Followup was 3 months. The primary endpoints included Lequesne index, pain on a visual analogue scale (VAS), WOMAC, analgesic usage, the number of Tregs and proinflammatory/anti-inflammatory cytokine-expressing peripheral cells. Secondary outcomes were Likert score and drug evaluation. Clinical and immunological improvement was determined if the decrease in pain exceeds 20 mm on a VAS, 20% of clinical outcomes, and inflammatory parameters from baseline. Urinary levels of C-terminal crosslinking telopeptide of collagen type II (CTXII) and erythrocyte sedimentation rate (ESR) were determined. Polymerized collagen was safe and well tolerated. Patients had a statistically significant improvement (P < 0.05) from baseline versus polymerized collagen and versus placebo at 6 months on Lequesne index, VAS, ESR, Tregs IL-1β, and IL-10 peripheral-expressing cells. Urinary levels of CTXII were decreased 44% in polymerized collagen versus placebo. No differences were found on incidence of adverse events between groups. Polymerized collagen is safe and effective on downregulation of inflammation in patients with knee OA.

Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives.

PubMed

Zhang, Ying; Wu, Ningjing; Bai, Xinyan; Xu, Changqi; Liu, Yi; Wang, Yong

2013-10-01

The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022 mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022-0.088 mmol/g). HAp (2-8 wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding. Copyright © 2013 Elsevier B.V. All rights reserved.

Kinetics of waterborne fluoropolymers prepared by one-step semi-continuous emulsion polymerization of chlorotrifluoroethylene, vinyl acetate, butyl acrylate and Veova 10

NASA Astrophysics Data System (ADS)

Liu, H. Z.; Wang, M. H.; Wang, Z. F.; Bian, J. M.

2018-01-01

Due to using gaseous fluorine monomer with toxicity, waterborne fluoropolymers are synthesized by semi-continuous high-pressure emulsion polymerization method which differs from free-pressure emulsion polymerization. To dates, the research on preparing process and kinetics for high-pressure emulsion polymerization is reported relatively less, which hinders researchers from understanding of mechanisms for monomer-fluorinated emulsion polymerization. The paper also provides a new method by element auxiliary analysis to calculate kinetics parameters of high-pressure emulsion polymerization. Based on aforementioned consideration, waterborne fluoropolymers were prepared by copolymerization of chlorotrifluoroethylene (CTFE), vinyl acetate (VAc), butyl acrylate (BA) and vinyl ester of versatic acid (Veova 10) using potassium persulfate as initiator and mixed surfactants. The kinetics of emulsion polymerization of waterborne fluoropolymers was then investigated. Effects of emulsifier concentration, initiator concentration, and polymerization temperature on polymerization rate (Rp) were evaluated, and relationship was described as Rp∝[I]0.10 and Rp∝[E]0.12. The apparent activation energy was determined to be 33.61 kJ·mol-1. Moreover, the relative conversion rate of CTFE with the other monomers was observed, and results indicated that CTFE monomer more uniformly copolymerized with the other monomers. The resulting emulsion properties and pressure change in an autoclave were evaluated at different stirring rates. The initial reaction time, defined as the beginning time of dropwise addition, was determined by the change in solid content and particle size of emulsion.

Escalation of polymerization in a thermal gradient

PubMed Central

Mast, Christof B.; Schink, Severin; Gerland, Ulrich; Braun, Dieter

2013-01-01

For the emergence of early life, the formation of biopolymers such as RNA is essential. However, the addition of nucleotide monomers to existing oligonucleotides requires millimolar concentrations. Even in such optimistic settings, no polymerization of RNA longer than about 20 bases could be demonstrated. How then could self-replicating ribozymes appear, for which recent experiments suggest a minimal length of 200 nt? Here, we demonstrate a mechanism to bridge this gap: the escalated polymerization of nucleotides by a spatially confined thermal gradient. The gradient accumulates monomers by thermophoresis and convection while retaining longer polymers exponentially better. Polymerization and accumulation become mutually self-enhancing and result in a hyperexponential escalation of polymer length. We describe this escalation theoretically under the conservative assumption of reversible polymerization. Taking into account the separately measured thermophoretic properties of RNA, we extrapolate the results for primordial RNA polymerization inside a temperature gradient in pores or fissures of rocks. With a dilute, nanomolar concentration of monomers the model predicts that a pore length of 5 cm and a temperature difference of 10 K suffice to polymerize 200-mers of RNA in micromolar concentrations. The probability to generate these long RNAs is raised by a factor of >10600 compared with polymerization in a physical equilibrium. We experimentally validate the theory with the reversible polymerization of DNA blocks in a laser-driven thermal trap. The results confirm that a thermal gradient can significantly enlarge the available sequence space for the emergence of catalytically active polymers. PMID:23630280

Preparation of molecularly imprinted polymers for strychnine by precipitation polymerization and multistep swelling and polymerization and their application for the selective extraction of strychnine from nux-vomica extract powder.

PubMed

Nakamura, Yukari; Matsunaga, Hisami; Haginaka, Jun

2016-04-01

Monodisperse molecularly imprinted polymers for strychnine were prepared by precipitation polymerization and multistep swelling and polymerization, respectively. In precipitation polymerization, methacrylic acid and divinylbenzene were used as a functional monomer and crosslinker, respectively, while in multistep swelling and polymerization, methacrylic acid and ethylene glycol dimethacrylate were used as a functional monomer and crosslinker, respectively. The retention and molecular recognition properties of the molecularly imprinted polymers prepared by both methods for strychnine were evaluated using a mixture of sodium phosphate buffer and acetonitrile as a mobile phase by liquid chromatography. In addition to shape recognition, ionic and hydrophobic interactions could affect the retention of strychnine in low acetonitrile content. Furthermore, molecularly imprinted polymers prepared by both methods could selectively recognize strychnine among solutes tested. The retention factors and imprinting factors of strychnine on the molecularly imprinted polymer prepared by precipitation polymerization were 220 and 58, respectively, using 20 mM sodium phosphate buffer (pH 6.0)/acetonitrile (50:50, v/v) as a mobile phase, and those on the molecularly imprinted polymer prepared by multistep swelling and polymerization were 73 and 4.5. These results indicate that precipitation polymerization is suitable for the preparation of a molecularly imprinted polymer for strychnine. Furthermore, the molecularly imprinted polymer could be successfully applied for selective extraction of strychnine in nux-vomica extract powder. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives

PubMed Central

Zhang, Ying; Wu, Ningjing; Bai, Xinyan; Xu, Changqi; Liu, Yi; Wang, Yong

2013-01-01

The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022 mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022–0.088 mmol/g). HAp (2–8 wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding. PMID:23910263

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

PubMed

Coari, Kristin M; Martin, Rebecca C; Jain, Kopal; McGown, Linda B

2017-09-01

In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

NASA Astrophysics Data System (ADS)

Coari, Kristin M.; Martin, Rebecca C.; Jain, Kopal; McGown, Linda B.

2017-09-01

In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

Selective Plasma Etching of Polymeric Substrates for Advanced Applications

PubMed Central

Puliyalil, Harinarayanan; Cvelbar, Uroš

2016-01-01

In today’s nanoworld, there is a strong need to manipulate and process materials on an atom-by-atom scale with new tools such as reactive plasma, which in some states enables high selectivity of interaction between plasma species and materials. These interactions first involve preferential interactions with precise bonds in materials and later cause etching. This typically occurs based on material stability, which leads to preferential etching of one material over other. This process is especially interesting for polymeric substrates with increasing complexity and a “zoo” of bonds, which are used in numerous applications. In this comprehensive summary, we encompass the complete selective etching of polymers and polymer matrix micro-/nanocomposites with plasma and unravel the mechanisms behind the scenes, which ultimately leads to the enhancement of surface properties and device performance. PMID:28335238

Degradable Polymers and Block Copolymers from Electron-deficient Carbonyl Compounds (STIR) (7.3 Polymer Chemistry - Synthesis: Architecture and Composition)

DTIC Science & Technology

2015-04-23

polymerization results Illustrations: Scheme 1. Polymerization of aldehydes and depolymerization of polyacetals. Scheme 2. Optimized methods for...oligomers) to the pure aldehyde monomer requires several distillations and transfer of the monomer at reflux directly to the polymerization vessel. Low...the controlled organocatalytic chain polymerization of ethyl glyoxylate and other reactive aldehydes , which will enable the preparation of

Estimation of degree of polymerization of poly-acrylonitrile-grafted carbon nanotubes using Guinier plot of small angle x-ray scattering

NASA Astrophysics Data System (ADS)

Cho, Hyunjung; Jin, Kyeong Sik; Lee, Jaegeun; Lee, Kun-Hong

2018-07-01

Small angle x-ray scattering (SAXS) was used to estimate the degree of polymerization of polymer-grafted carbon nanotubes (CNTs) synthesized using a ‘grafting from’ method. This analysis characterizes the grafted polymer chains without cleaving them from CNTs, and provides reliable data that can complement conventional methods such as thermogravimetric analysis or transmittance electron microscopy. Acrylonitrile was polymerized from the surface of the CNTs by using redox initiation to produce poly-acrylonitrile-grafted CNTs (PAN-CNTs). Polymerization time and the initiation rate were varied to control the degree of polymerization. Radius of gyration (R g ) of PAN-CNTs was determined using the Guinier plot obtained from SAXS solution analysis. The results showed consistent values according to the polymerization condition, up to a maximum R g = 125.70 Å whereas that of pristine CNTs was 99.23 Å. The dispersibility of PAN-CNTs in N,N-dimethylformamide was tested using ultraviolet–visible-near infrared spectroscopy and was confirmed to increase as the degree of polymerization increased. This analysis will be helpful to estimate the degree of polymerization of any polymer-grafted CNTs synthesized using the ‘grafting from’ method and to fabricate polymer/CNT composite materials.

Estimation of degree of polymerization of poly-acrylonitrile-grafted carbon nanotubes using Guinier plot of small angle x-ray scattering.

PubMed

Cho, Hyunjung; Jin, Kyeong Sik; Lee, Jaegeun; Lee, Kun-Hong

2018-07-06

Small angle x-ray scattering (SAXS) was used to estimate the degree of polymerization of polymer-grafted carbon nanotubes (CNTs) synthesized using a 'grafting from' method. This analysis characterizes the grafted polymer chains without cleaving them from CNTs, and provides reliable data that can complement conventional methods such as thermogravimetric analysis or transmittance electron microscopy. Acrylonitrile was polymerized from the surface of the CNTs by using redox initiation to produce poly-acrylonitrile-grafted CNTs (PAN-CNTs). Polymerization time and the initiation rate were varied to control the degree of polymerization. Radius of gyration (R g ) of PAN-CNTs was determined using the Guinier plot obtained from SAXS solution analysis. The results showed consistent values according to the polymerization condition, up to a maximum R g  = 125.70 Å whereas that of pristine CNTs was 99.23 Å. The dispersibility of PAN-CNTs in N,N-dimethylformamide was tested using ultraviolet-visible-near infrared spectroscopy and was confirmed to increase as the degree of polymerization increased. This analysis will be helpful to estimate the degree of polymerization of any polymer-grafted CNTs synthesized using the 'grafting from' method and to fabricate polymer/CNT composite materials.

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes

NASA Astrophysics Data System (ADS)

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-01

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes.

PubMed

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-06

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

Scintillator reflective layer coextrusion

DOEpatents

Yun, Jae-Chul; Para, Adam

2001-01-01

A polymeric scintillator has a reflective layer adhered to the exterior surface thereof. The reflective layer comprises a reflective pigment and an adhesive binder. The adhesive binder includes polymeric material from which the scintillator is formed. A method of forming the polymeric scintillator having a reflective layer adhered to the exterior surface thereof is also provided. The method includes the steps of (a) extruding an inner core member from a first amount of polymeric scintillator material, and (b) coextruding an outer reflective layer on the exterior surface of the inner core member. The outer reflective layer comprises a reflective pigment and a second amount of the polymeric scintillator material.

Effect of polymerization technique and glass fiber addition on the surface roughness and hardness of PMMA denture base material.

PubMed

Gad, Mohammed M; Rahoma, Ahmed; Al-Thobity, Ahmad M

2018-06-20

The current study evaluated the effects of autoclave polymerization both with and without glass fiber (GF) reinforcement on the surface roughness and hardness of acrylic denture base material. Ninety disc specimens (30×2.5 mm) were prepared from Vertex resin and divided according to polymerization techniques into a water bath, short and long autoclave polymerization groups. Tested groups were divided into three subgroups according to the GF concentration (0, 2.5, and 5 wt%). Profilometer and Vickers hardness tests were performed to measure surface roughness and hardness. ANOVA and Tukey-Kramer multiple comparison tests analyzed the results, and p≤0.05 was considered statistically significant. Autoclave polymerization significantly decreased the surface roughness and increased the hardness of acrylic resin without GF reinforcement (p<0.05). However, 5 wt% GF addition significantly increased surface roughness and decreased hardness of the autoclave polymerized denture base resin (p<0.05). Surface properties of Polymethyl methacrylate (PMMA) denture base material improved with autoclave polymerization and negatively affected with GFs addition.

Recent progress of atomic layer deposition on polymeric materials.

PubMed

Guo, Hong Chen; Ye, Enyi; Li, Zibiao; Han, Ming-Yong; Loh, Xian Jun

2017-01-01

As a very promising surface coating technology, atomic layer deposition (ALD) can be used to modify the surfaces of polymeric materials for improving their functions and expanding their application areas. Polymeric materials vary in surface functional groups (number and type), surface morphology and internal structure, and thus ALD deposition conditions that typically work on a normal solid surface, usually do not work on a polymeric material surface. To date, a large variety of research has been carried out to investigate ALD deposition on various polymeric materials. This paper aims to provide an in-depth review of ALD deposition on polymeric materials and its applications. Through this review, we will provide a better understanding of surface chemistry and reaction mechanism for controlled surface modification of polymeric materials by ALD. The integrated knowledge can aid in devising an improved way in the reaction between reactant precursors and polymer functional groups/polymer backbones, which will in turn open new opportunities in processing ALD materials for better inorganic/organic film integration and potential applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Nonperturbative Renormalization Group Approach to Polymerized Membranes

NASA Astrophysics Data System (ADS)

Essafi, Karim; Kownacki, Jean-Philippe; Mouhanna, Dominique

2014-03-01

Membranes or membrane-like materials play an important role in many fields ranging from biology to physics. These systems form a very rich domain in statistical physics. The interplay between geometry and thermal fluctuations lead to exciting phases such flat, tubular and disordered flat phases. Roughly speaking, membranes can be divided into two group: fluid membranes in which the molecules are free to diffuse and thus no shear modulus. On the other hand, in polymerized membranes the connectivity is fixed which leads to elastic forces. This difference between fluid and polymerized membranes leads to a difference in their critical behaviour. For instance, fluid membranes are always crumpled, whereas polymerized membranes exhibit a phase transition between a crumpled phase and a flat phase. In this talk, I will focus only on polymerized phantom, i.e. non-self-avoiding, membranes. The critical behaviour of both isotropic and anisotropic polymerized membranes are studied using a nonperturbative renormalization group approach (NPRG). This allows for the investigation of the phase transitions and the low temperature flat phase in any internal dimension D and embedding d. Interestingly, graphene behaves just as a polymerized membrane in its flat phase.

Comparison of a polymeric pseudostationary phase in EKC with ODS stationary phase in RP-HPLC.

PubMed

Ni, Xinjiong; Zhang, Min; Xing, Xiaoping; Cao, Yuhua; Cao, Guangqun

2018-01-01

Poly(stearyl methacrylate-co-methacrylic acid) (P(SMA-co-MAA)) was induced as pseudostationary phase (PSP) in electrokinetic chromatography (EKC). The n-octadecyl groups in SMA were the same as that in octadecylsilane (ODS) C18 column. Thus, the present work focused on the comparison of selectivity between polymeric PSP and ODS stationary phase (SP), and the effect of organic modifiers on the selectivity of polymeric PSP and ODS SP. 1-butanol could directly interacted with PSP as a Class I modifier, and improved both of the methylene selectivity and polar group selectivity. When the analysis times were similar, the polymeric PSP exhibited better methylene selectivity and polar group selectivity. Although the hydrophobic groups were similar, the substituted benzenes elution order was different between polymeric PSP and ODS SP. Linear solvation energy relationships (LSER) model analysis found that polymeric PSP and ODS SP exhibited two same key factors in selectivity: hydrophobic interaction and hydrogen bonding acidity. But polymeric PSP exhibited relatively strong n- and π-electrons interaction to the analytes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silicon and aluminum doping effects on the microstructure and properties of polymeric amorphous carbon films

NASA Astrophysics Data System (ADS)

Liu, Xiaoqiang; Hao, Junying; Xie, Yuntao

2016-08-01

Polymeric amorphous carbon films were prepared by radio frequency (R.F. 13.56 MHz) magnetron sputtering deposition. The microstructure evolution of the deposited polymeric films induced by silicon (Si) and aluminum(Al) doping were scrutinized through infrared spectroscopy, multi-wavelength Raman spectroscopy, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The comparative results show that Si doping can enhance polymerization and Al doping results in an increase in the ordered carbon clusters. Si and Al co-doping into polymeric films leads to the formation of an unusual dual nanostructure consisting of cross-linked polymer-like hydrocarbon chains and fullerene-like carbon clusters. The super-high elasticity and super-low friction coefficients (<0.002) under a high vacuum were obtained through Si and Al co-doping into the films. Unconventionally, the co-doped polymeric films exhibited a superior wear resistance even though they were very soft. The relationship between the microstructure and properties of the polymeric amorphous carbon films with different elements doping are also discussed in detail.

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

PubMed

El-Shall, M Samy

2008-07-01

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

Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

DOE PAGES

Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; ...

2015-11-02

Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10 -3 S cm -1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

Unlocking the Structure and Dynamics of Thin Polymeric Films

DTIC Science & Technology

2016-11-13

AFRL-AFOSR-JP-TR-2016-0092 Unlocking the Structure and Dynamics of Thin Polymeric Films Andrew Whittaker THE UNIVERSITY OF QUEENSLAND Final Report 11...Final 3. DATES COVERED (From - To)  15 Jun 2015 to 16 Jun 2016 4. TITLE AND SUBTITLE Unlocking the Structure and Dynamics of Thin Polymeric Films 5a...the interfacial structure that are inherent in thin films affects how polymers behave. A number of technically relevant polymeric systems were

Application of in situ polymerization for design and development of oral drug delivery systems.

PubMed

Ngwuluka, Ndidi

2010-12-01

Although preformed polymers are commercially available for use in the design and development of drug delivery systems, in situ polymerization has also been employed. In situ polymerization affords the platform to tailor and optimize the drug delivery properties of polymers. This review brings to light the benefits of in situ polymerization for oral drug delivery and the possibilities it provides to overcome the challenges of oral route of administration.

Multiple wavelength photolithography for preparing multilayer microstructures

DOEpatents

Dentinger, Paul Michael; Krafcik, Karen Lee

2003-06-24

The invention relates to a multilayer microstructure and a method for preparing thereof. The method involves first applying a first photodefinable composition having a first exposure wavelength on a substrate to form a first polymeric layer. A portion of the first photodefinable composition is then exposed to electromagnetic radiation of the first exposure wavelength to form a first pattern in the first polymeric layer. After exposing the first polymeric layer, a second photodefinable composition having a second exposure wavelength is applied on the first polymeric layer to form a second polymeric layer. A portion of the second photodefinable composition is then exposed to electromagnetic radiation of the second exposure wavelength to form a second pattern in the second polymeric layer. In addition, a portion of each layer is removed according to the patterns to form a multilayer microstructure having a cavity having a shape that corresponds to the portions removed.

SOM neural network fault diagnosis method of polymerization kettle equipment optimized by improved PSO algorithm.

PubMed

Wang, Jie-sheng; Li, Shu-xia; Gao, Jie

2014-01-01

For meeting the real-time fault diagnosis and the optimization monitoring requirements of the polymerization kettle in the polyvinyl chloride resin (PVC) production process, a fault diagnosis strategy based on the self-organizing map (SOM) neural network is proposed. Firstly, a mapping between the polymerization process data and the fault pattern is established by analyzing the production technology of polymerization kettle equipment. The particle swarm optimization (PSO) algorithm with a new dynamical adjustment method of inertial weights is adopted to optimize the structural parameters of SOM neural network. The fault pattern classification of the polymerization kettle equipment is to realize the nonlinear mapping from symptom set to fault set according to the given symptom set. Finally, the simulation experiments of fault diagnosis are conducted by combining with the industrial on-site historical data of the polymerization kettle and the simulation results show that the proposed PSO-SOM fault diagnosis strategy is effective.

Dual drug release from hydrogels covalently containing polymeric micelles that possess different drug release properties.

PubMed

Murata, Mari; Uchida, Yusuke; Takami, Taku; Ito, Tomoki; Anzai, Ryosuke; Sonotaki, Seiichi; Murakami, Yoshihiko

2017-05-01

In the present study, we designed hydrogels for dual drug release: the hydrogels that covalently contained the polymeric micelles that possess different drug release properties. The hydrogels that were formed from polymeric micelles possessing a tightly packed (i.e., well-entangled) inner core exhibited a higher storage modulus than the hydrogels that were formed from the polymeric micelles possessing a loosely packed structure. Furthermore, we conducted release experiments and fluorescent observations to evaluate the profiles depicting the release of two compounds, rhodamine B and auramine O, from either polymeric micelles or hydrogels. According to our results, (1) hydrogels that covalently contains polymeric micelles that possess different drug release properties successfully exhibit the independent release behaviors of the two compounds and (2) fluorescence microscopy can greatly facilitate efforts to evaluate drug release properties of materials. Copyright © 2017 Elsevier B.V. All rights reserved.

Targeted polymeric nanoparticles for cancer gene therapy

PubMed Central

Kim, Jayoung; Wilson, David R.; Zamboni, Camila G.; Green, Jordan J.

2015-01-01

In this article, advances in designing polymeric nanoparticles for targeted cancer gene therapy are reviewed. Characterization and evaluation of biomaterials, targeting ligands, and transcriptional elements are each discussed. Advances in biomaterials have driven improvements to nanoparticle stability and tissue targeting, conjugation of ligands to the surface of polymeric nanoparticles enable binding to specific cancer cells, and the design of transcriptional elements has enabled selective DNA expression specific to the cancer cells. Together, these features have improved the performance of polymeric nanoparticles as targeted non-viral gene delivery vectors to treat cancer. As polymeric nanoparticles can be designed to be biodegradable, non-toxic, and to have reduced immunogenicity and tumorigenicity compared to viral platforms, they have significant potential for clinical use. Results of polymeric gene therapy in clinical trials and future directions for the engineering of nanoparticle systems for targeted cancer gene therapy are also presented. PMID:26061296

Biodegradable polymeric microsphere-based vaccines and their applications in infectious diseases.

PubMed

Lin, Chi-Ying; Lin, Shih-Jie; Yang, Yi-Chen; Wang, Der-Yuan; Cheng, Hwei-Fang; Yeh, Ming-Kung

2015-01-01

Vaccination, which provides effective, safe infectious disease protection, is among the most important recent public health and immunological achievements. However, infectious disease remains the leading cause of death in developing countries because several vaccines require repeated administrations and children are often incompletely immunized. Microsphere-based systems, providing controlled release delivery, can obviate the need for repeat immunizations. Here, we review the function of sustained and pulsatile release of biodegradable polymeric microspheres in parenteral and mucosal single-dose vaccine administration. We also review the active-targeting function of polymeric particles. With their shield and co-delivery functions, polymeric particles are applied to develop single-dose and mucosally administered vaccines as well as to improve subunit vaccines. Because polymeric particles are easily surface-modified, they have been recently used in vaccine development for cancers and many infectious diseases without effective vaccines (e.g., human immunodeficiency virus infection). These polymeric particle functions yield important vaccine carriers and multiple benefits.

Sensitive fluorescence detection of nucleic acids based on isothermal circular strand-displacement polymerization reaction.

PubMed

Guo, Qiuping; Yang, Xiaohai; Wang, Kemin; Tan, Weihong; Li, Wei; Tang, Hongxing; Li, Huimin

2009-02-01

Here we have developed a sensitive DNA amplified detection method based on isothermal strand-displacement polymerization reaction. This method takes advantage of both the hybridization property of DNA and the strand-displacement property of polymerase. Importantly, we demonstrate that our method produces a circular polymerization reaction activated by the target, which essentially allows it to self-detect. Functionally, this DNA system consists of a hairpin fluorescence probe, a short primer and polymerase. Upon recognition and hybridization with the target ssDNA, the stem of the hairpin probe is opened, after which the opened probe anneals with the primer and triggers the polymerization reaction. During this process of the polymerization reaction, a complementary DNA is synthesized and the hybridized target is displaced. Finally, the displaced target recognizes and hybridizes with another probe, triggering the next round of polymerization reaction, reaching a target detection limit of 6.4 x 10(-15) M.

Thio-amide functionalized polymers via polymerization or post-polymerization modification

NASA Astrophysics Data System (ADS)

Ozcam, Ali; Henke, Adam; Stibingerova, Iva; Srogl, Jiri; Genzer, Jan

2011-03-01

Decreasing supplies of fresh water and increasing population necessitates development of advanced water cleaning technologies, which would facilitate the removal of water pollutants. Amongst the worst of such contaminants are heavy metals and cyanides, infamous for their high toxicity. To assist the water purification processes, we aim to synthesize functionalized macromolecules that would contribute in the decontamination processes by scavenging detrimental chemicals. Epitomizing this role thio-amide unit features remarkable chemical flexibility that facilitates reversible catch-release of the ions, where the behavior controlled by subtle red-ox changes in the environment. Chemical tunability of the thio-amide moiety enables synthesis of thio-amide based monomers and post-polymerization modification agents. Two distinct synthetic pathways, polymerization and post-polymerization modification, have been exploited, leading to functional thioamide-based macromolecules: thioamide-monomers were copolymerized with N-isopropylacrylamide and post-polymerization modifications of poly(dimethylaminoethyl methacrylate) and poly(propargyl methacrylate) were accomplished via quarternization and ``click'' reactions, respectively.

Sulfonated poly(ether ether ketone)/polypyrrole core-shell nanofibers: a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors.

PubMed

Wang, Wei; Li, Zhenyu; Jiang, Tingting; Zhao, Zhiwei; Li, Ye; Wang, Zhaojie; Wang, Ce

2012-11-01

Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form one-dimensional polymeric adsorbent/conducting polymer core-shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH₃ can facilitate the mass diffusion of NH₃ through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH₃ (20 ppb) at room temperature.

A new method for the preparation of polymeric porous layer open tubular columns for GC application

NASA Technical Reports Server (NTRS)

Shen, T. C.; Wang, M. L.

1995-01-01

A new method to prepare polymeric PLOT columns by using in situ polymerization technology is described. The method involves a straightforward in situ polymerization of the monomer. The polymer produced is directly coated on the metal tubing. This eliminates many of the steps needed in conventional polymeric PLOT column preparation. Our method is easy to operate and produces very reproducible columns, as shown previously (T. C. Shen. J. Chromatogr. Sci. 30, 239, 1992). The effects of solvents, tubing pretreatments, initiators and reaction temperatures in the preparation of PLOT columns are studied. Several columns have been developed to separate (1) highly polar compounds, such as water and ammonia or water and HCN, and (2) hydrocarbons and inert gases. A recent improvement has allowed us to produce bonded polymeric PLOT columns. These were studied, and the results are included also.

Cooperative polymerization of α-helices induced by macromolecular architecture

NASA Astrophysics Data System (ADS)

Baumgartner, Ryan; Fu, Hailin; Song, Ziyuan; Lin, Yao; Cheng, Jianjun

2017-07-01

Catalysis observed in enzymatic processes and protein polymerizations often relies on the use of supramolecular interactions and the organization of functional elements in order to gain control over the spatial and temporal elements of fundamental cellular processes. Harnessing these cooperative interactions to catalyse reactions in synthetic systems, however, remains challenging due to the difficulty in creating structurally controlled macromolecules. Here, we report a polypeptide-based macromolecule with spatially organized α-helices that can catalyse its own formation. The system consists of a linear polymeric scaffold containing a high density of initiating groups from which polypeptides are grown, forming a brush polymer. The folding of polypeptide side chains into α-helices dramatically enhances the polymerization rate due to cooperative interactions of macrodipoles between neighbouring α-helices. The parameters that affect the rate are elucidated by a two-stage kinetic model using principles from nucleation-controlled protein polymerizations; the key difference being the irreversible nature of this polymerization.

Tubulin polymerization-stimulating activity of Ganoderma triterpenoids.

PubMed

Kohno, Toshitaka; Hai-Bang, Tran; Zhu, Qinchang; Amen, Yhiya; Sakamoto, Seiichi; Tanaka, Hiroyuki; Morimoto, Satoshi; Shimizu, Kuniyoshi

2017-04-01

Tubulin polymerization is an important target for anticancer therapies. Even though the potential of Ganoderma triterpenoids against various cancer targets had been well documented, studies on their tubulin polymerization-stimulating activity are scarce. This study was conducted to evaluate the effect of Ganoderma triterpenoids on tubulin polymerization. A total of twenty-four compounds were investigated using an in vitro tubulin polymerization assay. Results showed that most of the studied triterpenoids exhibited microtuble-stabilizing activity to different degrees. Among the investigated compounds, ganoderic acid T-Q, ganoderiol F, ganoderic acid S, ganodermanontriol and ganoderic acid TR were found to have the highest activities. A structure-activity relationship (SAR) analysis was performed. Extensive investigation of the SAR suggests the favorable structural features for the tubulin polymerization-stimulating activity of lanostane triterpenes. These findings would be helpful for further studies on the potential mechanisms of the anticancer activity of Ganoderma triterpenoids and give some indications on the design of tubulin-targeting anticancer agents.

Experiments of the Essential Amino Acids at high temperature and high pressure using DAC

NASA Astrophysics Data System (ADS)

Kubo, K.; Okamoto, K.

2017-12-01

Amino acids are organic compounds that form the fundamental part of life. Proteins are formed by peptide binding and polymerization of amino acids. Amino acids are polymerized in the ridge hydrothermal field, formed proteins, and might be evolved into life. Experimental studies on the polymerization of amino acids in hydrothermal environments have been conducted. However, they were hydrothermal experiments and after the experiments. All run products (amid-acids) were observed at ambient condition. Few in-situ observations of amino acids were done in experiments in hydrothermal condition. In order to perform in-situ observation of the polymerization of amino acids, we have conducted the DAC experiments. Amino acids were filled in the DAC, pressures were applied, then heated to high temperature with Raman analysis. In preliminary experiment using glycine, polymerization forming diglycine, were completed. Investigation amino acids polymerization under hydrothermal condition would shed light for new view of early life science.

Optical Imaging and Gene Therapy with Neuroblastoma-Targeting Polymeric Nanoparticles for Potential Theranostic Applications.

PubMed

Lee, Jangwook; Jeong, Eun Ju; Lee, Yeon Kyung; Kim, Kwangmeyung; Kwon, Ick Chan; Lee, Kuen Yong

2016-03-02

Recently, targeted delivery systems based on functionalized polymeric nanoparticles have attracted a great deal of attention in cancer diagnosis and therapy. Specifically, as neuroblastoma occurs in infancy and childhood, targeted delivery may be critical to reduce the side effects that can occur with conventional approaches, as well as to achieve precise diagnosis and efficient therapy. Thus, biocompatible poly(d,l-lactide-co-glycolide) (PLG) nanoparticles containing an imaging probe and therapeutic gene are prepared, followed by modification with rabies virus glycoprotein (RVG) peptide for neuroblastoma-targeting delivery. RVG peptide is a well-known neuronal targeting ligand and is chemically conjugated to PLG nanoparticles without changing their size or shape. RVG-modified nanoparticles are effective in specifically targeting neuroblastoma both in vitro and in vivo. RVG-modified nanoparticles loaded with a fluorescent probe are useful to detect the tumor site in a neuroblastoma-bearing mouse model, and those encapsulating a therapeutic gene cocktail (siMyc, siBcl-2, and siVEGF) significantly suppressed tumor growth in the mouse model. This approach to designing and tailoring of polymeric nanoparticles for targeted delivery may be useful in the development of multimodality systems for theranostic approaches. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Externally initiated regioregular P3HT with controlled molecular weight and narrow polydispersity.

PubMed

Bronstein, Hugo A; Luscombe, Christine K

2009-09-16

The ability of chemists to design and synthesize pi-conjugated organic polymers with precise control remains the key to technological breakthroughs for using polymer materials in electronic and photonic devices. In this communication, the controlled chain-growth polymerization of regioregular poly(3-hexylthiophene) (P3HT) from an external initiator using 1,3-bis(diphenylphosphino)propane (dppp) as a catalyst ligand is reported. The complexes cis-chloro(phenyl)(dppp)nickel(II) and cis-chloro(o-tolyl)(dppp)nickel(II) were synthesized and characterized by (31)P NMR spectroscopy. These complexes served as initiators in the polymerization of 2-bromo-5-chloromagnesio-3-hexylthiophene in THF at room temperature, affording fully regioregular P3HT with controlled molecular weights and narrow molecular weight distributions, as demonstrated by gel-permeation chromatography and (1)H NMR spectroscopy. MALDI-TOF mass spectrometry revealed that the polymers had almost complete incorporation of the initiating aryl group, and when the aryl group was o-tolyl, only Tol/H end groups were observed. Although external initiators have been used previously with a PPh(3) ligand, that methodology led to polymers with broad molecular weight distributions. This is the first example in which complete control over the externally initiated P3HT polymerization has been achieved.

Potentiometric determination of trypsin using a polymeric membrane polycation-sensitive electrode based on current-controlled reagent delivery.

PubMed

Chen, Yan; Ding, Jiawang; Qin, Wei

2012-12-01

A potentiometric biosensor for the determination of trypsin is described based on current-controlled reagent delivery. A polymeric membrane protamine-sensitive electrode with dinonylnaphthalene sulfonate as cation exchanger is used for in situ generation of protamine. Diffusion of protamine across the polymeric membrane can be controlled precisely by applying an external current. The hydrolysis catalyzed with trypsin in sample solution decreases the concentration of free protamine released at the sample-membrane interface and facilitates the stripping of protamine out of the membrane surface via the ion-exchange process with sodium ions from the sample solution, thus decreasing the membrane potential, by which the protease can be sensed potentiometrically. The influences of anodic current amplitude, current pulse duration and protamine concentration in the inner filling solution on the membrane potential response have been studied. Under optimum conditions, the proposed protamine-sensitive electrode is useful for continuous and reversible detection of trypsin over the concentration range of 0.5-5UmL(-1) with a detection limit of 0.3UmL(-1). The proposed detection strategy provides a rapid and reagentless way for the detection of protease activities and offers great potential in the homogeneous immunoassays using proteases as labels. Copyright © 2012 Elsevier B.V. All rights reserved.

A Versatile Click-Compatible Monolignol Probe to Study Lignin Deposition in Plant Cell Walls

PubMed Central

Pandey, Jyotsna L.; Wang, Bo; Diehl, Brett G.; Richard, Tom L.; Chen, Gong; Anderson, Charles T.

2015-01-01

Lignin plays important structural and functional roles in plants by forming a hydrophobic matrix in secondary cell walls that enhances mechanical strength and resists microbial decay. While the importance of the lignin matrix is well documented and the biosynthetic pathways for monolignols are known, the process by which lignin precursors or monolignols are transported and polymerized to form this matrix remains a subject of considerable debate. In this study, we have synthesized and tested an analog of coniferyl alcohol that has been modified to contain an ethynyl group at the C-3 position. This modification enables fluorescent tagging and imaging of this molecule after its incorporation into plant tissue by click chemistry-assisted covalent labeling with a fluorescent azide dye, and confers a distinct Raman signature that could be used for Raman imaging. We found that this monolignol analog is incorporated into in vitro-polymerized dehydrogenation polymer (DHP) lignin and into root epidermal cell walls of 4-day-old Arabidopsis seedlings. Incorporation of the analog in stem sections of 6-week-old Arabidopsis thaliana plants and labeling with an Alexa-594 azide dye revealed the precise locations of new lignin polymerization. Results from this study indicate that this molecule can provide high-resolution localization of lignification during plant cell wall maturation and lignin matrix assembly. PMID:25884205

Oxygen sensitive polymeric nanocapsules for optical dissolved oxygen sensors

NASA Astrophysics Data System (ADS)

Sun, Zhijuan; Cai, Chenxin; Guo, Fei; Ye, Changhuai; Luo, Yingwu; Ye, Shuming; Luo, Jianchao; Zhu, Fan; Jiang, Chunyue

2018-04-01

Immobilization of the oxygen-sensitive probes (OSPs) in the host matrix greatly impacts the performance and long-term usage of the optical dissolved oxygen (DO) sensors. In this work, fluorescent dyes, as the OSPs, were encapsulated with a crosslinked fluorinated polymer shell by interfacial confined reversible addition fragmentation chain transfer miniemulsion polymerization to fabricate oxygen sensitive polymeric nanocapsules (NCs). The location of fluorescent dyes and the fluorescent properties of the NCs were fully characterized by fourier transform infrared spectrometer, x-ray photoelectron spectrometer and fluorescent spectrum. Dye-encapsulated capacity can be precisely tuned from 0 to 1.3 wt% without self-quenching of the fluorescent dye. The crosslinked fluorinated polymer shell is not only extremely high gas permeability, but also prevents the fluorescent dyes from leakage in aqueous as well as in various organic solvents, such as ethanol, acetone and tetrahydrofuran (THF). An optical DO sensor based on the oxygen sensitive NCs was fabricated, showing high sensitivity, short response time, full reversibility, and long-term operational stability of online monitoring DO. The sensitivity of the optical DO sensor is 7.02 (the ratio of the response value in fully deoxygenated and saturated oxygenated water) in the range 0.96-14.16 mg l-1 and the response time is about 14.3 s. The sensor’s work curve was fit well using the modified Stern-Volmer equation by two-site model, and its response values are hardly affected by pH ranging from 2 to 12 and keep constant during continuous measurement for 3 months. It is believed that the oxygen sensitive polymeric NCs-based optical DO sensor could be particularly useful in long-term online DO monitoring in both aqueous and organic solvent systems.

Preparation of stir cake sorptive extraction based on polymeric ionic liquid for the enrichment of benzimidazole anthelmintics in water, honey and milk samples.

PubMed

Wang, Yulei; Zhang, Jie; Huang, Xiaojia; Yuan, Dongxing

2014-08-20

In this work, a new stir cake sorptive extraction (SCSE) using polymeric ionic liquid monolith as sorbent was prepared. The sorbent was obtained by in situ copolymerization of an ionic liquid, 1-allyl-3-methylimidazolium bis[(trifluoro methyl)sulfonyl]imide (AMII) and divinylbenzene (DB) in the presence of N,N-dimethylformamide. The influence of the content of ionic liquid and the porogen in the polymerization mixture on extraction performance was studied thoroughly. The physicochemical properties of the polymeric ionic liquid were characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry. The usefulness of SCSE-AMIIDB was demonstrated by the enrichment of trace benzimidazole anthelmintics. Several parameters affecting the extraction efficiency were investigated, and under the optimized conditions, a simple and effective method for the determination of trace benzimidazoles residues in water, milk and honey samples was established by coupling SCSE-AMIIDB with high performance liquid chromatography/diode array detection (SCSE-AMIIDB-HPLC/DAD). Results indicated that the limits of detection (S/N=3) for target compounds were 0.020-0.072 μg L(-1), 0.035-0.10 μg L(-1) and 0.026-0.076 μg L(-1) in water, milk and honey samples, respectively. In addition, an acceptable reproducibility was achieved by evaluating the repeatability and intermediate precision with relative standard deviations (RSD) of less than 9% and 11%, respectively. Finally, the established AMII-SCSE-HPLC/DAD method was successfully applied for the determination of benzimidazoles residues in milk, honey and environmental water samples. Recoveries obtained for the determination of benzimidazole anthelmintics in spiking samples ranged from 70.2% to 117.6%, with RSD below 12% in all cases. Copyright © 2014 Elsevier B.V. All rights reserved.

The Growth-Suppressive Function of the Polycomb Group Protein Polyhomeotic Is Mediated by Polymerization of Its Sterile Alpha Motif (SAM) Domain*

PubMed Central

Robinson, Angela K.; Leal, Belinda Z.; Chadwell, Linda V.; Wang, Renjing; Ilangovan, Udayar; Kaur, Yogeet; Junco, Sarah E.; Schirf, Virgil; Osmulski, Pawel A.; Gaczynska, Maria; Hinck, Andrew P.; Demeler, Borries; McEwen, Donald G.; Kim, Chongwoo A.

2012-01-01

Polyhomeotic (Ph), a member of the Polycomb Group (PcG), is a gene silencer critical for proper development. We present a previously unrecognized way of controlling Ph function through modulation of its sterile alpha motif (SAM) polymerization leading to the identification of a novel target for tuning the activities of proteins. SAM domain containing proteins have been shown to require SAM polymerization for proper function. However, the role of the Ph SAM polymer in PcG-mediated gene silencing was uncertain. Here, we first show that Ph SAM polymerization is indeed required for its gene silencing function. Interestingly, the unstructured linker sequence N-terminal to Ph SAM can shorten the length of polymers compared with when Ph SAM is individually isolated. Substituting the native linker with a random, unstructured sequence (RLink) can still limit polymerization, but not as well as the native linker. Consequently, the increased polymeric Ph RLink exhibits better gene silencing ability. In the Drosophila wing disc, Ph RLink expression suppresses growth compared with no effect for wild-type Ph, and opposite to the overgrowth phenotype observed for polymer-deficient Ph mutants. These data provide the first demonstration that the inherent activity of a protein containing a polymeric SAM can be enhanced by increasing SAM polymerization. Because the SAM linker had not been previously considered important for the function of SAM-containing proteins, our finding opens numerous opportunities to manipulate linker sequences of hundreds of polymeric SAM proteins to regulate a diverse array of intracellular functions. PMID:22275371

Glycosylated and nonglycosylated recombinant human granulocyte colony-stimulating factor differently modifies actin polymerization in neutrophils.

PubMed

Zucca, A; Brizzi, S; Riccioni, R; Azzarà, A; Ghimenti, M; Carulli, G

2006-01-01

Several neutrophil functions can be modified by rhG-CSF administration. Neutrophil morphology changes in the course of treatment with Filgrastim (nonglycosylated rhG-CSF), along with impairment of chemotaxis. Both morphology and chemotaxis are not affected by treatment with Lenograstim (glycosylated rhG-CSF). Thus, we evaluated actin polymerization in neutrophils induced by treatment with the two forms of rhG-CSF. In fact, actin polymerization is crucial for neutrophil motility. We evaluated twelve healthy subjects undergoing peripheral blood stem cells (PBSC) mobilization for allogeneic transplantation to HLA-identical siblings. Neutrophils were isolated by peripheral venous blood before and after administration of either Filgrastim (six PBSC donors) or Lenograstim (six PBSC donors). Actin polymerization was investigated by a flow cytometric assay, using FITC-phalloidin as a specific probe for F-actin, and two parameters were measured: spontaneous actin polymerization in resting neutrophils; fMLP-stimulated actin polymerization. Results were expressed as relative F-actin content. Fifteen blood donors were studied as a control group. Filgrastim administration induced an increased relative F-actin content in resting neutrophils; however, no further actin polymerization was observed after fMLP stimulation. Neutrophils from subjects treated with Lenograstim showed a normal behaviour in terms of both spontaneous and stimulated actin polymerization. Glycosylated and nonglycosylated rhG-CSF differently affect actin polymerization in newly generated neutrophils. Such effects may explain some previous findings concerning both morphology and chemotactic properties and may be due to different effects of the two forms of rhG-CSF on proteins involved in neutrophil motility regulation.

Complexity in modeling of residual stresses and strains during polymerization of bone cement: effects of conversion, constraint, heat transfer, and viscoelastic property changes.

PubMed

Gilbert, Jeremy L

2006-12-15

Aseptic loosening of cemented joint prostheses remains a significant concern in orthopedic biomaterials. One possible contributor to cement loosening is the development of porosity, residual stresses, and local fracture of the cement that may arise from the in-situ polymerization of the cement. In-situ polymerization of acrylic bone cement is a complex set of interacting processes that involve polymerization reactions, heat generation and transfer, full or partial mechanical constraint, evolution of conversion- and temperature-dependent viscoelastic material properties, and thermal and conversion-driven changes in the density of the cement. Interactions between heat transfer and polymerization can lead to polymerization fronts moving through the material. Density changes during polymerization can, in the presence of mechanical constraint, lead to the development of locally high residual strain energy and residual stresses. This study models the interactions during bone cement polymerization and determines how residual stresses develop in cement and incorporates temperature and conversion-dependent viscoelastic behavior. The results show that the presence of polymerization fronts in bone cement result in locally high residual strain energies. A novel heredity integral approach is presented to track residual stresses incorporating conversion and temperature dependent material property changes. Finally, the relative contribution of thermal- and conversion-dependent strains to residual stresses is evaluated and it is found that the conversion-based strains are the major contributor to the overall behavior. This framework provides the basis for understanding the complex development of residual stresses and can be used as the basis for developing more complex models of cement behavior.

Polymerized-Type I Collagen Downregulates Inflammation and Improves Clinical Outcomes in Patients with Symptomatic Knee Osteoarthritis Following Arthroscopic Lavage: A Randomized, Double-Blind, and Placebo-Controlled Clinical Trial

PubMed Central

Furuzawa-Carballeda, Janette; Lima, Guadalupe; Llorente, Luis; Nuñez-Álvarez, Carlos; Ruiz-Ordaz, Blanca H.; Echevarría-Zuno, Santiago; Hernández-Cuevas, Virgilio

2012-01-01

Objectives. Polymerized-type I collagen (polymerized collagen) is a downmodulator of inflammation and cartilage regenerator biodrug. Aim. To evaluate the effect of intraarticular injections of polymerized collagen after arthroscopic lavage on inflammation and clinical improvement in patients with knee osteoarthritis (OA). Methods. Patients (n = 19) were treated with 6 intraarticular injections of 2 mL of polymerized collagen (n = 10) or 2 mL of placebo (n = 9) during 3 months. Followup was 3 months. The primary endpoints included Lequesne index, pain on a visual analogue scale (VAS), WOMAC, analgesic usage, the number of Tregs and proinflammatory/anti-inflammatory cytokine-expressing peripheral cells. Secondary outcomes were Likert score and drug evaluation. Clinical and immunological improvement was determined if the decrease in pain exceeds 20 mm on a VAS, 20% of clinical outcomes, and inflammatory parameters from baseline. Urinary levels of C-terminal crosslinking telopeptide of collagen type II (CTXII) and erythrocyte sedimentation rate (ESR) were determined. Results. Polymerized collagen was safe and well tolerated. Patients had a statistically significant improvement (P < 0.05) from baseline versus polymerized collagen and versus placebo at 6 months on Lequesne index, VAS, ESR, Tregs IL-1β, and IL-10 peripheral-expressing cells. Urinary levels of CTXII were decreased 44% in polymerized collagen versus placebo. No differences were found on incidence of adverse events between groups. Conclusion. Polymerized collagen is safe and effective on downregulation of inflammation in patients with knee OA. PMID:22545014

SOURCE ASSESSMENT: POLYVINYL CHLORIDE

EPA Science Inventory

This report summarizes data on air emissions from the polyvinyl chloride (PVC) industry. PVC is manufactured by 20 companies at 35 plants. Each plant uses one or more of four possible polymerization processes: (1) suspension polymerization, (2) emulsion polymerization, (3) bulk p...

Development, optimization and evaluation of polymeric electrospun nanofiber: A tool for local delivery of fluconazole for management of vaginal candidiasis.

PubMed

Sharma, Rahul; Garg, Tarun; Goyal, Amit K; Rath, Goutam

2016-01-01

The present study is designed to explore the localized delivery of fluconazole using mucoadhesive polymeric nanofibers. Drug-loaded polymeric nanofibers were fabricated by the electrospinning method using polyvinyl alcohol (PVA) as the polymeric constituent. The prepared nanofibers were found to be uniform, non-beaded and non-woven, with the diameter of the fibers ranging from 150 to 180 nm. Further drug release studies indicate a sustained release of fluconazole over a period of 6 h. The results of studies on anti-microbial activity indicated that drug-loaded polymeric nanofibers exhibit superior anti-microbial activity against Candida albicans, when compared to the plain drug.

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

DOEpatents

Abney, Kent D.; Kinkead, Scott A.; Mason, Caroline F. V.; Rais, Jiri

1997-01-01

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

Effect of initial temperature and concentration of catalyst in polyeugenol production

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

Widayat, E-mail: yayat-99@yahoo.com; Center of Biomass and Renewable Energy Center of Research and Service Diponegoro University Jln Prof. Soedarto, SH. Semarang 50 239, Tel / Fax:; Fatuchrohman, Alviano

2015-12-29

Objective of this research to study influencing of sulfuric acid concentration and initials temperature on polymerization of eugenol. Eugenol is the largest compound in the clove oil that used as raw material. Eugenol was polymerized laboratory scale. Polymerization processing conducted in reactor at 30 minutes. Polyeugenol was obtained in polymerization was conducted at temperature 40°C and ratio eugenol to sulfuric acid 1:15 mole. This research was pbtained the highest yield 81.49%. However, the weight would be increase in according with increasing of initial temperature. The polymerization in temperature 50°C with 1:1.5 mole ratio has the heaviest molecule weight; 47,530.76 gr/mole.

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

PubMed

Yoon, Ki-Young; Dong, Guangbin

2018-05-23

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

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

DOEpatents

Abney, K.D.; Kinkead, S.A.; Mason, C.F.V.; Rais, J.

1997-09-09

Preparation and use is described for polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

Chemical Polymerization and Langmuir-Blodgett Techniques. 2. The Polymerization of Monolayers of 3-Substituted Pyrroles

DTIC Science & Technology

1993-09-12

the liquid -air interface could be monitored by changes in the surface area. Deposition of monolayers by Langmuir - Blodgett technique is possible and...polymerization product from the LB trough in chloroform solution. Figure 10 Langmuir - Blodgett transfer of poly (3-hexadecyl pyrrole) onto hydrophobized glass... Langmuir - Blodgett Techniques, 2: The Polymerization of Monolayers of 3-Substituted Pyrroles by W.M. Sigmund, C. Marestin, S. Keil, H. Zhou and R.S

The effect of environmental pH on polymeric transfection efficiency.

PubMed

Kang, Han Chang; Samsonova, Olga; Kang, Sun-Woong; Bae, You Han

2012-02-01

Although polymers, polyplexes, and cells are exposed to various extracellular and intracellular pH environments during polyplex preparation and polymeric transfection, the impact of environmental pH on polymeric transfection has not yet been investigated. This study aims to understand the influence of environmental pH on polymeric transfection by modulating the pH of the transfection medium or the culture medium. Changes in the extracellular pH affected polymeric transfection by way of complex factors such as pH-induced changes in polymer characteristics (e.g., proton buffering capacity and ionization), polyplex characteristics (e.g., size, surface charge, and decomplexation), and cellular characteristics (e.g., cellular uptake, cell cycle phases, and intracellular pH environment). Notably, acidic medium delayed endocytosis, endosomal acidification, cytosolic release, and decomplexation of polyplexes, thereby negatively affecting gene expression. However, acidic medium inhibited mitosis and reduced dilution of gene expression, resulting in increased transfection efficiency. Compared to pH 7.4 medium, acidic transfection medium reduced gene expression 1.6-7.7-fold whereas acidic culture medium enhanced transfection efficiency 2.1-2.6-fold. Polymeric transfection was affected more by the culture medium than by the transfection medium. Understanding the effects of extracellular pH during polymeric transfection may stimulate new strategies for determining effective and safe polymeric gene carriers. Copyright © 2011 Elsevier Ltd. All rights reserved.

Radiation-induced controlled polymerization of acrylic acid by RAFT and RAFT-MADIX methods in protic solvents

NASA Astrophysics Data System (ADS)

Sütekin, S. Duygu; Güven, Olgun

2018-01-01

The kinetic investigation of one-pot synthesis of poly(acrylic acid) (PAA) prepared via gamma radiation induced controlled polymerization was reported. PAA homopolymers were prepared by Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization in the presence of trithiocarbonate-based chain transfer agent (CTA) 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) and also by Reversible Addition-Fragmentation/Macromolecular Design by Inter-change of Xanthates (RAFT/MADIX) polymerization in the presence of a xanthate based CTA O-ethyl-S-(1-methoxycarbonyl) ethyl dithiocarbonate (RA1). The polymerizations were performed at room temperature by the virtue of ionizing radiation. Protic solvents were used for the RAFT polymerization of AA considering environmental profits. The linear first-order kinetic plot, close control of molecular weight by the monomer/CTA molar ratio supported that the polymerization proceeds in a living fashion. The linear increase in molecular weight with conversion monitored by Size Exclusion Chromatography (SEC) is another proof of controlling of polymerization. [Monomer]/[RAFT] ratio and conversion was controlled to obtain PAA in the molecular weight range of 6900-35,800 with narrow molecular weight distributions. Reaction kinetics and effect of the amount of RAFT agent were investigated in detail. Between two different types of CTA, trithiocarbonate based DDMAT was found to be more efficient in terms of low dispersity (Đ) and linear first-order kinetic behavior for the radiation induced controlled synthesis of PAA homopolymers.

Mechanism of Cdc42-induced Actin Polymerization in Neutrophil Extracts

PubMed Central

Zigmond, Sally H.; Joyce, Michael; Yang, Changsong; Brown, Kevin; Huang, Minzhou; Pring, Martin

1998-01-01

Cdc42, activated with GTPγS, induces actin polymerization in supernatants of lysed neutrophils. This polymerization, like that induced by agonists, requires elongation at filament barbed ends. To determine if creation of free barbed ends was sufficient to induce actin polymerization, free barbed ends in the form of spectrin-actin seeds or sheared F-actin filaments were added to cell supernatants. Neither induced polymerization. Furthermore, the presence of spectrin-actin seeds did not increase the rate of Cdc42-induced polymerization, suggesting that the presence of Cdc42 did not facilitate polymerization from spectrin-actin seeds such as might have been the case if Cdc42 inhibited capping or released G-actin from a sequestered pool. Electron microscopy revealed that Cdc42-induced filaments elongated rapidly, achieving a mean length greater than 1 μm in 15 s. The mean length of filaments formed from spectrin-actin seeds was <0.4 μm. Had spectrin-actin seeds elongated at comparable rates before they were capped, they would have induced longer filaments. There was little change in mean length of Cdc42-induced filaments between 15 s and 5 min, suggesting that the increase in F-actin over this time was due to an increase in filament number. These data suggest that Cdc42 induction of actin polymerization requires both creation of free barbed ends and facilitated elongation at these ends. PMID:9722612

Mechanism of Cdc42-induced actin polymerization in neutrophil extracts.

PubMed

Zigmond, S H; Joyce, M; Yang, C; Brown, K; Huang, M; Pring, M

1998-08-24

Cdc42, activated with GTPgammaS, induces actin polymerization in supernatants of lysed neutrophils. This polymerization, like that induced by agonists, requires elongation at filament barbed ends. To determine if creation of free barbed ends was sufficient to induce actin polymerization, free barbed ends in the form of spectrin-actin seeds or sheared F-actin filaments were added to cell supernatants. Neither induced polymerization. Furthermore, the presence of spectrin-actin seeds did not increase the rate of Cdc42-induced polymerization, suggesting that the presence of Cdc42 did not facilitate polymerization from spectrin-actin seeds such as might have been the case if Cdc42 inhibited capping or released G-actin from a sequestered pool. Electron microscopy revealed that Cdc42-induced filaments elongated rapidly, achieving a mean length greater than 1 micron in 15 s. The mean length of filaments formed from spectrin-actin seeds was <0.4 micron. Had spectrin-actin seeds elongated at comparable rates before they were capped, they would have induced longer filaments. There was little change in mean length of Cdc42-induced filaments between 15 s and 5 min, suggesting that the increase in F-actin over this time was due to an increase in filament number. These data suggest that Cdc42 induction of actin polymerization requires both creation of free barbed ends and facilitated elongation at these ends.

Step-Growth Polymerization.

ERIC Educational Resources Information Center

Stille, J. K.

1981-01-01

Following a comparison of chain-growth and step-growth polymerization, focuses on the latter process by describing requirements for high molecular weight, step-growth polymerization kinetics, synthesis and molecular weight distribution of some linear step-growth polymers, and three-dimensional network step-growth polymers. (JN)

Making Polymeric Microspheres

NASA Technical Reports Server (NTRS)

Rhim, Won-Kyu; Hyson, Michael T.; Chung, Sang-Kun; Colvin, Michael S.; Chang, Manchium

1989-01-01

Combination of advanced techniques yields uniform particles for biomedical applications. Process combines ink-jet and irradiation/freeze-polymerization techniques to make polymeric microspheres of uniform size in diameters from 100 to 400 micrometer. Microspheres used in chromatography, cell sorting, cell labeling, and manufacture of pharmaceutical materials.

Polymerization Initiated at the Sidewalls of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Tour, James M.; Hudson, Jared L.

2011-01-01

A process has been developed for growing polymer chains via anionic, cationic, or radical polymerization from the side walls of functionalized carbon nanotubes, which will facilitate greater dispersion in polymer matrices, and will greatly enhance reinforcement ability in polymeric material.

TRANSITION METAL CATALYSIS IN CONTROLLED RADICAL POLYMERIZATION: ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

EPA Science Inventory

Novel and diversified macromolecular structures, which include polymers with designed topologies (top), compostions (middle), and functionalities (bottom), can be prepared by atom transfer radical polymerization processes. These polymers can be synthesized from a large variety of...

Immobilized Pd-Ag bimetallic nanoparticles on polymeric nanofibers as an effective catalyst: effective loading of Ag with bimetallic functionality through Pd nucleated nanofibers.

PubMed

Ranjith, Kugalur Shanmugam; Celebioglu, Asli; Uyar, Tamer

2018-06-15

Here, we present a precise process for synthesizing Pd-Ag bimetallic nanoparticles (NPs) onto polymeric nanofibers by decorating Pd-NPs through atomic layer deposition followed by a chemical reduction process for tagging Ag nanostructures with bimetallic functionality. The results show that Pd-NPs act as a nucleation platform for tagging Ag and form Pd-Ag bimetallic NPs with a monodisperse nature with significant catalytic enhancement to the reaction rate over the bimetallic nature of the Pd-Ag ratio. A Pd-NP decorated polymeric nanofibrous web acts as an excellent platform for the encapsulation or interaction of Ag, which prevents agglomeration and promotes the interaction of Ag ions only on the surface of the Pd-NPs. We observed an effective reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride (NaBH 4 ) to access the catalytic activity of Pd-Ag bimetallic NPs on a free-standing flexible polymeric nanofibrous web as a support. The captive formation of the polymeric nanofibrous web with Pd-Ag bimetallic functionality exhibited superior and stable catalytic performance with reduction rates of 0.0719, 0.1520, and 0.0871 min -1 for different loadings of Ag on Pd decorated nanofibrous webs such as Pd/Ag(0.01), Pd/Ag(0.03), and Pd/Ag(0.05), respectively. The highly faceted Pd-Ag NPs with an immobilized nature improves the catalytic functionality by enhancing the binding energy of the 4-NP adsorbate to the surface of the NPs. With the aid of bimetallic functionality, the nanofibrous web was demonstrated as a hybrid heterogeneous photocatalyst with a 3.16-fold enhancement in the reaction rate as compared with the monometallic decorative nature of NaBH 4 as a reducing agent. The effective role of the monodisperse nature of Pd ions with an ultralow content as low as 3 wt% and the tunable ratio of Ag on the nanofibrous web induced effective catalytic activity over multiple cycles.

Immobilized Pd-Ag bimetallic nanoparticles on polymeric nanofibers as an effective catalyst: effective loading of Ag with bimetallic functionality through Pd nucleated nanofibers

NASA Astrophysics Data System (ADS)

Shanmugam Ranjith, Kugalur; Celebioglu, Asli; Uyar, Tamer

2018-06-01

Here, we present a precise process for synthesizing Pd-Ag bimetallic nanoparticles (NPs) onto polymeric nanofibers by decorating Pd-NPs through atomic layer deposition followed by a chemical reduction process for tagging Ag nanostructures with bimetallic functionality. The results show that Pd-NPs act as a nucleation platform for tagging Ag and form Pd-Ag bimetallic NPs with a monodisperse nature with significant catalytic enhancement to the reaction rate over the bimetallic nature of the Pd-Ag ratio. A Pd-NP decorated polymeric nanofibrous web acts as an excellent platform for the encapsulation or interaction of Ag, which prevents agglomeration and promotes the interaction of Ag ions only on the surface of the Pd-NPs. We observed an effective reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride (NaBH4) to access the catalytic activity of Pd-Ag bimetallic NPs on a free-standing flexible polymeric nanofibrous web as a support. The captive formation of the polymeric nanofibrous web with Pd-Ag bimetallic functionality exhibited superior and stable catalytic performance with reduction rates of 0.0719, 0.1520, and 0.0871 min‑1 for different loadings of Ag on Pd decorated nanofibrous webs such as Pd/Ag(0.01), Pd/Ag(0.03), and Pd/Ag(0.05), respectively. The highly faceted Pd-Ag NPs with an immobilized nature improves the catalytic functionality by enhancing the binding energy of the 4-NP adsorbate to the surface of the NPs. With the aid of bimetallic functionality, the nanofibrous web was demonstrated as a hybrid heterogeneous photocatalyst with a 3.16-fold enhancement in the reaction rate as compared with the monometallic decorative nature of NaBH4 as a reducing agent. The effective role of the monodisperse nature of Pd ions with an ultralow content as low as 3 wt% and the tunable ratio of Ag on the nanofibrous web induced effective catalytic activity over multiple cycles.

Highly efficient reversible addition-fragmentation chain-transfer polymerization in ethanol/water via flow chemistry

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

Ye, Piaoran; Cao, Peng -Fei; Su, Zhe

Here, utilization of a flow reactor under high pressure allows highly efficient polymer synthesis via reversible addition–fragmentation chain-transfer (RAFT) polymerization in an aqueous system. Compared with the batch reaction, the flow reactor allows the RAFT polymerization to be performed in a high-efficiency manner at the same temperature. The adjustable pressure of the system allows further elevation of the reaction temperature and hence faster polymerization. Other reaction parameters, such as flow rate and initiator concentration, were also well studied to tune the monomer conversion and the molar mass dispersity (Ð) of the obtained polymers. Gel permeation chromatography, nuclear magnetic resonance (NMR),more » and Fourier transform infrared spectroscopies (FTIR) were utilized to monitor the polymerization process. With the initiator concentration of 0.15 mmol L –1, polymerization of poly(ethylene glycol) methyl ethermethacrylate with monomer conversion of 52% at 100 °C under 73 bar can be achieved within 40 min with narrow molar mass dispersity (D) Ð (<1.25). The strategy developed here provides a method to produce well-defined polymers via RAFT polymerization with high efficiency in a continuous manner.« less

Shaping the Future of Nanomedicine: Anisotropy in Polymeric Nanoparticle Design

PubMed Central

Meyer, Randall A.; Green, Jordan J.

2015-01-01

Nanofabrication and biomedical applications of polymeric nanoparticles have become important areas of research. Biocompatible polymeric nanoparticles have been investigated for their use as delivery vehicles for therapeutic and diagnostic agents. Although polymeric nanoconstructs have traditionally been fabricated as isotropic spheres, anisotropic, non-spherical nanoparticles have gained interest in the biomaterials community due to their unique interactions with biological systems. Polymeric nanoparticles with different forms of anisotropy have been manufactured utilizing a variety of novel methods in recent years. In addition, they have enhanced physical, chemical, and biological properties compared to spherical nanoparticles, including increased targeting avidity and decreased non-specific in vivo clearance. With these desirable properties, anisotropic nanoparticles have been successfully utilized in many biomedical settings and have performed superiorly to analogous spherical nanoparticles. We summarize the current state-of-the-art fabrication methods for anisotropic polymeric nanoparticles including top-down, bottom-up, and microfluidic design approaches. We also summarize the current and potential future applications of these nanoparticles, including drug delivery, biological targeting, immunoengineering, and tissue engineering. Ongoing research into the properties and utility of anisotropic polymeric nanoparticles will prove critical to realizing their potential in nanomedicine. PMID:25981390

Sieving polymer synthesis by reversible addition fragmentation chain transfer polymerization.

PubMed

Nai, Yi Heng; Jones, Roderick C; Breadmore, Michael C

2013-12-01

Replaceable sieving polymers are the fundamental component for high resolution nucleic acids separation in CE. The choice of polymer and its physical properties play significant roles in influencing separation performance. Recently, reversible addition fragmentation chain transfer (RAFT) polymerization has been shown to be a versatile polymerization technique capable of yielding well defined polymers previously unattainable by conventional free radical polymerization. In this study, a high molecular weight PDMA at 765 000 gmol-1 with a PDI of 1.55 was successfully synthesized with the use of chain transfer agent - 2-propionic acidyl butyl trithiocarbonate (PABTC) in a multi-step sequential RAFT polymerization approach. This study represents the first demonstration of RAFT polymerization for synthesizing polymers with the molecular weight range suitable for high resolution DNA separation in sieving electrophoresis. Adjustment of pH in the reaction was found to be crucial for the successful RAFT polymerization of high molecular weight polymer as the buffered condition minimizes the effect of hydrolysis and aminolysis commonly associated with trithiocarbonate chain transfer agents. The separation efficiency of PABTC-PDMA was found to have marginally superior separation performance compared to a commercial PDMA formulation, POP™-CAP, of similar molecular weight range.

The polymeric nanofilm of triazinedithiolsilane fabricated by self-assembled technique on copper surface. Part 2: Characterization of composition and morphology

NASA Astrophysics Data System (ADS)

Wang, Yabin; Liu, Zhong; Huang, Yudong; Qi, Yutai

2015-11-01

In the first part, a novel design route for metal protection against corrosion was proposed, and a class of triazinedithiolsilane compounds was conceived as protector for copper. The protective capability of the polymeric nanofilm, fabricated by self-assembling one representative (abbreviated as TESPA) of triazinedithiolsilane compounds onto copper surface, has been investigated and evaluated by electrochemical tests. The results show that the polymeric nanofilm significantly inhibits copper corrosion. This study, on the one hand, concentrates on the chemical composition of the TESPA polymeric nanofilm by means of X-ray photoelectron spectroscopy (XPS). The XPS results reveal that the chemical bonds between copper and TESPA monomers, three dimensional disulfide units and siloxane networks are responsible for the satisfactory protection of TESPA polymeric nanofilm against copper corrosion. On the other hand, scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS) are utilized to reveal the morphology and the uniformity of the TESPA polymeric nanofilm. The SEM-EDS results demonstrate that the copper surfaces are uniformly covered with TESPA self-assembled monolayer and the polymeric nanofilm. The TESPA-covered copper surfaces turn out to be smoother than that of the bare copper surface.

Polymeric endovascular strut and lumen detection algorithm for intracoronary optical coherence tomography images

NASA Astrophysics Data System (ADS)

Amrute, Junedh M.; Athanasiou, Lambros S.; Rikhtegar, Farhad; de la Torre Hernández, José M.; Camarero, Tamara García; Edelman, Elazer R.

2018-03-01

Polymeric endovascular implants are the next step in minimally invasive vascular interventions. As an alternative to traditional metallic drug-eluting stents, these often-erodible scaffolds present opportunities and challenges for patients and clinicians. Theoretically, as they resorb and are absorbed over time, they obviate the long-term complications of permanent implants, but in the short-term visualization and therefore positioning is problematic. Polymeric scaffolds can only be fully imaged using optical coherence tomography (OCT) imaging-they are relatively invisible via angiography-and segmentation of polymeric struts in OCT images is performed manually, a laborious and intractable procedure for large datasets. Traditional lumen detection methods using implant struts as boundary limits fail in images with polymeric implants. Therefore, it is necessary to develop an automated method to detect polymeric struts and luminal borders in OCT images; we present such a fully automated algorithm. Accuracy was validated using expert annotations on 1140 OCT images with a positive predictive value of 0.93 for strut detection and an R2 correlation coefficient of 0.94 between detected and expert-annotated lumen areas. The proposed algorithm allows for rapid, accurate, and automated detection of polymeric struts and the luminal border in OCT images.

Organo-Lewis acid as cocatalyst for cationic homogenous metallocene Ziegler-Natta olefin polymerizations

DOEpatents

Marks, Tobin J.; Chen, You-Xian

2000-01-01

The synthesis of the organo-Lewis acid perfluorobiphenylborane (PBB) and the activation of metallocenes for the formation of a variety of highly active homogeneous Ziegler-Natta metallocene olefin polymerization, copolymerization and ring-opening polymerization catalysts is described.

Metallocene-Containing Homopolymers and Heterobimetallic Block Copolymers via Photoinduced RAFT Polymerization

PubMed Central

Yang, Peng; Pageni, Parasmani; Kabir, Mohammad Pabel; Zhu, Tianyu; Tang, Chuanbing

2017-01-01

We report the synthesis of cationic cobaltocenium and neutral ferrocene containing homopolymers mediated by photoinduced reversible addition-fragmentation chain transfer (RAFT) polymerization with a photocatalyst fac-[Ir(ppy)3]. The homopolymers were further used as macromolecular chain transfer agents to synthesize diblock copolymers via chain extension. Controlled/“living” feature of photoinduced RAFT polymerization was confirmed by kinetic studies even without prior deoxygenation. A light switch between ON and OFF provided a spatiotemporal control of polymerization. PMID:29276651

Vacuum stability requirements of polymeric material for spacecraft application

NASA Technical Reports Server (NTRS)

Craig, J. W.

1984-01-01

The purpose of this document is to establish outgassing requirements and test guidelines for polymeric materials used in the space thermal/vacuum environment around sensitive optical or thermal control surfaces. The scope of this document covers the control of polymeric materials used near or adjacent to optical or thermal control surfaces that are exposed to the thermal/vacuum environment of space. This document establishes the requirements and defines the test method to evaluate polymeric materials used in the vicinity of these surfaces in space applications.

Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources.

PubMed

Lalevée, Jacques; Mokbel, Haifaa; Fouassier, Jean-Pierre

2015-04-20

Photoinitiators (PI) or photoinitiating systems (PIS) usable in light induced cationic polymerization (CP) and free radical promoted cationic polymerization (FRPCP) reactions (more specifically for cationic ring opening polymerization (ROP)) together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided.

Porous Structure Design of Polymeric Membranes for Gas Separation

DOE PAGES

Zhang, Jinshui; Schott, Jennifer Ann; Mahurin, Shannon Mark; ...

2017-04-04

High-performance polymeric membranes for gas separation are of interest for molecular-level separations in industrial-scale chemical, energy and environmental processes. To overcome the inherent trade-off relationship between permeability and selectivity, the creation of permanent microporosity in polymeric matrices is highly desirable because the porous structures can provide a high fractional free volume to facilitate gas transport through the dense layer. In this feature article, recent developments in the formation of porous polymeric membranes and potential strategies for pore structure design are reviewed.

Synthesis and Characterization of Polyethylene/Starch Nanocomposites: A Spherical Starch-Supported Catalyst and In Situ Ethylene Polymerization.

PubMed

Zhanga, Hao; Xi, Shixia; Wang, Shuwei; Liu, Jingsheng; Yoon, Keun-Byoung; Lee, Dong-Ho; Zhang, Hexin; Zhang, Xuequan

2017-01-01

In the present article, a novel spherical starch-supported vanadium (V)-based Ziegler-Natta catalyst was synthesized. The active centers of the obtained catalyst well dispersed in the starch through the SEM-EDX analysis. The effects of reaction conditions on ethylene polymerization were studied. The synthesized catalyst exhibited high activity toward ethylene polymerization in the presence of ethylaluminium sesquichloride (EASC) cocatalyst. Interestingly, the fiber shape PE was obtained directly during the polymerization process.

Oxyphosphorus-containing polymers as binders for battery cathodes

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

Pratt, Russell Clayton; Mullin, Scott Allen; Eitouni, Hany Basam

A class of polymeric phosphorous esters can be used as binders for battery cathodes. Metal salts can be added to the polymers to provide ionic conductivity. The polymeric phosphorous esters can be formulated with other polymers either as mixtures or as copolymers to provide additional desirable properties. Examples of such properties include even higher ionic conductivity and improved mechanical properties. Furthermore, cathodes that include the polymeric phosphorous esters can be assembled with a polymeric electrolyte separator and an anode to form a complete battery.

Self-assembly of block copolymers on topographically patterned polymeric substrates

DOEpatents

Russell, Thomas P.; Park, Soojin; Lee, Dong Hyun; Xu, Ting

2016-05-10

Highly-ordered block copolymer films are prepared by a method that includes forming a polymeric replica of a topographically patterned crystalline surface, forming a block copolymer film on the topographically patterned surface of the polymeric replica, and annealing the block copolymer film. The resulting structures can be used in a variety of different applications, including the fabrication of high density data storage media. The ability to use flexible polymers to form the polymeric replica facilitates industrial-scale processes utilizing the highly-ordered block copolymer films.

Polymeric Beads for Organic Coatings

DTIC Science & Technology

1982-10-31

Clear Solid Polymeric Beads A solid polymeric bead is comprised of a sol id mass of polymerized unsaturated polyester/styrene resin mixture . 2. lear...than the current unsaturated polyester resin . For example, a bead male from acrylic resin could be more trans- - parent, more durable and provide more...0.44 Isopropyl Alcohol I 11.26 I 1 .73 60% Wt. Alkyd Resin - Volume I 251.26 i 30.52 " Sol ids 51% 1 I Anti.-Skinning Agent I 0.90 I 0.12 Mineral

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

PubMed

Sand, Wolfgang; Gehrke, Tilman

2006-01-01

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

Radiation-induced polymerization of glass forming systems. VI. Polymerization rate at higher conversion in binary systems

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

Kaetsu, I.; Ito, A.; Hayashi, K.

1973-08-01

The effect of temperature and composition on the inflection point in the time-conversion curve and the saturated conversion was investigated in the gamma -radio-induced radical polymerization of binary systems consisting of a glass- forming monomer and a solvent. In the polymerization of completely homogeneous systems such as glycidyl methacrylate (GMA) -triacetin and hydroxyethyl methacrylate (HEMA) --propylene glycol systems, the time-conversion curve has an inflection point at polymerization temperatures between T/sub vm/(T/sub v/ of monomer system) and T/sub vp/ (T/sub v/ of polymer system). Such conversions at the inflection point changed monotonically between 0 and 100% in this temperature range. T/submore » v/ was found to be 30 to 50 deg C higher than T/sub g/ (glass transition temperature) and a monotonic function of composition (monomer -- polymer -- solvent). The acceleration effect continued to 100% conversion above T/sub vp/, and no acceleration effect was observed below T/sub vm/. The saturated conversion in homogeneous systems changed monotonically between 0 and 100% for polymerization temperatures between T/sub gm/ (T/sub g/ of monomer system) and T/sub gp/(T of polymer system). T/sub g/ was also a monotonic function of composition. No saturation in conversion was observed above T/sub gp/ , and no polymerization occurred below T/sub gm/. In the polymerization of completely heterogeneous systems such as HEMA-dioctyl phthalate, no acceleration effect was observed at any temperature and composition. The saturated conversion was 100% sbove T/sub g/ of pure HEMA, and no polymerization occurred below this temperature in this system. (auth)« less

Elucidation of a side reaction occurring during nitroxide-mediated polymerization of cyclic ketene acetals by tandem mass spectrometric end-group analysis of aliphatic polyesters.

PubMed

Albergaria Pereira, Bruna de Fátima; Tardy, Antoine; Monnier, Valérie; Guillaneuf, Yohann; Gigmes, Didier; Charles, Laurence

2015-12-15

In order to prevent side reactions while developing new polymerization processes, their mechanism has to be understood and one first key insight is the structure of the end-groups in polymeric by-products. The synthetic method scrutinized here is the nitroxide-mediated polymerization (NMP) of a cyclic ketene acetal, a promising alternative process to the production of polyesters. Polymer end-group characterization was performed by mass spectrometry (MS), combining elemental composition information derived from accurate mass data in the MS mode with fragmentation features recorded in the MS/MS mode. Electrospray was used as the ionization method to ensure the integrity of original chain terminations and a quadrupole time-of-flight (QTOF) instrument was employed for high-resolution mass measurements in both MS and tandem mass spectrometry (MS/MS) modes. Occurrence of side reactions in the studied polymerization method, first evidenced by an unusual increase in dispersity with conversion, was confirmed in MS with the detection of two polymeric impurities in addition to the expected species. Fragmentation rules were first established for this new polyester family in order to derive useful structural information from MS/MS data. In addition to a usual NMP by-product, the initiating group of the second polymeric impurities revealed the degradation of the nitroxide moiety. Unambiguous MS/MS identification of end-groups in by-products sampled from the polymerization medium allowed an unusual side reaction to be identified during the NMP preparation of polyesters. On-going optimization of the polymerization method aims at preventing this undesired process. Copyright © 2015 John Wiley & Sons, Ltd.

Synthesis and applications of MANs/poly(MMA-co-BA) nanocomposite latex by miniemulsion polymerization

PubMed Central

Chen, Huayao; Zhou, Xinhua; Gunasekaran, Sundaram

2017-01-01

We have synthesized core-shell structured 3-methacryloxypropyltrimethoxysilane (MPS) functionalized antimony-doped tin oxide nanoparticles (MANs)–poly(methyl methacrylate-co-butyl acrylate) (PMMA-co-BA, PMB) nanocomposite latex particles via miniemulsion polymerization method. Polymerizable anionic surfactant DNS-86 (allyloxy polyoxyethylene(10) nonyl ammonium sulfate) was first introduced to synthesize core-shell nanocomposite. The morphologies of synthesized MANs and MANs/PMB latex nanocomposite particles were studied with transmission electron microscopy, which revealed particles, on average 70 nm in size, with a core-shell structure. Owing to the uniformity and hydrophobicity of MANs, the MANs-embedded PMB latex nanocomposite can be tailored more precisely than other nanoparticles-embedded nanocomposites. Films incorporating 10 wt% of MANs in the MAN/PMB latex nanocomposite exhibit good transmittance in the visible region, and excellent opacity in the near infrared region. The MANs/PMB nanocomposite film also appears suitable for heat insulation applications. PMID:29291076

Determination of main components in the extracellular polymeric substances extracted from activated sludge using a spectral probing method.

PubMed

Shen, Rong; Sheng, Guo-Ping; Yu, Han-Qing

2012-06-01

In this study, a spectral probing method was applied to determine the content of the main components, i.e., proteins, polysaccharides and humic substances, in the extracellular polymeric substances (EPS) extracted from activated sludge. The measurement results were consistent with those obtained from the conventional methods, such as the anthrone for polysaccharide determination, the modified Lowry method for protein and humic substance determination. The recoveries for the determination of proteins, humic substances and polysaccharides in the EPS extracted from six sludge samples using standard additional method were between 92.4 and 108.9%, 84.8 and 108.9%, 75.1 and 117.2%, respectively. These results indicate that the propose method has a good accuracy and precision, and can be used as an effective approach to determine the main components in sludge EPS. Copyright © 2012 Elsevier B.V. All rights reserved.

A Model-based B2B (Batch to Batch) Control for An Industrial Batch Polymerization Process

NASA Astrophysics Data System (ADS)

Ogawa, Morimasa

This paper describes overview of a model-based B2B (batch to batch) control for an industrial batch polymerization process. In order to control the reaction temperature precisely, several methods based on the rigorous process dynamics model are employed at all design stage of the B2B control, such as modeling and parameter estimation of the reaction kinetics which is one of the important part of the process dynamics model. The designed B2B control consists of the gain scheduled I-PD/II2-PD control (I-PD with double integral control), the feed-forward compensation at the batch start time, and the model adaptation utilizing the results of the last batch operation. Throughout the actual batch operations, the B2B control provides superior control performance compared with that of conventional control methods.

Optical characterization of composite layers prepared by plasma polymerization

NASA Astrophysics Data System (ADS)

Radeva, E.; Hikov, T.; Mitev, D.; Stroescu, H.; Nicolescu, M.; Gartner, M.; Presker, R.; Pramatarova, L.

2016-02-01

Thin composite layers from polymer/nanoparticles (Ag-nanoparticles and detonation nanodiamonds) were prepared by plasma polymerization process on the base of hexamethyldisiloxane. The variation of the layer composition was achieved by changing the type of nanoparticles. The optical measurement techniques used were UV-VIS-NIR ellipsometry (SE), Fourier-transformed infrared spectroscopy (FTIR) and Raman spectroscopy. The values of the refractive index determined are in the range 1.30 to 1.42. All samples are transparent with transmission between 85-95% and very smooth. The change in Raman and FTIR spectra of the composites verify the expected bonding between polymer and diamond nanoparticles due to the penetration of the fillers in the polymer matrix. The comparison of the spectra of the corresponding NH3 plasma treated composites revealed that the composite surface becomes more hydrophilic. The obtained results indicate that preparation of layers with desired compositions is possible at a precise control of the detonation nanodiamond materials.

Modeling random methyl branching in ethylene/ propylene copolymers using metathesis chemistry: synthesis and thermal behavior.

PubMed

Sworen, John C; Smith, Jason A; Wagener, Kenneth B; Baugh, Lisa S; Rucker, Steven P

2003-02-26

The structure of random ethylene/propylene (EP) copolymers has been modeled using step polymerization chemistry. Six ethylene/propylene model copolymers have been prepared via acyclic diene metathesis (ADMET) polymerization and characterized for primary and higher level structure using in-depth NMR, IR, DSC, WAXD, and GPC analysis. These copolymers possess 1.5, 7.1, 13.6, 25.0, 43.3, and 55.6 methyl branches per 1000 carbons. Examination of these macromolecules by IR and WAXD analysis has demonstrated the first hexagonal phase in EP copolymers containing high ethylene content (90%) without the influence of sample manipulation (temperature, pressure, or radiation). Thermal behavior studies have shown that the melting point and heat of fusion decrease as the branch content increases. Further, comparisons have been made between these random ADMET EP copolymers, random EP copolymers made by typical chain addition techniques, and precisely branched ADMET EP copolymers.

A One-Step Route to CO2 -Based Block Copolymers by Simultaneous ROCOP of CO2 /Epoxides and RAFT Polymerization of Vinyl Monomers.

PubMed

Wang, Yong; Zhao, Yajun; Ye, Yunsheng; Peng, Haiyan; Zhou, Xingping; Xie, Xiaolin; Wang, Xianhong; Wang, Fosong

2018-03-26

The one-step synthesis of well-defined CO 2 -based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO 2 /epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC-COOH) as the bifunctional chain transfer agent (CTA). The double chain-transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09-1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC-COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO 2 -based polycarbonates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of Bottlebrush Block Copolymers as Photonic Crystals.

PubMed

Liberman-Martin, Allegra L; Chu, Crystal K; Grubbs, Robert H

2017-07-01

Brush block copolymers are a class of comb polymers that feature polymeric side chains densely grafted to a linear backbone. These polymers display interesting properties due to their dense functionality, low entanglement, and ability to rapidly self-assemble to highly ordered nanostructures. The ability to prepare brush polymers with precise structures has been enabled by advancements in controlled polymerization techniques. This Feature Article highlights the development of brush block copolymers as photonic crystals that can reflect visible to near-infrared wavelengths of light. Fabrication of these materials relies on polymer self-assembly processes to achieve nanoscale ordering, which allows for the rapid preparation of photonic crystals from common organic chemical feedstocks. The characteristic physical properties of brush block copolymers are discussed, along with methods for their preparation. Strategies to induce self-assembly at ambient temperatures and the use of blending techniques to tune photonic properties are emphasized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical assembly of microsnap-fits fabricated by two-photon polymerization

NASA Astrophysics Data System (ADS)

Köhler, Jannis; Kutlu, Yunus; Zyla, Gordon; Ksouri, Sarah I.; Esen, Cemal; Gurevich, Evgeny L.; Ostendorf, Andreas

2017-10-01

To respond to current demands of nano- and microtechnologies, e.g., miniaturization and integration, different bottom-up strategies have been developed. These strategies are based on picking, placing, and assembly of multiple components to produce microsystems with desired features. This paper covers the fabrication of arbitrary-shaped microcomponents by two-photon polymerization and the trapping, moving, and aligning of these structures by the use of a holographic optical tweezer. The main focus is on the assembly technique based on a cantilever microsnap-fit. More precisely, mechanical properties are characterized by optical forces and a suitable geometry of the snap-fit is designed. As a result of these investigations, a fast and simple assembly technique is developed. Furthermore, disassembly is provided by an optimized design. These findings suggest that the microsnap-fit is suitable for the assembly of miniaturized systems and could broaden the application opportunities of bottom-up strategies.

Dispersion Polymerization of Polystyrene Particles Using Alcohol as Reaction Medium

NASA Astrophysics Data System (ADS)

Cho, Young-Sang; Shin, Cheol Hwan; Han, Sujin

2016-02-01

In this study, monodisperse polystyrene nanospheres were prepared by dispersion polymerization using alcohol as reaction medium to prepare colloidal clusters of the latex beads. Polyvinylpyrrolidone (PVP) and 2-(methacryloyloxy)ethyltrimethylammonium chloride (MTC) were used as dispersion stabilizer and comonomer, respectively. The particle size could be controlled by adjusting the reactant compositions such as the amount of stabilizer, comonomer, and water in the reactant mixture. The size and monodispersity of the polymeric particles could be also controlled by changing the reaction medium with different alcohols other than ethanol or adjusting the polymerization temperature. The synthesized particles could be self-organized inside water-in-oil emulsion droplets by evaporation-driven self-assembly to produce colloidal clusters of the polymeric nanospheres.

Mass and Charge Transport in Electronically Conductive Polymers

DTIC Science & Technology

1990-08-02

This method is based on coating an electrode surface with an insulating nitrile butadiene rubber ( NBR ). The electrolyte for polymerization (LiCIO4...in acetonitrile) etches channels through the NBR ; pyrrole is then polymerized in these channels. After polymerization the NBR is extracted away with

Anisotropic microporous supports impregnated with polymeric ion-exchange materials

DOEpatents

Friesen, Dwayne; Babcock, Walter C.; Tuttle, Mark

1985-05-07

Novel ion-exchange media are disclosed, the media comprising polymeric anisotropic microporous supports containing polymeric ion-exchange or ion-complexing materials. The supports are anisotropic, having small exterior pores and larger interior pores, and are preferably in the form of beads, fibers and sheets.

Technique for the polymerization of monomers for PPQ/graphite fiber composites

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

1973-01-01

Impregnation of fiber prior to appreciable polymerization completely eliminates impregnation problems encountered with use of high viscosity high molecular weight polyphenylquinoxalines (PPQ) solutions. Major part of polymerization of reactant mixture is conducted on fiber during solvent removal and final curing stages.

A balance between membrane elasticity and polymerization energy sets the shape of spherical clathrin coats

NASA Astrophysics Data System (ADS)

Saleem, Mohammed; Morlot, Sandrine; Hohendahl, Annika; Manzi, John; Lenz, Martin; Roux, Aurélien

2015-02-01

In endocytosis, scaffolding is one of the mechanisms to create membrane curvature by moulding the membrane into the spherical shape of the clathrin cage. However, the impact of membrane elastic parameters on the assembly and shape of clathrin lattices has never been experimentally evaluated. Here, we show that membrane tension opposes clathrin polymerization. We reconstitute clathrin budding in vitro with giant unilamellar vesicles (GUVs), purified adaptors and clathrin. By changing the osmotic conditions, we find that clathrin coats cause extensive budding of GUVs under low membrane tension while polymerizing into shallow pits under moderate tension. High tension fully inhibits polymerization. Theoretically, we predict the tension values for which transitions between different clathrin coat shapes occur. We measure the changes in membrane tension during clathrin polymerization, and use our theoretical framework to estimate the polymerization energy from these data. Our results show that membrane tension controls clathrin-mediated budding by varying the membrane budding energy.

Biodegradable polymeric microsphere-based vaccines and their applications in infectious diseases

PubMed Central

Lin, Chi-Ying; Lin, Shih-Jie; Yang, Yi-Chen; Wang, Der-Yuan; Cheng, Hwei-Fang; Yeh, Ming-Kung

2015-01-01

Vaccination, which provides effective, safe infectious disease protection, is among the most important recent public health and immunological achievements. However, infectious disease remains the leading cause of death in developing countries because several vaccines require repeated administrations and children are often incompletely immunized. Microsphere-based systems, providing controlled release delivery, can obviate the need for repeat immunizations. Here, we review the function of sustained and pulsatile release of biodegradable polymeric microspheres in parenteral and mucosal single-dose vaccine administration. We also review the active-targeting function of polymeric particles. With their shield and co-delivery functions, polymeric particles are applied to develop single-dose and mucosally administered vaccines as well as to improve subunit vaccines. Because polymeric particles are easily surface-modified, they have been recently used in vaccine development for cancers and many infectious diseases without effective vaccines (e.g., human immunodeficiency virus infection). These polymeric particle functions yield important vaccine carriers and multiple benefits. PMID:25839217

Formation of Polymer Particles by Direct Polymerization on the Surface of a Supramolecular Template.

PubMed

Schmuck, Carsten; Li, Mao; Zellermann, Elio

2018-04-06

Formation of polymeric materials on the surface of supramolecular assemblies is rather challenging due to the often weak non-covalent interactions between the self-assembled template and the monomers before polymerization. We herein describe that the introduction of a supramolecular anion recognition motif, the guanidiniocarbonyl pyrrole cation (GCP), into a short Fmoc-dipeptide 1 leads to self-assembled spherical nanoparticles in aqueous solution. Onto the surface of these nanoparticles negatively charged diacetylene monomers can be attached which after UV polymerization lead to the formation of a polymer shell around the self-assembled template. The hybrid supramolecular and polymeric nanoparticles demonstrated intriguing thermal hysteresis phenomenon. The template nanoparticle could be disassembled through the treatment with organic base which cleaved the Fmoc moiety on 1. This strategy thus showed that a supramolecular anion recognition motif allows the post-assembly formation of polymeric nanomaterials from anionic monomers around a cationic self-assembled template. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Applications of polymeric micelles with tumor targeted in chemotherapy

NASA Astrophysics Data System (ADS)

Ding, Hui; Wang, Xiaojun; Zhang, Song; Liu, Xinli

2012-11-01

Polymeric micelles (PMs) have gained more progress as a carrier system with the quick development of biological and nanoparticle techniques. In particular, PMs with smart targeting can deliver anti-cancer drugs directly into tumor cells at a sustained rate. PMs with core-shell structure (with diameters of 10 100 nm) have been prepared by a variety of biodegradable and biocompatible polymers via a self-assembly process. The preparation of polymeric micelles with stimuli-responsive block copolymers or modification of target molecules on polymeric micelles' surface are able to significantly improve the efficiency of drug delivery. Polymeric micelles, which have been considered as a novel promising drug carrier for cancer therapeutics, are rapidly evolving and being introduced in an attempt to overcome several limitations of traditional chemotherapeutics, including water solubility, tumor-specific accumulation, anti-tumor efficacy, and non-specific toxicity. This review describes the preparation of polymeric micelles and the targeted modification which greatly enhance the effects of chemotherapeutic agents.

A master equation approach to actin polymerization applied to endocytosis in yeast.

PubMed

Wang, Xinxin; Carlsson, Anders E

2017-12-01

We present a Master Equation approach to calculating polymerization dynamics and force generation by branched actin networks at membranes. The method treats the time evolution of the F-actin distribution in three dimensions, with branching included as a directional spreading term. It is validated by comparison with stochastic simulations of force generation by actin polymerization at obstacles coated with actin "nucleation promoting factors" (NPFs). The method is then used to treat the dynamics of actin polymerization and force generation during endocytosis in yeast, using a model in which NPFs form a ring around the endocytic site, centered by a spot of molecules attaching the actin network strongly to the membrane. We find that a spontaneous actin filament nucleation mechanism is required for adequate forces to drive the process, that partial inhibition of branching and polymerization lead to different characteristic responses, and that a limited range of polymerization-rate values provide effective invagination and obtain correct predictions for the effects of mutations in the active regions of the NPFs.

Design and testing of tubular polymeric capsules for self-healing of concrete

NASA Astrophysics Data System (ADS)

Araújo, M.; Van Tittelboom, K.; Feiteira, J.; Gruyaert, E.; Chatrabhuti, S.; Raquez, J.-M.; Šavija, B.; Alderete, N.; Schlangen, E.; De Belie, N.

2017-10-01

Polymeric healing agents have proven their efficiency to heal cracks in concrete in an autonomous way. However, the bottleneck for valorisation of self-healing concrete with polymeric healing agents is their encapsulation. In the present work, the suitability of polymeric materials such as poly(methyl methacrylate) (PMMA), polystyrene (PS) and poly(lactic acid) (PLA) as carriers for healing agents in self-healing concrete has been evaluated. The durability of the polymeric capsules in different environments (demineralized water, salt water and simulated concrete pore solution) and their compatibility with various healing agents have been assessed. Next, a numerical model was used to simulate capsule rupture when intersected by a crack in concrete and validated experimentally. Finally, two real-scale self-healing concrete beams were made, containing the selected polymeric capsules (with the best properties regarding resistance to concrete mixing and breakage upon crack formation) or glass capsules and a reference beam without capsules. The self-healing efficiency was determined after crack creation by 3-point-bending tests.

Synthesis and characterization of hydrolysed starch-g-poly(methacrylic acid) composite.

PubMed

Zahran, Magdy K; Ahmed, Enas M; El-Rafie, Mohamed H

2016-06-01

A novel method for the synthesis of starch-g-poly(methacrylic acid) composite was adopted by graft polymerization of hydrolysed starch (HS) and methacrylic acid (MAA) in aqueous medium using an efficient sodium perborate (SPB)-thiourea (TU) redox initiation system. The parameters influencing the redox system efficiency and thence the polymerization method were considered. These parameters comprehended the concentrations of MAA, SPB, TU and SPB/TU molar ratio as well as the polymerization temperature. The polymerization reaction was scrutinized through calculation of the MAA total conversion percent (TC%). The resultant poly(MAA-HS) composite was assessed by evaluating the polymer criteria (the graft yield, GY%; the grafting efficiency, GE%; the homopolymer, HP%; and the total conversion). The comportment of the apparent viscosity of the cooked poly(MAA)-starch composite paste, obtained under diverse polymerization conditions, was examined. Tentative mechanisms, which depict all occasions that happen amid the entire course of the polymerization reaction, have been proffered. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed

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

2016-04-01

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

Frontal Polymerization of Dicyclopentadiene: A Numerical Study.

PubMed

Goli, Elyas; Robertson, Ian D; Geubelle, Philippe H; Moore, Jeffrey S

2018-04-26

As frontal polymerization is being considered as a faster and more energy efficient manufacturing technique for polymer-matrix fiber-reinforced composites, we perform a finite-element-based numerical study of the initiation and propagation of a polymerization front in dicyclopentadiene (DCPD). The transient thermochemical simulations are complemented by an analytical study of the steady-state propagation of the polymerization front, allowing to draw a direct link between the cure kinetics model and the key characteristics of the front, i.e., front velocity and characteristic length scales. The second part of this study focuses on the prediction of the temperature spike associated with the merger of two polymerization fronts. The thermal peak, which might be detrimental to the properties of the polymerized material, is due to the inability of the heat associated with the highly exothermic reaction to be dissipated when the two fronts merge. The analysis investigates how the amplitude of the thermal spike is affected by the degree of cure at the time of the front merger.

A master equation approach to actin polymerization applied to endocytosis in yeast

PubMed Central

Wang, Xinxin

2017-01-01

We present a Master Equation approach to calculating polymerization dynamics and force generation by branched actin networks at membranes. The method treats the time evolution of the F-actin distribution in three dimensions, with branching included as a directional spreading term. It is validated by comparison with stochastic simulations of force generation by actin polymerization at obstacles coated with actin “nucleation promoting factors” (NPFs). The method is then used to treat the dynamics of actin polymerization and force generation during endocytosis in yeast, using a model in which NPFs form a ring around the endocytic site, centered by a spot of molecules attaching the actin network strongly to the membrane. We find that a spontaneous actin filament nucleation mechanism is required for adequate forces to drive the process, that partial inhibition of branching and polymerization lead to different characteristic responses, and that a limited range of polymerization-rate values provide effective invagination and obtain correct predictions for the effects of mutations in the active regions of the NPFs. PMID:29240771

ABC Triblock Copolymer Worms: Synthesis, Characterization, and Evaluation as Pickering Emulsifiers for Millimeter-Sized Droplets

PubMed Central

2016-01-01

Polymerization-induced self-assembly (PISA) is used to prepare linear poly(glycerol monomethacrylate)–poly(2-hydroxypropyl methacrylate)–poly(benzyl methacrylate) [PGMA–PHPMA–PBzMA] triblock copolymer nano-objects in the form of a concentrated aqueous dispersion via a three-step synthesis based on reversible addition–fragmentation chain transfer (RAFT) polymerization. First, GMA is polymerized via RAFT solution polymerization in ethanol, then HPMA is polymerized via RAFT aqueous solution polymerization, and finally BzMA is polymerized via “seeded” RAFT aqueous emulsion polymerization. For certain block compositions, highly anisotropic worm-like particles are obtained, which are characterized by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The design rules for accessing higher order morphologies (i.e., worms or vesicles) are briefly explored. Surprisingly, vesicular morphologies cannot be accessed by targeting longer PBzMA blocks—instead, only spherical nanoparticles are formed. SAXS is used to rationalize these counterintuitive observations, which are best explained by considering subtle changes in the relative enthalpic incompatibilities between the three blocks during the growth of the PBzMA block. Finally, the PGMA–PHPMA–PBzMA worms are evaluated as Pickering emulsifiers for the stabilization of oil-in-water emulsions. Millimeter-sized oil droplets can be obtained using low-shear homogenization (hand-shaking) in the presence of 20 vol % n-dodecane. In contrast, control experiments performed using PGMA–PHPMA diblock copolymer worms indicate that these more delicate nanostructures do not survive even these mild conditions. PMID:27795581

Recent Advances in Polymeric Materials Used as Electron Mediators and Immobilizing Matrices in Developing Enzyme Electrodes

PubMed Central

Moyo, Mambo; Okonkwo, Jonathan O.; Agyei, Nana M.

2012-01-01

Different classes of polymeric materials such as nanomaterials, sol-gel materials, conducting polymers, functional polymers and biomaterials have been used in the design of sensors and biosensors. Various methods have been used, for example from direct adsorption, covalent bonding, crossing-linking with glutaraldehyde on composites to mixing the enzymes or use of functionalized beads for the design of sensors and biosensors using these polymeric materials in recent years. It is widely acknowledged that analytical sensing at electrodes modified with polymeric materials results in low detection limits, high sensitivities, lower applied potential, good stability, efficient electron transfer and easier immobilization of enzymes on electrodes such that sensing and biosensing of environmental pollutants is made easier. However, there are a number of challenges to be addressed in order to fulfill the applications of polymeric based polymers such as cost and shortening the long laboratory synthetic pathways involved in sensor preparation. Furthermore, the toxicological effects on flora and fauna of some of these polymeric materials have not been well studied. Given these disadvantages, efforts are now geared towards introducing low cost biomaterials that can serve as alternatives for the development of novel electrochemical sensors and biosensors. This review highlights recent contributions in the development of the electrochemical sensors and biosensors based on different polymeric material. The synergistic action of some of these polymeric materials and nanocomposites imposed when combined on electrode during sensing is discussed. PMID:22368503

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

PubMed

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

2013-02-26

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

Anisotropic microporous supports impregnated with polymeric ion-exchange materials

DOEpatents

Friesen, D.; Babcock, W.C.; Tuttle, M.

1985-05-07

Novel ion-exchange media are disclosed, the media comprising polymeric anisotropic microporous supports containing polymeric ion-exchange or ion-complexing materials. The supports are anisotropic, having small exterior pores and larger interior pores, and are preferably in the form of beads, fibers and sheets. 5 figs.

ATOM TRANSFER RADICAL POLYMERIZATION OF N-BUTYL METHACRYLATE IN AQUEOUS DISPERSED SYSTEMS: A MINIEMULSION APPROACH. (R826735)

EPA Science Inventory

Ultrasonication was applied in combination with a hydrophobe for the copper-mediated atom transfer radical polymerization of n-butyl methacrylate in an aqueous dispersed system. A controlled polymerization was successfully achieved, as demonstrated by a linear correlation between...

21 CFR 870.3650 - Pacemaker polymeric mesh bag.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870.3650 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric...

High-efficiency preparation of poly(2-methacryloyloxyethyl phosphorylcholine) grafting layer on poly(ether ether ketone) by photoinduced and self-initiated graft polymerization in an aqueous solution in the presence of inorganic salt additives.

PubMed

Shiojima, Taro; Inoue, Yuuki; Kyomoto, Masayuki; Ishihara, Kazuhiko

2016-08-01

A highly efficient methodology for preparing a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer on the surface of poly(ether ether ketone) (PEEK) was examined by photoinduced and self-initiated graft polymerization. To enhance the polymerization rate, we demonstrated the effects of inorganic salt additives in the feed monomer solution on thickness of grafted PMPC layer. Photoinduced polymerization occurred and the PMPC graft layer was successfully formed on the PEEK surface, regardless of inorganic salt additives. Moreover, it was clearly observed that the addition of inorganic salt enhanced the grafting thickness of PMPC layer on the surface even when the photoirradiation time was shortened. The addition of inorganic salt additives in the feed monomer solution enhanced the polymerization rate of MPC and resulted in thicker PMPC layers. In particular, we evaluated the effect of NaCl concentration and how this affected the polymerization rate and layer thickness. We considered that this phenomenon was due to the hydration of ions in the feed monomer solution and subsequent apparent increase in the MPC concentration. A PMPC layer with over 100-nm-thick, which was prepared by 5-min photoirradiation in 2.5mol/L inorganic salt aqueous solution, showed good wettability and protein adsorption resistance compared to that of untreated PEEK. Hence, we concluded that the addition of NaCl into the MPC feed solution would be a convenient and efficient method for preparing a graft layer on PEEK. Photoinduced and self-initiated graft polymerization on the PEEK surface is one of the several methodologies available for functionalization. However, in comparison with free-radical polymerization, the efficiency of polymerization at the solid-liquid interface is limited. Enhancement of the polymerization rate for grafting could solve the problem. In this study, we observed the acceleration of the polymerization rate of MPC in an aqueous solution by the addition of inorganic salt. The salt itself did not show any adverse effects on the radical polymerization; however, the apparent concentration of the monomer in feed may be increased due to the hydration of ions attributed to salt additives. We could obtain PMPC-grafted PEEK with sufficient PMPC thickness to obtain good functionality with only 5-min photoirradiation by using 2.5mol/L NaCl in the feed solution. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Polymerization Simulator for Introductory Polymer and Material Science Courses

ERIC Educational Resources Information Center

Chirdon, William M.

2010-01-01

This work describes how molecular simulation of polymerization reactions can be used to enrich introductory polymer or material science courses to give students a deeper understanding of free-radical chain and stepwise growth polymerization reactions. These simulations have proven to be effective media for instruction that do not require material…

Coating of plasma polymerized film

NASA Technical Reports Server (NTRS)

Morita, S.; Ishibashi, S.

1980-01-01

Plasma polymerized thin film coating and the use of other coatings is suggested for passivation film, thin film used for conducting light, and solid body lubrication film of dielectrics of ultra insulators for electrical conduction, electron accessories, etc. The special features of flow discharge development and the polymerized film growth mechanism are discussed.

Spring-loaded polymeric gel actuators

DOEpatents

Shahinpoor, Mohsen

1995-01-01

Spring-loaded electrically controllable polymeric gel actuators are disclosed. The polymeric gels can be polyvinyl alcohol, polyacrylic acid, or polyacrylamide, and are contained in an electrolytic solvent bath such as water plus acetone. The action of the gel is mechanically biased, allowing the expansive and contractile forces to be optimized for specific applications.

Intrinsic embedded sensors for polymeric mechatronics: flexure and force sensing.

PubMed

Jentoft, Leif P; Dollar, Aaron M; Wagner, Christopher R; Howe, Robert D

2014-02-25

While polymeric fabrication processes, including recent advances in additive manufacturing, have revolutionized manufacturing, little work has been done on effective sensing elements compatible with and embedded within polymeric structures. In this paper, we describe the development and evaluation of two important sensing modalities for embedding in polymeric mechatronic and robotic mechanisms: multi-axis flexure joint angle sensing utilizing IR phototransistors, and a small (12 mm), three-axis force sensing via embedded silicon strain gages with similar performance characteristics as an equally sized metal element based sensor.

Polymeric Micelles as Novel Carriers for Poorly Soluble Drugs--A Review.

PubMed

Reddy, B Pavan Kumar; Yadav, Hemant K S; Nagesha, Dattatri K; Raizaday, Abhay; Karim, Abdul

2015-06-01

Polymeric micelles are used as 'smart drug carriers' for targeting certain areas of the body by making them stimuli-sensitive or by attachment of a specific ligand molecule onto their surface. The main aim of using polymeric micelles is to deliver the poorly water soluble drugs. Now-a-days they are used especially in the areas of cancer therapy also. In this article we have reviewed several aspects of polymeric micelles concerning their mechanism of formation, chemical nature, preparation and characterization techniques, and their applications in the areas of drug delivery.

A Novel Polymeric Organosilazane Precursor to Si3N4/SiC Ceramics.

DTIC Science & Technology

1985-02-06

prepared by pyrolysis of the appropriately-shaped polymeric precursor. These polysilazanes also may prove to be useful as dispersants for SiC and Si3N4...I[AD-Ri58 748 A NOVEL POLYMERIC ORGANOSILAZANE PRECURSOR TO S13N4/ SIC i/I CERRMICS(U) MASSACHUSETTS INST OF TECH CAMBRIDGE DEPT OF CHEMISTRY D...Security C ificatlion" 0322 A Novel Polymeric Organosilazane Precursor to Si3N/ SiC C_ramics._I 12. PERSONAL AUTHOR(S) Dietmar Seyferth and Gary H. Wiseman 13

Melting line of polymeric nitrogen

NASA Astrophysics Data System (ADS)

Yakub, L. N.

2013-05-01

We made an attempt to predict location of the melting line of polymeric nitrogen using two equations for Helmholtz free energy: proposed earlier for cubic gauche-structure and developed recently for liquid polymerized nitrogen. The P-T relation, orthobaric densities and latent heat of melting were determined using a standard double tangent construction. The estimated melting temperature decreases with increasing pressure, alike the temperature of molecular-nonmolecular transition in solid. We discuss the possibility of a triple point (solid-molecular fluid-polymeric fluid) at ˜80 GPa and observed maximum of melting temperature of nitrogen.

Gelcasting methods

DOEpatents

Walls, Claudia A.; Kirby, Glen H.; Janney, Mark A.; Omatete, Ogbemi O.; Nunn, Stephen D.; McMillan, April D.

2000-01-01

A method of gelcasting includes the steps of providing a solution of at least hydroxymethylacrylamide (HMAM) and water. At least one inorganic powder is added to the mixture. At least one initiator system is provided to polymerize the HMAM. The initiator polymerizes the HMAM and water, to form a firm hydrogel that contains the inorganic powder. One or more comonomers can be polymerized with the HMAM monomer, to alter the final properties of the gelcast material. Additionally, one or more additives can be included in the polymerization mixture, to alter the properties of the gelcast material.

Intrinsic Embedded Sensors for Polymeric Mechatronics: Flexure and Force Sensing

PubMed Central

Jentoft, Leif P.; Dollar, Aaron M.; Wagner, Christopher R.; Howe, Robert D.

2014-01-01

While polymeric fabrication processes, including recent advances in additive manufacturing, have revolutionized manufacturing, little work has been done on effective sensing elements compatible with and embedded within polymeric structures. In this paper, we describe the development and evaluation of two important sensing modalities for embedding in polymeric mechatronic and robotic mechanisms: multi-axis flexure joint angle sensing utilizing IR phototransistors, and a small (12 mm), three-axis force sensing via embedded silicon strain gages with similar performance characteristics as an equally sized metal element based sensor. PMID:24573310

Nanoscale High Energetic Materials: A Polymeric Nitrogen Chain N8 Confined inside a Carbon Nanotube

NASA Astrophysics Data System (ADS)

Abou-Rachid, Hakima; Hu, Anguang; Timoshevskii, Vladimir; Song, Yanfeng; Lussier, Louis-Simon

2008-05-01

We present a theoretical study of a new hybrid material, nanostructured polymeric nitrogen, where a polymeric nitrogen chain is encapsulated in a carbon nanotube. The electronic and structural properties of the new system are studied by means of ab initio electronic structure and molecular dynamics calculations. Finite temperature simulations demonstrate the stability of this nitrogen phase at ambient pressure and room temperature using carbon nanotube confinement. This nanostructured confinement may open a new path towards stabilizing polynitrogen or polymeric nitrogen at ambient conditions.

Highly reflective polymeric substrates functionalized utilizing atomic layer deposition

NASA Astrophysics Data System (ADS)

Zuzuarregui, Ana; Coto, Borja; Rodríguez, Jorge; Gregorczyk, Keith E.; Ruiz de Gopegui, Unai; Barriga, Javier; Knez, Mato

2015-08-01

Reflective surfaces are one of the key elements of solar plants to concentrate energy in the receivers of solar thermal electricity plants. Polymeric substrates are being considered as an alternative to the widely used glass mirrors due to their intrinsic and processing advantages, but optimizing both the reflectance and the physical stability of polymeric mirrors still poses technological difficulties. In this work, polymeric surfaces have been functionalized with ceramic thin-films by atomic layer deposition. The characterization and optimization of the parameters involved in the process resulted in surfaces with a reflection index of 97%, turning polymers into a real alternative to glass substrates. The solution we present here can be easily applied in further technological areas where seemingly incompatible combinations of polymeric substrates and ceramic coatings occur.

Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution

NASA Technical Reports Server (NTRS)

Kolb, V.; Orgel, L. E.; Miller, S. L. (Principal Investigator)

1994-01-01

We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.

Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes

PubMed Central

Tabernero, Vanessa; Camejo, Claudimar; Terreros, Pilar; Alba, María Dolores; Cuenca, Tomás

2010-01-01

In this work we report the polymerization behaviour of natural clays (montmorillonites, MMT) as activating supports. These materials have been modified by treatment with different aluminium compounds in order to obtain enriched aluminium clays and to modify the global Brönsted/Lewis acidity. As a consequence, the intrinsic structural properties of the starting materials have been changed. These changes were studied and these new materials used for ethylene polymerization using a zirconocene complex as catalyst. All the systems were shown to be active in ethylene polymerization. The catalyst activity and the dependence on acid strength and textural properties have been also studied. The behaviour of an artificial silica (SBA 15) modified with an aluminium compound to obtain a silicoaluminate has been studied, but no ethylene polymerization activity has been found yet.

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

PubMed

Xu, Kongli; Chen, Guangming; Qiu, Dong

2015-05-01

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

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

PubMed

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

2018-01-01

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

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

PubMed Central

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

2018-01-01

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

Developments of the studies on the polymerization under microgravity

NASA Astrophysics Data System (ADS)

Li, Ping; Yi, Zongchun

Microgravity has been recognized as a new and useful way of processing materials for pharmacology biology and microelectronic In microgravity there is no direction for gravity sensitive processes which take part in crystal growth convection sedimentation physical--chemical processes in biological objects The absent of gravity leads to the possibility of synthesis of new materials which cannot be prepared on Earth The perspective for possible biotechnological applications gave an impetus to a series of experiments on polymerization in space by NASA Rocket-Space Corporation RSC ENERGIYA the Institute of Bioorganic Chemistry Uzbekistan and so on The influence of microgravity on polymerization is based on the exclusion of convection and sedimentation processes in curing polymer Under microgravity condition a frontal polymerization process and creation of high homogeneous polyacrilamide gel were observed 1 Thus a much better resolution result of proteins by electrophoresis on orbital PAG matrices was obtained than that on terrestrial PAG matrices A deeper understanding of conditions responsible for generation of physical properties of PAG synthesized on the Earth was a strong motivation for seeking gravity-sensitive mechanisms of polymerization The polymerization under microgravity can potentially applied on functional polymer The conductive polymer such as polypyrrole is usually utilized especially for microelectronics The polymerization of pyrrole in microgravity conditions was made to prepare polymer particles having shapes

Polystyrene/Fe3O4 magnetic emulsion and nanocomposite prepared by ultrasonically initiated miniemulsion polymerization.

PubMed

Qiu, Guihua; Wang, Qi; Wang, Chao; Lau, Willie; Guo, Yili

2007-01-01

Ultrasonically initiated miniemulsion polymerization of styrene in the presence of Fe3O4 nanoparticles was successfully employed to prepare polystyrene (PS)/Fe3O4 magnetic emulsion and nanocomposite. The effects of Fe3O4 nanoparticles on miniemulsion polymerization process, the structure, morphology and properties of PS/Fe3O4 nanocomposite were investigated. The increase in the amount of Fe3O4 nanoparticles drastically increases the polymerization rate due to that Fe3O4 nanoparticles increase the number of radicals and the cavitation bubbles. Polymerization kinetics of ultrasonically initiated miniemulsion polymerization is similar to that of conventional miniemulsion polymerization. PS/Fe3O4 magnetic emulsion consists of two types of particles: latex particles with Fe3O4 nanoparticles and latex particles with no encapsulated Fe3O4 nanoparticles. Fe3O4 nanoparticles lower the molecular weight of PS and broaden the molecular weight and particle size distribution. Thermal stability of PS/Fe3O4 nanocomposite increases with the increase in Fe3O4 content. PS/Fe3O4 emulsion and nanocomposite exhibit magnetic properties. PS/Fe3O4 magnetic particles can be separated from the magnetic emulsion by an external magnetic field and redispersed into the emulsion with agitation.

Two Photon Polymerization of Microneedles for Transdermal Drug Delivery

PubMed Central

Gittard, Shaun D.; Ovsianikov, Aleksandr; Chichkov, Boris N.; Doraiswamy, Anand; Narayan, Roger J.

2010-01-01

Importance of the field Microneedles are small-scale devices that are finding use for transdermal delivery of protein-based pharmacologic agents and nucleic acid-based pharmacologic agents; however, microneedles prepared using conventional microelectronics-based technologies have several shortcomings, which have limited translation of these devices into widespread clinical use. Areas covered in this review Two photon polymerization is a laser-based rapid prototyping technique that has been recently used for direct fabrication of hollow microneedles with a wide variety of geometries. In addition, an indirect rapid prototyping method that involves two photon polymerization and polydimethyl siloxane micromolding has been used for fabrication of solid microneedles with exceptional mechanical properties. What the reader will gain In this review, the use of two photon polymerization for fabricating in-plane and out-of-plane hollow microneedle arrays is described. The use of two photon polymerization-micromolding for fabrication of solid microneedles is also reviewed. In addition, fabrication of microneedles with antimicrobial properties is discussed; antimicrobial microneedles may reduce the risk of infection associated with formation of channels through the stratum corneum. Take home message It is anticipated that the use of two photon polymerization as well as two photon polymerization-micromolding for fabrication of microneedles and other microstructured drug delivery devices will increase over the coming years. PMID:20205601

A microtitre-based method for measuring the haem polymerization inhibitory activity (HPIA) of antimalarial drugs.

PubMed

Basilico, N; Pagani, E; Monti, D; Olliaro, P; Taramelli, D

1998-07-01

The malaria parasite metabolizes haemoglobin and detoxifies the resulting haem by polymerizing it to form haemozoin (malaria pigment). A polymer identical to haemozoin, beta-haematin, can be obtained in vitro from haematin at acidic pH. Quinoline-containing anti-malarials (e.g. chloroquine) inhibit the formation of either polymer. Haem polymerization is an essential and unique pharmacological target. To identify molecules with haem polymerization inhibitory activity (HPIA) and quantify their potency, we developed a simple, inexpensive, quantitative in-vitro spectrophotometric microassay of haem polymerization. The assay uses 96-well U-bottomed polystyrene microplates and requires 24 h and a microplate reader. The relative amounts of polymerized and unpolymerized haematin are determined, based on solubility in DMSO, by measuring absorbance at 405 nm in the presence of test compounds as compared with untreated controls. The final product (a solid precipitate of polymerized haematin) was validated using infrared spectroscopy and the assay proved reproducible; in this assay, activity could be partly predicted based on the compound's chemical structure. Both water-soluble and water-insoluble compounds can be quantified by this method. Although the throughput of this assay is lower than that of radiometric methods, the assay is easier to set up and cheaper, and avoids the problems related to radioactive waste disposal.

Production methodologies of polymeric and hydrogel particles for drug delivery applications.

PubMed

Lima, Ana Catarina; Sher, Praveen; Mano, João F

2012-02-01

Polymeric particles are ideal vehicles for controlled delivery applications due to their ability to encapsulate a variety of substances, namely low- and high-molecular mass therapeutics, antigens or DNA. Micro and nano scale spherical materials have been developed as carriers for therapies, using appropriated methodologies, in order to achieve a prolonged and controlled drug administration. This paper reviews the methodologies used for the production of polymeric micro/nanoparticles. Emulsions, phase separation, spray drying, ionic gelation, polyelectrolyte complexation and supercritical fluids precipitation are all widely used processes for polymeric micro/nanoencapsulation. This paper also discusses the recent developments and patents reported in this field. Other less conventional methodologies are also described, such as the use of superhydrophobic substrates to produce hydrogel and polymeric particulate biomaterials. Polymeric drug delivery systems have gained increased importance due to the need for improving the efficiency and versatility of existing therapies. This allows the development of innovative concepts that could create more efficient systems, which in turn may address many healthcare needs worldwide. The existing methods to produce polymeric release systems have some critical drawbacks, which compromise the efficiency of these techniques. Improvements and development of new methodologies could be achieved by using multidisciplinary approaches and tools taken from other subjects, including nanotechnologies, biomimetics, tissue engineering, polymer science or microfluidics.

Determining the influence of fibre post light transmission on polymerization depth and viscoelastic behaviour of dual-cured resin cement.

PubMed

Dogar, A; Altintas, S C; Kavlak, S; Guner, A

2012-12-01

To evaluate the effect of quartz-fibre posts on the depth of polymerization of a dual-cure resin cement using Raman spectroscopy and to determine the physical properties of the polymerized cement using a dynamic mechanical analyzer (DMA). Twenty-five fibre and 25 CrNi posts were used to evaluate depth of polymerization. Posts were cemented with dual-cure resin into root canals formed from silicone moulds, without using bonding or etching agents. After polymerization, resin layers on each sample were removed using a curette and cut into three equal parts (apical, middle and coronal). All resin specimens for every third were gathered and crushed. Resin powder samples were analysed using Dynamic Mechanical Analysis and Raman spectroscopy for each third. The numerical data revealed that the thermal transitions of the materials took place at higher temperatures from the apical to the coronal sections in both groups. C=C double bond intensity was lower in fibre post-resin cement samples when compared to their intensity in metal post-resin cement samples. Dual-cured resin cements had more rigid properties and better polymerization for fibre posts when compared with metal posts. Polymerization quantity was affected by position in the canal. © 2012 International Endodontic Journal.

Rapid profiling of polymeric phenolic acids in Salvia miltiorrhiza by hybrid data-dependent/targeted multistage mass spectrometry acquisition based on expected compounds prediction and fragment ion searching.

PubMed

Shen, Yao; Feng, Zijin; Yang, Min; Zhou, Zhe; Han, Sumei; Hou, Jinjun; Li, Zhenwei; Wu, Wanying; Guo, De-An

2018-04-01

Phenolic acids are the major water-soluble components in Salvia miltiorrhiza (>5%). According to previous studies, many of them contribute to the cardiovascular effects and antioxidant effects of S. miltiorrhiza. Polymeric phenolic acids can be considered as the tanshinol derived metabolites, e.g., dimmers, trimers, and tetramers. A strategy combined with tanshinol-based expected compounds prediction, total ion chromatogram filtering, fragment ion searching, and parent list-based multistage mass spectrometry acquisition by linear trap quadropole-orbitrap Velos mass spectrometry was proposed to rapid profile polymeric phenolic acids in S. miltiorrhiza. More than 480 potential polymeric phenolic acids could be screened out by this strategy. Based on the fragment information obtained by parent list-activated data dependent multistage mass spectrometry acquisition, 190 polymeric phenolic acids were characterized by comparing their mass information with literature data, and 18 of them were firstly detected from S. miltiorrhiza. Seven potential compounds were tentatively characterized as new polymeric phenolic acids from S. miltiorrhiza. This strategy facilitates identification of polymeric phenolic acids in complex matrix with both selectivity and sensitivity, which could be expanded for rapid discovery and identification of compounds from complex matrix. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metastable Polymeric Nitrogen: The Ultimate Green High-Energy-Density Material

NASA Astrophysics Data System (ADS)

Ciezak, Jennifer

2007-06-01

High-energy-high-density materials offering increased stability, vulnerability, and environmental safety are being aggressively pursued to meet the requirements of the DoD Joint Visions and Future Force. Nearly two decades ago, it was proposed that polymeric nitrogen would exceed all of these requirements and possess nearly five times the energy of any conventional energetic material in use today. The present study details an investigation into nitrogen polymerization using a novel high-pressure approach utilizing sodium azide as the starting material. Due to the weaker bonding structure of the anionic azide chains in comparison to a N-N triple bond, one expects that the azide chains will create single-covalently bonded polymeric networks more easily than diatomic nitrogen. A polymeric form of sodium azide was synthesized at high pressures, but the material was not metastable at ambient conditions, which precluded performance testing. Quantum chemical calculations have indicated stabilization of the polymeric structure at ambient conditions may be possible with the addition of hydrogen. Vibrational spectroscopic characterization suggests that a meta-stable polymeric form of nitrogen has been synthesized under high-pressure using sodium azide/hydrogen as the starting materials. This material remains stable at ambient conditions upwards of two weeks depending on the storage conditions.

Self-Propagating Frontal Polymerization in Water at Ambient Pressure

NASA Technical Reports Server (NTRS)

Olten, Nesrin; Kraigsley, Alison; Ronney, Paul D.

2003-01-01

Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High boiling point solutions are needed because in order to produce a propagating front, a high front temperature is needed to produce sufficiently rapid decomposition of the free radical initiator and subsequent free radical polymerization and heat release at a rate faster than heat losses remove thermal energy from the system. (While the conduction heat loss rate increases linearly with temperature, the free radical initiator decomposition is a high activation energy process whose rate increases much more rapidly than linearly with temperature, thus as the temperature decreases, the ratio of heat loss to heat generation increases, eventually leading to extinction of the front if the temperature is too low.) In order to obtain atmospheric pressure frontal polymerization in water, it is necessary to identify a monomer/initiator combination that is water soluble and will not extinguish even when the peak temperature (T*) is less than 100 C. In this work acrylic acid (AA) was chosen as the monomer because is it one of the most reactive monomers and can polymerize readily at low temperatures even without initiators. Ammonium persulfate (AP) was chosen as the initiator because it decomposes readily at low temperatures, produces relatively few bubbles and is commercially available. The propagation rates and extinction conditions of the fronts are studied for a range of AA and AP concentrations. Small amounts of fumed silica powder (Cab-o-sil, Cabot Corporation) were added to the solutions to inhibit buoyancy induced convection in the solutions; future studies will investigate the effects of buoyant convection within the solutions.

A model for shrinkage strain in photo polymerization of dental composites.

PubMed

Petrovic, Ljubomir M; Atanackovic, Teodor M

2008-04-01

We formulate a new model for the shrinkage strain developed during photo polymerization in dental composites. The model is based on the diffusion type fractional order equation, since it has been proved that polymerization reaction is diffusion controlled (Atai M, Watts DC. A new kinetic model for the photo polymerization shrinkage-strain of dental composites and resin-monomers. Dent Mater 2006;22:785-91). Our model strongly confirms the observation by Atai and Watts (see reference details above) and their experimental results. The shrinkage strain is modeled by a nonlinear differential equation in (see reference details above) and that equation must be solved numerically. In our approach, we use the linear fractional order differential equation to describe the strain rate due to photo polymerization. This equation is solved exactly. As shrinkage is a consequence of the polymerization reaction and polymerization reaction is diffusion controlled, we postulate that shrinkage strain rate is described by a diffusion type equation. We find explicit form of solution to this equation and determine the strain in the resin monomers. Also by using equations of linear viscoelasticity, we determine stresses in the polymer due to the shrinkage. The time evolution of stresses implies that the maximal stresses are developed at the very beginning of the polymerization process. The stress in a dental composite that is light treated has the largest value short time after the treatment starts. The strain settles at the constant value in the time of about 100s (for the cases treated in Atai and Watts). From the model developed here, the shrinkage strain of dental composites and resin monomers is analytically determined. The maximal value of stresses is important, since this value must be smaller than the adhesive bond strength at cavo-restoration interface. The maximum stress determined here depends on the diffusivity coefficient. Since diffusivity coefficient increases as polymerization proceeds, it follows that the periods of light treatments should be shorter at the beginning of the treatment and longer at the end of the treatment, with dark interval between the initial low intensity and following high intensity curing. This is because at the end of polymerization the stress relaxation cannot take place.

Human polyhomeotic homolog 3 (PHC3) sterile alpha motif (SAM) linker allows open-ended polymerization of PHC3 SAM.

PubMed

Robinson, Angela K; Leal, Belinda Z; Nanyes, David R; Kaur, Yogeet; Ilangovan, Udayar; Schirf, Virgil; Hinck, Andrew P; Demeler, Borries; Kim, Chongwoo A

2012-07-10

Sterile alpha motifs (SAMs) are frequently found in eukaryotic genomes. An intriguing property of many SAMs is their ability to self-associate, forming an open-ended polymer structure whose formation has been shown to be essential for the function of the protein. What remains largely unresolved is how polymerization is controlled. Previously, we had determined that the stretch of unstructured residues N-terminal to the SAM of a Drosophila protein called polyhomeotic (Ph), a member of the polycomb group (PcG) of gene silencers, plays a key role in controlling Ph SAM polymerization. Ph SAM with its native linker created shorter polymers compared to Ph SAM attached to either a random linker or no linker. Here, we show that the SAM linker for the human Ph ortholog, polyhomeotic homolog 3 (PHC3), also controls PHC3 SAM polymerization but does so in the opposite fashion. PHC3 SAM with its native linker allows longer polymers to form compared to when attached to a random linker. Attaching the PHC3 SAM linker to Ph SAM also resulted in extending Ph SAM polymerization. Moreover, in the context of full-length Ph protein, replacing the SAM linker with PHC3 SAM linker, intended to create longer polymers, resulted in greater repressive ability for the chimera compared to wild-type Ph. These findings show that polymeric SAM linkers evolved to modulate a wide dynamic range of SAM polymerization abilities and suggest that rationally manipulating the function of SAM containing proteins through controlling their SAM polymerization may be possible.

Hydrolyzable Poly[Poly(Ethylene Glycol) Methyl Ether Acrylate]-Colistin Prodrugs through Copper-Mediated Photoinduced Living Radical Polymerization.

PubMed

Zhu, Chongyu; Schneider, Elena K; Nikolaou, Vasiliki; Klein, Tobias; Li, Jian; Davis, Thomas P; Whittaker, Michael R; Wilson, Paul; Kempe, Kristian; Velkov, Tony; Haddleton, David M

2017-07-19

Through the recently developed copper-mediated photoinduced living radical polymerization (CP-LRP), a novel and well-defined polymeric prodrug of the antimicrobial lipopeptide colistin has been developed. A colistin initiator (Boc 5 -col-Br 2 ) was synthesized through the modification of colistin on both of its threonine residues using a cleavable initiator linker, 2-(2-bromo-2-methylpropanoyloxy) acetic acid (BMPAA), and used for the polymerization of acrylates via CP-LRP. Polymerization proceeds from both sites of the colistin initiator, and through the polymerization of poly(ethylene glycol) methyl ether acrylate (PEGA 480 ), three water-soluble polymer-colistin conjugates (col-PPEGA, having degrees of polymerization of 5, 10, and 20) were achieved with high yield (conversion of ≥93%) and narrow dispersities (Đ < 1.3) in 2-4 h. Little or no effect on the structure and activity of the colistin was observed during the synthesis, and most of the active colistin can be recovered from the conjugates in vitro within 2 days. Furthermore, in vitro biological analyses including disk diffusion, broth microdilution, and time-kill studies suggested that all of the conjugates have the ability to inhibit the growth of multidrug-resistant (MDR) Gram-negative bacteria, of which col-PPEGA DP5 and DP10 showed similar or better antibacterial performance compared to the clinically relevant colistin prodrug CMS, indicating their potential as an alternative antimicrobial therapy. Moreover, considering the control over the polymerization, the CP-LRP technique has the potential to provide an alternative platform for the development of polymer bioconjugates.

Hyper-activated motility in sperm capacitation is mediated by phospholipase D-dependent actin polymerization.

PubMed

Itach, Sarit Bar-Sheshet; Finklestein, Maya; Etkovitz, Nir; Breitbart, Haim

2012-02-15

In order to fertilize the oocyte, sperm must undergo a series of biochemical changes in the female reproductive tract, known as capacitation. Once capacitated, spermatozoon can bind to the zona pellucida of the egg and undergo the acrosome reaction (AR), a process that enables its penetration and fertilization of the oocyte. Important processes that characterize sperm capacitation are actin polymerization and the development of hyper-activated motility (HAM). Previously, we showed that Phospholipase D (PLD)-dependent actin polymerization occurs during sperm capacitation, however the role of this process in sperm capacitation is not yet known. In the present study, we showed for the first time the involvement of PLD-dependent actin polymerization in sperm motility during mouse and human capacitation. Sperm incubated under capacitation conditions revealed a time dependent increase in actin polymerization and HAM. Inhibition of Phosphatidic Acid (PA) formation by PLD using butan-1-ol, inhibited actin polymerization and motility, as well as in vitro fertilization (IVF) and the ability of the sperm to undergo the AR. The inhibition of sperm HAM by low concentration of butan-1-ol is completely restored by adding PA, further indicating the involvement of PLD in these processes. Furthermore, exogenous PA enhanced rapid actin polymerization that was followed by a rise in the HAM, as well as an increased in IVF rate. In conclusion, our results demonstrate that PLD-dependent actin polymerization is a critical step needed for the development of HAM during mouse and human sperm capacitation. Copyright © 2011 Elsevier Inc. All rights reserved.

Physico-chemical characterization of polymeric micelles loaded with platinum derivatives by capillary electrophoresis and related methods.

PubMed

Oukacine, Farid; Bernard, Stephane; Bobe, Iulian; Cottet, Hervé

2014-12-28

(1,2-diamino-cyclohexane)Platinum(II) ((DACH)Pt) loaded polymeric micelles of poly(ethylene glycol-b-sodium glutamate) (PEG-b-PGlu) are currently studied as a potential candidate to replace oxaliplatin in the treatment of cancers with the aim to reduce side effects like cumulative peripheral distal neurotoxicity and acute dysesthesias. As for all synthetic polymeric drug delivery systems, the characterization of the (co)polymer precursors and of the final drug delivery system (polymeric micelles) is crucial to control the repeatability of the different batches and to get correlation between physico-chemical structure and biological activity. In this work, the use of capillary electrophoresis (CE) and related methods for the characterization of (DACH)Pt-loaded polymeric micelles and their precursor (PEG-b-PGlu copolymer) has been investigated in detail. The separation and quantification of residual PGlu homopolymer in the PEG-b-PGlu sample were performed by free solution capillary zone electrophoresis mode. This mode brought also information on the PEG-b-PGlu copolymer composition and polydispersity. It also permitted to monitor the decomposition of polymeric micelles in the presence of NaCl at room temperature. Interactions between PEG-b-PGlu unimers, on one hand, and polymeric micelles or surfactants, on the other hand, were studied by using the Micellar Electrokinetic Chromatography and Frontal Analysis Capillary Electrophoresis modes. Finally, weight-average hydrodynamic radii of the loaded polymeric micelles and of the PEG-b-PGlu unimers were determined by Taylor Dispersion Analysis (an absolute size determination method that can be easily implemented on CE apparatus). Copyright © 2014 Elsevier B.V. All rights reserved.

A new method to measure the polymerization shrinkage kinetics of light cured composites.

PubMed

Lee, I B; Cho, B H; Son, H H; Um, C M

2005-04-01

This study was undertaken to develop a new measurement method to determine the initial dynamic volumetric shrinkage of composite resins during polymerization, and to investigate the effect of curing light intensity on the polymerization shrinkage kinetics. The instrument was basically an electromagnetic balance that was constructed with a force transducer using a position sensitive photo detector (PSPD) and a negative feedback servo amplifier. The volumetric change of composites during polymerization was detected continuously as a buoyancy change in distilled water by means of the Archimedes' principle. Using this new instrument, the dynamic patterns of the polymerization shrinkage of seven commercial composite resins were measured. The polymerization shrinkage of the composites was 1.92 approximately 4.05 volume %. The shrinkage of a packable composite was the lowest, and that of a flowable composite was the highest. The maximum rate of polymerization shrinkage increased with increasing light intensity but the peak shrinkage rate time decreased with increasing light intensity. A strong positive relationship was observed between the square root of the light intensity and the maximum shrinkage rate. The shrinkage rate per unit time, dVol%/dt, showed that the instrument can be a valuable research method for investigating the polymerization reaction kinetics. This new shrinkage-measuring instrument has some advantages that it was insensitive to temperature changes and could measure the dynamic volumetric shrinkage in real time without complicated processes. Therefore, it can be used to characterize the shrinkage kinetics in a wide range of commercial and experimental visible-light-cure materials in relation to their composition and chemistry.

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy.

PubMed

Marín-Yaseli, Margarita R; Moreno, Miguel; de la Fuente, José L; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-15

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH 4 CN and NaCN, at middle temperatures between 4 and 38°C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH 4 CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study. Copyright © 2017 Elsevier B.V. All rights reserved.

Polymerization-Incompetent Uromodulin in the Pregnant Stroke-Prone Spontaneously Hypertensive Rat

PubMed Central

Mary, Sheon; Small, Heather Yvonne; Siwy, Justyna; Mullen, William; Giri, Ashok

2017-01-01

The kidney is centrally involved in blood pressure regulation and undergoes extensive changes during pregnancy. Hypertension during pregnancy may result in an altered urinary peptidome that could be used to indicate new targets of therapeutic or diagnostic interest. The stroke-prone spontaneously hypertensive rat (SHRSP) is a model of maternal chronic hypertension. Capillary electrophoresis-mass spectrometry was conducted to interrogate the urinary peptidome in SHRSP and the control Wistar–Kyoto strain at three time points: prepregnancy and gestational days 12 and 18. The comparison within and between the Wistar–Kyoto and SHRSP peptidome at all time points detected 123 differentially expressed peptides (fold change >1.5; P<0.05). Sequencing of these peptides identified fragments of collagen α-chains, albumin, prothrombin, actin, serpin A3K, proepidermal growth factor, and uromodulin. Uromodulin peptides showed a pregnancy-specific alteration in SHRSP with a 7.8-fold (P<0.01) and 8.8-fold (P<0.05) increase at gestational days 12 and 18, respectively, relative to the Wistar–Kyoto. Further investigation revealed that these peptides belonged to the polymerization-inhibitory region of uromodulin. Two forms of uromodulin (polymerization competent and polymerization incompetent) were found in urine from both Wistar–Kyoto and SHRSP, where the polymerization-incompetent form was increased in a pregnancy-specific manner in SHRSP. Nifedipine-treated pregnant SHRSP showed only polymerization-competent uromodulin, indicating that calcium may be mechanistically involved in uromodulin polymerization. This study highlights, for the first time, a potential role of uromodulin and its polymerization in hypertensive pregnancy. PMID:28348009

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy

NASA Astrophysics Data System (ADS)

Marín-Yaseli, Margarita R.; Moreno, Miguel; de la Fuente, José L.; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-01

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH4CN and NaCN, at middle temperatures between 4 and 38 °C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH4CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study.

Synthesis of poly(N-isopropylacrylamide)-co-poly(phenylboronate ester) acrylate and study on their glucose-responsive behavior.

PubMed

Yao, Yuan; Shen, Heyun; Zhang, Guanghui; Yang, Jing; Jin, Xu

2014-10-01

We introduced thermo-sensitive poly(N-isopropylacrylamide) (PNIPAM) into the polymer structure of poly(ethylene glycol)-block-poly(phenylboronate ester) acrylate (MPEG-block-PPBDEMA) by block and random polymerization pathways in order to investigate the effect of polymer architecture on the glucose-responsiveness and enhance their insulin release controllability. By following the structure, the continuous PNIPAM shell of the triblock polymer MPEG-block-PNIPAM-block-PPBDEMA collapsing on the glucose-responsive PPBDEMA core formed the polymeric micelles with a core-shell-corona structure, and MPEG-block-(PNIPAM-rand-PPBDEMA) exhibited core-corona micelles in which the hydrophobic core consisted of PNIPAM and PPBDEMA segments when the environmental temperature was increased above low critical solution temperature (LCST) of PNIPAM. The micellar morphologies can be precisely controlled by temperature change between 15 and 37°C. As a result, the introduction of PNIPAM greatly enhanced the overall stability of insulin encapsulated in the polymeric micelles in the absence of glucose over incubation 80 h at 37°C. Comparing to MPEG-block-PNIPAM-block-PPBDEMA, the nanocarriers from MPEG-block-(PNIPAM-rand-PPBDEMA) showed great insulin release behavior which is zero insulin release without glucose, low release at normal blood glucose concentration (1.0 mg/mL). Therefore, these nanocarriers may be served as promising self-regulated insulin delivery system for diabetes treatment. Copyright © 2014 Elsevier Inc. All rights reserved.

Synthesis and characterization of a material derived from 4-mercaptobenzoic acid: A novel platform for oligonucleotide immobilization.

PubMed

Alves, Rafael da Fonseca; da Silva, Amanda Gonçalves; Ferreira, Lucas Franco; Franco, Diego Leoni

2017-04-01

This paper reports the electrochemical modification of pencil carbon graphite electrodes with a polymeric material derived from 4-mercaptobenzoic acid. Acidic solutions (pH 0 and 5.02) yielded an insulating polymeric film with anionic permselective properties. Scanning Electron Microscopy (SEM) analysis showed a complete coverage of the carbon graphite electrodes with a laminar-like polymeric structure. Different characterization studies indicate that the carboxyl group remained unchanged since the absorbance peak and oxidation potential did not change with the increase in pH at the pK a accounting for the carboxyl/carboxylate redox transition. The functionalized matrix was activated using carbodiimide, succinimide and an amine-modified oligonucleotide. The immobilization and hybridization processes were successfully verified using the redox electroactive indicator methylene blue, where better electrochemical signals were obtained when compared with the traditional self-assembled monolayer system. The selectivity of the system was verified using a noncomplementary target where no significant difference in electric current was observed when compared to the system containing only the probe. The method showed a good linear correlation coefficient (r 2 =0.9915), low limit of detection (1.17nmolL -1 ), and an acceptable precision (RSD=2.75%). The proposed method is suitable for further studies using different sequences of oligonucleotides. Copyright © 2016 Elsevier B.V. All rights reserved.

Potentiometric flow injection system for determination of reductants using a polymeric membrane permanganate ion-selective electrode based on current-controlled reagent delivery.

PubMed

Song, Wenjing; Ding, Jiawang; Liang, Rongning; Qin, Wei

2011-10-17

A polymeric membrane permanganate-selective electrode has been developed as a current-controlled reagent release system for potentiometric detection of reductants in flow injection analysis. By applying an external current, diffusion of permanganate ions across the polymeric membrane can be controlled precisely. The permanganate ions released at the sample-membrane interface from the inner filling solution of the electrode are consumed by reaction with a reductant in the sample solution thus changing the measured membrane potential, by which the reductant can be sensed potentiometrically. Ascorbate, dopamine and norepinephrine have been employed as the model reductants. Under the optimized conditions, the potential peak heights are proportional to the reductant concentrations in the ranges of 1.0×10(-5) to 2.5×10(-7)M for ascorbate, of 1.0×10(-5) to 5.0×10(-7)M for dopamine, and of 1.0×10(-5) to 5.0×10(-7)M for norepinephrine, respectively with the corresponding detection limits of 7.8×10(-8), 1.0×10(-7) and 1.0×10(-7)M. The proposed system has been successfully applied to the determination of reductants in pharmaceutical preparations and vegetables, and the results agree well with those of iodimetric analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

DOE PAGES

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun; ...

2016-12-23

Poly(2-isopropenyl-2-oxazoline) (PIPOx) has drawn significant attention for numerous applications. However, the successful living anionic polymerization of 2-isopropenyl-2-oxazoline has not been reported previously. In this paper, we describe how well-defined PIPOx with quantitative yields, controlled molecular weights from 6800 to over 100 000 g/mol and low polydispersity indices (PDI ≤ 1.17) were synthesized successfully via living anionic polymerization using diphenylmethylpotassium/diethylzinc (DPM-K/Et 2Zn) in tetrahydrofuran (THF) at 0 °C. In particular, we report the precise synthesis of well-defined PIPOx with the highest molecular weight ever reported (over 100 000 g/mol) and low PDI of 1.17. The resulting polymers were characterized by 1Hmore » and 13C nuclear magnetic resonance spectroscopy (NMR) along with size exclusion chromatography (SEC). Additionally, the reactivity of living PIPOx was investigated by crossover block copolymerization with styrene (St), 2-vinylpyridine (2VP), and methyl methacrylate (MMA). It was found that the nucleophilicity of living PIPOx is of this order: living PS > living P2VP > living PMMA > living PIPOx. The self-assembly behavior in bulk of PIPOx-b-PS-b-PIPOx triblock copolymers having different block ratios of 10:80:10 and 25:50:25 was studied using transmission electron microscopy (TEM). Finally, the formation of spherical and lamellar nanostructures, respectively, was observed.« less

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

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

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun

Poly(2-isopropenyl-2-oxazoline) (PIPOx) has drawn significant attention for numerous applications. However, the successful living anionic polymerization of 2-isopropenyl-2-oxazoline has not been reported previously. In this paper, we describe how well-defined PIPOx with quantitative yields, controlled molecular weights from 6800 to over 100 000 g/mol and low polydispersity indices (PDI ≤ 1.17) were synthesized successfully via living anionic polymerization using diphenylmethylpotassium/diethylzinc (DPM-K/Et 2Zn) in tetrahydrofuran (THF) at 0 °C. In particular, we report the precise synthesis of well-defined PIPOx with the highest molecular weight ever reported (over 100 000 g/mol) and low PDI of 1.17. The resulting polymers were characterized by 1Hmore » and 13C nuclear magnetic resonance spectroscopy (NMR) along with size exclusion chromatography (SEC). Additionally, the reactivity of living PIPOx was investigated by crossover block copolymerization with styrene (St), 2-vinylpyridine (2VP), and methyl methacrylate (MMA). It was found that the nucleophilicity of living PIPOx is of this order: living PS > living P2VP > living PMMA > living PIPOx. The self-assembly behavior in bulk of PIPOx-b-PS-b-PIPOx triblock copolymers having different block ratios of 10:80:10 and 25:50:25 was studied using transmission electron microscopy (TEM). Finally, the formation of spherical and lamellar nanostructures, respectively, was observed.« less

Nifedipine-loaded polymeric nanocapsules: validation of a stability-indicating HPLC method to evaluate the drug entrapment efficiency and in vitro release profiles.

PubMed

Granada, Andréa; Tagliari, Monika Piazzon; Soldi, Valdir; Silva, Marcos António Segatto; Zanetti-Ramos, Betina Ghiel; Fernandes, Daniel; Stulzer, Hellen Karine

2013-01-01

A simple stability-indicating analytical method was developed and validated to quantify nifedipine in polymeric nanocapsule suspensions; an in vitro drug release study was then carried out. The analysis was performed using an RP C18 column, UV-Vis detection at 262 nm, and methanol-water (70 + 30, v/v) mobile phase at a flow rate of 1.2 mL/min. The method was validated in terms of specificity, linearity and range, LOQ, accuracy, precision, and robustness. The results obtained were within the acceptable ranges. The nanocapsules, made of poly(epsilon-caprolactone), were prepared by the solvent displacement technique and showed high entrapment efficiency. The entrapment efficiency was 97.6 and 98.2% for the nifedipine-loaded polymeric nanocapsules prepared from polyvinyl alcohol (PVA) and Pluronic F68 (PF68), respectively. The particle size and zeta potential of nanocapsules were found to be influenced by the nature of the stabilizer used. The mean diameter and zeta potential for nanocapsules with PVA and PF68 were 290.9 and 179.9 nm, and -17.7 mV and -32.7 mV, respectively. The two formulations prepared showed a drug release of up to 70% over 4 days. This behavior indicates the viability of this drug delivery system for use as a controlled-release system.

Ring-Opening Polymerization of Lactide to Form a Biodegradable Polymer

ERIC Educational Resources Information Center

Robert, Jennifer L.; Aubrecht, Katherine B.

2008-01-01

In this laboratory activity for introductory organic chemistry, students carry out the tin(II) bis(2-ethylhexanoate)/benzyl alcohol mediated ring-opening polymerization of lactide to form the biodegradable polymer polylactide (PLA). As the mechanism of the polymerization is analogous to that of a transesterification reaction, the experiment can be…

Spring-loaded polymeric gel actuators

DOEpatents

Shahinpoor, M.

1995-02-14

Spring-loaded electrically controllable polymeric gel actuators are disclosed. The polymeric gels can be polyvinyl alcohol, polyacrylic acid, or polyacrylamide, and are contained in an electrolytic solvent bath such as water plus acetone. The action of the gel is mechanically biased, allowing the expansive and contractile forces to be optimized for specific applications. 5 figs.

Polymeric Additives For Graphite/Epoxy Composites

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Nir, Z.

1990-01-01

Report describes experimental studies of properties of several graphite/epoxy composites containing polymeric additives as flexibilizing or toughening agents. Emphasizes effects of brominated polymeric additives (BPA's) with or without carboxy-terminated butadiene acrylonitrile rubber. Reviews effects of individual and combined additives on fracture toughnesses, environmental stabilities, hot/wet strengths, thermomechanical behaviors, and other mechanical properties of composites.

Photocontrol in Complex Polymeric Materials: Fact or Illusion?

PubMed

Jerca, Valentin Victor; Hoogenboom, Richard

2018-06-04

Photoswitches: Exciting recent progress realized in the field of light-controlled polymeric materials is highlighted. It is discussed how the rational choice of azobenzene molecules and their incorporation into complex materials by making use of physical interactions can lead to genuine photocontrollable polymeric systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Hermes, Robert E.

An encapsulated composition for polymerization includes an initiator composition for initiating a polymerization reaction, and a capsule prepared from an elemental metal or fusible alloy having a melting temperature from about 20.degree. C. to about 200.degree. C. A fluid for polymerization includes the encapsulated composition and a monomer. When the capsule melts or breaks open, the initiator is released.

Coherent X-ray diffraction imaging of nanoengineered polymeric capsules

NASA Astrophysics Data System (ADS)

Erokhina, S.; Pastorino, L.; Di Lisa, D.; Kiiamov, A. G.; Faizullina, A. R.; Tayurskii, D. A.; Iannotta, S.; Erokhin, V.

2017-10-01

For the first time, nanoengineered polymeric capsules and their architecture have been studied with coherent X-ray diffraction imaging technique. The use of coherent X-ray diffraction imaging technique allowed us to analyze the samples immersed in a liquid. We report about the significant difference between polymeric capsule architectures under dry and liquid conditions.

Polymerization method for formation of thermally exfoliated graphite oxide containing polymer

NASA Technical Reports Server (NTRS)

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

2010-01-01

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

Mechanical properties of light-curing composites polymerized with different laboratory photo-curing units.

PubMed

da Silva, Gisele Rodrigues; Simamoto-Júnior, Paulo Cezar; da Mota, Adérito Soares; Soares, Carlos José

2007-03-01

This study aimed to analyze the microhardness (KHN) and diametral tensile strength (DTS) of two hybrid resin composites (TPH Spectrum and Filtek Z250). To this end, the composites were polymerized with six laboratory photo-curing units (LPUs) and the results compared with an alternative polymerization method using conventional halogen light source in conjunction with additional polymerization in an autoclave (15 minutes/100 degrees C). LPUs were used following the manufacturers' instructions. Diametral tensile strength and Knoop hardness tests were conducted for all groups (n=5). Data were statistically compared using ANOVA and Tukey's test (alpha = 0.05). Among the LPUs, the one that provided light curing in conjunction with heat and nitrogen pressure resulted in a significant increase in KHN and DTS of resin composites. Between the resin composites, Filtek Z250 showed higher hardness values than TPH Spectrum. It was concluded that the use of alternative polymerization with conventional light polymerization and autoclave was feasible with a wide implication for the general public in terms of reduced dental treatment cost.

Biphasic interactions between a cationic dendrimer and actin.

PubMed

Ruenraroengsak, Pakatip; Florence, Alexander T

2010-12-01

Gene delivery systems face the problem not only of the route toward the cell and tissues in question, but also of the molecularly crowded environment of both the cytoplasm and the nucleus itself. One of the physical barriers in the cytoplasm for diffusing nanoparticles is an actin network. Here, we describe the finding that a self-fluorescent sixth generation cationic dendrimer (6 nm in diameter) interacts reversibly and possibly electrostatically with actin filaments in vitro. Not only does this interaction slow the diffusion of the dendrimer but it also affects actin polymerization in a biphasic manner. At low concentrations the dendrimer behaves like a G-binding actin protein, retarding actin polymerization, whereas at high concentrations the dendrimer acts as a nucleating protein accelerating the polymerization. Thus in vivo the diffusion of a dendrimer carrier such as this has both physical and chemical elements: by decreasing polymerization it might accelerate its own transport, and by enhancing actin polymerization retard it. This finding suggests that such a dendrimer may have a role as an anticancer agent through its inhibitory effect on actin polymerization.

Molecular Sensing by Nanoporous Crystalline Polymers

PubMed Central

Pilla, Pierluigi; Cusano, Andrea; Cutolo, Antonello; Giordano, Michele; Mensitieri, Giuseppe; Rizzo, Paola; Sanguigno, Luigi; Venditto, Vincenzo; Guerra, Gaetano

2009-01-01

Chemical sensors are generally based on the integration of suitable sensitive layers and transducing mechanisms. Although inorganic porous materials can be effective, there is significant interest in the use of polymeric materials because of their easy fabrication process, lower costs and mechanical flexibility. However, porous polymeric absorbents are generally amorphous and hence present poor molecular selectivity and undesired changes of mechanical properties as a consequence of large analyte uptake. In this contribution the structure, properties and some possible applications of sensing polymeric films based on nanoporous crystalline phases, which exhibit all identical nanopores, will be reviewed. The main advantages of crystalline nanoporous polymeric materials with respect to their amorphous counterparts are, besides a higher selectivity, the ability to maintain their physical state as well as geometry, even after large guest uptake (up to 10–15 wt%), and the possibility to control guest diffusivity by controlling the orientation of the host polymeric crystalline phase. The final section of the review also describes the ability of suitable polymeric films to act as chirality sensors, i.e., to sense and memorize the presence of non-racemic volatile organic compounds. PMID:22303150

Conjugation of diisocyanate side chains to dimethacrylate reduces polymerization shrinkage and increases the hardness of composite resins.

PubMed

Jan, Yih-Dean; Lee, Bor-Shiunn; Lin, Chun-Pin; Tseng, Wan-Yu

2014-04-01

Polymerization shrinkage is one of the main causes of dental restoration failure. This study tried to conjugate two diisocyanate side chains to dimethacrylate resins in order to reduce polymerization shrinkage and increase the hardness of composite resins. Diisocyanate, 2-hydroxyethyl methacrylate, and bisphenol A dimethacrylate were reacted in different ratios to form urethane-modified new resin matrices, and then mixed with 50 wt.% silica fillers. The viscosities of matrices, polymerization shrinkage, surface hardness, and degrees of conversion of experimental composite resins were then evaluated and compared with a non-modified control group. The viscosities of resin matrices increased with increasing diisocyanate side chain density. Polymerization shrinkage and degree of conversion, however, decreased with increasing diisocyanate side chain density. The surface hardness of all diisocyanate-modified groups was equal to or significantly higher than that of the control group. Conjugation of diisocyanate side chains to dimethacrylate represents an effective means of reducing polymerization shrinkage and increasing the surface hardness of dental composite resins. Copyright © 2012. Published by Elsevier B.V.

Large-scale filament formation inhibits the activity of CTP synthetase

PubMed Central

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

2014-01-01

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

Structural basis of reverse nucleotide polymerization

PubMed Central

Nakamura, Akiyoshi; Nemoto, Taiki; Heinemann, Ilka U.; Yamashita, Keitaro; Sonoda, Tomoyo; Komoda, Keisuke; Tanaka, Isao; Söll, Dieter; Yao, Min

2013-01-01

Nucleotide polymerization proceeds in the forward (5′-3′) direction. This tenet of the central dogma of molecular biology is found in diverse processes including transcription, reverse transcription, DNA replication, and even in lagging strand synthesis where reverse polymerization (3′-5′) would present a “simpler” solution. Interestingly, reverse (3′-5′) nucleotide addition is catalyzed by the tRNA maturation enzyme tRNAHis guanylyltransferase, a structural homolog of canonical forward polymerases. We present a Candida albicans tRNAHis guanylyltransferase-tRNAHis complex structure that reveals the structural basis of reverse polymerization. The directionality of nucleotide polymerization is determined by the orientation of approach of the nucleotide substrate. The tRNA substrate enters the enzyme’s active site from the opposite direction (180° flip) compared with similar nucleotide substrates of canonical 5′-3′ polymerases, and the finger domains are on opposing sides of the core palm domain. Structural, biochemical, and phylogenetic data indicate that reverse polymerization appeared early in evolution and resembles a mirror image of the forward process. PMID:24324136

Supramolecular "Step Polymerization" of Preassembled Micelles: A Study of "Polymerization" Kinetics.

PubMed

Yang, Chaoying; Ma, Xiaodong; Lin, Jiaping; Wang, Liquan; Lu, Yingqing; Zhang, Liangshun; Cai, Chunhua; Gao, Liang

2018-03-01

In nature, sophisticated functional materials are created through hierarchical self-assembly of nanoscale motifs, which has inspired the fabrication of man-made materials with complex architectures for a variety of applications. Herein, a kinetic study on the self-assembly of spindle-like micelles preassembled from polypeptide graft copolymers is reported. The addition of dimethylformamide and, subsequently, a selective solvent (water) can generate a "reactive point" at both ends of the spindles as a result of the existence of structural defects, which induces the "polymerization" of the spindles into nanowires. Experimental results combined with dissipative particle dynamics simulations show that the polymerization of the micellar subunits follows a step-growth polymerization mechanism with a second-order reaction characteristic. The assembly rate of the micelles is dependent on the subunit concentration and on the activity of the reactive points. The present work reveals a law governing the self-assembly kinetics of micelles with structural defects and opens the door for the construction of hierarchical structures with a controllable size through supramolecular step polymerization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Untemplated nonenzymatic polymerization of 3',5'cGMP: a plausible route to 3',5'-linked oligonucleotides in primordia.

PubMed

Šponer, Judit E; Šponer, Jiří; Giorgi, Alessandra; Di Mauro, Ernesto; Pino, Samanta; Costanzo, Giovanna

2015-02-19

The high-energy 3',5' phosphodiester linkages conserved in 3',5' cyclic GMPs offer a genuine solution for monomer activation required by the transphosphorylation reactions that could lead to the emergence of the first simple oligonucleotide sequences on the early Earth. In this work we provide an in-depth characterization of the effect of the reaction conditions on the yield of the polymerization reaction of 3',5' cyclic GMPs both in aqueous environment as well as under dehydrating conditions. We show that the threshold temperature of the polymerization is about 30 °C lower under dehydrating conditions than in solution. In addition, we present a plausible exergonic reaction pathway for the polymerization reaction, which involves transient formation of anionic centers at the O3' positions of the participating riboses. We suggest that excess Na(+) cations inhibit the polymerization reaction because they block the anionic mechanism via neutralizing the negatively charged O3'. Our experimental findings are compatible with a prebiotic scenario, where gradual desiccation of the environment could induce polymerization of 3',5' cyclic GMPs synthesized in liquid.

Intriguing Morphology Evolution from Noncrosslinked Poly(tert-butyl acrylate) Seeds with Polar Functional Groups in Soap-Free Emulsion Polymerization of Styrene.

PubMed

Wang, Lu; Pan, Mingwang; Song, Shaofeng; Zhu, Lei; Yuan, Jinfeng; Liu, Gang

2016-08-09

Herein, we demonstrate a facile approach to prepare anisotropic poly(tert-butyl acrylate)/polystyrene (PtBA/PS) composite particles with controllable morphologies by soap-free seeded emulsion polymerization (SSEP). In the first step, noncrosslinked PtBA seeds with self-stabilizing polar functional groups (e.g., ester groups and radicals) are synthesized by soap-free emulsion polymerization. During the subsequent SSEP of styrene (St), PS bulges are nucleated on the PtBA seeds due to the microphase separation confined in the latex particles. The morphology evolution of PtBA/PS composite particles is tailored by varying the monomer/seed feed ratio, polymerization time, and polymerization temperature. Many intriguing morphologies, including hamburger-like, litchi-like, mushroom-like, strawberry-like, bowl-like, and snowman-like, have been acquired for PtBA/PS composite particles. The polar groups on the PtBA seed surface greatly influence the formation and further merging of PS/St bulges during the polymerization. A possible formation mechanism is proposed on the basis of experimental results. These complex composite particles are promising for applications in superhydrophobic coatings.

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

PubMed

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

2012-05-18

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

Facile and Reliable in Situ Polymerization of Poly(Ethyl Cyanoacrylate)-Based Polymer Electrolytes toward Flexible Lithium Batteries.

PubMed

Cui, Yanyan; Chai, Jingchao; Du, Huiping; Duan, Yulong; Xie, Guangwen; Liu, Zhihong; Cui, Guanglei

2017-03-15

Polycyanoacrylate is a very promising matrix for polymer electrolyte, which possesses advantages of strong binding and high electrochemical stability owing to the functional nitrile groups. Herein, a facile and reliable in situ polymerization strategy of poly(ethyl cyanoacrylate) (PECA) based gel polymer electrolytes (GPE) via a high efficient anionic polymerization was introduced consisting of PECA and 4 M LiClO 4 in carbonate solvents. The in situ polymerized PECA gel polymer electrolyte achieved an excellent ionic conductivity (2.7 × 10 -3 S cm -1 ) at room temperature, and exhibited a considerable electrochemical stability window up to 4.8 V vs Li/Li + . The LiFePO 4 /PECA-GPE/Li and LiNi 1.5 Mn 0.5 O 4 /PECA-GPE/Li batteries using this in-situ-polymerized GPE delivered stable charge/discharge profiles, considerable rate capability, and excellent cycling performance. These results demonstrated this reliable in situ polymerization process is a very promising strategy to prepare high performance polymer electrolytes for flexible thin-film batteries, micropower lithium batteries, and deformable lithium batteries for special purpose.

Self-catalyzed photo-initiated RAFT polymerization for fabrication of fluorescent polymeric nanoparticles with aggregation-induced emission feature.

PubMed

Zeng, Guangjian; Liu, Meiying; Jiang, Ruming; Huang, Qiang; Huang, Long; Wan, Qing; Dai, Yanfeng; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2018-02-01

In recent years, the fluorescent polymeric nanoparticles (FPNs) with aggregation-induced emission (AIE) feature have been extensively exploited in various biomedical fields owing to their advantages, such as low toxicity, biodegradation, excellent biocompatibility, good designability and optical properties. Therefore, development of a facile, efficient and well designable strategy should be of great importance for the biomedical applications of these AIE-active FPNs. In this work, a novel method for the fabrication of AIE-active FPNs has been developed through the self-catalyzed photo-initiated reversible addition fragmentation chain transfer (RAFT) polymerization using an AIE dye containing chain transfer agent (CTA), which could initiate the RAFT polymerization under light irradiation. The results suggested that the final AIE-active FPNs (named as TPE-poly(St-PEGMA)) showed great potential for biomedical applications owing to their optical and biological properties. More importantly, the method described in the work is rather simple and effective and can be further extended to prepare many other different AIE-active FPNs owing to the good monomer adoptability of RAFT polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel function of twins, B subunit of protein phosphatase 2A, in regulating actin polymerization.

PubMed

Yeh, Po-An; Chang, Ching-Jin

2017-01-01

Actin is an important component of the cytoskeleton and its polymerization is delicately regulated by several kinases and phosphatases. Heterotrimeric protein phosphatase 2A (PP2A) is a potent phosphatase that is crucial for cell proliferation, apoptosis, tumorigenesis, signal transduction, cytoskeleton arrangement, and neurodegeneration. To facilitate these varied functions, different regulators determine the different targets of PP2A. Among these regulators of PP2A, the B subunits in particular may be involved in cytoskeleton arrangement. However, little is known about the role of PP2A in actin polymerization in vivo. Using sophisticated fly genetics, we demonstrated a novel function for the fly B subunit, twins, to promote actin polymerization in varied tissue types, suggesting a broad and conserved effect. Furthermore, our genetic data suggest that twins may act upstream of the actin-polymerized-proteins, Moesin and Myosin-light-chain, and downstream of Rho to promote actin polymerization. This work opens a new avenue for exploring the biological functions of a PP2A regulator, twins, in cytoskeleton regulation.

A novel function of twins, B subunit of protein phosphatase 2A, in regulating actin polymerization

PubMed Central

Chang, Ching-Jin

2017-01-01

Actin is an important component of the cytoskeleton and its polymerization is delicately regulated by several kinases and phosphatases. Heterotrimeric protein phosphatase 2A (PP2A) is a potent phosphatase that is crucial for cell proliferation, apoptosis, tumorigenesis, signal transduction, cytoskeleton arrangement, and neurodegeneration. To facilitate these varied functions, different regulators determine the different targets of PP2A. Among these regulators of PP2A, the B subunits in particular may be involved in cytoskeleton arrangement. However, little is known about the role of PP2A in actin polymerization in vivo. Using sophisticated fly genetics, we demonstrated a novel function for the fly B subunit, twins, to promote actin polymerization in varied tissue types, suggesting a broad and conserved effect. Furthermore, our genetic data suggest that twins may act upstream of the actin-polymerized-proteins, Moesin and Myosin-light-chain, and downstream of Rho to promote actin polymerization. This work opens a new avenue for exploring the biological functions of a PP2A regulator, twins, in cytoskeleton regulation. PMID:28977036

Polymeric micelles for multi-drug delivery in cancer.

PubMed

Cho, Hyunah; Lai, Tsz Chung; Tomoda, Keishiro; Kwon, Glen S

2015-02-01

Drug combinations are common in cancer treatment and are rapidly evolving, moving beyond chemotherapy combinations to combinations of signal transduction inhibitors. For the delivery of drug combinations, i.e., multi-drug delivery, major considerations are synergy, dose regimen (concurrent versus sequential), pharmacokinetics, toxicity, and safety. In this contribution, we review recent research on polymeric micelles for multi-drug delivery in cancer. In concurrent drug delivery, polymeric micelles deliver multi-poorly water-soluble anticancer agents, satisfying strict requirements in solubility, stability, and safety. In sequential drug delivery, polymeric micelles participate in pretreatment strategies that "prime" solid tumors and enhance the penetration of secondarily administered anticancer agent or nanocarrier. The improved delivery of multiple poorly water-soluble anticancer agents by polymeric micelles via concurrent or sequential regimens offers novel and interesting strategies for drug combinations in cancer treatment.

Tension modulates actin filament polymerization mediated by formin and profilin

PubMed Central

Courtemanche, Naomi; Lee, Ja Yil; Pollard, Thomas D.; Greene, Eric C.

2013-01-01

Formins promote processive elongation of actin filaments for cytokinetic contractile rings and other cellular structures. In vivo, these structures are exposed to tension, but the effect of tension on these processes was unknown. Here we used single-molecule imaging to investigate the effects of tension on actin polymerization mediated by yeast formin Bni1p. Small forces on the filaments dramatically slowed formin-mediated polymerization in the absence of profilin, but resulted in faster polymerization in the presence of profilin. We propose that force shifts the conformational equilibrium of the end of a filament associated with formin homology 2 domains toward the closed state that precludes polymerization, but that profilin–actin associated with formin homology 1 domains reverses this effect. Thus, physical forces strongly influence actin assembly by formin Bni1p. PMID:23716666

Syntheses, structures and properties of polycarbosilanes formed directly by polymerization of Alkenylsilanes

NASA Technical Reports Server (NTRS)

Masnovi, John; Bu, Xin Y.; Beyene, Kassahun; Heimann, Paula; Kacik, Terrence; Andrist, A. Harry; Hurwitz, Frances I.

1993-01-01

Vinylsilane polymerizes to form predominantly a carbosilane polymer using dimethyltitanocene catalyst. This is in contrast to alkylsilanes, which afford polysilanes under the same conditions. The mechanism of polymerization of alkenylsilanes has been shown to be fundamentally different from that for the polymerization of alkylsilanes. The silyl substitute apparently activates a double bond to participate in a number of polymerization processes in this system, particularly hydrosilation. Isotopic labeling indicates the involvement of silametallocyclic intermediates, accompanied by extensive nuclear rearrangement. Polymers and copolymers derived from alkenylsilanes have relatively high char yields even for conditions which afford low molecular weight distributions. Formation of crystalline beta-SiC is optimum for a copolymer of an alkylsilane and an alkenylsilane having a silane/carbosilane backbone ratio of 85/15 and a C/Si ratio of 1.3/1.

Relationship between Leakage Current and Pollution Deposits on the Surface of Polymeric Insulator

NASA Astrophysics Data System (ADS)

Miyake, Takuma; Seo, Yuya; Sakoda, Tatsuya; Otsubo, Masahisa

Application of polymeric materials used for housing insulators is considered. However, because polymeric insulator is organic matter, the aged deterioration is anxious. The lifetime of polymeric insulator is influenced by environmental conditions such as ultraviolet, acid rain, and polluted deposits. A change of the surface condition of polymeric material causes the dry band arc discharge and the discharge may lower the insulation strength. To investigate the relationship between insoluble pollution and occurrence of dry band arc discharge, we performed a salt-fog test with ethylene vinyl acetate (EVA) samples. The results showed that the heavy erosion caused by frequent dry band arc discharges occurred even in the case of a light polluted condition. Additionally, a very characteristic increase tendency in leakage current with a period of about 5 h was observed during the mist period.

Arrays of size and distance controlled platinum nanoparticles fabricated by a colloidal method

NASA Astrophysics Data System (ADS)

Manzke, Achim; Vogel, Nicolas; Weiss, Clemens K.; Ziener, Ulrich; Plettl, Alfred; Landfester, Katharina; Ziemann, Paul

2011-06-01

Based on emulsion polymerization in the presence of a Pt complex, polystyrene (PS) particles were prepared exhibiting a well defined average diameter with narrow size-distribution. Furthermore, the colloids contain a controlled concentration of the Pt precursor complex. Optimized coating of Si substrates with such colloids leads to extended areas of hexagonally ordered close-packed PS particles. Subsequent application of plasma etching and annealing steps allows complete removal of the PS carriers and in parallel nucleation and growth of Pt nanoparticles (NPs) which are located at the original center of the PS colloids. In this way, hexagonally arranged spherical Pt NPs are obtained with controlled size and interparticle distances demonstrating variability and precision with so far unknown parameter scalability. This control is demonstrated by the fabrication of Pt NP arrays at a fixed particle distance of 185 nm while systematically varying the diameters between 8 and 15 nm. Further progress could be achieved by seeded emulsion polymerization. Here, Pt loaded PS colloids of 130 nm were used as seeds for a subsequent additional emulsion polymerization, systematically enlarging the diameter of the PS particles. Applying the plasma and annealing steps as above, in this way hexagonally ordered arrays of 9 nm Pt NPs could be obtained at distances up to 260 nm. To demonstrate their stability, such Pt particles were used as etching masks during reactive ion etching thereby transferring their hexagonal pattern into the Si substrate resulting in corresponding arrays of nanopillars.Based on emulsion polymerization in the presence of a Pt complex, polystyrene (PS) particles were prepared exhibiting a well defined average diameter with narrow size-distribution. Furthermore, the colloids contain a controlled concentration of the Pt precursor complex. Optimized coating of Si substrates with such colloids leads to extended areas of hexagonally ordered close-packed PS particles. Subsequent application of plasma etching and annealing steps allows complete removal of the PS carriers and in parallel nucleation and growth of Pt nanoparticles (NPs) which are located at the original center of the PS colloids. In this way, hexagonally arranged spherical Pt NPs are obtained with controlled size and interparticle distances demonstrating variability and precision with so far unknown parameter scalability. This control is demonstrated by the fabrication of Pt NP arrays at a fixed particle distance of 185 nm while systematically varying the diameters between 8 and 15 nm. Further progress could be achieved by seeded emulsion polymerization. Here, Pt loaded PS colloids of 130 nm were used as seeds for a subsequent additional emulsion polymerization, systematically enlarging the diameter of the PS particles. Applying the plasma and annealing steps as above, in this way hexagonally ordered arrays of 9 nm Pt NPs could be obtained at distances up to 260 nm. To demonstrate their stability, such Pt particles were used as etching masks during reactive ion etching thereby transferring their hexagonal pattern into the Si substrate resulting in corresponding arrays of nanopillars. Electronic supplementary information (ESI) available: Detailed description of the experimental part (S1-S4) platinum concentration inside the polymer particles synthesized by a seeded polymerization from the same seed particles measured by ICP-OES (Fig. S1 and S5); SEM image of Pt complex containing PS particles after oxygen plasma treatment (Fig. S2 and S6); effect of hydrofluoric acid treatment on silicon oxide elevation under Pt NPs (Fig. S3 and S6); SEM images demonstrating the variability of Pt NP distance while keeping the diameter constant (Fig. S4 and S8); results of experimental determination of Pt content by ICP-OES (Tables S1 and S9); diameter of the particles at different fabrication states (Tables S2 and S10). See DOI: 10.1039/c1nr10169b

α1-antitrypsin polymerizes in alveolar macrophages of smokers with and without α1-antitrypsin deficiency.

PubMed

Bazzan, Erica; Tinè, Mariaenrica; Biondini, Davide; Benetti, Riccardo; Baraldo, Simonetta; Turato, Graziella; Fagiuoli, Stefano; Sonzogni, Aurelio; Rigobello, Chiara; Rea, Federico; Calabrese, Fiorella; Foschino-Barbaro, Maria Pia; Miranda, Elena; Lomas, David A; Saetta, Marina; Cosio, Manuel G

2018-05-12

The deficiency of α 1 -antitrypsin (AAT) is secondary to misfolding and polymerization of the abnormal Z-AAT in liver cells and is associated with lung emphysema. Alveolar macrophages (AM) produce AAT, however it is not known if Z-AAT can polymerize in AM, further decreasing lung AAT and promoting lung inflammation. To investigate if AAT polymerizes in human AM and to study the possible relation between polymerization and degree of lung inflammation. Immunohistochemical analysis with 2C1 monoclonal antibody specific for polymerized AAT was performed in sections of: 9 lungs from individuals with AAT deficiency (AATD) and severe COPD, 35 smokers with normal AAT levels of which 24 with severe COPD and 11 without COPD, and 13 non-smokers. AM positive for AAT polymers were counted and expressed as percentage of total AM in lung. AAT polymerization was detected in [27(4-67)%] of AM from individuals with AATD but also in AM from smokers with normal AAT with [24(0-70)%] and without [24(0-60)%] COPD, but not in AM from non-smokers [0(0-1.5)%] (p<0.0001). The percentage of AM with polymerized AAT correlated with pack-years smoked (r=0.53,p=0.0001), FEV 1 /FVC (r=-0.41,p=0.005), Small Airways Disease (r=0.44,p=0.004), number of CD8+T-cells and neutrophils in alveolar walls (r=0.51,p=0.002; r=0.31,p=0.05 respectively). Polymerization of AAT in alveolar macrophages occurs in lungs of individuals with AATD but also in smokers with normal AAT levels with or without COPD. Our findings highlight the similarities in the pathophysiology of COPD in individuals with and without AATD, adding a potentially important step to the mechanism of COPD. Copyright © 2018. Published by Elsevier Inc.

Compatibility between dental adhesive systems and dual-polymerizing composite resins.

PubMed

Michaud, Pierre-Luc; MacKenzie, Alexandra

2016-10-01

Information is lacking about incompatibilities between certain types of adhesive systems and dual-polymerizing composite resins, and universal adhesives have yet to be tested with these resins. The purpose of this in vitro study was to investigate the bonding outcome of dual-polymerizing foundation composite resins by using different categories of adhesive solutions and to determine whether incompatibilities were present. One hundred and eighty caries-free, extracted third molar teeth were allocated to 9 groups (n=20), in which 3 different bonding agents (Single Bond Plus [SB]), Scotchbond Multi-purpose [MP], and Scotchbond Universal [SU]) were used to bond 3 different composite resins (CompCore AF [CC], Core Paste XP [CP], and Filtek Supreme Ultra [FS]). After restorations had been fabricated using an Ultradent device, the specimens were stored in water at 37°C for 24 hours. The specimens were tested under shear force at a rate of 0.5 mm/min. The data were analyzed with Kruskal-Wallis tests and post hoc pairwise comparisons (α=.05). All 3 composite resins produced comparable shear bond strengths when used with MP (P=.076). However, when either SB or SU was used, the light-polymerized composite resin (FS) and 1 dual-polymerized foundation composite resin (CC) bonded significantly better than the other dual-polymerized foundation composite resin (CP) (P<.005). Both FS and CC performed best with SU but had acceptable results with all of the bonding agents. CP only performed acceptably with MP (P=.023) and had poor results with both other agents. Dual-polymerizing composite resins can obtain equally good bond strengths as light-polymerizing alternatives. However, not all dual-polymerizing composite resins perform well with all bonding systems; some incompatibilities exist between different products. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Synthesis of amphipathic block copolymers based on polyisobutylene and polyoxyethylene and their application in emulsion polymerization

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

Sar, B.

1992-12-31

Polymer colloids stabilized by polymeric surfactants are of great interest both commercially and academically. It has been found that these materials enhance latex stabilization in a number of applications. The polymeric surfactants are amphipathic block and graft copolymers containing both hydrophilic and hydrophobic moieties. The current study involved the synthesis of a series of amphipathic triblock copolymers, polyisobutylene-block-polyoxyethylene-block-polyisobutylene (PIB-b-POE-b-PIB), for use in the emulsion polymerization of styrene (STY), methyl methacrylate (MMA), and vinyl acetate (VAc). The stabilizing effectiveness of these triblock copolymers was studied as a function of their blocklength. When the molecular weight of the POE center block wasmore » changed from M{sub n} = 2,000 to 20,000 g/mole, stable lattices were obtained in emulsion polymerization with MMA, STY, and VAc as the monomers. In all cases, the polymerization rates remained constant, while the number of particles/volume decreased with increasing POE chain length. When the molecular weight of the PIB end blocks was changed from M{sub n} = 400 to 2,600 g/mole keeping the molecular weight of the POE center block constant at M{sub n} = 20,000 g/mole, the poly(methyl methacrylate) and poly(vinyl acetate) lattices exhibited similar behavior, i.e., the number of particles and particle sizes remained the same, but the rate of polymerization reached a maximum at 87 wt% POE content. In the case of poly(styrene) both the rate of polymerization and the number of particles remained constant. The emulsion polymerization of other monomers such as butadiene, acrylonitrile, methyl acrylate, ethyl acrylate, and butyl acrylate was carried out by using one triblock copolymer, i.e., PIB(400)-b-POE (8,000)-b-PIB-(400). Stable lattices were also formed in all cases.« less

Fibronectin Matrix Polymerization Regulates Smooth Muscle Cell Phenotype through a Rac1 Dependent Mechanism

PubMed Central

Shi, Feng; Long, Xiaochun; Hendershot, Allison; Miano, Joseph M.; Sottile, Jane

2014-01-01

Smooth muscle cells are maintained in a differentiated state in the vessel wall, but can be modulated to a synthetic phenotype following injury. Smooth muscle phenotypic modulation is thought to play an important role in the pathology of vascular occlusive diseases. Phenotypically modulated smooth muscle cells exhibit increased proliferative and migratory properties that accompany the downregulation of smooth muscle cell marker proteins. Extracellular matrix proteins, including fibronectin, can regulate the smooth muscle phenotype when used as adhesive substrates. However, cells produce and organize a 3-dimensional fibrillar extracellular matrix, which can affect cell behavior in distinct ways from the protomeric 2-dimensional matrix proteins that are used as adhesive substrates. We previously showed that the deposition/polymerization of fibronectin into the extracellular matrix can regulate the deposition and organization of other extracellular matrix molecules in vitro. Further, our published data show that the presence of a fibronectin polymerization inhibitor results in increased expression of smooth muscle cell differentiation proteins and inhibits vascular remodeling in vivo. In this manuscript, we used an in vitro cell culture system to determine the mechanism by which fibronectin polymerization affects smooth muscle phenotypic modulation. Our data show that fibronectin polymerization decreases the mRNA levels of multiple smooth muscle differentiation genes, and downregulates the levels of smooth muscle α-actin and calponin proteins by a Rac1-dependent mechanism. The expression of smooth muscle genes is transcriptionally regulated by fibronectin polymerization, as evidenced by the increased activity of luciferase reporter constructs in the presence of a fibronectin polymerization inhibitor. Fibronectin polymerization also promotes smooth muscle cell growth, and decreases the levels of actin stress fibers. These data define a Rac1-dependent pathway wherein fibronectin polymerization promotes the SMC synthetic phenotype by modulating the expression of smooth muscle cell differentiation proteins. PMID:24752318

Molecularly uniform poly(ethylene glycol) certified reference material

NASA Astrophysics Data System (ADS)

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

2015-02-01

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

Polymersome nanoreactors for enzymatic ring-opening polymerization.

PubMed

Nallani, Madhavan; de Hoog, Hans-Peter M; Cornelissen, Jeroen J L M; Palmans, Anja R A; van Hest, Jan C M; Nolte, Roeland J M

2007-12-01

Polystyrene-polyisocyanopeptide (PS-PIAT) polymersomes containing CALB in two different locations, one in the aqueous inner compartment and one in the bilayer, were investigated for enzymatic ring-opening polymerization of lactones in water. It is shown that the monomers 8-octanolactone and dodecalactone yield oligomers with this polymersome system. It is also observed that the polymerization activity is dependent on the position of the enzyme in the polymersome. SEM investigations show that the polymersome structures were destabilized during the polymerization. Further investigations show that the vesicular morphology of the polymersomes was destabilized only in the case of polymer product formation.

Size matters: smart copolymeric nanohydrogels: synthesis and applications.

PubMed

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

2012-01-01

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

Polymeric drugs: Advances in the development of pharmacologically active polymers

PubMed Central

Li, Jing; Yu, Fei; Chen, Yi; Oupický, David

2015-01-01

Synthetic polymers play a critical role in pharmaceutical discovery and development. Current research and applications of pharmaceutical polymers are mainly focused on their functions as excipients and inert carriers of other pharmacologically active agents. This review article surveys recent advances in alternative pharmaceutical use of polymers as pharmacologically active agents known as polymeric drugs. Emphasis is placed on the benefits of polymeric drugs that are associated with their macromolecular character and their ability to explore biologically relevant multivalency processes. We discuss the main therapeutic uses of polymeric drugs as sequestrants, antimicrobials, antivirals, and anticancer and anti-inflammatory agents. PMID:26410809

Facile preparation of cobaltocenium-containing polyelectrolyte via click chemistry and RAFT polymerization.

PubMed

Yan, Yi; Zhang, Jiuyang; Qiao, Yali; Tang, Chuanbing

2014-01-01

A facile method to prepare cationic cobaltocenium-containing polyelectrolyte is reported. Cobaltocenium monomer with methacrylate is synthesized by copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction between 2-azidoethyl methacrylate and ethynylcobaltocenium hexafluorophosphate. Further controlled polymerization is achieved by reversible addition-fragmentation chain transfer polymerization (RAFT) by using cumyl dithiobenzoate (CDB) as a chain transfer agent. Kinetic study demonstrates the controlled/living process of polymerization. The obtained side-chain cobaltocenium-containing polymer is a metal-containing polyelectrolyte that shows characteristic redox behavior of cobaltocenium. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cyclopropenimine superbases: Competitive initiation processes in lactide polymerization

DOE PAGES

Stukenbroeker, Tyler S.; Bandar, Jeffrey S.; Zhang, Xiangyi; ...

2015-07-30

Cyclopropenimine superbases were employed in this study to catalyze the ring-opening polymerization of lactide. Polymerization occurred readily in the presence and absence of alcohol initiators. Polymerizations in the absence of alcohol initiators revealed a competitive initiation mechanism involving deprotonation of lactide by the cyclopropenimine to generate an enolate. NMR and MALDI-TOF analysis of the poly(lactides) generated from cyclopropenimines in the absence of alcohol initiators showed acylated lactide and hydroxyl end groups. Finally, model studies and comparative experiments with guanidine and phosphazene catalysts revealed the subtle influence of the nature of the superbase on competitive initiation processes.

Spatially controlled, in situ synthesis of polymers

DOEpatents

Caneba, Gerard T.; Tirumala, Vijaya Raghavan; Mancini, Derrick C.; Wang, Hsien-Hau

2005-03-22

An in situ polymer microstructure formation method. The monomer mixture is polymerized in a solvent/precipitant through exposure to ionizing radiation in the absence any chemical mediators. If an exposure mask is employed to block out certain regions of the radiation cross section, then a patterned microstructure is formed. The polymerization mechanism is based on the so-called free-radical retrograde-precipitation polymerization process, in which polymerization occurs while the system is phase separating above the lower critical solution temperature. This method was extended to produce a crosslinked line grid-pattern of poly (N-isopropylacrylamide), which has been known to have thermoreversible properties.

Synthesis of nanostructured materials in inverse miniemulsions and their applications.

PubMed

Cao, Zhihai; Ziener, Ulrich

2013-11-07

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

Ac102 Participates in Nuclear Actin Polymerization by Modulating BV/ODV-C42 Ubiquitination during Autographa californica Multiple Nucleopolyhedrovirus Infection.

PubMed

Zhang, Yongli; Hu, Xue; Mu, Jingfang; Hu, Yangyang; Zhou, Yuan; Zhao, He; Wu, Chunchen; Pei, Rongjuan; Chen, Jizheng; Chen, Xinwen; Wang, Yun

2018-06-15

As a virus-encoded actin nucleation promoting factor (NPF), P78/83 induces actin polymerization to assist in Autographa californica multiple nucleopolyhedrovirus (AcMNPV) propagation. According to our previous study, although P78/83 actively undergoes ubiquitin-independent proteasomal degradation, AcMNPV encodes budded virus/occlusion derived virus (BV/ODV)-C42 (C42), which allows P78/83 to function as a stable NPF by inhibiting its degradation during viral infection. However, whether there are other viral proteins involved in regulating P78/83-induced actin polymerization has yet to be determined. In this study, we found that Ac102, an essential viral gene product previously reported to play a key role in mediating the nuclear accumulation of actin during AcMNPV infection, is a novel regulator of P78/83-induced actin polymerization. By characterizing an ac102 knockout bacmid, we demonstrated that Ac102 participates in regulating nuclear actin polymerization as well as the morphogenesis and distribution of capsid structures in the nucleus. These regulatory effects are heavily dependent on an interaction between Ac102 and C42. Further investigation revealed that Ac102 binds to C42 to suppress K48-linked ubiquitination of C42, which decreases C42 proteasomal degradation and consequently allows P78/83 to function as a stable NPF to induce actin polymerization. Thus, Ac102 and C42 form a regulatory cascade to control viral NPF activity, representing a sophisticated mechanism for AcMNPV to orchestrate actin polymerization in both a ubiquitin-dependent and ubiquitin-independent manner. IMPORTANCE Actin is one of the most functionally important proteins in eukaryotic cells. Morphologically, actin can be found in two forms: a monomeric form called globular actin (G-actin) and a polymeric form called filamentous actin (F-actin). G-actin can polymerize to form F-actin, and nucleation promoting factor (NPF) is the initiator of this process. Many viral pathogens harness the host actin polymerization machinery to assist in virus propagation. Autographa californica multiple nucleopolyhedrovirus (AcMNPV) induces actin polymerization in host cells. P78/83, a viral NPF, is responsible for this process. Previously, we identified that BV/ODV-C42 (C42) binds to P78/83 and protects it from degradation. In this report, we determined that another viral protein, Ac102, is involved in modulating C42 ubiquitination and, consequently, ensures P78/83 activity as an NPF to initiate actin polymerization. This regulatory cascade represents a novel mechanism by which a virus can harness the cellular actin cytoskeleton to assist in viral propagation. Copyright © 2018 American Society for Microbiology.

The first products made in space: Monodisperse latex particles

NASA Technical Reports Server (NTRS)

Vanderhoff, J. W.; El-Aasser, M. S.; Micale, F. J.; Sudol, E. D.; Tseng, C.-M.; Sheu, H.-R.; Kornfeld, D. M.

1988-01-01

The preparation of large particle size 3 to 30 micrometer monodisperse latexes in space confirmed that original rationale unequivocally. The flight polymerizations formed negligible amounts of coagulum as compared to increasing amounts for the ground-based polymerizations. The number of offsize large particles in the flight latexes was smaller than in the ground-based latexes. The particle size distribution broadened and more larger offsize particles were formed when the polymerizations of the partially converted STS-4 latexes were completed on Earth. Polymerization in space also showed other unanticipated advantages. The flight latexes had narrower particle size distributions than the ground-based latexes. The particles of the flight latexes were more perfect spheres than those of the ground-based latexes. The superior uniformity of the flight latexes was confirmed by the National Bureau of Standards acceptance of the 10 micrometer STS-6 latex and the 30 micrometer STS-11 latexes as Standard Reference Materials, the first products made in space for sale on Earth. The polymerization rates in space were the same as those on Earth within experimental error. Further development of the ground-based polymerization recipes gave monodisperse particles as large as 100 micrometer with tolerable levels of coagulum, but their uniformity was significantly poorer than the flight latexes. Careful control of the polymerization parameters gave uniform nonspherical particles: symmetrical and asymmetrical doublets, ellipsoids, egg-shaped, ice cream cone-shaped, and popcorn-shaped particles.

HPMA-based polymeric micelles for curcumin solubilization and inhibition of cancer cell growth.

PubMed

Naksuriya, Ornchuma; Shi, Yang; van Nostrum, Cornelus F; Anuchapreeda, Songyot; Hennink, Wim E; Okonogi, Siriporn

2015-08-01

Curcumin (CM) has been reported as a potential anticancer agent. However, its pharmaceutical applications as therapeutic agent are hampered because of its poor aqueous solubility. The present study explores the advantages of polymeric micelles composed of block copolymers of methoxypoly(ethylene glycol) (mPEG) and N-(2-hydroxypropyl) methacrylamide (HPMA) modified with monolactate, dilactate and benzoyl side groups to enhance CM solubility and inhibitory activity against cancer cells. Amphiphilic block copolymers, ω-methoxypoly(ethylene glycol)-b-(N-(2-benzoyloxypropyl) methacrylamide) (PEG-HPMA-Bz) were synthesized and characterized by (1)H NMR and GPC. One polymer with a molecular weight of 28,000Da was used to formulate CM and compared with other aromatic substituted polymers. CM was loaded by a fast heating method (PEG-HPMA-DL and PEG-HPMA-Bz-L) and a nanoprecipitation method (PEG-HPMA-Bz). Physicochemical characteristics and cytotoxicity/cytocompatibility of the CM loaded polymeric micelles were evaluated. It was found that HPMA-based polymeric micelles significantly enhanced the solubility of CM. The PEG-HPMA-Bz micelles showed the best solubilization properties. CM loaded polymeric micelles showed sustained release of the loading CM for more than 20days. All of CM loaded polymeric micelles formulations showed a significantly potent cytotoxic effect against three cancer cell lines. HPMA-based polymeric micelles are therefore promising nanodelivery systems of CM for cancer therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Barnacle cement: a polymerization model based on evolutionary concepts

PubMed Central

Dickinson, Gary H.; Vega, Irving E.; Wahl, Kathryn J.; Orihuela, Beatriz; Beyley, Veronica; Rodriguez, Eva N.; Everett, Richard K.; Bonaventura, Joseph; Rittschof, Daniel

2009-01-01

Summary Enzymes and biochemical mechanisms essential to survival are under extreme selective pressure and are highly conserved through evolutionary time. We applied this evolutionary concept to barnacle cement polymerization, a process critical to barnacle fitness that involves aggregation and cross-linking of proteins. The biochemical mechanisms of cement polymerization remain largely unknown. We hypothesized that this process is biochemically similar to blood clotting, a critical physiological response that is also based on aggregation and cross-linking of proteins. Like key elements of vertebrate and invertebrate blood clotting, barnacle cement polymerization was shown to involve proteolytic activation of enzymes and structural precursors, transglutaminase cross-linking and assembly of fibrous proteins. Proteolytic activation of structural proteins maximizes the potential for bonding interactions with other proteins and with the surface. Transglutaminase cross-linking reinforces cement integrity. Remarkably, epitopes and sequences homologous to bovine trypsin and human transglutaminase were identified in barnacle cement with tandem mass spectrometry and/or western blotting. Akin to blood clotting, the peptides generated during proteolytic activation functioned as signal molecules, linking a molecular level event (protein aggregation) to a behavioral response (barnacle larval settlement). Our results draw attention to a highly conserved protein polymerization mechanism and shed light on a long-standing biochemical puzzle. We suggest that barnacle cement polymerization is a specialized form of wound healing. The polymerization mechanism common between barnacle cement and blood may be a theme for many marine animal glues. PMID:19837892

Research regarding biodegradable properties of food polymeric products under microorganism activity

NASA Astrophysics Data System (ADS)

Opran, Constantin; Lazar, Veronica; Fierascu, Radu Claudiu; Ditu, Lia Mara

2018-02-01

Aim of this research is the structural analysis by comparison of the biodegradable properties of two polymeric products made by non-biodegradable polymeric material (polypropylene TIPPLEN H949 A) and biodegradable polymeric material (ECOVIO IS 1335), under microorganism activity in order to give the best solution for the manufacture of food packaging biodegradable products. It presents the results of experimental determinations on comparative analysis of tensile strength for the two types of polymers. The sample weight variations after fungal biodegradation activity revealed that, after 3 months, there are no significant changes in polymeric substratum for non-biodegradable polymeric. The microscopically analysis showed that the fungal filaments did not strongly adhered on the non-biodegradable polymeric material, instead, both filamentous fungi strains adhered and covered the surface of the biodegradable sample with germinated filamentous conidia. The spectral analysis of polymer composition revealed that non-biodegradable polymer polypropylene spectra are identical for control and for samples that were exposed to fungal activity, suggesting that this type of sample was not degraded by the fungi strains. Instead, for biodegradable polymer sample, it was observed significant structural changes across multiple absorption bands, suggesting enzyme activity manifested mainly by Aspergillus niger strain. Structural analysis of interdisciplinary research results, lead, to achieving optimal injection molded technology emphasizing technological parameters, in order to obtain food packaging biodegradable products.

Hydrophobic Coatings on Cotton Obtained by in Situ Plasma Polymerization of a Fluorinated Monomer in Ethanol Solutions.

PubMed

Molina, Ricardo; Teixidó, Josep Maria; Kan, Chi-Wai; Jovančić, Petar

2017-02-15

Plasma polymerization using hydrophobic monomers in the gas phase is a well-known technology to generate hydrophobic coatings. However, synthesis of functional hydrophobic coatings using plasma technology in liquids has not yet been accomplished. This work is consequently focused on polymerization of a liquid fluorinated monomer on cotton fabric initiated by atmospheric plasma in a dielectric barrier discharge configuration. Functional hydrophobic coatings on cotton were successfully achieved using in situ atmospheric plasma-initiated polymerization of fluorinated monomer dissolved in ethanol. Gravimetric measurements reveal that the amount of polymer deposited on cotton substrates can be modulated with the concentration of monomer in ethanol solution, and cross-linking reactions occur during plasma polymerization of a fluorinated monomer even without the presence of a cross-linking agent. FTIR and XPS analysis were used to study the chemical composition of hydrophobic coatings and to get insights into the physicochemical processes involved in plasma treatment. SEM analysis reveals that at high monomer concentration, coatings possess a three-dimensional pattern with a characteristic interconnected porous network structure. EDX analysis reveals that plasma polymerization of fluorinated monomers takes place preferentially at the surface of cotton fabric and negligible polymerization takes place inside the cotton fabric. Wetting time measurements confirm the hydrophobicity of cotton coatings obtained although equilibrium moisture content was slightly decreased. Additionally, the abrasion behavior and resistance to washing of plasma-coated cotton has been evaluated.

Analytical methods for the measurement of polymerization kinetics and stresses of dental resin-based composites: A review

PubMed Central

Ghavami-Lahiji, Mehrsima; Hooshmand, Tabassom

2017-01-01

Resin-based composites are commonly used restorative materials in dentistry. Such tooth-colored restorations can adhere to the dental tissues. One drawback is that the polymerization shrinkage and induced stresses during the curing procedure is an inherent property of resin composite materials that might impair their performance. This review focuses on the significant developments of laboratory tools in the measurement of polymerization shrinkage and stresses of dental resin-based materials during polymerization. An electronic search of publications from January 1977 to July 2016 was made using ScienceDirect, PubMed, Medline, and Google Scholar databases. The search included only English-language articles. Only studies that performed laboratory methods to evaluate the amount of the polymerization shrinkage and/or stresses of dental resin-based materials during polymerization were selected. The results indicated that various techniques have been introduced with different mechanical/physical bases. Besides, there are factors that may contribute the differences between the various methods in measuring the amount of shrinkages and stresses of resin composites. The search for an ideal and standard apparatus for measuring shrinkage stress and volumetric polymerization shrinkage of resin-based materials in dentistry is still required. Researchers and clinicians must be aware of differences between analytical methods to make proper interpretation and indications of each technique relevant to a clinical situation. PMID:28928776

Quantification and characterization of enzymatically produced hyaluronan with fluorophore-assisted carbohydrate electrophoresis.

PubMed

Kooy, Floor K; Ma, Muyuan; Beeftink, Hendrik H; Eggink, Gerrit; Tramper, Johannes; Boeriu, Carmen G

2009-01-15

Hyaluronan (HA) is a polysaccharide with high-potential medical applications, depending on the chain length and the chain length distribution. Special interest goes to homogeneous HA oligosaccharides, which can be enzymatically produced using Pasteurella multocida hyaluronan synthase (PmHAS). We have developed a sensitive, simple, and fast method, based on fluorophore-assisted carbohydrate electrophoresis (FACE), for characterization and quantification of polymerization products. A chromatographic pure fluorescent template was synthesized from HA tetrasaccharide (HA4) and 2-aminobenzoic acid. HA4-fluor and HA4 were used as template for PmHAS-mediated polymerization of nucleotide sugars. All products, fluorescent and nonfluorescent, were analyzed with gel electrophoresis and quantified using lane densitometry. Comparison of HA4- and HA4-fluor-derived polymers showed that the fluorophore did not negatively influence the PmHAS-mediated polymerization. Only even-numbered oligosaccharide products were observed using HA4-fluor or HA4 as template. The fluorophore intensity was linearly related to its concentration, and the limit of detection was determined to be 7.4pmol per product band. With this assay, we can now differentiate oligosaccharides of size range DP2 (degree of polymerization 2) to approximately DP400, monitor the progress of polymerization reactions, and measure subtle differences in polymerization rate. Quantifying polymerization products enables us to study the influence of experimental conditions on HA synthesis.

Evidence against impaired brain microtubule protein polymerization at high glucose concentrations or during diabetes mellitus.

PubMed

Eaker, E Y; Angelastro, J M; Purich, D L; Sninsky, C A

1991-06-01

Previous studies suggest that brain microtubule protein exposed to high glucose levels or isolated from diabetic rats can become glucosylated and that this impairs GTP-induced microtubule polymerization. We set out to extend that investigation to define the mechanistic basis for inhibition of microtubule assembly during diabetes or on incubation at high glucose levels. Rat and bovine brain microtubule protein was purified by cycles of polymerization/depolymerization. When microtubules were incubated for 1 h in either buffer or buffer containing glucose (up to 165 mM), there was no difference in polymerization, a finding contrary to the earlier study. Other rats were injected with vehicle or streptozotocin (90 mg/kg) to induce diabetes as evidenced by serum glucose in excess of 300 mg%, and at 4 weeks, brain microtubule protein was isolated by the polymerization cycling method. Again, there was no difference in the amount or purity of isolated microtubule protein between control or diabetic rats. We also observed no increase in microtubule glucosylation, and GTP-induced polymerization in vitro was indistinguishable for protein derived from brains of normal rats and rats with diabetes as measured by turbidity or electron microscopy. Our results suggest that in vitro incubation with glucose or in vivo elevation of glucose during diabetes fails to impair microtubule polymerization, pointing to other mechanisms for the neuropathy associated with diabetes.

A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization.

PubMed

Keddie, Daniel J

2014-01-21

The discovery of reversible-deactivation radical polymerization (RDRP) has provided an avenue for the synthesis of a vast array of polymers with a rich variety of functionality and architecture. The preparation of block copolymers has received significant focus in this burgeoning research field, due to their diverse properties and potential in a wide range of research environments. This tutorial review will address the important concepts behind the design and synthesis of block copolymers using reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerization is arguably the most versatile of the RDRP methods due to its compatibility with a wide range of functional monomers and reaction media along with its relative ease of use. With an ever increasing array of researchers that possess a variety of backgrounds now turning to RDRP, and RAFT in particular, to prepare their required polymeric materials, it is pertinent to discuss the important points which enable the preparation of high purity functional block copolymers with targeted molar mass and narrow molar mass distribution using RAFT polymerization. The key principles of appropriate RAFT agent selection, the order of monomer addition in block synthesis and potential issues with maintaining high end-group fidelity are addressed. Additionally, techniques which allow block copolymers to be accessed using a combination of RAFT polymerization and complementary techniques are touched upon.

Controlled Bioactive Molecules Delivery Strategies for Tendon and Ligament Tissue Engineering using Polymeric Nanofibers.

PubMed

Hiong Teh, Thomas Kok; Hong Goh, James Cho; Toh, Siew Lok

2015-01-01

The interest in polymeric nanofibers has escalated over the past decade given its promise as tissue engineering scaffolds that can mimic the nanoscale structure of the native extracellular matrix. With functionalization of the polymeric nanofibers using bioactive molecules, localized signaling moieties can be established for the attached cells, to stimulate desired biological effects and direct cellular or tissue response. The inherently high surface area per unit mass of polymeric nanofibers can enhance cell adhesion, bioactive molecules loading and release efficiencies, and mass transfer properties. In this review article, the application of polymeric nanofibers for controlled bioactive molecules delivery will be discussed, with a focus on tendon and ligament tissue engineering. Various polymeric materials of different mechanical and degradation properties will be presented along with the nanofiber fabrication techniques explored. The bioactive molecules of interest for tendon and ligament tissue engineering, including growth factors and small molecules, will also be reviewed and compared in terms of their nanofiber incorporation strategies and release profiles. This article will also highlight and compare various innovative strategies to control the release of bioactive molecules spatiotemporally and explore an emerging tissue engineering strategy involving controlled multiple bioactive molecules sequential release. Finally, the review article concludes with challenges and future trends in the innovation and development of bioactive molecules delivery using polymeric nanofibers for tendon and ligament tissue engineering.

Effect of flour polymeric proteins on dough thermal properties and breadmaking characteristics for hard red spring wheat genotypes

USDA-ARS?s Scientific Manuscript database

The aim of this research was to investigate the effect of variation of flour polymeric proteins on rheological properties of dough under continuous mixing and thermal treatment for hard red spring (HRS) wheat genotypes grown in North Dakota, USA. Flour polymeric proteins were analyzed by size exclus...

Photopolymerization Of Levitated Droplets

NASA Technical Reports Server (NTRS)

Rembaum, Alan; Rhim, Won-Kyu; Hyson, Michael T.; Chang, Manchium

1989-01-01

Experimental containerless process combines two established techniques to make variety of polymeric microspheres. In single step, electrostatically-levitated monomer droplets polymerized by ultraviolet light. Faster than multiple-step emulsion polymerization process used to make microspheres. Droplets suspended in cylindrical quadrupole electrostatic levitator. Alternating electrostatic field produces dynamic potential along axis. Process enables tailoring of microspheres for medical, scientific, and industrial applications.

Synthesis of soybean oil-based polymeric surfactants in supercritical carbon dioxide and investigation of their surface properties

USDA-ARS?s Scientific Manuscript database

This paper reports the preparation of polymeric surfactants (HPSO) via a two-step synthetic procedure: polymerization of soybean oil (PSO) in supercritical carbon dioxide and followed by hydrolysis of PSO with a base. HPSO was characterized and identified by using a combination of FTIR, 1H NMR, 13C...

Mechanical Testing of Common-Use Polymeric Materials with an In-House-Built Apparatus

ERIC Educational Resources Information Center

Pedrosa, Cristiana; Mendes, Joaquim; Magalhaes, Fernao D.

2006-01-01

A low-cost tensile testing machine was built for testing polymeric films. This apparatus also allows for tear-strength and flexural tests. The experimental results, obtained from common-use materials, selected by the students, such as plastic bags, illustrate important aspects of the mechanical behavior of polymeric materials. Some of the tests…

A technique for improved maxillary record base adaptation through controlled polymerization of light-activated dental resins.

PubMed

Hopkins, D S; Phoenix, R D; Abrahamsen, T C

1997-09-01

A technique for the fabrication of light-activated maxillary record bases is described. The use of a segmental polymerization process provides improved palatal adaptation by minimizing the effects of polymerization shrinkage. Utilization of this technique results in record bases that are well adapted to the corresponding master casts.

Functional, photochemically active, and chemically asymmetric membranes by interfacial polymerization of derivatized multifunctional prepolymers

DOEpatents

Lonsdale, H.K.; Wamser, C.C.

1990-04-17

The preparation of a novel class of thin film membranes by interfacial polymerization is disclosed, said membranes incorporating as part of their polymeric structure the functionality of monomeric or oligomeric precursors. Specific embodiments include porphyrin and phthalocyanine derivatives that are photochemically or electrochemically active, as well as chemically asymmetric membranes.

Functional, photochemically active, and chemically asymmetric membranes by interfacial polymerization of derivatized multifunctional prepolymers

DOEpatents

Lonsdale, Harold K.; Wamser, Carl C.

1990-01-01

The preparation of a novel class of thin film membranes by interfacial polymerization is disclosed, said membranes incorporating as part of their polymeric structure the functionality of monomeric or oligomeric precursors. Specific embodiments include porphyrin and phthalocyanine derivatives that are photochemically or electrochemically active, as well as chemically asymmetric membranes.

Functional, photochemically active, and chemically asymmetric membranes by interfacial polymerization of derivatized multifunctional prepolymers

DOEpatents

Lonsdale, Harold K.; Wamser, Carl C.

1988-01-01

The preparation of a novel class of thin film membranes by interfacial polymerization is disclosed, said membanes incorporating as part of their polymeric structure the functionality of monomeric or oligomeric precursors. Specific embodiments include porphyrin and phthalocyanime derivatives that are photochemically or electrochemically active, as well as chemically asymmetric membranes.

Azo polymeric micelles designed for colon-targeted dimethyl fumarate delivery for colon cancer therapy.

PubMed

Ma, Zhen-Gang; Ma, Rui; Xiao, Xiao-Lin; Zhang, Yong-Hui; Zhang, Xin-Zi; Hu, Nan; Gao, Jin-Lai; Zheng, Yu-Feng; Dong, De-Li; Sun, Zhi-Jie

2016-10-15

Colon-targeted drug delivery and circumventing drug resistance are extremely important for colon cancer chemotherapy. Our previous work found that dimethyl fumarate (DMF), the approved drug by the FDA for the treatment of multiple sclerosis, exhibited anti-tumor activity on colon cancer cells. Based on the pharmacological properties of DMF and azo bond in olsalazine chemical structure, we designed azo polymeric micelles for colon-targeted dimethyl fumarate delivery for colon cancer therapy. We synthesized the star-shape amphiphilic polymer with azo bond and fabricated the DMF-loaded azo polymeric micelles. The four-arm polymer star-PCL-azo-mPEG (sPCEG-azo) (constituted by star-shape PCL (polycaprolactone) and mPEG (methoxypolyethylene glycols)-olsalazine) showed self-assembly ability. The average diameter and polydispersity index of the DMF-loaded sPCEG-azo polymeric micelles were 153.6nm and 0.195, respectively. In vitro drug release study showed that the cumulative release of DMF from the DMF-loaded sPCEG-azo polymeric micelles was no more than 20% in rat gastric fluid within 10h, whereas in the rat colonic fluids, the cumulative release of DMF reached 60% in the initial 2h and 100% within 10h, indicating that the DMF-loaded sPCEG-azo polymeric micelles had excellent colon-targeted property. The DMF-loaded sPCEG-azo polymeric micelles had no significant cytotoxicity on colon cancer cells in phosphate buffered solution (PBS) and rat gastric fluid. In rat colonic fluid, the micelles showed significant cytotoxic effect on colon cancer cells. The blank sPCEG-azo polymeric micelles (without DMF) showed no cytotoxic effect on colon cancer cells in rat colonic fluids. In conclusion, the DMF-loaded sPCEG-azo polymeric micelles show colon-targeted DMF release and anti-tumor activity, providing a novel approach potential for colon cancer therapy. Colon-targeted drug delivery and circumventing drug resistance are extremely important for colon cancer chemotherapy. Our previous work found that dimethyl fumarate (DMF), the approved drug by the FDA for the treatment of multiple sclerosis, exhibited anti-tumor activities on colon cancer cells (Br J Pharmacol. 2015 172(15):3929-43.). Based on the pharmacological properties of DMF and azo bond in olsalazine chemical structure, we designed azo polymeric micelles for colon-targeted dimethyl fumarate delivery for colon cancer therapy. We found that the DMF-loaded sPCEG-azo polymeric micelles showed colon-targeted DMF release and anti-tumor activities, providing a novel approach potential for colon cancer therapy. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Evaluation of metal-polymeric fixed partial prosthesis using optical coherence tomography

NASA Astrophysics Data System (ADS)

Sinescu, C.; Negrutiu, M. L.; Duma, V. F.; Marcauteanu, C.; Topala, F. I.; Rominu, M.; Bradu, A.; Podoleanu, A. Gh.

2013-11-01

Metal-Polymeric fixed partial prosthesis is the usual prosthetic treatment for many dental patients. However, during the mastication the polymeric component of the prosthesis is fractured and will be lost. This fracture is caused by the material defects or by the fracture lines trapped inside the esthetic components of the prosthesis. This will finally lead to the failure of the prosthetic treatment. Nowadays, there is no method of identification and forecast for the materials defects of the polymeric materials. The aim of this paper is to demonstrate the capability of Optical Coherence Tomography (OCT) as a non-invasive clinical method that can be used for the evaluation of metal-polymeric fixed partial prostheses. Twenty metal-polymeric fixed partial prostheses were used for this study. The esthetic component of the prostheses has been Adoro (Ivoclar). Optical investigations of the metal prostheses have revealed no material defects or fracture lines. All the prostheses were temporary cemented in the oral cavities of the patients for six month. The non-invasive method used for the investigations was OCT working in Time Domain mode at 1300 nm. The evaluations of the prostheses were performed before and after their cementation in the patient mouths. All the imagistic results were performed in 2D and than in 3D, after the reconstruction. The results obtained after the OCT evaluation allowed for the identification of 4 metal-polymeric fixed partial prostheses with material defects immediately after finishing the technological procedures. After 6 month in the oral environment other 3 fixed partial prostheses revealed fracture lines. In conclusion, OCT proved to be a valuable tool for the noninvasive evaluation of the metal-polymeric fixed partial prostheses.

Color Stability Behavior of Methacrylate-based Resin Composites Polymerized with Light-emitting Diodes and Quartz-Tungsten-Halogen.

PubMed

Sabatini, C

2015-01-01

Despite significant developments in improving the optical properties of resin composite materials, their color stability remains a challenge. This study aimed to evaluate the shade stability of light-polymerized, methacrylate-based resin composites with different filler particle composition (microfill, minifill, nanohybrids, and microhybrids) polymerized with quartz-tungsten-halogen (QTH) and light-emitting diodes (LED). Composite discs were fabricated from Tetric EvoCeram, Premise, Artiste, and Beautifil II (nanohybrids); Filtek Supreme Plus and Vit-l-escence (microhybrids); Heliomolar (microfill); and Estelite Sigma Quick (minifill) using a Teflon mold. The specimens were irradiated either with QTH (Elipar 2500; 600 mW/cm(2)) for 40 seconds or with LED (Bluephase G2; 1200 mW/cm(2)) for 20 seconds. Color parameters were measured with a colorimeter before and after polymerization and at 24 hours, one week, one month, and three months. Color change was calculated among the different storage periods. There was a significant effect of the composite, time, and their interaction (p<0.001) but no effect of the polymerization unit on the color stability. Color changes immediately after polymerization and at 24 hours (4.22 and 3.88 for LED; and 4.08 and 3.82 for QTH) were not significantly different from each other but were both significantly higher than changes after one week (0.96 and 0.78), one month (1.12 and 1.02), and three months (1.27 and 1.11) for LED and QTH, respectively (p<0.001). Color changes were observed for all the materials that were dependent on the type of composite but not on the polymerization unit. These color shifts took place primarily immediately after polymerization and after 24 hours and were additive in nature.

Alternative methods for determining shrinkage in restorative resin composites.

PubMed

de Melo Monteiro, Gabriela Queiroz; Montes, Marcos Antonio Japiassú Resende; Rolim, Tiago Vieira; de Oliveira Mota, Cláudia Cristina Brainer; de Barros Correia Kyotoku, Bernardo; Gomes, Anderson Stevens Leônidas; de Freitas, Anderson Zanardi

2011-08-01

The purpose of this study was to evaluate polymerization shrinkage of resin composites using a coordinate measuring machine, optical coherence tomography and a more widely known method, such as Archimedes Principle. Two null hypothesis were tested: (1) there are no differences between the materials tested; (2) there are no differences between the methods used for polymerization shrinkage measurements. Polymerization shrinkage of seven resin-based dental composites (Filtek Z250™, Filtek Z350™, Filtek P90™/3M ESPE, Esthet-X™, TPH Spectrum™/Dentsply 4 Seasons™, Tetric Ceram™/Ivoclar-Vivadent) was measured. For coordinate measuring machine measurements, composites were applied to a cylindrical Teflon mold (7 mm × 2 mm), polymerized and removed from the mold. The difference between the volume of the mold and the volume of the specimen was calculated as a percentage. Optical coherence tomography was also used for linear shrinkage evaluations. The thickness of the specimens was measured before and after photoactivation. Polymerization shrinkage was also measured using Archimedes Principle of buoyancy (n=5). Statistical analysis of the data was performed with ANOVA and the Games-Howell test. The results show that polymerization shrinkage values vary with the method used. Despite numerical differences the ranking of the resins was very similar with Filtek P90 presenting the lowest shrinkage values. Because of the variations in the results, reported values could only be used to compare materials within the same method. However, it is possible rank composites for polymerization shrinkage and to relate these data from different test methods. Independently of the method used, reduced polymerization shrinkage was found for silorane resin-based composite. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Stereo-, Temporal and Chemical Control through Photoactivation of Living Radical Polymerization: Synthesis of Block and Gradient Copolymers.

PubMed

Shanmugam, Sivaprakash; Boyer, Cyrille

2015-08-12

Nature has developed efficient polymerization processes, which allow the synthesis of complex macromolecules with a perfect control of tacticity as well as molecular weight, in response to a specific stimulus. In this contribution, we report the synthesis of various stereopolymers by combining a photoactivated living polymerization, named photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) with Lewis acid mediators. We initially investigated the tolerance of two different photoredox catalysts, i.e., Ir(ppy)3 and Ru(bpy)3, in the presence of a Lewis acid, i.e., Y(OTf)3 and Yb(OTf)3, to mediate the polymerization of N,N-dimethyl acrylamide (DMAA). An excellent control of tacticity as well as molecular weight and dispersity was observed when Ir(ppy)3 and Y(OTf)3 were employed in a methanol/toluene mixture, while no polymerization or poor control was observed with Ru(bpy)3. In comparison to a thermal system, a lower amount of Y(OTf)3 was required to achieve good control over the tacticity. Taking advantage of the temporal control inherent in our system, we were able to design complex macromolecular architectures, such as atactic block-isotactic and isotactic-block-atactic polymers in a one-pot polymerization approach. Furthermore, we discovered that we could modulate the degree of tacticity through a chemical stimulus, by varying [DMSO]0/[Y(OTf)3]0 ratio from 0 to 30 during the polymerization. The stereochemical control afforded by the addition of a low amount of DMSO in conjunction with the inherent temporal control enabled the synthesis of stereogradient polymer consisting of five different stereoblocks in one-pot polymerization.

Surfactant-free, cationic latices of poly(BMA-co-MMA) using AIBA initiator.

PubMed

Lee, Ki-Chang

2013-09-01

When polymer particles come into use, especially, for photonic crystal applications, their diameter, dispersivity, and refractive indices become very important. Poly(benzyl methacrylate) is known to be a kind of high refracive materials (n = 1.57) compared to poly(methyl methacrylate) (n = 1.49). Not many work was concerned for surfactant-free emulsion polymerization of benzyl methacrylate or its copolymerization using cationic initiators. Narrowly dispersed cationic poly(BMA-co-MMA) and PBMA latices were synthesized successfully by surfactant-free emulsion polymerization with AIBA. The influences of BMA/MMA ratio, BMA/MMA monomer and initiator concentrations, addition of DVB/EGDMA crosslink agent, and polymerization temperature on the kinetics and on the particle size and molecular weight were studied. Monodisperse cationic charged PBMA and poly(BMA-coMMA) latices with particle diameters varying between 160-494 nm and polymer molecular weights of the order 1.25 x 10(4) to 7.55 x 10(4) g/mol were prepared. The rate of polymerization increased with increasing MMA concentration in BMA/MMA ratio, AIBA concentration, DVB crosslink agent, and polymerization temperature. The particle diameter increased with BMA concentration in BMA/MMA ratio, AIBA concentration, and BMA/MMA monomer concentration. The molecular weight increased with BMA concentration in BMA/MMA ratio and BMA/MMA monomer concentration. The glass transition temperature of the latex copolymers decreased with increasing amount of BMA from 375 K for PMMA to 321 K for PBMA. It was, thus, found that the particle diameter and rate of polymerization as well as the polymer molecular weight for surfactant-free emulsion polymerization of BMA and MMA can be controlled easily by controlling the BMA/MMA ratio, BMA/MMA monomer concentration, AIBA concentration, and polymerization temperature.

How actin binds and assembles onto plasma membranes from Dictyostelium discoideum

PubMed Central

1988-01-01

We have shown previously (Schwartz, M. A., and E. J. Luna. 1986. J. Cell Biol. 102: 2067-2075) that actin binds with positive cooperativity to plasma membranes from Dictyostelium discoideum. Actin is polymerized at the membrane surface even at concentrations well below the critical concentration for polymerization in solution. Low salt buffer that blocks actin polymerization in solution also prevents actin binding to membranes. To further explore the relationship between actin polymerization and binding to membranes, we prepared four chemically modified actins that appear to be incapable of polymerizing in solution. Three of these derivatives also lost their ability to bind to membranes. The fourth derivative (EF actin), in which histidine-40 is labeled with ethoxyformic anhydride, binds to membranes with reduced affinity. Binding curves exhibit positive cooperativity, and cross- linking experiments show that membrane-bound actin is multimeric. Thus, binding and polymerization are tightly coupled, and the ability of these membranes to polymerize actin is dramatically demonstrated. EF actin coassembles weakly with untreated actin in solution, but coassembles well on membranes. Binding by untreated actin and EF actin are mutually competitive, indicating that they bind to the same membrane sites. Hill plots indicate that an actin trimer is the minimum assembly state required for tight binding to membranes. The best explanation for our data is a model in which actin oligomers assemble by binding to clustered membrane sites with successive monomers on one side of the actin filament bound to the membrane. Individual binding affinities are expected to be low, but the overall actin-membrane avidity is high, due to multivalency. Our results imply that extracellular factors that cluster membrane proteins may create sites for the formation of actin nuclei and thus trigger actin polymerization in the cell. PMID:3392099

Ion-dependent Polymerization Differences between Mammalian β- and γ-Nonmuscle Actin Isoforms*

PubMed Central

Bergeron, Sarah E.; Zhu, Mei; Thiem, Suzanne M.; Friderici, Karen H.; Rubenstein, Peter A.

2010-01-01

β- and γ-nonmuscle actins differ by 4 amino acids at or near the N terminus and distant from polymerization interfaces. β-Actin contains an Asp1-Asp2-Asp3 and Val10 whereas γ-actin has a Glu1-Glu2-Glu3 and Ile10. Despite these small changes, conserved across mammals, fish, and birds, their differential localization in the same cell suggests they may play different roles reflecting differences in their biochemical properties. To test this hypothesis, we established a baculovirus-driven expression system for producing these actins in isoform-pure populations although contaminated with 20–25% insect actin. Surprisingly, Ca-γ-actin exhibits a slower monomeric nucleotide exchange rate, a much longer nucleation phase, and a somewhat slower elongation rate than β-actin. In the Mg-form, this difference between the two is much smaller. Ca-γ-actin depolymerizes half as fast as does β-actin. Mixing experiments with Ca-actins reveal the two will readily co-polymerize. In the Ca-form, phosphate release from polymerizing β-actin occurs much more rapidly and extensively than polymerization, whereas phosphate release lags behind polymerization with γ-actin. Phosphate release during treadmilling is twice as fast with β- as with γ-actin. With Mg-actin in the initial stages, phosphate release for both actins correlates much more closely with polymerization. Calcium bound in the high affinity binding site of γ-actin may cause a selective energy barrier relative to β-actin that retards the equilibration between G- and F-monomer conformations resulting in a slower polymerizing actin with greater filament stability. This difference may be particularly important in sites such as the γ-actin-rich cochlear hair cell stereocilium where local mm calcium concentrations may exist. PMID:20308063

Polymerization of amino acids under high-pressure conditions: Implication to chemical evolution on the early Earth

NASA Astrophysics Data System (ADS)

Kakegawa, T.; Ohara, S.; Ishiguro, T.; Abiko, H.; Nakazawa, H.

2008-12-01

Prebiotic polymerization of amino acids is the most fundamental reaction to promote the chemical evolution for origin of life. Polymerization of amino acids is the dehydration reaction. This questions as to if submarine hydrothermal conditions, thus hydrated enironments, were appropreate for peptide formations. Our previous experiments implied that non-aqueous and high-pressure environments (more than 20 MPa) would be suitable for polymerization of amino acids (Ohara et al., 2006). This leads to the hypothesis that the first peptides may have formed in the Hadean oceanic crustal environments, where dehydration proceeded with availability of appropriate temperatures and pressures. In the present study, experiments simulating the crustal conditions were performed with various pressures (1-175 MPa) and temperatures (100- 200 C degree) using autoclaves. Purified powders (100 mg) of alanine, glycine, valine and aspartic acid were used in the experiments without mixing water in order to examine the solid-solid reactions. The products were analyzed using HPLC and LC-MS. Results indicate that: (1) longer time is required to form peptide compared to those of previous aqueous experiments; (2) pressure has a role to limit the production of melanoidine and cyclic amino acids, which are inhibitors for elongation of peptides; (3) glycine was polymerized up to 11-mer, which was not formed in any previous experiments without catalyses; (4) valine was polymerized up to 3-mer; and (5) aspartic acid was polymerized to 4-mer, accompanied with production of other amino acids. It is noteworthy that high-pressure environments favor all examined polymerization reactions. Such situations would have happened inside of deep oceanic crusts of the early Earth.

Nanoimages show disruption of tubulin polymerization by chlorpyrifos oxon: Implications for neurotoxicity

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

Grigoryan, Hasmik; Lockridge, Oksana

2009-10-15

Organophosphorus agents cause cognitive deficits and depression in some people. We hypothesize that the mechanism by which organophosphorus agents cause these disorders is by modification of proteins in the brain. One such protein could be tubulin. Tubulin polymerizes to make the microtubules that transport cell components to nerve axons. The goal of the present work was to measure the effect of the organophosphorus agent chlorpyrifos oxon on tubulin polymerization. An additional goal was to identify the amino acids covalently modified by chlorpyrifos oxon in microtubule polymers and to compare them to the amino acids modified in unpolymerized tubulin dimers. Purifiedmore » bovine tubulin (0.1 mM) was treated with 0.005-0.1 mM chlorpyrifos oxon for 30 min at room temperature and then polymerized by addition of 1 mM GTP to generate microtubules. Microtubules were visualized by atomic force microscopy. Chlorpyrifos oxon-modified residues were identified by tandem ion trap electrospray ionization and matrix-assisted laser desorption/ionization mass spectrometry of tryptic peptides. Nanoimaging showed that low concentrations (0.005 and 0.01 mM) of chlorpyrifos oxon yielded short, thin microtubules. A concentration of 0.025 mM stimulated polymerization, while high concentrations (0.05 and 0.1 mM) caused aggregation. Of the 17 tyrosines covalently modified by chlorpyrifos oxon in unpolymerized tubulin dimers, only 2 tyrosines were labeled in polymerized microtubules. The two labeled tyrosines in polymerized tubulin were Tyr 103 in EDAANNY*R of alpha tubulin, and Tyr 281 in GSQQY*R of beta tubulin. In conclusion, chlorpyrifos oxon binding to tubulin disrupts tubulin polymerization. These results may lead to an understanding of the neurotoxicity of organophosphorus agents.« less

Nanoimages show disruption of tubulin polymerization by chlorpyrifos oxon; implications for neurotoxicity

PubMed Central

Grigoryan, Hasmik; Lockridge, Oksana

2009-01-01

Organophosphorus agents cause cognitive deficits and depression in some people. We hypothesize that the mechanism by which organophosphorus agents cause these disorders is by modification of proteins in the brain. One such protein could be tubulin. Tubulin polymerizes to make the microtubules that transport cell components to nerve axons. The goal of the present work was to measure the effect of the organophosphorus agent chlorpyrifos oxon on tubulin polymerization. An additional goal was to identify the amino acids covalently modified by chlorpyrifos oxon in microtubule polymers and to compare them to the amino acids modified in unpolymerized tubulin dimers. Purified bovine tubulin (0.1 mM) was treated with 0.005-0.1 mM chlorpyrifos oxon for 30 min at room temperature and then polymerized by addition of 1 mM GTP to generate microtubules. Microtubules were visualized by atomic force microscopy. Chlorpyrifos oxon-modified residues were identified by tandem ion trap electrospray ionization and matrix-assisted laser desorption/ionization mass spectrometry of tryptic peptides. Nanoimaging showed that low concentrations (0.005 and 0.01 mM) of chlorpyrifos oxon yielded short, thin microtubules. A concentration of 0.025 mM stimulated polymerization, while high concentrations (0.05 and 0.1 mM) caused aggregation. Of the 17 tyrosines covalently modified by chlorpyrifos oxon in unpolymerized tubulin dimers, only 2 tyrosines were labeled in polymerized microtubules. The two labeled tyrosines in polymerized tubulin were Tyr 103 in EDAANNY*R of alpha tubulin, and Tyr 281 in GSQQY*R of beta tubulin. In conclusion, chlorpyrifos oxon binding to tubulin disrupts tubulin polymerization. These results may lead to an understanding of the neurotoxicity of organophosphorus agents. PMID:19631231

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

Skotheim, Terje A.; Okamoto, Yoshiyuki; Lee, Hung S.

1989-01-01

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10.sup.-4 to 10.sup.-7 S cm.sup.-1 at room temperature.

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

Skotheim, T.A.; Okamoto, Yoshiyuki; Lee, H.S.

1989-11-21

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10[sup [minus]4] to 10[sup [minus]7] S cm[sup [minus]1] at room temperature.

End-Functionalized Palladium SCS Pincer Polymers via Controlled Radical Polymerizations.

PubMed

Lye, Diane S; Cohen, Aaron E; Wong, Madeleine Z; Weck, Marcus

2017-07-01

A direct and facile route toward semitelechelic polymers, end-functionalized with palladated sulfur-carbon-sulfur pincer (Pd II -pincer) complexes is reported that avoids any post-polymerization step. Key to our methodology is the combination of reversible addition-fragmentation chain-transfer (RAFT) polymerization with functionalized chain-transfer agents. This strategy yields Pd end-group-functionalized materials with monomodal molar mass dispersities (Đ) of 1.18-1.44. The RAFT polymerization is investigated using a Pd II -pincer chain-transfer agent for three classes of monomers: styrene, tert-butyl acrylate, and N-isopropylacrylamide. The ensuing Pd II -pincer end-functionalized polymers are analyzed using 1 H NMR spectroscopy, gel-permeation chromatography, and elemental analysis. The RAFT polymerization methodology provides a direct pathway for the fabrication of Pd II -pincer functionalized polymers with complete end-group functionalization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2013-01-01

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

A model for the enantiomeric enrichment of polypeptides on the primitive earth

NASA Technical Reports Server (NTRS)

Blair, N. E.; Bonner, W. A.

1981-01-01

A potential model is presented for the origin of optical activity in polypeptides on the primitive earth due to enantiomeric enrichment in succeeding polymerization-hydrolysis cycles. The model was developed in experiments with the polymerization of a DL-leucine N-carboxyanhydride mixture with a 31.2% enantiomeric excess of the L isomer with sodium methoxide initiator to yield a polyleucine product which was in turn partially hydrolyzed by acid. The polymerization-hydrolysis was found to produce a net 23.8% increase in the enantiomeric excess of the remaining unhydrolyzed polypeptide (14.2% from the polymerization and 9.6% from the partial hydrolysis). On the basis of these results, it is suggested that a slight excess produced by an appropriate chiral physical process may be enhanced by cycles of stereoselective polymerization and hydrolysis driven by fluctuating wet and dry environmental cycles on the primitive earth.

Hydrocarbon polymeric binder for advanced solid propellant

NASA Technical Reports Server (NTRS)

Potts, J. E. (Editor)

1972-01-01

A series of DEAB initiated isoprene polymerizations were run in the 5-gallon stirred autoclave reactor. Polymerization run parameters such as initiator concentration and feed rate were correlated with the molecular weight to provide a basis for molecular weight control in future runs. Synthetic methods were developed for the preparation of n-1,3-alkadienes. By these methods, 1,3-nonadiene was polymerized using DEAB initiator to give an ester-telechelic polynonadiene. This was subsequently hydrogenated with copper chromite catalyst to give a hydroxyl terminated saturated liquid hydrocarbon prepolymer having greatly improved viscosity characteristics and a Tg 18 degrees lower than that of the hydrogenated polyisoprenes. The hydroxyl-telechelic saturated polymers prepared by the hydrogenolysis of ester-telechelic polyisoprene were reached with diisocyanates under conditions favoring linear chain extension gel permeation chromatography was used to monitor this condensation polymerization. Fractions having molecular weights above one million were produced.

Polymerization of anionic wormlike micelles.

PubMed

Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

2006-01-31

Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles.

Polymeric Micelles and Alternative Nanonized Delivery Vehicles for Poorly Soluble Drugs

PubMed Central

Lu, Ying; Park, Kinam

2013-01-01

Poorly soluble drugs often encounter low bioavailability and erratic absorption patterns in the clinical setting. Due to the rising number of compounds having solubility issues, finding ways to enhance the solubility of drugs is one of the major challenges in the pharmaceutical industry today. Polymeric micelles, which form upon self-assembly of amphiphilic macromolecules, can act as solubilizing agents for delivery of poorly soluble drugs. This manuscript examines the fundamentals of polymeric micelles through reviews of representative literature and demonstrates possible applications through recent examples of clinical trial developments. In particular, the potential of polymeric micelles for delivery of poorly water-soluble drugs, especially in the areas of oral delivery and in cancer therapy, is discussed. Key considerations in utilizing polymeric micelles’ advantages and overcoming potential disadvantages have been highlighted. Lastly, other possible strategies related to particle size reduction for enhancing solubilization of poorly water-soluble drugs are introduced. PMID:22944304

The unusual dynamics of parasite actin result from isodesmic polymerization

PubMed Central

Skillman, Kristen M.; Ma, Christopher I.; Fremont, Daved H.; Diraviyam, Karthikeyan; Cooper, John A.; Sept, David; Sibley, L. David

2013-01-01

Previous reports have indicated that parasite actins are short and inherently unstable, despite being required for motility. Here, we re-examine the polymerization properties of actin in Toxoplasma gondii (TgACTI), unexpectedly finding that it exhibits isodesmic polymerization in contrast to the conventional nucleation-elongation process of all previously studied actins from both eukaryotes and bacteria. TgACTI polymerization kinetics lacks both a lag phase and critical concentration, normally characteristic of actins. Unique among actins, the kinetics of assembly can be fit with a single set of rate constants for all subunit interactions, without need for separate nucleation and elongation rates. This isodesmic model accurately predicts the assembly, disassembly, and the size distribution of TgACTI filaments in vitro, providing a mechanistic explanation for actin dynamics in vivo. Our findings expand the repertoire of mechanisms by which actin polymerization is governed and offer clues about the evolution of self-assembling, stabilized protein polymers. PMID:23921463

Actin Polymerization is Stimulated by Actin Crosslinking Protein Palladin

PubMed Central

Gurung, Ritu; Yadav, Rahul; Brungardt, Joseph G.; Orlova, Albina; Egelman, Edward H.; Beck, Moriah R.

2016-01-01

The actin scaffold protein palladin regulates both normal cell migration and invasive cell motility, processes that require the coordinated regulation of actin dynamics. However, the potential effect of palladin on actin dynamics has remained elusive. Here we show that the actin binding immunoglobulin-like domain of palladin, which is directly responsible for both actin binding and bundling, also stimulates actin polymerization in vitro. Palladin eliminated the lag phase that is characteristic of the slow nucleation step of actin polymerization. Furthermore, palladin dramatically reduced depolymerization, slightly enhanced the elongation rate, and did not alter the critical concentration. Microscopy and in vitro crosslinking assays reveal differences in actin bundle architecture when palladin is incubated with actin before or after polymerization. These results suggest a model whereby palladin stimulates a polymerization-competent form of G-actin, akin to metal ions, either through charge neutralization or conformational changes. PMID:26607837

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Using in-situ polymerization of conductive polymers to enhance the electrical properties of solution-processed carbon nanotube films and fibers.

PubMed

Allen, Ranulfo; Pan, Lijia; Fuller, Gerald G; Bao, Zhenan

2014-07-09

Single-walled carbon nanotubes/polymer composites typically have limited conductivity due to a low concentration of nanotubes and the insulating nature of the polymers used. Here we combined a method to align carbon nanotubes with in-situ polymerization of conductive polymer to form composite films and fibers. Use of the conducting polymer raised the conductivity of the films by 2 orders of magnitude. On the other hand, CNT fiber formation was made possible with in-situ polymerization to provide more mechanical support to the CNTs from the formed conducting polymer. The carbon nanotube/conductive polymer composite films and fibers had conductivities of 3300 and 170 S/cm, respectively. The relatively high conductivities were attributed to the polymerization process, which doped both the SWNTs and the polymer. In-situ polymerization can be a promising solution-processable method to enhance the conductivity of carbon nanotube films and fibers.

A Self-Reporting Photocatalyst for Online Fluorescence Monitoring of High Throughput RAFT Polymerization.

PubMed

Yeow, Jonathan; Joshi, Sanket; Chapman, Robert; Boyer, Cyrille Andre Jean Marie

2018-04-25

Translating controlled/living radical polymerization (CLRP) from batch to the high throughput production of polymer libraries presents several challenges in terms of both polymer synthesis and characterization. Although recently there have been significant advances in the field of low volume, high throughput CLRP, techniques able to simultaneously monitor multiple polymerizations in an "online" manner have not yet been developed. Here, we report our discovery that 5,10,15,20-tetraphenyl-21H,23H-porphine zinc (ZnTPP) is a self-reporting photocatalyst that can mediate PET-RAFT polymerization as well as report on monomer conversion via changes in its fluorescence properties. This enables the use of a microplate reader to conduct high throughput "online" monitoring of PET-RAFT polymerizations performed directly in 384-well, low volume microtiter plates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of the Thermal Polymerization of Linseed and Passion Fruit Oils

NASA Astrophysics Data System (ADS)

Lopes, R. V. V.; Loureiro, N. P. D.; Fonseca, P. S.; Macedo, J. L.; Santos, M. L.; Sales, M. J.

2008-08-01

Researches involving ecofriendliness materials are growing up, as well as, a current interest in developing materials from inexpensive and renewable resources. Vegetable oils show a number of excellent properties, which could be utilized to produce valuable polymeric materials. In this work is described the synthesis of polymeric materials from linseed oil (Linum usitatissimum L.) and passion fruit oil (Passiflora edulis) and their characterization by thermogravimetry (TG), differential scanning calorimetry (DSC) and Raman spectroscopy. The TG curve shows that those polymeric materials present two stages of decomposition. DSC plots of the vegetable oils showed some endothermic and exothermic transitions which are not present in the DSC curves corresponding to oil-based polymers. The Raman spectra of the polymers indicate declining of absorbance in the region of C = C stretching (˜1600 cm-1). This absorption was used to estimate the degree of polymerization (79% and 67.5% for linseed and passion fruit oils, respectively)

Reciprocating sliding wear evaluation of a polymeric/coating tribological system

NASA Astrophysics Data System (ADS)

Braza, J. F.; Furst, R. E.

1993-04-01

Reciprocating screening tests aimed at simulating a control bearing in a contaminated environment to discern the optimum polymeric/coating combination are described. The polymeric/coating systems were compared with the wear of a baseline phenolic impregnated polytetrafluoroethylene (PTFE) polyester woven fabric composite against an uncoated stainless steel substrate. The polymeric composites under consideration include a polyamide-imide (PAI), a polybenzimidazole, and an injection-moldable PEEK. Results indicate that the system of either PEEK or PAI with an E-Ni-PTFE- or TiN-coated substrate produced the best tribological system. These two composites also exhibited a significant improvement over the baseline fabric when tested against the high-velocity oxygen-fuel thermal spray coating. To discern better the optimum polymeric composite/coating system, full-scale testing must be conducted to study system dynamics, vibrations, counterface hardness and roughness, temperature, external environment and application specific conditions.

Delivery Device and Method for Forming the Same

NASA Technical Reports Server (NTRS)

Liu, Xiaohua (Inventor); Ma, Peter X. (Inventor); McCauley, Laurie (Inventor)

2014-01-01

A delivery device includes a hollow container, and a plurality of biodegradable and/or erodible polymeric layers established in the container. A layer including a predetermined substance is established between each of the plurality of polymeric layers, whereby degradation of the polymeric layer and release of the predetermined substance occur intermittently. Methods for forming the device are also disclosed herein.

Heat resistant polymers of oxidized styrylphosphine

NASA Technical Reports Server (NTRS)

Paciorek, K. J. L. (Inventor)

1978-01-01

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

Method for making block siloxane copolymers

DOEpatents

Butler, N.L.; Jessop, E.S.; Kolb, J.R.

1981-02-25

A method for synthesizing block polysiloxane copolymers is disclosed. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

Method for making block siloxane copolymers

DOEpatents

Butler, Nora; Jessop, Edward S.; Kolb, John R.

1982-01-01

A method for synthesizing block polysiloxane copolymers. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

Miniemulsion polymerization as a versatile tool for the synthesis of functionalized polymers

PubMed Central

Crespy, Daniel

2010-01-01

Summary The miniemulsion technique is a particular case in the family of heterophase polymerizations, which allows the formation of functionalized polymers by polymerization or modification of polymers in stable nanodroplets. We present here an overview of the different polymer syntheses within the miniemulsion droplets as reported in the literature, and of the current trends in the field. PMID:21160567

Method for forming polymerized microfluidic devices

DOEpatents

Sommer, Gregory J [Livermore, CA; Hatch, Anson V [Tracy, CA; Wang, Ying-Chih [Pleasanton, CA; Singh, Anup K [Danville, CA; Renzi, Ronald F [Tracy, CA; Claudnic, Mark R [Livermore, CA

2011-11-01

Methods for making a micofluidic device according to embodiments of the present invention include defining a cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

Method for forming polymerized microfluidic devices

DOEpatents

Sommer, Gregory J.; Hatch, Anson V.; Wang, Ying-Chih; Singh, Anup K.; Renzi, Ronald F.; Claudnic, Mark R.

2013-03-12

Methods for making a microfluidic device according to embodiments of the present invention include defining.about.cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

New ROMP Synthesis of Ferrocenyl Dendronized Polymers.

PubMed

Liu, Xiong; Ling, Qiangjun; Zhao, Li; Qiu, Guirong; Wang, Yinghong; Song, Lianxiang; Zhang, Ying; Ruiz, Jaime; Astruc, Didier; Gu, Haibin

2017-10-01

First- and second-generation Percec-type dendronized ferrocenyl norbornene macromonomers containing, respectively, three and nine ferrocenyl termini are synthesized and polymerized by ring-opening metathesis polymerization using Grubbs' third-generation olefin metathesis catalyst with several monomer/catalyst feed ratios between 10 and 50. The rate of polymerization is highly dependent on the generation of the dendronized macromonomers, but all these ring-opening metathesis polymerization reactions are controlled, and near-quantitative monomer conversions are achieved. The numbers of ferrocenyl groups obtained are in agreement with the theoretical ones according to the cyclic voltammetry studies as determined using the Bard-Anson method. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New method to access hyperbranched polymers with uniform structure via one-pot polymerization of inimer in microemulsion.

PubMed

Min, Ke; Gao, Haifeng

2012-09-26

A facile approach is presented for successful synthesis of hyperbranched polymers with high molecular weight and uniform structure by a one-pot polymerization of an inimer in a microemulsion. The segregated space in the microemulsion confined the inimer polymerization and particularly the polymer-polymer reaction within discrete nanoparticles. At the end of polymerization, each nanoparticle contained one hyperbranched polymer that had thousands of inimer units and low polydispersity. The hyperbranched polymers were used as multifunctional macroinitiators for synthesis of "hyper-star" polymers. When a degradable inimer was applied, the hyper-stars showed fast degradation into linear polymer chains with low molecular weight.

Polymer-modified opal nanopores.

PubMed

Schepelina, Olga; Zharov, Ilya

2006-12-05

The surface of nanopores in opal films, assembled from 205 nm silica spheres, was modified with poly(acrylamide) brushes using surface-initiated atom transfer radical polymerization. The colloidal crystal lattice remained unperturbed by the polymerization. The polymer brush thickness was controlled by polymerization time and was monitored by measuring the flux of redox species across the opal film using cyclic voltammetry. The nanopore size and polymer brush thickness were calculated on the basis of the limiting current change. Polymer brush thickness increased over the course of 26 h of polymerization in a logarithmic manner from 1.3 to 8.5 nm, leading to nanopores as small as 7.5 nm.

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

NASA Technical Reports Server (NTRS)

Wingard, C. D.

2018-01-01

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

Radical molecule and ion-molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in R.F. plasmas at low pressures (below 1.0 Torr)

NASA Technical Reports Server (NTRS)

Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.

1984-01-01

The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.

Radical and ion molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in RF plasmas at low pressures ( 1.0 torr)

NASA Technical Reports Server (NTRS)

Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.

1984-01-01

The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.

Synthesis of silica-polymer core-shell nanoparticles by reversible addition-fragmentation chain transfer polymerization.

PubMed

Moraes, John; Ohno, Kohji; Maschmeyer, Thomas; Perrier, Sébastien

2013-10-14

Hybrid nanoparticles hold great promise for a range of applications such as drug-delivery vectors or colloidal crystal self-assemblies. The challenge of preparing highly monodisperse particles for these applications has recently been overcome by using living radical polymerization techniques. In particular, the use of reversible addition-fragmentation chain transfer (RAFT), initiated from silica surfaces, yields well-defined particles from a range of precursor monomers resulting in nanoparticles of tailored sizes that are accessible via the rational selection of polymerization conditions. Furthermore, using RAFT allows post-polymerization modification to afford multifunctional, monodisperse, nanostructures under mild and non-stringent reaction conditions.

Hydrocarbon polymeric binder for advanced solid propellant

NASA Technical Reports Server (NTRS)

Potts, J. E. (Editor); Ashcraft, A. C., Jr.; Wise, E. W.

1971-01-01

Various experimental factors were examined to determine the source of difficulty in an isoprene polymerization in the 5-gallon reactor which gave a non-uniform product of low functionality. It was concluded that process improvements relating to initiator and monomer purity were desirable, but that the main difficulty was in the initiator feed system. A new pumping system was installed and an analog simulation of the reactor, feed system and initiator decomposition kinetics was devised which permits the selection of initial initiator concentrations and feed rates to use to give a nearly uniform initiator concentration throughout a polymerization run. An isoprene polymerization was run in which the process improvements were implemented.

Flexible fluoropolymer filled protective coatings

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

Well-Defined Macromolecules Using Horseradish Peroxidase as a RAFT Initiase.

PubMed

Danielson, Alex P; Bailey-Van Kuren, Dylan; Lucius, Melissa E; Makaroff, Katherine; Williams, Cameron; Page, Richard C; Berberich, Jason A; Konkolewicz, Dominik

2016-02-01

Enzymatic catalysis and control over macromolecular architectures from reversible addition-fragmentation chain transfer polymerization (RAFT) are combined to give a new method of making polymers. Horseradish peroxidase (HRP) is used to catalytically generate radicals using hydrogen peroxide and acetylacetone as a mediator. RAFT is used to control the polymer structure. HRP catalyzed RAFT polymerization gives acrylate and acrylamide polymers with relatively narrow molecular weight distributions. The polymerization is rapid, typically exceeding 90% monomer conversion in 30 min. Complex macromolecular architectures including a block copolymer and a protein-polymer conjugate are synthesized using HRP to catalytically initiate RAFT polymerization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DH and ESPI laser interferometry applied to the restoration shrinkage assessment

NASA Astrophysics Data System (ADS)

Campos, L. M. P.; Parra, D. F.; Vasconcelos, M. R.; Vaz, M.; Monteiro, J.

2014-01-01

In dental restoration postoperative marginal leakage is commonly associated to polymerization shrinkage effects. In consequence the longevity and quality of restorative treatment depends on the shrinkage mechanisms of the composite filling during the polymerization. In this work the development of new techniques for evaluation of those effects under light-induced polymerization of dental nano composite fillings is reported. The composite resins activated by visible light, initiate the polymerization process by absorbing light in wavelengths at about 470 nm. The techniques employed in the contraction assessment were digital holography (DH) and Electronic Speckle Pattern Interferometry (ESPI) based on laser interferometry. A satisfactory resolution was achieved in the non-contact displacement field measurements on small objects concerning the experimental dental samples. According to a specific clinical protocol, natural teeth were used (human mandibular premolars). A class I cavity was drilled and restored with nano composite material, according to Black principles. The polymerization was monitored by DH and ESPI in real time during the cure reaction of the restoration. The total displacement reported for the material in relation of the tooth wall was 3.7 μm (natural tooth). The technique showed the entire tooth surface (wall) deforming during polymerization shrinkage.

Roles of N-glycans in the polymerization-dependent aggregation of mutant Ig-μ chains in the early secretory pathway.

PubMed

Giannone, Chiara; Fagioli, Claudio; Valetti, Caterina; Sitia, Roberto; Anelli, Tiziana

2017-02-03

The polymeric structure of secretory IgM allows efficient antigen binding and complement fixation. The available structural models place the N-glycans bound to asparagines 402 and 563 of Ig-μ chains within a densely packed core of native IgM. These glycans are found in the high mannose state also in secreted IgM, suggesting that polymerization hinders them to Golgi processing enzymes. Their absence alters polymerization. Here we investigate their role following the fate of aggregation-prone mutant μ chains lacking the Cμ1 domain (μ∆). Our data reveal that μ∆ lacking 563 glycans (μ∆5) form larger intracellular aggregates than μ∆ and are not secreted. Like μ∆, they sequester ERGIC-53, a lectin previously shown to promote polymerization. In contrast, μ∆ lacking 402 glycans (μ∆4) remain detergent soluble and accumulate in the ER, as does a double mutant devoid of both (μ∆4-5). These results suggest that the two C-terminal Ig-μ glycans shape the polymerization-dependent aggregation by engaging lectins and acting as spacers in the alignment of individual IgM subunits in native polymers.

The Use of the Ex Vivo Chandler Loop Apparatus to Assess the Biocompatibility of Modified Polymeric Blood Conduits

PubMed Central

Slee, Joshua B.; Alferiev, Ivan S.; Levy, Robert J.; Stachelek, Stanley J.

2014-01-01

The foreign body reaction occurs when a synthetic surface is introduced to the body. It is characterized by adsorption of blood proteins and the subsequent attachment and activation of platelets, monocyte/macrophage adhesion, and inflammatory cell signaling events, leading to post-procedural complications. The Chandler Loop Apparatus is an experimental system that allows researchers to study the molecular and cellular interactions that occur when large volumes of blood are perfused over polymeric conduits. To that end, this apparatus has been used as an ex vivo model allowing the assessment of the anti-inflammatory properties of various polymer surface modifications. Our laboratory has shown that blood conduits, covalently modified via photoactivation chemistry with recombinant CD47, can confer biocompatibility to polymeric surfaces. Appending CD47 to polymeric surfaces could be an effective means to promote the efficacy of polymeric blood conduits. Herein is the methodology detailing the photoactivation chemistry used to append recombinant CD47 to clinically relevant polymeric blood conduits and the use of the Chandler Loop as an ex vivo experimental model to examine blood interactions with the CD47 modified and control conduits. PMID:25178087

Polymeric Micelles: Recent Advancements in the Delivery of Anticancer Drugs.

PubMed

Gothwal, Avinash; Khan, Iliyas; Gupta, Umesh

2016-01-01

Nanotechnology, in health and medicine, extensively improves the safety and efficacy of different therapeutic agents, particularly the aspects related to drug delivery and targeting. Among various nano-carriers, polymer based macromolecular approaches have resulted in improved drug delivery for the diseases like cancers, diabetes, autoimmune disorders and many more. Polymeric micelles consisting of hydrophilic exterior and hydrophobic core have established a record of anticancer drug delivery from the laboratory to commercial reality. The nanometric size, tailor made functionality, multiple choices of polymeric micelle synthesis and stability are the unique properties, which have attracted scientists and researchers around the world to work upon in this opportunistic drug carrier. The capability of polymeric micelles as nano-carriers are nowhere less significant than nanoparticles, liposomes and other nanocarriers, as per as the commercial feasibility and presence is concerned. In fact polymeric micelles are among the most extensively studied delivery platforms for the effective treatment of different cancers as well as non-cancerous disorders. The present review highlights the sequential and recent developments in the design, synthesis, characterization and evaluation of polymeric micelles to achieve the effective anticancer drug delivery. The future possibilities and clinical outcome have also been discussed, briefly.

First-principles study of pollutant molecules absorbed on polymeric adsorbents using the vdW-DF2 functional

NASA Astrophysics Data System (ADS)

Zhu, Jinguo; Wang, Yapeng; Tian, Ting; Zhang, Qianfan

2018-03-01

Polymeric adsorbents have been attracting increasing attention because of their favorable structrual properties and effectiveness of solving small molecules contaminants. However, due to the absence of deep insight into the adsorption mechanism of polymeric adsorbents, researches on new polymeric adsorbents can only be carried out by repeated experiments and tests, which is extremely inefficient. Therefore, investigating the adsorption process of polymeric adsorbents, especially the mechanism of adsorbing various air pollutant molecules by materials modelling and simulation, is of great significance. Here in this work, we systematically studied the adsorption mechanism by first-principles computation with van der Waals interaction. It demonstrates that the adsorption between them was pure physisorption originating from the hydrogen bond and intermolecular forces consisting of Keesom force, Debye force and London dispersion force. The proportions of these forces varied according to different adsorption systems. The adsorption effects were determined by the polymers’ dipole moment and polarizability. The adsorption performance of some polymers with special structures was also investigated to explore their possibility as potential adsorbents. The results of our simulation can provide some guidance for developing new polymeric adsorbents with better performance.

Self-folding polymeric containers for encapsulation and delivery of drugs

PubMed Central

Fernandes, Rohan; Gracias, David H.

2012-01-01

Self-folding broadly refers to self-assembly processes wherein thin films or interconnected planar templates curve, roll-up or fold into three dimensional (3D) structures such as cylindrical tubes, spirals, corrugated sheets or polyhedra. The process has been demonstrated with metallic, semiconducting and polymeric films and has been used to curve tubes with diameters as small as 2 nm and fold polyhedra as small as 100 nm, with a surface patterning resolution of 15 nm. Self-folding methods are important for drug delivery applications since they provide a means to realize 3D, biocompatible, all-polymeric containers with well-tailored composition, size, shape, wall thickness, porosity, surface patterns and chemistry. Self-folding is also a highly parallel process, and it is possible to encapsulate or self-load therapeutic cargo during assembly. A variety of therapeutic cargos such as small molecules, peptides, proteins, bacteria, fungi and mammalian cells have been encapsulated in self-folded polymeric containers. In this review, we focus on self-folding of all-polymeric containers. We discuss the mechanistic aspects of self-folding of polymeric containers driven by differential stresses or surface tension forces, the applications of self-folding polymers in drug delivery and we outline future challenges. PMID:22425612

New insight into the unresolved HPLC broad peak of Cabernet Sauvignon grape seed polymeric tannins by combining CPC and Q-ToF approaches.

PubMed

Ma, Wen; Waffo-Téguo, Pierre; Alessandra Paissoni, Maria; Jourdes, Michäel; Teissedre, Pierre-Louis

2018-05-30

Polymeric tannins from grapes have always been reported as an unresolved broad peak in HPLC chromatograms, and this has severely limited their identification to date. This study aimed to disassemble this broad peak and explore the polymeric tannin molecules inside. By applying centrifugal partition chromatography (CPC), an efficient separation approach was developed to split the broad peak of grape seed tannins into fractions. Then, the fractions were analyzed by Q-ToF (quadrupole time-of-flight mass spectrometry) to determine the corresponding structures of the tannins. The results suggest that grape seed polymeric tannins were eluted consecutively according to their degree of polymerization (DP). Condensed tannins identified in wine grape seed have a range of DP and degree of galloylation (DG) up to 20 and 11, respectively. The molecular mass of the largest molecule detected was 6067. To our knowledge, this is the first report to offer an insight into the broad peak of polymeric tannins found with HPLC and to characterize the tannins with a DP up to 20 as shown by HRMS and MS/MS data. Copyright © 2018 Elsevier Ltd. All rights reserved.

Production of large-particle-size monodisperse latexes

NASA Technical Reports Server (NTRS)

Vanderhoff, J. W.; El-Aasser, M. L.; Micale, F. J.; Sudol, E. D.; Tseng, C. M.; Silwanowicz, A.

1984-01-01

The research program achieved two objectives: (1) it has refined and extended the experimental techniques for preparing monodisperse latexes in quantity on the ground up to a particle diameter of 10 microns; and (2) it has demonstrated that a microgravity environment can be used to grow monodisperse latexes to larger sizes, where the limitations in size have yet to be defined. The experimental development of the monodisperse latex reactor (MLR) and the seeded emulsion polymerizations carried out in the laboratory prototype of the flight hardware, as a function of the operational parameters is discussed. The emphasis is directed towards the measurement, interpretation, and modeling of the kinetics of seeded emulsion polymerization and successive seeded emulsion polymerization. The recipe development of seeded emulsion polymerization as a function of particle size is discussed. The equilibrium swelling of latex particles with monomers was investigated both theoretically and experimentally. Extensive studies are reported on both the type and concentration of initiators, surfactants, and inhibitors, which eventually led to the development of the flight recipes. The experimental results of the flight experiments are discussed, as well as the experimental development of inhibition of seeded emulsion polymerization in terms of time of inhibition and the effect of inhibitors on the kinetics of polymerization.

Separation of time scales in one-dimensional directed nucleation-growth processes

NASA Astrophysics Data System (ADS)

Pierobon, Paolo; Miné-Hattab, Judith; Cappello, Giovanni; Viovy, Jean-Louis; Lagomarsino, Marco Cosentino

2010-12-01

Proteins involved in homologous recombination such as RecA and hRad51 polymerize on single- and double-stranded DNA according to a nucleation-growth kinetics, which can be monitored by single-molecule in vitro assays. The basic models currently used to extract biochemical rates rely on ensemble averages and are typically based on an underlying process of bidirectional polymerization, in contrast with the often observed anisotropic polymerization of similar proteins. For these reasons, if one considers single-molecule experiments, the available models are useful to understand observations only in some regimes. In particular, recent experiments have highlighted a steplike polymerization kinetics. The classical model of one-dimensional nucleation growth, the Kolmogorov-Avrami-Mehl-Johnson (KAMJ) model, predicts the correct polymerization kinetics only in some regimes and fails to predict the steplike behavior. This work illustrates by simulations and analytical arguments the limitation of applicability of the KAMJ description and proposes a minimal model for the statistics of the steps based on the so-called stick-breaking stochastic process. We argue that this insight might be useful to extract information on the time and length scales involved in the polymerization kinetics.

Roles of N-glycans in the polymerization-dependent aggregation of mutant Ig-μ chains in the early secretory pathway

PubMed Central

Giannone, Chiara; Fagioli, Claudio; Valetti, Caterina; Sitia, Roberto; Anelli, Tiziana

2017-01-01

The polymeric structure of secretory IgM allows efficient antigen binding and complement fixation. The available structural models place the N-glycans bound to asparagines 402 and 563 of Ig-μ chains within a densely packed core of native IgM. These glycans are found in the high mannose state also in secreted IgM, suggesting that polymerization hinders them to Golgi processing enzymes. Their absence alters polymerization. Here we investigate their role following the fate of aggregation-prone mutant μ chains lacking the Cμ1 domain (μ∆). Our data reveal that μ∆ lacking 563 glycans (μ∆5) form larger intracellular aggregates than μ∆ and are not secreted. Like μ∆, they sequester ERGIC-53, a lectin previously shown to promote polymerization. In contrast, μ∆ lacking 402 glycans (μ∆4) remain detergent soluble and accumulate in the ER, as does a double mutant devoid of both (μ∆4–5). These results suggest that the two C-terminal Ig-μ glycans shape the polymerization-dependent aggregation by engaging lectins and acting as spacers in the alignment of individual IgM subunits in native polymers. PMID:28157181

Plasma polymerized high energy density dielectric films for capacitors

NASA Technical Reports Server (NTRS)

Yamagishi, F. G.

1983-01-01

High energy density polymeric dielectric films were prepared by plasma polymerization of a variety of gaseous monomers. This technique gives thin, reproducible, pinhole free, conformable, adherent, and insoluble coatings and overcomes the processing problems found in the preparation of thin films with bulk polymers. Thus, devices are prepared completely in a vacuum environment. The plasma polymerized films prepared all showed dielectric strengths of greater than 1000 kV/cm and in some cases values of greater than 4000 kV/cm were observed. The dielectric loss of all films was generally less than 1% at frequencies below 10 kHz, but this value increased at higher frequencies. All films were self healing. The dielectric strength was a function of the polymerization technique, whereas the dielectric constant varied with the structure of the starting material. Because of the thin films used (thickness in the submicron range) surface smoothness of the metal electrodes was found to be critical in obtaining high dielectric strengths. High dielectric strength graft copolymers were also prepared. Plasma polymerized ethane was found to be thermally stable up to 150 C in the presence of air and 250 C in the absence of air. No glass transitions were observed for this material.

Effect of universal adhesive etching modes on bond strength to dual-polymerizing composite resins.

PubMed

Michaud, Pierre-Luc; Brown, Matthew

2018-04-01

Information is lacking as to the effect on bond strength of the etching modes of universal adhesives when they are used to bond dual-polymerizing composite resins to dentin. The purpose of this in vitro study was to investigate the bonding of dual-polymerizing foundation composite resins to dentin when universal bonding agents are used in self-etch or etch-and-rinse modes. Sixty caries-free, extracted third molar teeth were sectioned transversely in the apical third of the crown and allocated to 12 groups (n=5). Three different bonding agents (Scotchbond Universal, OptiBond XTR, All-Bond Universal) were used to bond 2 different dual-polymerizing composite resins (CompCore AF or CoreFlo DC) to dentin, using 2 different etching approaches (etch-and-rinse or self-etch). The specimens were sectioned into sticks (1×1×8 mm) with a precision saw. The bond strength of the specimens was tested under microtensile force at a crosshead speed of 0.5 mm/min. The data were analyzed using a 3-way ANOVA, a Games-Howell post hoc comparisons model, and Student t tests with Bonferroni corrections (α=.05). In the overall model, the composite resin used had no effect on bond strength (P=.830). The etching protocol by itself also did not have a significant effect (P=.059), although a trend was present. The bonding agent, however, did have an effect (P<.001) on bond strength. Also, a significant interaction effect was found for the bonding agent and etching protocol on bond strength (P<.001). The etching protocol influenced the bond strength when Scotchbond Universal (P<.008) and All-Bond Universal (P<.004) were used but not when OptiBond XTR was used (P=1.00). A self-etch protocol provided significantly higher bond strength when Scotchbond Universal was used, whereas with All-Bond Universal, an etch-and-rinse protocol, provided higher bond strength. When universal bonding agents were used to secure dual-polymerizing composite resins to dentin, no single etching protocol is better than another. Depending on which bonding agent is being used, one etching mode may perform better. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Tip-localized actin polymerization and remodeling, reflected by the localization of ADF, profilin and villin, are fundamental for gravity-sensing and polar growth in characean rhizoids.

PubMed

Braun, Markus; Hauslage, Jens; Czogalla, Aleksander; Limbach, Christoph

2004-07-01

Polar organization and gravity-oriented, polarized growth of characean rhizoids are dependent on the actin cytoskeleton. In this report, we demonstrate that the prominent center of the Spitzenkörper serves as the apical actin polymerization site in the extending tip. After cytochalasin D-induced disruption of the actin cytoskeleton, the regeneration of actin microfilaments (MFs) starts with the reappearance of a flat, brightly fluorescing actin array in the outermost tip. The actin array rounds up, produces actin MFs that radiate in all directions and is then relocated into its original central position in the center of the Spitzenkörper. The emerging actin MFs rearrange and cross-link to form the delicate, subapical meshwork, which then controls the statolith positioning, re-establishes the tip-high calcium gradient and mediates the reorganization of the Spitzenkörper with its central ER aggregate and the accumulation of secretory vesicles. Tip growth and gravitropic sensing, which includes control of statolith positioning and gravity-induced sedimentation, are not resumed until the original polar actin organization is completely restored. Immunolocalization of the actin-binding proteins, actin-depolymerizing factor (ADF) and profilin, which both accumulate in the center of the Spitzenkörper, indicates high actin turnover and gives additional support for the actin-polymerizing function of this central, apical area. Association of villin immunofluorescence with two populations of thick undulating actin cables with uniform polarity underlying rotational cytoplasmic streaming in the basal region suggests that villin is the major actin-bundling protein in rhizoids. Our results provide evidence that the precise coordination of apical actin polymerization and dynamic remodeling of actin MFs by actin-binding proteins play a fundamental role in cell polarization, gravity sensing and gravity-oriented polarized growth of characean rhizoids.

Effect of polymerization method and fabrication method on occlusal vertical dimension and occlusal contacts of complete-arch prosthesis.

PubMed

Lima, Ana Paula Barbosa; Vitti, Rafael Pino; Amaral, Marina; Neves, Ana Christina Claro; da Silva Concilio, Lais Regiane

2018-04-01

This study evaluated the dimensional stability of a complete-arch prosthesis processed by conventional method in water bath or microwave energy and polymerized by two different curing cycles. Forty maxillary complete-arch prostheses were randomly divided into four groups (n = 10): MW1 - acrylic resin cured by one microwave cycle; MW2 - acrylic resin cured by two microwave cycles: WB1 - conventional acrylic resin polymerized using one curing cycle in a water bath; WB2 - conventional acrylic resin polymerized using two curing cycles in a water bath. For evaluation of dimensional stability, occlusal vertical dimension (OVD) and area of contact points were measured in two different measurement times: before and after the polymerization method. A digital caliper was used for OVD measurement. Occlusal contact registration strips were used between maxillary and mandibular dentures to measure the contact points. The images were measured using the software IpWin32, and the differences before and after the polymerization methods were calculated. The data were statistically analyzed using the one-way ANOVA and Tukey test (α = .05). he results demonstrated significant statistical differences for OVD between different measurement times for all groups. MW1 presented the highest OVD values, while WB2 had the lowest OVD values ( P <.05). No statistical differences were found for area of contact points among the groups ( P =.7150). The conventional acrylic resin polymerized using two curing cycles in a water bath led to less difference in OVD of complete-arch prosthesis.

Effects of polymerization and nucleotide identity on the conformational dynamics of the bacterial actin homolog MreB

PubMed Central

Colavin, Alexandre; Hsin, Jen; Huang, Kerwyn Casey

2014-01-01

The assembly of protein filaments drives many cellular processes, from nucleoid segregation, growth, and division in single cells to muscle contraction in animals. In eukaryotes, shape and motility are regulated through cycles of polymerization and depolymerization of actin cytoskeletal networks. In bacteria, the actin homolog MreB forms filaments that coordinate the cell-wall synthesis machinery to regulate rod-shaped growth and contribute to cellular stiffness through unknown mechanisms. Like actin, MreB is an ATPase and requires ATP to polymerize, and polymerization promotes nucleotide hydrolysis. However, it is unclear whether other similarities exist between MreB and actin because the two proteins share low sequence identity and have distinct cellular roles. Here, we use all-atom molecular dynamics simulations to reveal surprising parallels between MreB and actin structural dynamics. We observe that MreB exhibits actin-like polymerization-dependent structural changes, wherein polymerization induces flattening of MreB subunits, which restructures the nucleotide-binding pocket to favor hydrolysis. MreB filaments exhibited nucleotide-dependent intersubunit bending, with hydrolyzed polymers favoring a straighter conformation. We use steered simulations to demonstrate a coupling between intersubunit bending and the degree of flattening of each subunit, suggesting cooperative bending along a filament. Taken together, our results provide molecular-scale insight into the diversity of structural states of MreB and the relationships among polymerization, hydrolysis, and filament properties, which may be applicable to other members of the broad actin family. PMID:24550504

Effects of polymerization and nucleotide identity on the conformational dynamics of the bacterial actin homolog MreB.

PubMed

Colavin, Alexandre; Hsin, Jen; Huang, Kerwyn Casey

2014-03-04

The assembly of protein filaments drives many cellular processes, from nucleoid segregation, growth, and division in single cells to muscle contraction in animals. In eukaryotes, shape and motility are regulated through cycles of polymerization and depolymerization of actin cytoskeletal networks. In bacteria, the actin homolog MreB forms filaments that coordinate the cell-wall synthesis machinery to regulate rod-shaped growth and contribute to cellular stiffness through unknown mechanisms. Like actin, MreB is an ATPase and requires ATP to polymerize, and polymerization promotes nucleotide hydrolysis. However, it is unclear whether other similarities exist between MreB and actin because the two proteins share low sequence identity and have distinct cellular roles. Here, we use all-atom molecular dynamics simulations to reveal surprising parallels between MreB and actin structural dynamics. We observe that MreB exhibits actin-like polymerization-dependent structural changes, wherein polymerization induces flattening of MreB subunits, which restructures the nucleotide-binding pocket to favor hydrolysis. MreB filaments exhibited nucleotide-dependent intersubunit bending, with hydrolyzed polymers favoring a straighter conformation. We use steered simulations to demonstrate a coupling between intersubunit bending and the degree of flattening of each subunit, suggesting cooperative bending along a filament. Taken together, our results provide molecular-scale insight into the diversity of structural states of MreB and the relationships among polymerization, hydrolysis, and filament properties, which may be applicable to other members of the broad actin family.

Reactive centre loop mutants of α-1-antitrypsin reveal position-specific effects on intermediate formation along the polymerization pathway

PubMed Central

Haq, Imran; Irving, James A.; Faull, Sarah V.; Dickens, Jennifer A.; Ordóñez, Adriana; Belorgey, Didier; Gooptu, Bibek; Lomas, David A.

2013-01-01

The common severe Z mutation (E342K) of α1-antitrypsin forms intracellular polymers that are associated with liver cirrhosis. The native fold of this protein is well-established and models have been proposed from crystallographic and biophysical data for the stable inter-molecular configuration that terminates the polymerization pathway. Despite these molecular ‘snapshots’, the details of the transition between monomer and polymer remain only partially understood. We surveyed the RCL (reactive centre loop) of α1-antitrypsin to identify sites important for progression, through intermediate states, to polymer. Mutations at P14P12 and P4, but not P10P8 or P2P1′, resulted in a decrease in detectable polymer in a cell model that recapitulates the intracellular polymerization of the Z variant, consistent with polymerization from a near-native conformation. We have developed a FRET (Förster resonance energy transfer)-based assay to monitor polymerization in small sample volumes. An in vitro assessment revealed the position-specific effects on the unimolecular and multimolecular phases of polymerization: the P14P12 region self-inserts early during activation, while the interaction between P6P4 and β-sheet A presents a kinetic barrier late in the polymerization pathway. Correspondingly, mutations at P6P4, but not P14P12, yield an increase in the overall apparent activation energy of association from ~360 to 550 kJ mol−1. PMID:23659468

Mapping Polymerization and Allostery of Hemoglobin S Using Point Mutations

PubMed Central

Weinkam, Patrick; Sali, Andrej

2014-01-01

Hemoglobin is a complex system that undergoes conformational changes in response to oxygen, allosteric effectors, mutations, and environmental changes. Here, we study allostery and polymerization of hemoglobin and its variants by application of two previously described methods: (i) AllosMod for simulating allostery dynamics given two allosterically related input structures and (ii) a machine-learning method for dynamics- and structure-based prediction of the mutation impact on allostery (Weinkam et al. J. Mol. Biol. 2013), now applicable to systems with multiple coupled binding sites such as hemoglobin. First, we predict the relative stabilities of substates and microstates of hemoglobin, which are determined primarily by entropy within our model. Next, we predict the impact of 866 annotated mutations on hemoglobin’s oxygen binding equilibrium. We then discuss a subset of 30 mutations that occur in the presence of the sickle cell mutation and whose effects on polymerization have been measured. Seven of these HbS mutations occur in three predicted druggable binding pockets that might be exploited to directly inhibit polymerization; one of these binding pockets is not apparent in the crystal structure but only in structures generated by AllosMod. For the 30 mutations, we predict that mutation-induced conformational changes within a single tetramer tend not to significantly impact polymerization; instead, these mutations more likely impact polymerization by directly perturbing a polymerization interface. Finally, our analysis of allostery allows us to hypothesize why hemoglobin evolved to have multiple subunits and a persistent low frequency sickle cell mutation. PMID:23957820

Studies with Laser Cooled Atoms and Single Molecules

DTIC Science & Technology

2007-09-01

between soda lime glass slides. The bond-setting time can be tailored to allow time for precision optical alignment. We also extended our previous single...This method achieves 100% successful bonding rates between soda lime glass slides. The bond-setting time and be can tailored to allow time for...simple method to bond optical components using silica nanoparticle sol-gel chemistry. The silica nanoparticles polymerize into highly branched

Polymeric lithography editor: Editing lithographic errors with nanoporous polymeric probes

PubMed Central

Rajasekaran, Pradeep Ramiah; Zhou, Chuanhong; Dasari, Mallika; Voss, Kay-Obbe; Trautmann, Christina; Kohli, Punit

2017-01-01

A new lithographic editing system with an ability to erase and rectify errors in microscale with real-time optical feedback is demonstrated. The erasing probe is a conically shaped hydrogel (tip size, ca. 500 nm) template-synthesized from track-etched conical glass wafers. The “nanosponge” hydrogel probe “erases” patterns by hydrating and absorbing molecules into a porous hydrogel matrix via diffusion analogous to a wet sponge. The presence of an interfacial liquid water layer between the hydrogel tip and the substrate during erasing enables frictionless, uninterrupted translation of the eraser on the substrate. The erasing capacity of the hydrogel is extremely high because of the large free volume of the hydrogel matrix. The fast frictionless translocation and interfacial hydration resulted in an extremely high erasing rate (~785 μm2/s), which is two to three orders of magnitude higher in comparison with the atomic force microscopy–based erasing (~0.1 μm2/s) experiments. The high precision and accuracy of the polymeric lithography editor (PLE) system stemmed from coupling piezoelectric actuators to an inverted optical microscope. Subsequently after erasing the patterns using agarose erasers, a polydimethylsiloxane probe fabricated from the same conical track-etched template was used to precisely redeposit molecules of interest at the erased spots. PLE also provides a continuous optical feedback throughout the entire molecular editing process—writing, erasing, and rewriting. To demonstrate its potential in device fabrication, we used PLE to electrochemically erase metallic copper thin film, forming an interdigitated array of microelectrodes for the fabrication of a functional microphotodetector device. High-throughput dot and line erasing, writing with the conical “wet nanosponge,” and continuous optical feedback make PLE complementary to the existing catalog of nanolithographic/microlithographic and three-dimensional printing techniques. This new PLE technique will potentially open up many new and exciting avenues in lithography, which remain unexplored due to the inherent limitations in error rectification capabilities of the existing lithographic techniques. PMID:28630898

Effect of Tunable Surface Potential on the Structure of Spin-Cast Polymeric Blend Films

NASA Astrophysics Data System (ADS)

Hawker, C.; Huang, E.; Russell, T. P.

1998-03-01

The demixing of binary polymeric mixtures has been studied with various surface potentials. This was performed by spin casting polystyrene/poly(methyl methacrylate) mixtures on to silicon substrates that had been modified with an end-grafted random copolymer brush layer. The composition of the random copolymer brush, containing the same monomeric components as the homopolymers can be varied in a precise manner over the entire concentration range. Atomic force and optical microscopy were used to study the morphology formed during spin casting and after annealing. Further insight into the structure was gained by rinsing these films with preferential solvents to remove one of the constituents and by performing the microscopy measurements. Finally, x-ray photoelectron spectroscopy, XPS, was used to elucidate the composition of the film near the air/polymer interface. Our data show that the resulting thin film structure depends strongly on the composition of the end grafted random copolymer film. Furthermore, the effect of thickness, solvent used in casting, and annealing conditions will be addressed.

Study on temperature and near-infrared driving characteristics of hydrogel actuator fabricated via molding and 3D printing.

PubMed

Zhao, Qian; Liang, Yunhong; Ren, Lei; Qiu, Feng; Zhang, Zhihui; Ren, Luquan

2018-02-01

A hydrogel material system which was fit for molding and 3D printing was developed to fabricate bilayer hydrogel actuators with controllable temperature and near infrared laser responses. Polymerization on interface boundary of layered structure enhanced the bonding strength of hydrogel actuators. By utilizing anisotropic of microstructure along with thickness direction, bilayer hydrogel actuators fabricated via molding realized intelligent bending/shrinking responses, which guided the preparation of hydrogel ink for 3D printing. In-situ free radical polymerization under vacuum realized the solidification of printed hydrogel actuators with graphene oxide. Based on anisotropic swelling/deswelling behaviors of precise structure fabricated via 3D printing, the printed bilayer hydrogel actuators achieved temperature and near infrared laser responsive deformation. Changes of programmable printing path effectively resulted in corresponding deformation patterns. Combination of advantages of molding and 3D printing can promote the design and fabrication of hydrogel actuators with high mechanical strength, response speed and deformation ability. Copyright © 2017 Elsevier Ltd. All rights reserved.

Waterborne polyurethane-acrylic hybrid nanoparticles by miniemulsion polymerization: applications in pressure-sensitive adhesives.

PubMed

Lopez, Aitziber; Degrandi-Contraires, Elise; Canetta, Elisabetta; Creton, Costantino; Keddie, Joseph L; Asua, José M

2011-04-05

Waterborne polyurethane-acrylic hybrid nanoparticles for application as pressure-sensitive adhesives (PSAs) were prepared by one-step miniemulsion polymerization. The addition of polyurethane to a standard waterborne acrylic formulation results in a large increase in the cohesive strength and hence a much higher shear holding time (greater than seven weeks at room temperature), which is a very desirable characteristic for PSAs. However, with the increase in cohesion, there is a decrease in the relative viscous component, and hence there is a decrease in the tack energy. The presence of a small concentration of methyl methacrylate (MMA) in the acrylic copolymer led to phase separation within the particles and created a hemispherical morphology. The tack energy was particularly low in the hybrid containing MMA because of the effects of lower energy dissipation and greater cross-linking. These results highlight the great sensitivity of the viscoelastic and adhesive properties to the details of the polymer network architecture and hence to the precise composition and synthesis conditions.

Colloidal inverse bicontinuous cubic membranes of block copolymers with tunable surface functional groups

NASA Astrophysics Data System (ADS)

La, Yunju; Park, Chiyoung; Shin, Tae Joo; Joo, Sang Hoon; Kang, Sebyung; Kim, Kyoung Taek

2014-06-01

Analogous to the complex membranes found in cellular organelles, such as the endoplasmic reticulum, the inverse cubic mesophases of lipids and their colloidal forms (cubosomes) possess internal networks of water channels arranged in crystalline order, which provide a unique nanospace for membrane-protein crystallization and guest encapsulation. Polymeric analogues of cubosomes formed by the direct self-assembly of block copolymers in solution could provide new polymeric mesoporous materials with a three-dimensionally organized internal maze of large water channels. Here we report the self-assembly of amphiphilic dendritic-linear block copolymers into polymer cubosomes in aqueous solution. The presence of precisely defined bulky dendritic blocks drives the block copolymers to form spontaneously highly curved bilayers in aqueous solution. This results in the formation of colloidal inverse bicontinuous cubic mesophases. The internal networks of water channels provide a high surface area with tunable surface functional groups that can serve as anchoring points for large guests such as proteins and enzymes.

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

PubMed

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

2012-09-18

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

Bio-inspired method to obtain multifunctional dynamic nanocomposites

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

Kushner, Aaron M.; Guan, Zhibin; Williams, Gregory

A method for a polymeric or nanocomposite material. The method includes assembling a multiphase hard-soft structure, where the structure includes a hard micro- or nano-phase, and a soft micro- or nano-phase that includes a polymeric scaffold. In the method, the polymeric scaffold includes dynamically interacting motifs and has a glass transition temperature (T.sub.g) lower than the intended operating temperature of the material.

Modern trends in industrial technology of production of optical polymeric components for night vision devices

NASA Astrophysics Data System (ADS)

Goev, A. I.; Knyazeva, N. A.; Potelov, V. V.; Senik, B. N.

2005-06-01

The present paper represents in detail the complex approach to creating industrial technology of production of polymeric optical components: information has been given on optical polymeric materials, automatic machines for injection moulding, the possibilities of the Moldflow system (the AB "Universal" company) used for mathematical simulation of the technological process of injection moulding and making the moulds.

Delivery of Vaccines By Biodegradable Polymeric Microcapsules with Bioadherence Properties. Phase 1.

DTIC Science & Technology

1995-10-01

DAMD17-95-C-5061 TITLE: Delivery of Vaccines by Biodegradable Polymeric Microcapsules with Bioadherence Properties PRINCIPAL INVESTIGATOR: Robert L...SUBTITLE 5. FUNDING NUMBERS Delivery of Vaccines By Biodegradable Polymeric Microcapsules with Bioadherence Properties DAMD17-95-C-5061 6. AUTHOR(S...SUBJECT TERMS 15. NUMBER OF PAGES Polymer microspheres 27 Microencapsulated vaccines 16. PRICE CODE 17. SECURITY CLASSIFICATION 18. SECURITY

Comparative study on the development of intestinal mucin 2, IgA and polymeric Ig receptor expressions between broiler chickens and Pekin ducks

USDA-ARS?s Scientific Manuscript database

Intestinal mucin2 (MUC2), a major gel-forming mucin, represents a primary barrier component of mucus layers and target site for secretory IgA. Polymeric Ig receptor (pIgR) expressed on the basolateral surface of epithelium, is used to transport polymeric IgA from the lamina propria into luminal muci...

Post polymerization cure shape memory polymers

DOEpatents

Wilson, Thomas S.; Hearon, II, Michael Keith; Bearinger, Jane P.

2017-01-10

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Post polymerization cure shape memory polymers

DOEpatents

Wilson, Thomas S; Hearon, Michael Keith; Bearinger, Jane P

2014-11-11

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Poly(vinyl alcohol) stabilization of acrylic emulsion polymers using the miniemulsion approach

NASA Astrophysics Data System (ADS)

Kim, Noma

Miniemulsion approach was employed to obtain stable acrylic latexes of n-butyl acrylate and methyl methacrylate (50/50 wt%) stabilized with poly(vinyl alcohol) (PVA) and to enhance the grafting reaction between PVA and acrylic monomers at the water/droplet interface. The stability of miniemulsions were studied in terms of the type and concentration of' the stabilizer, and the PVA partitioning were determined as a function of the PVA concentration. Using the comparison of PVA partitioning at droplet surface and grafted PVA as a function of concentration, it was suggested that the water/monomer interface is the main grafting site in the miniemulsion polymerization. Seeded emulsion and miniemulsion copolymerizations initiated with water-soluble (hydrogen peroxide, HPO), partially water-soluble (t-butyl peroxide, TBHP), and oil-soluble (t-butyl peroxyoctoate, TBPO) initiators were carried out to further investigate the oil/water interface as the grafting site for PVA. The interaction between the capillary wall in the CHDF (capillary hydrodynamic fractionation) chromatographic particle sizer and the water-soluble polymers adsorbed on the particle surface was studied using different types of water-soluble polymers and eluants. Different grafting architectures depending on the initiation site were suggested based on the CHDF results. The amounts of grafted PVA produced in miniemulsion polymers initiated with TBHP and TBPO were substantially less than those in the corresponding seeded emulsion polymerizations. The effect on the internal viscosity at the interface was proposed to explain the difference in grafting in terms of polymerization methods. Aqueous phase and interface grafting were studied using the measurement of the degree of hydrolysis (DH) of the serum PVA and adsorbed PVA after miniemulsion polymerizations. Based on the results, it was found that aqueous phase and interface grafting occurred in the HPO system; however, interface grafting dominated the TBHP system. Colloidal instability in conventional emulsion polymerizations was investigated and compared with the corresponding miniemulsion polymerization. It was found that the grafted PVA in conventional emulsion polymerizations was more hydrophobic presumably due to a greater amount of grafted chains than that in similar miniemulsion polymerizations and this could be correlated with the colloidal instability during conventional emulsion polymerizations.

Effect of different thermo-light polymerization on flexural strength of two glass ionomer cements and a glass carbomer cement.

PubMed

Gorseta, Kristina; Borzabadi-Farahani, Ali; Moshaverinia, Alireza; Glavina, Domagoj; Lynch, Edward

2017-07-01

Whether polymerization lights can be used for heating glass ionomer cements (GICs) or glass carbomer (GCP) to improve their mechanical properties is not well established. The purpose of this in vitro study was to assess the effect of thermo-light polymerization on the flexural strength (FS) of 2 GICs (Fuji IX GP Fast, Ketac Molar) and a GCP. Specimens (n=10) were prepared in stainless steel molds (2×2×25 mm), compressed, exposed to 3 polymerization lights (500, 1000, 1200 mW/cm 2 ) for 2 cycles of 40 seconds on each side, and stored in petroleum jelly (37°C, 24 hours). Significant FS differences were detected among groups after different thermo-light polymerization regimens (F=50.926, df=11, P<.001). GCP showed the highest mean FS (∼5 times, P<.001) after thermo-light polymerization with power outputs of 1000 (127.1 ±25.8 MPa) and 1200 mW/cm 2 (117.4 ±18.5 MPa), with no significance difference between them (P=.98), compared with 500 mW/cm 2 (24.1 ±1.7 MPa). For Ketac Molar, compared with autopolymerization setting (15.5 ±3.1 MPa), a significant increase in mean FS (∼2.5 times) was only observed in specimens treated with 1200 mW/cm 2 polymerization light (P=.03). For Fuji IX GP Fast, only the light with 1000 mW/cm 2 output significantly increased the FS (98.9 ±23.4 MPa, P<.001) compared with the autopolymerization setting (34.9 ±6.4 MPa). Thermo-light polymerization accelerated the development of FS in the tested GICs, potentially protecting against saliva contamination during the first 3 to 4 minutes after mixing GIC. Thermo-light polymerization of the glass carbomer with power outputs of 1000 and 1200 mW/cm 2 also substantially increased FS. The clinical advantages of the findings should be validated by in vivo studies. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Probing actin polymerization by intermolecular cross-linking.

PubMed

Millonig, R; Salvo, H; Aebi, U

1988-03-01

We have used N,N'-1,4-phenylenebismaleimide, a bifunctional sulfhydryl cross-linking reagent, to probe the oligomeric state of actin during the early stages of its polymerization into filaments. We document that one of the first steps in the polymerization of globular monomeric actin (G-actin) under a wide variety of ionic conditions is the dimerization of a significant fraction of the G-actin monomer pool. As polymerization proceeds, the yield of this initial dimer ("lower" dimer with an apparent molecular mass of 86 kD by SDS-PAGE [LD]) is attenuated, while an actin filament dimer ("upper" dimer with an apparent molecular mass of 115 kD by SDS-PAGE [UD] as characterized [Elzinga, M., and J. J. Phelan. 1984. Proc. Natl. Acad. Sci. USA. 81:6599-6602]) is formed. This shift from LD to UD occurs concomitant with formation of filaments as assayed by N-(1-pyrenyl)iodoacetamide fluorescence enhancement and electron microscopy. Isolated cross-linked LD does not form filaments, while isolated cross-linked UD will assemble into filaments indistinguishable from those polymerized from unmodified G-actin under typical filament-forming conditions. The presence of cross-linked LD does not effect the kinetics of polymerization of actin monomer, whereas cross-linked UD shortens the "lag phase" of the polymerization reaction in a concentration-dependent fashion. Several converging lines of evidence suggest that, although accounting for a significant oligomeric species formed during early polymerization, the LD is incompatible with the helical symmetry defining the mature actin filament; however, it could represent the interfilament dimer found in paracrystalline arrays or filament bundles. Furthermore, the LD is compatible with the unit cell structure and symmetry common to various types of crystalline actin arrays (Aebi, U., W. E. Fowler, G. Isenberg, T. D. Pollard, and P. R. Smith. 1981. J. Cell Biol. 91:340-351) and might represent the major structural state in which a mutant beta-actin (Leavitt, J., G. Bushar, T. Kakunaga, H. Hamada, T. Hirakawa, D. Goldman, and C. Merril. 1982. Cell. 28:259-268) is arrested under polymerizing conditions.

Recent advances and developments in composite dental restorative materials.

PubMed

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

2011-04-01

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

Transparent conductive nano-composites

DOEpatents

Geohegan, David Bruce; Ivanov, Ilia N; Puretzky, Alexander A; Jesse, Stephen; Hu, Bin; Garrett, Matthew; Zhao, Bin

2013-09-24

The present invention, in one embodiment, provides a method of forming an organic electric device that includes providing a plurality of carbon nanostructures; and dispersing the plurality of carbon nanostructures in a polymeric matrix to provide a polymeric composite, wherein when the plurality of carbon nanostructures are present at a first concentration an interface of the plurality of carbon nanostructures and the polymeric matrix is characterized by charge transport when an external energy is applied, and when the plurality of carbon nanostructures are present at a second concentration the interface of the plurality of carbon nanostructures and the polymeric matrix are characterized by exciton dissociation when an external energy is applied, wherein the first concentration is less than the second concentration.

Combinatorial and high-throughput approaches in polymer science

NASA Astrophysics Data System (ADS)

Zhang, Huiqi; Hoogenboom, Richard; Meier, Michael A. R.; Schubert, Ulrich S.

2005-01-01

Combinatorial and high-throughput approaches have become topics of great interest in the last decade due to their potential ability to significantly increase research productivity. Recent years have witnessed a rapid extension of these approaches in many areas of the discovery of new materials including pharmaceuticals, inorganic materials, catalysts and polymers. This paper mainly highlights our progress in polymer research by using an automated parallel synthesizer, microwave synthesizer and ink-jet printer. The equipment and methodologies in our experiments, the high-throughput experimentation of different polymerizations (such as atom transfer radical polymerization, cationic ring-opening polymerization and emulsion polymerization) and the automated matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS) sample preparation are described.

Preferential polymerization and adsorption of L-optical isomers of amino acids relative to D-optical isomers on kaolinite templates.

NASA Technical Reports Server (NTRS)

Jackson, T. A.

1971-01-01

Experiments on the polymerization of the L- and D-optical isomers of aspartic acid and serine using kaolinite as a catalyst showed that the L-optical isomers were polymerized at a much higher rate than the D-optical isomers; racemic (DL-) mixtures were polymerized at an intermediate rate. The peptides formed from the L-monomers were preferentially adsorbed by the clay. In the absence of kaolinite, no significant or consistent difference in the behavior of the L- and D-optical isomers was observed. In experiments on the adsorption of L- and D-phenylalanine by kaolinite, the L-optical isomer was preferentially adsorbed.

Measurement of in vitro microtubule polymerization by turbidity and fluorescence.

PubMed

Mirigian, Matthew; Mukherjee, Kamalika; Bane, Susan L; Sackett, Dan L

2013-01-01

Tubulin polymerization may be conveniently monitored by the increase in turbidity (optical density, or OD) or by the increase in fluorescence intensity of diamidino-phenylindole. The resulting data can be a quantitative measure of microtubule (MT) assembly, but some care is needed in interpretation, especially of OD data. Buffer formulations used for the assembly reaction significantly influence the polymerization, both by altering the critical concentration for polymerization and by altering the exact polymer produced-for example, by increasing the production of sheet polymers in addition to MT. Both the turbidity and the fluorescence methods are useful for demonstrating the effect of MT-stabilizing or -destabilizing additives. 2013 Published by Elsevier Inc.

Clays and other minerals in prebiotic processes

NASA Technical Reports Server (NTRS)

Paecht-Horowitz, M.

1984-01-01

Clays and other minerals have been investigated in context with prebiotic processes, mainly in polymerization of amino acids. It was found that peptides adsorbed on the clay, prior to polymerization, influence the reaction. The ratio between the amount of the peptides adsorbed and that of the clay is important for the yield as well as for the degrees of polymerization obtained. Adsorption prior to reaction produces a certain order in the aggregates of the clay particles which might induce better reaction results. Excess of added peptides disturbs this order and causes lesser degrees of polymerization. In addition to adsorption, clays are also able to occlude between their layers substances out of the environment, up to very high concentrations.

Transparent conductive nano-composites

DOEpatents

Geohegan, David Bruce [Knoxville, TN; Ivanov, Ilia N [Knoxville, TN; Puretzky, Alexander A [Knoxville, TN; Jesse, Stephen [Knoxville, TN; Hu, Bin [Knoxville, TN; Garrett, Matthew [Knoxville, TN; Zhao, Bin [Easley, SC

2011-04-12

The present invention, in one embodiment, provides a method of forming an organic electric device that includes providing a plurality of carbon nanostructures; and dispersing the plurality of carbon nanostructures in a polymeric matrix to provide a polymeric composite, wherein when the plurality of carbon nanostructures are present at a first concentration an interface of the plurality of carbon nanostructures and the polymeric matrix is characterized by charge transport when an external energy is applied, and when the plurality of carbon nanostructures are present at a second concentration the interface of the plurality of carbon nanostructures and the polymeric matrix are characterized by exciton dissociation when an external energy is applied, wherein the first concentration is less than the second concentration.

Molecular Probe Fluorescence Monitoring of Polymerization

NASA Technical Reports Server (NTRS)

Bunton, Patrick

2002-01-01

This project investigated the feasibility of using fluorescence spectroscopy to determine viscosity of polymer/monomer in support of Transient Interfacial Phenomena in Miscible Polymer Systems (TIPMPS). This project will attempt to measure gradient induced flow at a miscible interface during and / or after in-flight polymerization of dodecyl acrylate (lauryl acrylate). Concentration and temperature gradients will be intentionally introduced during polymerization and the resultant fluid flow determined by Particle Imaging Velocimetry (PIV). This report describes an investigation of the feasibility of using fluorescence of a probe molecule to monitor viscosity and/or concentration during and after polymerization. The probe used was pyrene which has been shown to be sensitive to its local environment in methyl methacrylate.

Chain polymerization of diacetylene compound multilayer films on the topmost surface initiated by a scanning tunneling microscope tip.

PubMed

Takajo, Daisuke; Okawa, Yuji; Hasegawa, Tsuyoshi; Aono, Masakazu

2007-05-08

Chain polymerizations of diacetylene compound multilayer films on graphite substrates were examined with a scanning tunneling microscope (STM) at the liquid/solid interface of the phenyloctane solution. The first layer grew very quickly into many small domains. This was followed by the slow formation of the piled up layers into much larger domains. Chain polymerization on the topmost surface layer could be initiated by applying a pulsed voltage between the STM tip and the substrate, usually producing a long polymer of submicrometer length. In contrast, polymerizations on the underlying layer were never observed. This can be explained by a conformation model in which the polymer backbone is lifted up.

The autowave modes of solid phase polymerization of metal-containing monomers in two- and three-dimensional fiberglass-filled matrices

NASA Astrophysics Data System (ADS)

Barelko, V. V.; Pomogailo, A. D.; Dzhardimalieva, G. I.; Evstratova, S. I.; Rozenberg, A. S.; Uflyand, I. E.

1999-06-01

The phenomenon of autowave (frontal) solid phase polymerization of metal-containing monomers based on metal-acrylamide complexes is considered. The comparison of the features of autowave processes realized in both the single-component matrices of the monomer and the matrices filled by the fiberglass materials is performed. The unstable regimes of the polymerization wave as well as the conditions for the stabilization of the flat front in the filled matrices are described. The peculiarities of the frontal regimes in the three- and two-dimensional media are studied. Some possibilities for using of autowave polymerization in the fabrication of the polymer-fiberglass composites and composition prepregs are discussed.

Recent Advances and Developments in Composite Dental Restorative Materials

PubMed Central

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

2011-01-01

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

Multiple polymer architectures of human Polyhomeotic homolog 3 (PHC3) SAM

PubMed Central

Nanyes, David R.; Junco, Sarah E.; Taylor, Alexander B.; Robinson, Angela K.; Patterson, Nicolle L.; Shivarajpur, Ambika; Halloran, Jonathan; Hale, Seth M.; Kaur, Yogeet; Hart, P. John; Kim, Chongwoo A.

2014-01-01

The self-association of sterile alpha motifs (SAMs) into a helical polymer architecture is a critical functional component of many different and diverse array of proteins. For the Drosophila Polycomb group (PcG) protein Polyhomeotic (Ph), its SAM polymerization serves as the structural foundation to cluster multiple PcG complexes, helping to maintain a silenced chromatin state. Ph SAM shares 64% sequence identity with its human ortholog, PHC3 SAM, and both SAMs polymerize. However, in the context of their larger protein regions, PHC3 SAM forms longer polymers compared to Ph SAM. Motivated to establish the precise structural basis for the differences, if any, between Ph and PHC3 SAM, we determined the crystal structure of the PHC3 SAM polymer. PHC3 SAM utilizes the same SAM-SAM interaction as the Ph SAM six-fold repeat polymer. Yet, PHC3 SAM polymerizes utilizing just five SAMs per turn of the helical polymer rather than the typical six per turn observed for all SAM polymers reported to date. Structural analysis suggested that malleability of the PHC3 SAM would allow formation of not just the five-fold repeat structure but possibly others. Indeed, a second PHC3 SAM polymer in a different crystal form forms a six-fold repeat polymer. These results suggest that the polymers formed by PHC3 SAM, and likely others, are quite dynamic. The functional consequence of the variable PHC3 SAM polymers may be to create different chromatin architectures. PMID:25044168

Two-photon polymerization technique for microfabrication of CAD-designed 3D scaffolds from commercially available photosensitive materials.

PubMed

Ovsianikov, Aleksandr; Schlie, Sabrina; Ngezahayo, Anaclet; Haverich, Axel; Chichkov, Boris N

2007-01-01

We report on recent advances in the fabrication of three-dimensional (3D) scaffolds for tissue engineering and regenerative medicine constructs using a two-photon polymerization technique (2PP). 2PP is a novel CAD/CAM technology allowing the fabrication of any computer-designed 3D structure from a photosensitive polymeric material. The flexibility of this technology and the ability to precisely define 3D construct geometry allows issues associated with vascularization and patient-specific tissue fabrication to be directly addressed. The fabrication of reproducible scaffold structures by 2PP is important for systematic studies of cellular processes and better understanding of in vitro tissue formation. In this study, 2PP was applied for the generation of 3D scaffold-like structures, using the photosensitive organic-inorganic hybrid polymer ORMOCER (ORganically MOdified CERamics) and epoxy-based SU8 materials. By comparing the proliferation rates of cells grown on flat material surfaces and under control conditions, it was demonstrated that ORMOCER and SU8 are not cytotoxic. Additional tests show that the DNA strand breaking of GFSHR-17 granulosa cells was not affected by the presence of ORMOCER. Furthermore, gap junction conductance measurements revealed that ORMOCER did not alter the formation of cell-cell junctions, critical for functional tissue growth. The possibilities of seeding 3D structures with cells were analysed. These studies demonstrate the great potential of 2PP technique for the manufacturing of scaffolds with controlled topology and properties.

Determination of volatile polycyclic aromatic hydrocarbons in waters using headspace solid-phase microextraction with a benzyl-functionalized crosslinked polymeric ionic liquid coating.

PubMed

Merdivan, Melek; Pino, Verónica; Anderson, Jared L

2017-08-01

A benzyl-functionalized crosslinked polymeric ionic liquid (PIL), produced through the co-polymerization of the 1-vinylbenzyl-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide (VBHDIM-NTf 2 ) ionic liquid (IL) monomer and 1,12-di(3-vinylbenzylimidazolium)dodecane bis[(trifluoromethyl)sulfonyl]imide ((DVBIM) 2 C 12- 2NTf 2 ) IL crosslinker, was successfully used as a sorbent coating in headspace solid-phase microextraction (SPME) coupled to gas chromatography (GC) with flame-ionization detection (FID) to determine seven volatile polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Optimum extraction conditions for the PAHs when using the novel sorbent include an extraction temperature of 50°C, an ionic strength content adjusted with 30% (w/v) NaCl in the aqueous sample, and an extraction time of 60 min. The extraction performance of the crosslinked PIL fiber was compared to the SPME commercial coating polydimethylsiloxane fiber. The calibration ranges of the studied PAHs were linear in the range of 0.02-20 µg L -1 for the crosslinked PIL fiber. The accuracy of the proposed method was demonstrated by examining the spiked recoveries of seven PAHs which produced values ranging from 67.2% to 130% (for river- and seawater samples), and precision values lower than 9.4% for a spiked level of 1 µg L -1 , and detection limits between 0.01 and 0.04 µg L -1 , which supports the sensitivity of the method using GC-FID.

Pathogenic Roles for Fungal Melanins

PubMed Central

Jacobson, Eric S.

2000-01-01

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

Regulating the surface poly(ethylene glycol) density of polymeric nanoparticles and evaluating its role in drug delivery in vivo.

PubMed

Du, Xiao-Jiao; Wang, Ji-Long; Liu, Wei-Wei; Yang, Jin-Xian; Sun, Chun-Yang; Sun, Rong; Li, Hong-Jun; Shen, Song; Luo, Ying-Li; Ye, Xiao-Dong; Zhu, Yan-Hua; Yang, Xian-Zhu; Wang, Jun

2015-11-01

Poly(ethylene glycol) (PEG) is usually used to protect nanoparticles from rapid clearance in blood. The effects are highly dependent on the surface PEG density of nanoparticles. However, there lacks a detailed and informative study in PEG density and in vivo drug delivery due to the critical techniques to precisely control the surface PEG density when maintaining other nano-properties. Here, we regulated the polymeric nanoparticles' size and surface PEG density by incorporating poly(ε-caprolactone) (PCL) homopolymer into poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-PCL) and adjusting the mass ratio of PCL to PEG-PCL during the nanoparticles preparation. We further developed a library of polymeric nanoparticles with different but controllable sizes and surface PEG densities by changing the molecular weight of the PCL block in PEG-PCL and tuning the molar ratio of repeating units of PCL (CL) to that of PEG (EG). We thus obtained a group of nanoparticles with variable surface PEG densities but with other nano-properties identical, and investigated the effects of surface PEG densities on the biological behaviors of nanoparticles in mice. We found that, high surface PEG density made the nanoparticles resistant to absorption of serum protein and uptake by macrophages, leading to a greater accumulation of nanoparticles in tumor tissue, which recuperated the defects of decreased internalization by tumor cells, resulting in superior antitumor efficacy when carrying docetaxel. Copyright © 2015 Elsevier Ltd. All rights reserved.

Polymethyl methacrylate-co-methacrylic acid coatings with controllable concentration of surface carboxyl groups: A novel approach in fabrication of polymeric platforms for potential bio-diagnostic devices

NASA Astrophysics Data System (ADS)

Hosseini, Samira; Ibrahim, Fatimah; Djordjevic, Ivan; Koole, Leo H.

2014-05-01

The generally accepted strategy in development of bio-diagnostic devices is to immobilize proteins on polymeric surfaces as a part of detection process for diseases and viruses through antibody/antigen coupling. In that perspective, polymer surface properties such as concentration of functional groups must be closely controlled in order to preserve the protein activity. In order to improve the surface characteristics of transparent polymethacrylate plastics that are used for diagnostic devices, we have developed an effective fabrication procedure of polymethylmetacrylate-co-metacrylic acid (PMMA-co-MAA) coatings with controlled number of surface carboxyl groups. The polymers were processed effectively with the spin-coating technique and the detailed control over surface properties is here by demonstrated through the variation of a single synthesis reaction parameter. The chemical structure of synthesized and processed co-polymers has been investigated with nuclear magnetic resonance spectroscopy (NMR) and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-ToF-MS). The surface morphology of polymer coatings have been analyzed with atomic force microscopy (AFM) and scanning electron microscopy (SEM). We demonstrate that the surface morphology and the concentration of surface -COOH groups (determined with UV-vis surface titration) on the processed PMMA-co-MAA coatings can be precisely controlled by variation of initial molar ratio of reactants in the free-radical polymerization reaction. The wettability of developed polymer surfaces also varies with macromolecular structure.

Water-soluble polymers bearing phosphorylcholine group and other zwitterionic groups for carrying DNA derivatives.

PubMed

Lin, Xiaojie; Ishihara, Kazuhiko

2014-01-01

Water-soluble polymers with equal positive and negative charges in the same monomer unit, such as the phosphorylcholine group and other zwitterionic groups, exhibit promising potential in gene delivery with appreciable transfection efficiency, compared with the traditional poly(ethylene glycol)-based polycation-gene complexes. These zwitterionic polymers with various architectural structures and properties have been synthesized by various polymerization methods, such as conventional radical polymerization, atom-transfer radical-polymerization, reversible addition-fragmentation chain-transfer polymerization, and nitroxide-mediated radical polymerization. These techniques have been used to efficiently facilitate gene therapy by fabrication of non-viral vectors with high cytocompatibility, large gene-carrying capacity, effective cell-membrane permeability, and in vivo gene-loading/releasing functionality. Zwitterionic polymer-based gene delivery vectors systems can be categorized into soluble-polymer/gene mixing, molecular self-assembly, and polymer-gene conjugation systems. This review describes the preparation and characterization of various zwitterionic polymer-based gene delivery vectors, specifically water-soluble phospholipid polymers for carrying gene derivatives.

Polymeric Flexible Immunosensor Based on Piezoresistive Micro-Cantilever with PEDOT/PSS Conductive Layer.

PubMed

Zhao, Rui; Sun, Ying

2018-02-03

In this paper, a fully polymeric micro-cantilever with the surface passivation layer of parylene-C and the strain resistor of poly(3,4-ethylenedioxythiophene)/poly (styrene sulfonate) (PEDOT/PSS) was proposed and demonstrated for immunoassays. By optimizing the design and fabrication of the polymeric micro-cantilever, a square resistance of 220 Ω/□ for PEDOT/PSS conductive layer have been obtained. The experimental spring constant and the deflection sensitivity were measured to be 0.017 N/m and 8.59 × 10 -7 nm -1 , respectively. The biological sensing performances of polymeric micro-cantilever were investigated by the immunoassay for human immunoglobulin G (IgG). The immunosensor was experimentally demonstrated to have a linear behavior for the detection of IgG within the concentrations of 10~100 ng/mL with a limit of detection (LOD) of 10 ng/mL. The experimental results indicate that the proposed polymeric flexible conductive layer-based sensors are capable of detecting trace biological substances.

Living supramolecular polymerization realized through a biomimetic approach

NASA Astrophysics Data System (ADS)

Ogi, Soichiro; Sugiyasu, Kazunori; Manna, Swarup; Samitsu, Sadaki; Takeuchi, Masayuki

2014-03-01

Various conventional reactions in polymer chemistry have been translated to the supramolecular domain, yet it has remained challenging to devise living supramolecular polymerization. To achieve this, self-organization occurring far from thermodynamic equilibrium—ubiquitously observed in nature—must take place. Prion infection is one example that can be observed in biological systems. Here, we present an ‘artificial infection’ process in which porphyrin-based monomers assemble into nanoparticles, and are then converted into nanofibres in the presence of an aliquot of the nanofibre, which acts as a ‘pathogen’. We have investigated the assembly phenomenon using isodesmic and cooperative models and found that it occurs through a delicate interplay of these two aggregation pathways. Using this understanding of the mechanism taking place, we have designed a living supramolecular polymerization of the porphyrin-based monomers. Despite the fact that the polymerization is non-covalent, the reaction kinetics are analogous to that of conventional chain growth polymerization, and the supramolecular polymers were synthesized with controlled length and narrow polydispersity.