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Polymers, Volume 3, Issue 4 (December 2011) – 32 articles , Pages 1575-2171

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501 KiB  
Article
Experimentally Justified Model-Like Description of Consolidation of Precipitated Silica
by Hussein Sahabi and Matthias Kind
Polymers 2011, 3(4), 2156-2171; https://doi.org/10.3390/polym3042156 - 20 Dec 2011
Cited by 2 | Viewed by 6267
Abstract
Colloidal gels are intermediates in the production of highly porous particle systems. In the production process, the gels are fragmented after their creation. These gel fragments consolidate to particles whose application-technological properties are determined by their size and porosity. A model of the [...] Read more.
Colloidal gels are intermediates in the production of highly porous particle systems. In the production process, the gels are fragmented after their creation. These gel fragments consolidate to particles whose application-technological properties are determined by their size and porosity. A model of the consolidation process is proposed: The consolidation process of a gel fragment is simulated with the Molecular Dynamics (MD) method with the assumption of van der Waals forces in interplay with the thermal motion as driving forces for the consolidation. The simulation results are compared with experimental data and with a Monte Carlo (MC) simulation. Full article
(This article belongs to the Special Issue Polymer Nanogels and Microgels)
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2754 KiB  
Article
Plasma Treated Multi-Walled Carbon Nanotubes (MWCNTs) for Epoxy Nanocomposites
by Andrew C. Ritts, Qingsong Yu, Hao Li, Stephen J. Lombardo, Xu Han, Zhenhai Xia and Jie Lian
Polymers 2011, 3(4), 2142-2155; https://doi.org/10.3390/polym3042142 - 19 Dec 2011
Cited by 27 | Viewed by 7733
Abstract
Plasma nanocoating of allylamine were deposited on the surfaces of multi-walled carbon nanotubes (MWCNTs) to provide desirable functionalities and thus to tailor the surface characteristics of MWCNTs for improved dispersion and interfacial adhesion in epoxy matrices. Plasma nanocoated MWCNTs were characterized using scanning [...] Read more.
Plasma nanocoating of allylamine were deposited on the surfaces of multi-walled carbon nanotubes (MWCNTs) to provide desirable functionalities and thus to tailor the surface characteristics of MWCNTs for improved dispersion and interfacial adhesion in epoxy matrices. Plasma nanocoated MWCNTs were characterized using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), surface contact angle, and pH change measurements. Mechanical testing results showed that epoxy reinforced with 1.0 wt % plasma coated MWCNTs increased the tensile strength by 54% as compared with the pure epoxy control, while epoxy reinforced with untreated MWCNTs have lower tensile strength than the pure epoxy control. Optical and electron microscopic images show enhanced dispersion of plasma coated MWCNTs in epoxy compared to untreated MWCNTs. Plasma nanocoatings from allylamine on MWCNTs could significantly enhance their dispersion and interfacial adhesion in epoxy matrices. Simulation results based on the shear-lag model derived from micromechanics also confirmed that plasma nanocoating on MWCNTs significantly improved the epoxy/fillers interface bonding and as a result the increased composite strength. Full article
(This article belongs to the Special Issue Polymer-Inorganic Hybrids and Their Applications)
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632 KiB  
Communication
Design of Improved Metal-Organic Framework (MOF) H2 Adsorbents
by Terumi Furuta, Izuru Kanoya, Hiroshi Sakai and Mitsuya Hosoe
Polymers 2011, 3(4), 2133-2141; https://doi.org/10.3390/polym3042133 - 12 Dec 2011
Cited by 8 | Viewed by 8003
Abstract
We attempted synthesis of the hydrogen adsorption material suitable for the fuel cell vehicles (FCEVs). The designed and synthesized Cu2(3,5-Pyridinedicarboxylate)2 (=Cu2PDC2) metal complex showed an extremely high volumetric uptake density for a physisorption material, even though [...] Read more.
We attempted synthesis of the hydrogen adsorption material suitable for the fuel cell vehicles (FCEVs). The designed and synthesized Cu2(3,5-Pyridinedicarboxylate)2 (=Cu2PDC2) metal complex showed an extremely high volumetric uptake density for a physisorption material, even though the specific surface area was only about 1,000 m2 g−1. Factors for high uptake properties are considered to be the increased adsorption sites per unit area, the increased adsorption energy, and the optimized design of pore shapes. High hydrogen uptake on volumetric basis is especially effective for FCEV because the tank volume is reduced. It is expected that property prediction using computational simulation and sophisticated analysis at the micro and nano levels will become an indispensable tool in the design of functional materials. Full article
(This article belongs to the Special Issue Coordination Polymers)
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1332 KiB  
Review
Water Soluble Responsive Polymer Brushes
by Michael P. Weir and Andrew J. Parnell
Polymers 2011, 3(4), 2107-2132; https://doi.org/10.3390/polym3042107 - 07 Dec 2011
Cited by 36 | Viewed by 10934
Abstract
Responsive polymer brushes possess many interesting properties that enable them to control a range of important interfacial behaviours, including adhesion, wettability, surface adsorption, friction, flow and motility. The ability to design a macromolecular response to a wide variety of external stimuli makes polymer [...] Read more.
Responsive polymer brushes possess many interesting properties that enable them to control a range of important interfacial behaviours, including adhesion, wettability, surface adsorption, friction, flow and motility. The ability to design a macromolecular response to a wide variety of external stimuli makes polymer brushes an exciting class of functional materials, and has been made possible by advances in modern controlled polymerization techniques. In this review we discuss the physics of polymer brush response along with a summary of the techniques used in their synthesis. We then review the various stimuli that can be used to switch brush conformation; temperature, solvent quality, pH and ionic strength as well as the relatively new area of electric field actuation We discuss examples of devices that utilise brush conformational change, before highlighting other potential applications of responsive brushes in real world devices. Full article
(This article belongs to the Special Issue Water-Soluble Polymers)
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559 KiB  
Article
Effects of D-Lysine Substitutions on the Activity and Selectivity of Antimicrobial Peptide CM15
by Heather M. Kaminski and Jimmy B. Feix
Polymers 2011, 3(4), 2088-2106; https://doi.org/10.3390/polym3042088 - 06 Dec 2011
Cited by 26 | Viewed by 6397
Abstract
Despite their potent antimicrobial activity, the usefulness of antimicrobial peptides (AMPs) as antibiotics has been limited by their toxicity to eukaryotic cells and a lack of stability in vivo. In the present study we examined the effects of introducing D-lysine residues into [...] Read more.
Despite their potent antimicrobial activity, the usefulness of antimicrobial peptides (AMPs) as antibiotics has been limited by their toxicity to eukaryotic cells and a lack of stability in vivo. In the present study we examined the effects of introducing D-lysine residues into a 15-residue hybrid AMP containing residues 1–7 of cecropin A and residues 2–9 of melittin (designated CM15). Diastereomeric analogs of CM15 containing between two and five D-lysine substitutions were evaluated for their antimicrobial activity, lysis of human erythrocytes, toxicity to murine macrophages, ability to disrupt cell membranes, and protease stability. All of the analogs caused rapid permeabilization of the Staphylococcus aureus cell envelope, as indicated by uptake of SYTOX green. Permeabilization of the plasma membrane of RAW264.7 macrophages was also observed for CM15, but this was substantially diminished for the D-lysine containing analogs. The introduction of D-lysine caused moderate decreases in antimicrobial activity for all analogs studied, with a much more pronounced reduction in toxicity to eukaryotic cells, leading to marked improvements in antimicrobial efficacy. Circular dichroism studies indicated a progressive loss of helical secondary structure upon introduction of D-lysine residues, with a good correspondence between helical content and eukaryotic cell cytotoxicity. Overall, these studies indicate that disruption of amphipathic secondary structure reduces both antimicrobial activity and eukaryotic cell toxicity, but that the reduction in eukaryotic cell cytotoxicity is more pronounced, leading to an overall gain in antimicrobial selectivity. Full article
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1555 KiB  
Communication
Embryonic Stem Cells Maintain an Undifferentiated State on Dendrimer-Immobilized Surface with d-Glucose Display
by Shohreh Mashayekhan, Mee-Hae Kim, Masahiro Kino-oka, Jun-ichi Miyazaki and Masahito Taya
Polymers 2011, 3(4), 2078-2087; https://doi.org/10.3390/polym3042078 - 05 Dec 2011
Cited by 1 | Viewed by 6513
Abstract
In serial passaging cultures of mouse embryonic stem (ES) cells, we employed a dendrimer-immobilized substrate that displayed d-glucose as a terminal ligand. The d-glucose-displaying dendrimer (GLU/D) surface caused the ES cells to form loosely attached spherical colonies, while those on a gelatin-coated surface [...] Read more.
In serial passaging cultures of mouse embryonic stem (ES) cells, we employed a dendrimer-immobilized substrate that displayed d-glucose as a terminal ligand. The d-glucose-displaying dendrimer (GLU/D) surface caused the ES cells to form loosely attached spherical colonies, while those on a gelatin-coated surface formed flatter colonies that were firmly attached to the surface. Despite the morphological similarities between the colonies on the GLU/D surface and aggregates on a conventional bacteriological dish, immunostaining and RT-PCR analyses revealed the maintenance of cells within the spherical colonies on the GLU/D surface in an undifferentiated state with very low expressions of primitive endoderm markers. On the bacteriological dish, however, the cells within the aggregates showed a different cellular state with partial differentiation into the primitive endoderm lineage, and the expression level increased gradually along with the number of passages. These results indicate that the GLU/D surface can be a potential tool for controlling the ES cell morphology and then govern their self-renewal and fate. Full article
(This article belongs to the Special Issue Dendrimers and Hyperbranched Polymers)
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764 KiB  
Review
Mechanisms of Light Energy Harvesting in Dendrimers and Hyperbranched Polymers
by David S. Bradshaw and David L. Andrews
Polymers 2011, 3(4), 2053-2077; https://doi.org/10.3390/polym3042053 - 05 Dec 2011
Cited by 32 | Viewed by 9048
Abstract
Since their earliest synthesis, much interest has arisen in the use of dendritic and structurally allied forms of polymer for light energy harvesting, especially as organic adjuncts for solar energy devices. With the facility to accommodate a proliferation of antenna chromophores, such materials [...] Read more.
Since their earliest synthesis, much interest has arisen in the use of dendritic and structurally allied forms of polymer for light energy harvesting, especially as organic adjuncts for solar energy devices. With the facility to accommodate a proliferation of antenna chromophores, such materials can capture and channel light energy with a high degree of efficiency, each polymer unit potentially delivering the energy of one photon—or more, when optical nonlinearity is involved. To ensure the highest efficiency of operation, it is essential to understand the processes responsible for photon capture and channelling of the resulting electronic excitation. Highlighting the latest theoretical advances, this paper reviews the principal mechanisms, which prove to involve a complex interplay of structural, spectroscopic and electrodynamic properties. Designing materials with the capacity to capture and control light energy facilitates applications that now extend from solar energy to medical photonics. Full article
(This article belongs to the Special Issue Dendrimers and Hyperbranched Polymers)
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815 KiB  
Article
The Influence of Synthesis Parameters on Particle Size and Photoluminescence Characteristics of Ligand Capped Tb3+:LaF3
by Kyle Gipson, Courtney Kucera, Derek Stadther, Kathryn Stevens, John Ballato and Phil Brown
Polymers 2011, 3(4), 2039-2052; https://doi.org/10.3390/polym3042039 - 29 Nov 2011
Cited by 11 | Viewed by 7267
Abstract
Organic ligand surface-treated Tb3+:LaF3 was synthesized in water and methanol for subsequent incorporation into polymethyl methacrylate (PMMA) via solution-precipitation chemistry in order to produce optically active polymer nanocomposites. Nanoparticle agglomerate diameters ranged from 388 ± 188 nm when synthesized in [...] Read more.
Organic ligand surface-treated Tb3+:LaF3 was synthesized in water and methanol for subsequent incorporation into polymethyl methacrylate (PMMA) via solution-precipitation chemistry in order to produce optically active polymer nanocomposites. Nanoparticle agglomerate diameters ranged from 388 ± 188 nm when synthesized in water and 37 ± 2 nm when synthesized in methanol. Suspension stability is paramount for producing optically transparent materials. Methanol nanoparticle synthesized at a pH of 3 exhibited the smallest agglomerate size. Optical spectroscopy, dynamic light scattering, transmission electron microscopy, scanning transmission electron microscopy, and zeta potential analysis were used to characterize the particles synthesized. Full article
(This article belongs to the Special Issue Polymers for Optical Applications)
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1091 KiB  
Article
Incorporation of Hyperbranched Supramolecules into Nafion Ionic Domains via Impregnation and In-Situ Photopolymerization
by Nadzrinahamin A. Nazir, Thein Kyu, Anna M. Reinsel, Matthew Espe, Mami Nosaka, Hiruto Kudo and Tadatomi Nishikubo
Polymers 2011, 3(4), 2018-2038; https://doi.org/10.3390/polym3042018 - 28 Nov 2011
Cited by 16 | Viewed by 11042
Abstract
Nafion membranes were impregnated with photocurable supramolecules, viz., hyperbranched polyester having pendant functional carboxylic acid groups (HBPEAc-COOH) by swelling in methanol and subsequently photocured in-situ after drying. Structure-property relationships of the HBPEAc-COOH impregnated Nafion membranes were analyzed on the basis of Fourier transform [...] Read more.
Nafion membranes were impregnated with photocurable supramolecules, viz., hyperbranched polyester having pendant functional carboxylic acid groups (HBPEAc-COOH) by swelling in methanol and subsequently photocured in-situ after drying. Structure-property relationships of the HBPEAc-COOH impregnated Nafion membranes were analyzed on the basis of Fourier transform infrared (FTIR) spectroscopy, solid-state nuclear magnetic resonance (SSNMR) and dynamic mechanical analysis (DMA). FTIR and SSNMR investigations revealed that about 7 wt % of HBPEAc-COOH was actually incorporated into the ionic domains of Nafion. The FTIR study suggests possible complexation via inter-species hydrogen bonding between the carboxylic groups of HBPEAc-COOH and the sulfonate groups of Nafion. The α-relaxation peak corresponding to the glass transition temperature of the ionic domains of the neat Nafion-acid form was found to increase from ~100 to ~130 °C upon impregnation with enhanced modulus afforded by the cured polyester network within the ionic domains. The AC impedance fuel cell measurement of the impregnated membrane exhibited an increasing trend of proton conductivity with increasing temperature, which eventually surpassed that of neat Nafion above 100 °C. Of particular importance is that the present paper is the first to successfully incorporate polymer molecules/networks into the Nafion ionic domains by means of impregnation with hyperbranched supramolecules followed by in-situ photopolymerization. Full article
(This article belongs to the Special Issue Dendrimers and Hyperbranched Polymers)
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173 KiB  
Review
Role of Antimicrobial Peptides in Inflammatory Bowel Disease
by Jan-Michel Otte and Stefan Vordenbäumen
Polymers 2011, 3(4), 2010-2017; https://doi.org/10.3390/polym3042010 - 16 Nov 2011
Cited by 14 | Viewed by 6261
Abstract
Inflammatory bowel diseases (IBD) are characterized by a chronic relapsing inflammation of the gastrointestinal mucosa. The etiology and pathogenesis of these disorders such as Crohn’s disease and ulcerative colitis are incompletely understood. Recently, antimicrobial peptides, which are expressed by leukocytes and epithelia, have [...] Read more.
Inflammatory bowel diseases (IBD) are characterized by a chronic relapsing inflammation of the gastrointestinal mucosa. The etiology and pathogenesis of these disorders such as Crohn’s disease and ulcerative colitis are incompletely understood. Recently, antimicrobial peptides, which are expressed by leukocytes and epithelia, have been implicated in the pathogenesis of IBD. Antimicrobial peptides are pivotal for intestinal defense, shaping the composition of the luminal flora and contributing thereby to the maintenance of intestinal homeostasis. Apart from their antimicrobial activity affecting commensal bacteria, immunomodulatory properties of antimicrobial peptides have been identified, which link innate and adaptive immune response. There is increasing evidence that alterations in mucosal levels of these peptides contribute to IBD pathogenensis. Full article
506 KiB  
Review
Water Soluble Polymers for Pharmaceutical Applications
by Veeran Gowda Kadajji and Guru V. Betageri
Polymers 2011, 3(4), 1972-2009; https://doi.org/10.3390/polym3041972 - 11 Nov 2011
Cited by 459 | Viewed by 66922
Abstract
Advances in polymer science have led to the development of novel drug delivery systems. Some polymers are obtained from natural resources and then chemically modified for various applications, while others are chemically synthesized and used. A large number of natural and synthetic polymers [...] Read more.
Advances in polymer science have led to the development of novel drug delivery systems. Some polymers are obtained from natural resources and then chemically modified for various applications, while others are chemically synthesized and used. A large number of natural and synthetic polymers are available. In the present paper, only water soluble polymers are described. They have been explained in two categories (1) synthetic and (2) natural. Drug polymer conjugates, block copolymers, hydrogels and other water soluble drug polymer complexes have also been explained. The general properties and applications of different water soluble polymers in the formulation of different dosage forms, novel delivery systems and biomedical applications will be discussed. Full article
(This article belongs to the Special Issue Water-Soluble Polymers)
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849 KiB  
Article
Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization
by Hidetaka Tobita
Polymers 2011, 3(4), 1944-1971; https://doi.org/10.3390/polym3041944 - 11 Nov 2011
Cited by 13 | Viewed by 6506
Abstract
Various types of controlled/living radical polymerizations, or using the IUPAC recommended term, reversible-deactivation radical polymerization (RDRP), conducted inside nano-sized reaction loci are considered in a unified manner, based on the polymerization rate expression, Rp = kp[M]K[Interm]/[ [...] Read more.
Various types of controlled/living radical polymerizations, or using the IUPAC recommended term, reversible-deactivation radical polymerization (RDRP), conducted inside nano-sized reaction loci are considered in a unified manner, based on the polymerization rate expression, Rp = kp[M]K[Interm]/[Trap]. Unique miniemulsion polymerization kinetics of RDRP are elucidated on the basis of the following two factors: (1) A high single molecule concentration in a nano-sized particle; and (2) a significant statistical concentration variation among particles. The characteristic particle diameters below which the polymerization rate start to deviate significantly (1) from the corresponding bulk polymerization, and (2) from the estimate using the average concentrations, can be estimated by using simple equations. For stable-radical-mediated polymerization (SRMP) and atom-transfer radical polymerization (ATRP), an acceleration window is predicted for the particle diameter range, . For reversible-addition-fragmentation chain-transfer polymerization (RAFT), degenerative-transfer radical polymerization (DTRP) and also for the conventional nonliving radical polymerization, a significant rate increase occurs for . On the other hand, for the polymerization rate is suppressed because of a large statistical variation of monomer concentration among particles. Full article
(This article belongs to the Special Issue Living Polymerization Techniques)
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682 KiB  
Article
Synthesis and Characterization of Novel Copper(II) 2D Coordination Polymers from a Fluorinated Flexible Ligand with Remarkable Clathration Ability
by Tomohiro Beni and Kayoko Kasai
Polymers 2011, 3(4), 1934-1943; https://doi.org/10.3390/polym3041934 - 07 Nov 2011
Cited by 44 | Viewed by 5806
Abstract
Two-dimensional (2D) grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyl)tetrafluorobenzene (bpf) with Cu(NO3)2 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf)2(NO3)2]·(biphenyl)2}n (1), {[Cu(bpf)2(NO [...] Read more.
Two-dimensional (2D) grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyl)tetrafluorobenzene (bpf) with Cu(NO3)2 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf)2(NO3)2]·(biphenyl)2}n (1), {[Cu(bpf)2(NO3)2]·(m-C6H4(OMe)2)2}n (2), {[Cu(bpf)2(NO3)2]·PhtBu}n (3) and {[Cu(bpf)2(NO3)(H2O)]NO3·(bpf)0.5}n (4) were determined. The grid networks were held together by C–H···O and C–H···F hydrogen bonds via the NO3 anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds. Full article
(This article belongs to the Special Issue Coordination Polymers)
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1940 KiB  
Review
Water-Soluble Stimuli Responsive Star-Shaped Segmented Macromolecules
by Zacharoula Iatridi and Constantinos Tsitsilianis
Polymers 2011, 3(4), 1911-1933; https://doi.org/10.3390/polym3041911 - 03 Nov 2011
Cited by 59 | Viewed by 13671
Abstract
Star shaped segmented macromolecules constitute an interesting class of polymeric materials whose properties differ remarkably from those appearing in their linear counterparts. This review highlights the work done in the last decade, dealing with the self-assembly of star-shaped block copolymers and terpolymers of [...] Read more.
Star shaped segmented macromolecules constitute an interesting class of polymeric materials whose properties differ remarkably from those appearing in their linear counterparts. This review highlights the work done in the last decade, dealing with the self-assembly of star-shaped block copolymers and terpolymers of various topologies in aqueous media. This article focuses on a specific class of star shaped macromolecules designated as stimuli responsive. These stars bearblock/arms undergo sharp phase transitions upon responding to stimuli, such as temperature, pH, ionic strength and so forth. These transitions impose dramatic transformations on the morphology and, accordingly, in the functionality of the nanostructured associates. The number of arms, the specific functionality and topology of the different arm/blocks and the overall macromolecular architecture of the star polymer, significantly influence their behavior in terms of self-assembly and responsiveness. Full article
(This article belongs to the Special Issue Water-Soluble Polymers)
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221 KiB  
Communication
Bacterial Inactivation Kinetics of Dialdehyde Starch Aqueous Suspension
by Le Song, Samuel R. Farrah and Ronald H. Baney
Polymers 2011, 3(4), 1902-1910; https://doi.org/10.3390/polym3041902 - 03 Nov 2011
Cited by 12 | Viewed by 6840
Abstract
The bacterial inactivation kinetics of dialdehyde starch (DAS) aqueous suspension was studied by the relationship between the minimal lethal concentration (MLC) and the inactivation time at four different temperatures. The relationship between MLC and exposure time was found to follow the first-order Chick-Watson [...] Read more.
The bacterial inactivation kinetics of dialdehyde starch (DAS) aqueous suspension was studied by the relationship between the minimal lethal concentration (MLC) and the inactivation time at four different temperatures. The relationship between MLC and exposure time was found to follow the first-order Chick-Watson law. This first-order inactivation kinetics was modeled by pseudo-first order chemical reaction. This model was validated by the successful predication of the bacterial inactivation response at room temperature. Full article
(This article belongs to the Collection Polysaccharides)
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607 KiB  
Review
Biomedical Activity of Chitin/Chitosan Based Materials—Influence of Physicochemical Properties Apart from Molecular Weight and Degree of N-Acetylation
by Jolanta Kumirska, Mirko X. Weinhold, Jorg Thöming and Piotr Stepnowski
Polymers 2011, 3(4), 1875-1901; https://doi.org/10.3390/polym3041875 - 03 Nov 2011
Cited by 216 | Viewed by 20496
Abstract
The physicochemical nature of chitin and chitosan, which influences the biomedical activity of these compounds, is strongly related to the source of chitin and the conditions of the chitin/chitosan production process. Apart from widely described key factors such as weight-averaged molecular weight (M [...] Read more.
The physicochemical nature of chitin and chitosan, which influences the biomedical activity of these compounds, is strongly related to the source of chitin and the conditions of the chitin/chitosan production process. Apart from widely described key factors such as weight-averaged molecular weight (MW) and degree of N-acetylation (DA), other physicochemical parameters like polydispersity (MW/MN), crystallinity or the pattern of acetylation (PA) have to be taken into consideration. From the biological point of view, these parameters affect a very important factor—the solubility of chitin and chitosan in water and organic solvents. The physicochemical properties of chitosan solutions can be controlled by manipulating solution conditions (temperature, pH, ionic strength, concentration, solvent). The degree of substitution of the hydroxyl and the amino groups or the degree of quaternization of the amino groups also influence the mechanical and biological properties of chitosan samples. Finally, a considerable research effort has been directed towards developing safe and efficient chitin/chitosan-based products because many factors, like the size of nanoparticles, can determine the biomedical characteristics of medicinal products. The influence of these factors on the biomedical activity of chitin/chitosan-based products is presented in this report in more detail. Full article
(This article belongs to the Collection Polysaccharides)
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349 KiB  
Article
One-Dimensional Helical Homochiral Metal-Organic Framework Built from 2,2′-Dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic Acid
by Koichi Tanaka, Yuki Kikumoto and Motoo Shiro
Polymers 2011, 3(4), 1866-1874; https://doi.org/10.3390/polym3041866 - 01 Nov 2011
Cited by 3 | Viewed by 7332
Abstract
A homochiral metal-organic framework (MOF) based on enantiopure (R)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid was synthesized. X-ray crystal diffraction studies revealed that the MOF adopts a one-dimensional infinite right-handed helical tubular structure along the a-axis, which serves as a host for the inclusion of [...] Read more.
A homochiral metal-organic framework (MOF) based on enantiopure (R)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid was synthesized. X-ray crystal diffraction studies revealed that the MOF adopts a one-dimensional infinite right-handed helical tubular structure along the a-axis, which serves as a host for the inclusion of guest dimethylformamide (DMF) molecules. Full article
(This article belongs to the Special Issue Coordination Polymers)
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1124 KiB  
Article
Preparation of Novel Hydrolyzing Urethane Modified Thiol-Ene Networks
by Nicole M. Mackey, Bridget S. Confait, James H. Wynne and J. Paige Buchanan
Polymers 2011, 3(4), 1849-1865; https://doi.org/10.3390/polym3041849 - 25 Oct 2011
Cited by 4 | Viewed by 9911
Abstract
Novel tetra-functional hydrolyzing monomers were prepared from the reaction of TEOS and select alkene-containing alcohols, ethylene glycol vinyl ether or 2-allyloxy ethanol, and combined with trimethylolpropane tris(3-mercaptopropionate) (tri-thiol) in a thiol-ene “click” polymerization reaction to produce clear, colorless thiol-ene networks using both radiation [...] Read more.
Novel tetra-functional hydrolyzing monomers were prepared from the reaction of TEOS and select alkene-containing alcohols, ethylene glycol vinyl ether or 2-allyloxy ethanol, and combined with trimethylolpropane tris(3-mercaptopropionate) (tri-thiol) in a thiol-ene “click” polymerization reaction to produce clear, colorless thiol-ene networks using both radiation and thermal-cure techniques. These networks were characterized for various mechanical characteristics, and found to posses Tg’s (DSC), hardness, tack, and thermal stability (TGA) consistent with their molecular structures. A new ene-modified urethane oligomer was prepared based on the aliphatic polyisocyanate Desmodur® N 3600 and added to the thiol-ene hydrolyzable network series in increasing amounts, creating a phase-segregated material having two Tg’s. An increase in water absorption in the ene-modified urethane formulations leading to a simultaneous increase in the rate of hydrolysis was supported by TGA data, film hardness measurements, and an NMR study of closely related networks. This phenomenon was attributed to the additional hydrogen bonding elements and polar functionality brought to the film with the addition of the urethane segment. SEM was utilized for visual analysis of topographical changes in the film’s surface upon hydrolysis and provides support for surface-driven erosion. Coatings prepared in this study are intended for use as hydrolyzing networks for marine coatings to protect against ship fouling. Full article
(This article belongs to the Special Issue Click Chemistry in Polymer Science)
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937 KiB  
Article
Gold-Poly(methyl methacrylate) Nanocomposite Films for Plasmonic Biosensing Applications
by Mohammed Alsawafta, Simona Badilescu, Abhilash Paneri, Vo-Van Truong and Muthukumaram Packirisamy
Polymers 2011, 3(4), 1833-1848; https://doi.org/10.3390/polym3041833 - 25 Oct 2011
Cited by 52 | Viewed by 9702
Abstract
Gold-poly(methyl methacrylate) nanocomposites are prepared by an in situ method, by irradiating spin-coated films containing the polymer and the gold precursor dissolved in acetone. The reduction of gold ions results in the formation of Au that nucleates and grows within the polymer film. [...] Read more.
Gold-poly(methyl methacrylate) nanocomposites are prepared by an in situ method, by irradiating spin-coated films containing the polymer and the gold precursor dissolved in acetone. The reduction of gold ions results in the formation of Au that nucleates and grows within the polymer film. It is shown that, depending on the energy source, gold nanoparticles with different shapes can be formed. Nanocomposites prepared through UV-, thermal-, and MW-irradiation, respectively, show a low sensitivity toward the environment. However, by annealing the samples at temperatures well above the glass transition temperature of the polymer, the response to dielectric environment appears to be enhanced significantly. The sensitivity of samples synthesized through the three different methods is found to be comparable, around 100 nm/RIU. The increased sensitivity of the annealed sample is accounted for by the increased mobility of both polymer chains and gold nanoparticles in the rubbery state of the material and the presence of the monomer. Gold nanoparticles “freed” from the strong interaction with the polymer are now able to feel the molecules from the surrounding environment. The results show that, by using adequate post-synthesis heat treatments, gold-polymer nanocomposites can be used as plasmonic sensing platforms. Full article
(This article belongs to the Special Issue Polymer-Inorganic Hybrids and Their Applications)
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1294 KiB  
Article
Polymer and Water Dynamics in Poly(vinyl alcohol)/Poly(methacrylate) Networks. A Molecular Dynamics Simulation and Incoherent Neutron Scattering Investigation
by Gaio Paradossi, Ivana Finelli, Francesca Natali, Mark T. F. Telling and Ester Chiessi
Polymers 2011, 3(4), 1805-1832; https://doi.org/10.3390/polym3041805 - 17 Oct 2011
Cited by 20 | Viewed by 10608
Abstract
Chemically cross-linked polymer networks of poly(vinyl alcohol)/poly(methacrylate) form monolitic hydrogels and microgels suitable for biomedical applications, such as in situ tissue replacement and drug delivery. In this work, molecular dynamics (MD) simulation and incoherent neutron scattering methods are used to study the local [...] Read more.
Chemically cross-linked polymer networks of poly(vinyl alcohol)/poly(methacrylate) form monolitic hydrogels and microgels suitable for biomedical applications, such as in situ tissue replacement and drug delivery. In this work, molecular dynamics (MD) simulation and incoherent neutron scattering methods are used to study the local polymer dynamics and the polymer induced modification of water properties in poly(vinyl alcohol)/poly(methacrylate) hydrogels. This information is particularly relevant when the diffusion of metabolites and drugs is a requirement for the polymer microgel functionality. MD simulations of an atomic detailed model of the junction domain at the experimental hydration degree were carried out at 283, 293 and 313 K. The polymer-water interaction, the polymer connectivity and the water dynamics were investigated as a function of temperature. Simulation results are compared with findings of elastic and quasi-elastic incoherent neutron scattering measurements, experimental approaches which sample the same space-time window of MD simulations. This combined analysis shows a supercooled water component and an increase of hydrophilicity and mobility with temperature of these amphiphilic polymer networks. Full article
(This article belongs to the Special Issue Polymer Nanogels and Microgels)
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428 KiB  
Article
Dependence of Optical and Microstructure Properties of Thiol-Capped Silver Nanoparticles Embedded in Polymeric Matrix
by Angela Longo, Gianfranco Carotenuto, Mariano Palomba and Sergio De Nicola
Polymers 2011, 3(4), 1794-1804; https://doi.org/10.3390/polym3041794 - 13 Oct 2011
Cited by 19 | Viewed by 7524
Abstract
Thiol-capped silver nanoparticles were prepared by in situ thermal decomposition of different silver(I)-thiolates precursors in a polymeric matrix. Depending on the structure of the organic coating, contact-free distribution of metal nanoparticles or nanoparticles aggregates were achieved. The structure and morphology of nanocomposites was [...] Read more.
Thiol-capped silver nanoparticles were prepared by in situ thermal decomposition of different silver(I)-thiolates precursors in a polymeric matrix. Depending on the structure of the organic coating, contact-free distribution of metal nanoparticles or nanoparticles aggregates were achieved. The structure and morphology of nanocomposites was analyzed by Transmission Electron Microscopy (TEM), and X-Ray Diffraction (XRD). Nanoparticles’ interaction was investigated by differential scanning calorimetry (DSC), and UV-Visible spectroscopy. In particular, only silver nanoparticles coated by n-alkyl thiols aggregated, while a contact-free dispersion was obtained by cyclohexyl thiol-capped silver nanoparticles. Full article
(This article belongs to the Special Issue Polymers for Optical Applications)
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1103 KiB  
Review
Regeneration Approaches for Dental Pulp and Periapical Tissues with Growth Factors, Biomaterials, and Laser Irradiation
by Chiaki Kitamura, Tatsuji Nishihara, Masamichi Terashita, Yasuhiko Tabata, Eijiro Jimi, Ayako Washio and Shizu Hirata
Polymers 2011, 3(4), 1776-1793; https://doi.org/10.3390/polym3041776 - 12 Oct 2011
Cited by 15 | Viewed by 12608
Abstract
In current dental practice, restorative and endodontic procedures have been developed in an attempt to preserve the vitality of dental pulp after exposure to external stimuli such as caries infection. When damage to dental pulp is reversible, pulp wound healing can proceed, whereas [...] Read more.
In current dental practice, restorative and endodontic procedures have been developed in an attempt to preserve the vitality of dental pulp after exposure to external stimuli such as caries infection. When damage to dental pulp is reversible, pulp wound healing can proceed, whereas irreversible damage induces pathological changes in dental pulp, eventually requiring its removal. Furthermore, dentists sometimes extract non-vital teeth because of severe caries progression, critical size of periapical lesion, and tooth fracture. To overcome the limitations of presently available therapies, it is important to develop regeneration therapy for dental pulp and periapical tissues. In this review, we focus on the regeneration of dental pulp and periapical tissues by application of exogenous growth factors and scaffolds, as well as low-intensity laser irradiation as an auxiliary therapy for regeneration therapy. Full article
(This article belongs to the Special Issue Polymers for Oro-Dental and Cranio- Maxillo-Facial Applications)
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4018 KiB  
Review
Coordination Polymers and Metal Organic Frameworks Derived from 1,2,4-Triazole Amino Acid Linkers
by Anil D. Naik, Marinela M. Dîrtu, Antoine P. Railliet, Jacqueline Marchand-Brynaert and Yann Garcia
Polymers 2011, 3(4), 1750-1775; https://doi.org/10.3390/polym3041750 - 11 Oct 2011
Cited by 57 | Viewed by 11913
Abstract
The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs) and metal-organic frameworks (MOFs) are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has [...] Read more.
The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs) and metal-organic frameworks (MOFs) are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has been established for amine derivatization in amino acids into 1,2,4-triazoles. A set of novel 1,2,4-triazole derivatized amino acids were introduced as superlative precursors in the design of 1D coordination polymers, 2D chiral helicates and 3D metal-organic frameworks. Applications associated with these compounds are diverse and include gas adsorption-porosity partitioning, soft sacrificial matrix for morphology and phase selective cadmium oxide synthesis, FeII spin crossover materials, zinc-b-lactamases inhibitors, logistics for generation of chiral/non-centrosymmetric networks; and thus led to a foundation of a new family of functional CPs and MOFs that are reviewed in this invited contribution. Full article
(This article belongs to the Special Issue Coordination Polymers)
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954 KiB  
Article
Effect of Compatibilization on Poly-ε-Caprolactone Grafting onto Poly(ethylene-co-vinyl alcohol)
by Samira Touhtouh, Frederic Becquart, Caroline Pillon and Mohamed Taha
Polymers 2011, 3(4), 1734-1749; https://doi.org/10.3390/polym3041734 - 11 Oct 2011
Cited by 9 | Viewed by 6964
Abstract
The non-miscibility of the reactants during solvent free poly-ε-caprolactone grafting onto poly(ethylene-co-vinyl alcohol) (EVOH) dramatically affects reaction kinetics. Different solutions were proposed to accelerate the exchange reactions between poly(ethylene-co-vinyl alcohol) and poly-ε-caprolactone. Reactions were conducted in a batch reactor [...] Read more.
The non-miscibility of the reactants during solvent free poly-ε-caprolactone grafting onto poly(ethylene-co-vinyl alcohol) (EVOH) dramatically affects reaction kinetics. Different solutions were proposed to accelerate the exchange reactions between poly(ethylene-co-vinyl alcohol) and poly-ε-caprolactone. Reactions were conducted in a batch reactor or a mini twin-screw extruder. The addition of a poly(ethylene-co-vinyl alcohol)-g-poly-ε-caprolactone copolymer increased the compatibility of the reactants and led to a higher reaction rate. This copolymer was either prepared separately and added at the reaction beginning or prepared in situ grafting caprolactone from EVOH. The reactive system evolution was analyzed using molar mass evolution, microstructure characterization, thermal properties and the reactive blend morphology. The compatibilization effect combined with optimized reaction conditions, such as concentration and nature of catalyst and temperature, resulted in an important increase in reaction rates. Among the tested catalysts, 1,5,7-Triazabicyclo [4.4.0]dec-5-ene was a more efficient catalyst for grafting reactions than Tin (II) 2-ethylhexanoate. Full article
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2313 KiB  
Review
Biodegradable Cell-Seeded Nanofiber Scaffolds for Neural Repair
by Dong Han and Karen C. Cheung
Polymers 2011, 3(4), 1684-1733; https://doi.org/10.3390/polym3041684 - 10 Oct 2011
Cited by 38 | Viewed by 11046
Abstract
Central and peripheral neural injuries are traumatic and can lead to loss of motor and sensory function, chronic pain, and permanent disability. Strategies that bridge the site of injury and allow axonal regeneration promise to have a large impact on restoring quality of [...] Read more.
Central and peripheral neural injuries are traumatic and can lead to loss of motor and sensory function, chronic pain, and permanent disability. Strategies that bridge the site of injury and allow axonal regeneration promise to have a large impact on restoring quality of life for these patients. Engineered materials can be used to guide axonal growth. Specifically, nanofiber structures can mimic the natural extracellular matrix, and aligned nanofibers have been shown to direct neurite outgrowth and support axon regeneration. In addition, cell-seeded scaffolds can assist in the remyelination of the regenerating axons. The electrospinning process allows control over fiber diameter, alignment, porosity, and morphology. Biodegradable polymers have been electrospun and their use in tissue engineering has been demonstrated. This paper discusses aspects of electrospun biodegradable nanofibers for neural regeneration, how fiber alignment affects cell alignment, and how cell-seeded scaffolds can increase the effectiveness of such implants. Full article
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412 KiB  
Article
Metal-Free Polymethyl Methacrylate (PMMA) Nanoparticles by Enamine “Click” Chemistry at Room Temperature
by Lorea Buruaga and José A. Pomposo
Polymers 2011, 3(4), 1673-1683; https://doi.org/10.3390/polym3041673 - 07 Oct 2011
Cited by 26 | Viewed by 9708
Abstract
“Click” chemistry has become an efficient avenue to unimolecular polymeric nanoparticles through the self-crosslinking of individual polymer chains containing appropriate functional groups. Herein we report the synthesis of ultra-small (7 nm in size) polymethyl methacrylate (PMMA) nanoparticles (NPs) by the “metal-free” cross-linking of [...] Read more.
“Click” chemistry has become an efficient avenue to unimolecular polymeric nanoparticles through the self-crosslinking of individual polymer chains containing appropriate functional groups. Herein we report the synthesis of ultra-small (7 nm in size) polymethyl methacrylate (PMMA) nanoparticles (NPs) by the “metal-free” cross-linking of PMMA-precursor chains prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization containing b-ketoester functional groups. Intramolecular collapse was performed by the one-pot reaction of b-ketoester moieties with alkyl diamines in tetrahydrofurane at r.t. (i.e., by enamine formation). The collapsing process was followed by size exclusion chromatography and by nuclear magnetic resonance spectroscopy. The size of the resulting PMMA-NPs was determined by dynamic light scattering. Enamine “click” chemistry increases the synthetic toolbox for the efficient synthesis of metal-free, ultra-small polymeric NPs. Full article
(This article belongs to the Special Issue Click Chemistry in Polymer Science)
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467 KiB  
Article
Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties
by Omar W. Steward, Miles V. Kaltenbach, Ashley B. Biernesser, Matthew J. Taylor, Katie J. Hovan, Jordan J. S. VerPlank, Ameera Haamid, Irina Karpov and Matasebia T. Munie
Polymers 2011, 3(4), 1662-1672; https://doi.org/10.3390/polym3041662 - 07 Oct 2011
Cited by 6 | Viewed by 7778
Abstract
Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function. Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd)2], where M = Co or Ni, and [...] Read more.
Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function. Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd)2], where M = Co or Ni, and quinoxaline; a 1:2:1 molar mixture of [M(acac)2], where M = Co or Ni, 2,2,6,6-tetramethyl-3,5-heptadione and quinoxaline; or a 1:2:1 molar mixture of [Co(acac)2], dibenzoylmethane, and quinoxaline, yielded the crystalline coordination polymers. In the presence of the nitrogenous base, ligand scrambling occurs yielding the most insoluble product. The synthesis and structures of the following wavelike polymers are reported: trans-[Co(DBM)2(qox)]n·nH2O (2), trans-[Co(tmhd)2(qox)]n (3), trans-[Ni(tmhd)2(qox)]n (4), where DBM= dibenzoylmethanate, tmhd= 2,2,6,6-tetramethyl-3,5-heptadionate, and qox = quinoxaline. The wavelike structures are generated by intramolecular steric interactions and crystal packing forces between the chains. Some of the tert-butyl groups show a two-fold disorder. The sine function, φ = A sin 2πx/λ, where φ = distance (Ǻ) along the polymer backbone, λ = wavelength (Ǻ), A = amplitude (Ǻ), x = distance (Ǻ) along the polymer axis, provides a method to approximate and visualize the polymer structures. Full article
(This article belongs to the Special Issue Coordination Polymers)
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499 KiB  
Article
Novel Countercation in MMX-Type Mixed-Valence Chain Compound: Coexistence of Neutral and Protonated Amino Substituents
by Hiroaki Iguchi, Deli Jiang, Jimin Xie, Shinya Takaishi and Masahiro Yamashita
Polymers 2011, 3(4), 1652-1661; https://doi.org/10.3390/polym3041652 - 06 Oct 2011
Cited by 6 | Viewed by 6386
Abstract
The first MMX-type quasi-one-dimensional (Q1D) Pt chain complex (MMX chain) that contains a mono-protonated diamine as countercation, {o-(H3NC6H4NH2)}4[Pt2(pop)4I]·H2O (pop = P2H2O [...] Read more.
The first MMX-type quasi-one-dimensional (Q1D) Pt chain complex (MMX chain) that contains a mono-protonated diamine as countercation, {o-(H3NC6H4NH2)}4[Pt2(pop)4I]·H2O (pop = P2H2O52–), was synthesized. According to the crystal structural analysis, –NH2 group was hydrogen-bonded to either lattice H2O molecule or –NH3+ group in addition to typical hydrogen bond between –NH3+ group and pop ligand. To control the partial deprotonation of the countercation will be an important method for achieving the high-conductive MMX-chain polymer by the hole doping. Full article
(This article belongs to the Special Issue Coordination Polymers)
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2117 KiB  
Review
Polysaccharides: The “Click” Chemistry Impact
by Pierre-Henri Elchinger, Pierre-Antoine Faugeras, Benjamin Boëns, François Brouillette, Daniel Montplaisir, Rachida Zerrouki and Romain Lucas
Polymers 2011, 3(4), 1607-1651; https://doi.org/10.3390/polym3041607 - 27 Sep 2011
Cited by 80 | Viewed by 16039
Abstract
Polysaccharides are complex but essential compounds utilized in many areas such as biomaterials, drug delivery, cosmetics, food chemistry or renewable energy. Modifications and functionalizations of such polymers are often necessary to achieve molecular structures of interest. In this area, the emergence of the [...] Read more.
Polysaccharides are complex but essential compounds utilized in many areas such as biomaterials, drug delivery, cosmetics, food chemistry or renewable energy. Modifications and functionalizations of such polymers are often necessary to achieve molecular structures of interest. In this area, the emergence of the “click” chemistry concept, and particularly the copper-catalyzed version of the Huisgen 1,3-dipolar cycloaddition reaction between terminal acetylenes and azides, had an impact on the polysaccharides chemistry. The present review summarizes the contribution of “click” chemistry in the world of polysaccharides. Full article
(This article belongs to the Collection Polysaccharides)
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230 KiB  
Article
Preparation and Characterization of Organic-Inorganic Hybrid Hydrogel Electrolyte Using Alkaline Solution
by Masanobu Chiku, Shoji Tomita, Eiji Higuchi and Hiroshi Inoue
Polymers 2011, 3(4), 1600-1606; https://doi.org/10.3390/polym3041600 - 26 Sep 2011
Cited by 6 | Viewed by 7201
Abstract
Organic-inorganic hybrid hydrogel electrolytes were prepared by mixing hydrotalcite, cross-linked potassium poly(acrylate) and 6 M KOH solution. The organic-inorganic hybrid hydrogel electrolytes had high ionic conductivity (0.456–0.540 S cm−1) at 30 °C. Moreover, the mechanical strength of the hydrogel electrolytes was [...] Read more.
Organic-inorganic hybrid hydrogel electrolytes were prepared by mixing hydrotalcite, cross-linked potassium poly(acrylate) and 6 M KOH solution. The organic-inorganic hybrid hydrogel electrolytes had high ionic conductivity (0.456–0.540 S cm−1) at 30 °C. Moreover, the mechanical strength of the hydrogel electrolytes was high enough to form a 2–3 mm thick freestanding membrane because of the reinforcement with hydrotalcite. Full article
(This article belongs to the Special Issue Polymer Nanogels and Microgels)
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