Polymers

4898 KiB

Open AccessArticle

Two-Photon-Induced Microstereolithography of Chitosan-g-Oligolactides as a Function of Their Stereochemical Composition

by Tatiana S. Demina, Kseniia N. Bardakova, Nikita V. Minaev, Eugenia A. Svidchenko, Alexander V. Istomin, Galina P. Goncharuk, Leonid V. Vladimirov, Andrey V. Grachev, Alexander N. Zelenetskii, Peter S. Timashev and Tatiana A. Akopova

Polymers 2017, 9(7), 302; https://doi.org/10.3390/polym9070302 - 24 Jul 2017

Cited by 28 | Viewed by 5858

Abstract

Chitosan-g-oligolactide copolymers with relatively long oligolactide grafted chains of various stereochemical compositions have been synthetized via a solvent-free mechanochemical technique and tailored to fabricate three-dimensional hydrogels using two-photon induced microstereolithography. An effect of the characteristics of chitosan and oligolactide used for [...] Read more.

Chitosan-g-oligolactide copolymers with relatively long oligolactide grafted chains of various stereochemical compositions have been synthetized via a solvent-free mechanochemical technique and tailored to fabricate three-dimensional hydrogels using two-photon induced microstereolithography. An effect of the characteristics of chitosan and oligolactide used for the synthesis on the grafting yield and copolymer’s behavior were evaluated using fractional analysis, FTIR-spectroscopy, dynamic light scattering, and UV-spectrophotometry. The lowest copolymer yield was found for the system based on chitosan with higher molecular weight, while the samples consisting of low-molecular weight chitosan showed higher grafting degrees, which were comparable in both the cases of l,l- or l,d-oligolactide grafting. The copolymer processability in the course of two-photon stereolithography was evaluated as a function of the copolymer’s characteristics and stereolithography conditions. The structure and mechanical properties of the model film samples and fabricated 3D hydrogels were studied using optical and scanning electron microscopy, as well as by using tensile and nanoindenter devices. The application of copolymer with oligo(l,d-lactide) side chains led to higher processability during two-photon stereolithography in terms of the response to the laser beam, reproduction of the digital model, and the mechanical properties of the fabricated hydrogels. Full article

(This article belongs to the Collection Polysaccharides)

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2346 KiB

Open AccessArticle

Synthesis and Phase Transition of Poly(N-isopropylacrylamide)-Based Thermo-Sensitive Cyclic Brush Polymer

by Xiaoyan Tu, Chao Meng, Zhe Liu, Lu Sun, Xianshuo Zhang, Mingkui Zhang, Mingrui Sun, Liwei Ma, Mingzhu Liu and Hua Wei

Polymers 2017, 9(7), 301; https://doi.org/10.3390/polym9070301 - 23 Jul 2017

Cited by 30 | Viewed by 6390

Abstract

Polymers with advanced topological architectures are promising materials for wide applications due to their structure-generated unique properties different from that of the linear analogues. The elegant integration of stimuli-responsive polymers with such advanced architectures can create novel materials with virtues from both moieties, [...] Read more.

Polymers with advanced topological architectures are promising materials for wide applications due to their structure-generated unique properties different from that of the linear analogues. The elegant integration of stimuli-responsive polymers with such advanced architectures can create novel materials with virtues from both moieties, are thus a hot subject of research for both fundamental and practical investigations. To fabricate cyclic brush polymer-based intelligent materials for biomedical applications, herein, we designed and synthesized thermo-sensitive cyclic brush polymers with poly(N-isopropylacrylamide) (PNIPAAm) brushes by controlled living radical polymerization using cyclic multimacroinitiator. The thermo-induced phase transition behaviors of the resultant cyclic brush polymers with different compositions were investigated in detail by temperature-dependent optical transmittance measurements, and compared with the properties of bottlebrush and linear counterparts. Interestingly, the cloud point transition temperature (Tcp) of cyclic brush PNIPAAm could be regulated by the chain length of PNIPAAm brush. Although the bottlebrush polymers with the same composition exhibited similarly structurally dependent Tcps behaviors to the cyclic brush polymers, the cyclic brush PNIPAAm did show higher critical aggregation concentration (CAC) and enhanced stability against dilution than the bottlebrush counterpart. The readily tailorable Tcps together with the ability to form highly stable nanoparticles makes thermo-sensitive cyclic brush PNIPAAm a promising candidate for controlled drug delivery. Full article

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5377 KiB

Open AccessArticle

Enhancement of Wound Healing in Normal and Diabetic Mice by Topical Application of Amorphous Polyphosphate. Superior Effect of a Host–Guest Composite Material Composed of Collagen (Host) and Polyphosphate (Guest)

by Werner E.G. Müller, Dinko Relkovic, Maximilian Ackermann, Shunfeng Wang, Meik Neufurth, Andrea Paravic Radicevic, Hiroshi Ushijima, Heinz-C Schröder and Xiaohong Wang

Polymers 2017, 9(7), 300; https://doi.org/10.3390/polym9070300 - 22 Jul 2017

Cited by 31 | Viewed by 6393

Abstract

The effect of polyphosphate (polyP) microparticles on wound healing was tested both in vitro and in a mice model in vivo. Two approaches were used: pure salts of polyphosphate, fabricated as amorphous microparticles (MPs, consisting of calcium and magnesium salts of polyP, “Ca–polyp-MPs” [...] Read more.

The effect of polyphosphate (polyP) microparticles on wound healing was tested both in vitro and in a mice model in vivo. Two approaches were used: pure salts of polyphosphate, fabricated as amorphous microparticles (MPs, consisting of calcium and magnesium salts of polyP, “Ca–polyp-MPs” and “Mg–polyp-MPs”), and host–guest composite particles, prepared from amorphous collagen (host) and polyphosphate (guest), termed “col/polyp-MPs”. Animal experiments with polyP on healing of excisional wounds were performed using both normal mice and diabetic mice. After a healing period of 7 days “Ca–polyp-MP” significantly improved re-epithelialization in normal mice from 31% (control) to 72% (polyP microparticle-treated). Importantly, in diabetic mice, particularly the host–guest particles “col/polyp-MP”, increased the rate of re-epithelialization to ≈40% (control, 23%). In addition, those particles increased the expression of COL-I and COL-III as well as the expression the α-smooth muscle actin and the plasminogen activator inhibitor-1. We propose that “Ca–polyp-MPs”, and particularly the host–guest “col/polyp-MPs” are useful for topical treatment of wounds. Full article

(This article belongs to the Special Issue Host-Guest Polymer Complexes)

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2414 KiB

Open AccessArticle

Upconversion Nanophosphor-Involved Molecularly Imprinted Fluorescent Polymers for Sensitive and Specific Recognition of Sterigmatocystin

by Jing-Min Liu, Feng-Zhen Cao, Guo-Zhen Fang and Shuo Wang

Polymers 2017, 9(7), 299; https://doi.org/10.3390/polym9070299 - 22 Jul 2017

Cited by 16 | Viewed by 5082

Abstract

Originated from the bottom-up synthetic strategy, molecularly imprinted polymers (MIPs) possess the inherent ability of selective and specific recognition and binding of the target analytes, with their structural cavities that can match the target molecules in respect to size, shape, and functional groups. [...] Read more.

Originated from the bottom-up synthetic strategy, molecularly imprinted polymers (MIPs) possess the inherent ability of selective and specific recognition and binding of the target analytes, with their structural cavities that can match the target molecules in respect to size, shape, and functional groups. Herein, based on the high selectivity of MIPs and the fluorescence properties of the β-NaYF₄:Yb³⁺, Er³⁺ upconversion nanoparticles, MIPs with both specificity and fluorescent signals are fabricated to recognize trace sterigmatocystin (ST) with high selectivity and sensitivity. The structure analogue of ST, 1,8-dihydroxyanthraquinone (DT), was employed as the template molecule, acrylamide as the functional monomer, 3-methacryloyloxypropyltrimethoxysilane as the crosslinking agent, and a new molecular imprinting technique of non-aqueous sol-gel method is used to synthesize a molecularly imprinted material with high selectivity to ST. Under optimal conditions, the fluorescence enhancement of fluorescent MIPs increased as the concentration of ST increased. In the range of 0.05–1.0 mg L⁻¹, fluorescence enhancement and the concentration showed a good linear relationship with a detection limit of 0.013 mg L⁻¹. Real sample analysis achieved the recoveries of 83.8–88.8% (RSD 5.1%) for rice, 82.1–87.5% (RSD 4.6%) for maize, and 80.6–89.2% (RSD 3.0%) for soybeans, respectively, revealing the feasibility of the developed method. Full article

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2331 KiB

Open AccessArticle

Additives Type Schiff’s Base as Modifiers of the Optical Response in Holographic Polymer-Dispersed Liquid Crystals

by Sandra Fenoll, Víctor Navarro-Fuster, Manuel Ortuño, Jose Luis Serrano, Andrés Márquez, Sergi Gallego, Inmaculada Pascual and Augusto Beléndez

Polymers 2017, 9(7), 298; https://doi.org/10.3390/polym9070298 - 21 Jul 2017

Cited by 6 | Viewed by 5385

Abstract

Schiff’s bases with specific π-electron system have been synthesized and used as additives in holographic polymer-dispersed liquid crystals. It was observed that these substances modify different parameters such as current intensity, voltage, and diffracted light intensity. In addition, the maximum diffraction efficiency obtained [...] Read more.

Schiff’s bases with specific π-electron system have been synthesized and used as additives in holographic polymer-dispersed liquid crystals. It was observed that these substances modify different parameters such as current intensity, voltage, and diffracted light intensity. In addition, the maximum diffraction efficiency obtained in the reconstruction of the holograms is related to the additive molecule. We propose a relationship between this behavior and the molecular structure of these substances. Full article

(This article belongs to the Special Issue Photo-Responsive Polymers)

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4232 KiB

Open AccessArticle

Biphasic Calcium Phosphate (BCP)-Immobilized Porous Poly (d,l-Lactic-co-Glycolic Acid) Microspheres Enhance Osteogenic Activities of Osteoblasts

by Kyu-Sik Shim, Sung Eun Kim, Young-Pil Yun, Somang Choi, Hak-Jun Kim, Kyeongsoon Park and Hae-Ryong Song

Polymers 2017, 9(7), 297; https://doi.org/10.3390/polym9070297 - 21 Jul 2017

Cited by 7 | Viewed by 6973

Abstract

The purpose of this study was to evaluate the potential of porous poly (d,l-lactic-co-glycolic acid) (PLGA) microspheres (PMSs) immobilized on biphasic calcium phosphate nanoparticles (BCP NPs) (BCP-IM-PMSs) to enhance osteogenic activity. PMSs were fabricated using a fluidic device, and their surfaces [...] Read more.

The purpose of this study was to evaluate the potential of porous poly (d,l-lactic-co-glycolic acid) (PLGA) microspheres (PMSs) immobilized on biphasic calcium phosphate nanoparticles (BCP NPs) (BCP-IM-PMSs) to enhance osteogenic activity. PMSs were fabricated using a fluidic device, and their surfaces were modified with l-lysine (aminated-PMSs), whereas the BCP NPs were modified with heparin–dopamine (Hep-DOPA) to obtain heparinized–BCP (Hep-BCP) NPs. BCP-IM-PMSs were fabricated via electrostatic interactions between the Hep-BCP NPs and aminated-PMSs. The fabricated BCP-IM-PMSs showed an interconnected pore structure. In vitro studies showed that MG-63 cells cultured on BCP-IM-PMSs had increased alkaline phosphatase activity, calcium content, and mRNA expression of osteocalcin (OCN) and osteopontin (OPN) compared with cells cultured on PMSs. These data suggest that BCP NP-immobilized PMSs have the potential to enhance osteogenic activity. Full article

(This article belongs to the Special Issue Advance of Polymers Applied to Biomedical Applications: Cell Scaffolds)

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6723 KiB

Open AccessArticle

Design and Study of a Novel Thermal-Resistant and Shear-Stable Amphoteric Polyacrylamide in High-Salinity Solution

by Caili Dai, Zhongliang Xu, Yining Wu, Chenwei Zou, Xuepeng Wu, Tao Wang, Xu Guo and Mingwei Zhao

Polymers 2017, 9(7), 296; https://doi.org/10.3390/polym9070296 - 21 Jul 2017

Cited by 34 | Viewed by 5987

Abstract

Abstract: Water-soluble polymers are widely used in oilfields. The rheological behaviors of these polymers in high-salinity solution are very important for stimulation of high-salinity reservoirs. In this work, a novel thermal-resistant and shear-stable amphoteric polyacrylamide (PASD), prepared from acrylamide (AM), sodium styrene [...] Read more.

Abstract: Water-soluble polymers are widely used in oilfields. The rheological behaviors of these polymers in high-salinity solution are very important for stimulation of high-salinity reservoirs. In this work, a novel thermal-resistant and shear-stable amphoteric polyacrylamide (PASD), prepared from acrylamide (AM), sodium styrene sulfonate (SSS), and acryloxyethyl trimethylammonium chloride (DAC) monomers, was prepared by free-radical polymerization in high-salinity solution. The amphoteric polyacrylamide was characterized by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance spectroscopy (¹H NMR), elemental analysis, thermogravimetric analysis (TG), and scanning electron microscopy (SEM). The amphoteric polyacrylamide exhibited excellent salinity tolerance. The slow increase in apparent viscosity of the polymer with increase in salinity was interesting. The amphoteric polyacrylamide showed perfect temperature resistance in high-salinity solution. The viscosity retention reached 38.9% at 120 °C and was restored to 87.8% of its initial viscosity when temperature was decreased to room temperature. The retention ratio of apparent viscosity reached 49.7% at 170 s⁻¹ and could still retain it at 25.8% at 1000 s⁻¹. All these results demonstrated that PASD had excellent thermal-resistance and shear-stability in high-salinity solution. We expect that this work could provide a new strategy to design polymers with excellent salinity-tolerance, thermal-resistance, and shear-stability performances. Full article

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4493 KiB

Open AccessArticle

Light-Driven Rotation and Pitch Tuning of Self-Organized Cholesteric Gratings Formed in a Semi-Free Film

by Ling-Ling Ma, Wei Duan, Ming-Jie Tang, Lu-Jian Chen, Xiao Liang, Yan-Qing Lu and Wei Hu

Polymers 2017, 9(7), 295; https://doi.org/10.3390/polym9070295 - 21 Jul 2017

Cited by 25 | Viewed by 6792

Abstract

Cholesteric liquid crystal (CLC) has attracted intensive attention due to its ability to form a periodic helical structure with broad tunability. CLC gratings in open systems are especially promising in sensing and micromanipulation. However, there is still much to learn about the inherent [...] Read more.

Cholesteric liquid crystal (CLC) has attracted intensive attention due to its ability to form a periodic helical structure with broad tunability. CLC gratings in open systems are especially promising in sensing and micromanipulation. However, there is still much to learn about the inherent mechanism of such gratings. We investigate the light-driven rotation and pitch-tuning behaviors of CLC gratings in semi-free films which are formed by spin-coating the CLC mixtures onto planarly photoaligned substrates. The doped azobenzene chiral molecular switch supplies great flexibility to realize the continuous grating rotation. The maximum continuous rotational angle reaches 987.8°. Moreover, dependencies of light-driven rotation and pitch tuning on the dopant concentration and exposure are studied. The model of director configuration in the semi-free film is constructed. Precise beam steering and synchronous micromanipulation are also demonstrated. Our work may provide new opportunities for the CLC grating in applications of beam steering, micromanipulation, and sensing. Full article

(This article belongs to the Special Issue Photo-Responsive Polymers)

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2362 KiB

Open AccessArticle

Gas Barrier, Thermal, Mechanical and Rheological Properties of Highly Aligned Graphene-LDPE Nanocomposites

by Karolina Gaska, Roland Kádár, Andrzej Rybak, Artur Siwek and Stanislaw Gubanski

Polymers 2017, 9(7), 294; https://doi.org/10.3390/polym9070294 - 21 Jul 2017

Cited by 59 | Viewed by 9189

Abstract

This contribution reports on properties of low-density polyethylene-based composites filled with different amounts of graphene nanoplatelets. The studied samples were prepared in the form of films by means of the precoating technique and single screw melt-extrusion, which yields a highly ordered arrangement of [...] Read more.

This contribution reports on properties of low-density polyethylene-based composites filled with different amounts of graphene nanoplatelets. The studied samples were prepared in the form of films by means of the precoating technique and single screw melt-extrusion, which yields a highly ordered arrangement of graphene flakes and results in a strong anisotropy of composites morphology. The performed tests of gas permeability reveal a drastic decrease of this property with increasing filler content. A clear correlation is found between permeability and free volume fraction in the material, the latter evaluated by means of positron annihilation spectroscopy. A strong anisotropy of the thermal conductivity is also achieved and the thermal conductivity along the extrusion direction for samples filled with 7.5 wt % of GnP (graphene nanoplatelets) reached 2.2 W/m·K. At the same time, when measured through a plane, a slight decrease of thermal conductivity is found. The use of GnP filler leads also to improvements of mechanical properties. The increase of Young’s modulus and tensile strength are reached as the composites become more brittle. Full article

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2974 KiB

Open AccessArticle

Self-Assembly of Double Hydrophilic Poly(2-ethyl-2-oxazoline)-b-poly(N-vinylpyrrolidone) Block Copolymers in Aqueous Solution

by Jochen Willersinn and Bernhard V.K.J. Schmidt

Polymers 2017, 9(7), 293; https://doi.org/10.3390/polym9070293 - 20 Jul 2017

Cited by 26 | Viewed by 6593

Abstract

The self-assembly of a novel combination of hydrophilic blocks in water is presented, namely poly(2-ethyl-2-oxazoline)-b-poly(N-vinylpyrrolidone) (PEtOx-b-PVP). The completely water-soluble double hydrophilic block copolymer (DHBC) is formed via copper-catalyzed polymer conjugation, whereas the molecular weight of the PVP [...] Read more.

The self-assembly of a novel combination of hydrophilic blocks in water is presented, namely poly(2-ethyl-2-oxazoline)-b-poly(N-vinylpyrrolidone) (PEtOx-b-PVP). The completely water-soluble double hydrophilic block copolymer (DHBC) is formed via copper-catalyzed polymer conjugation, whereas the molecular weight of the PVP is varied in order to study the effect of block ratio on the self-assembly process. Studies via dynamic light scattering, static light scattering as well as microscopy techniques, e.g., cryo scanning electron microscopy or laser scanning confocal microscopy, show the formation of spherical particles in an aqueous solution with sizes between 300 and 400 nm. Particles of the DHBCs are formed without the influence of external stimuli. Moreover, the efficiency of self-assembly formation relies significantly on the molar ratio of the utilized blocks. The nature of the formed structures relies further on the concentration, and indications of particular and vesicular structures are found. Full article

(This article belongs to the Special Issue Polymers and Block Copolymers at Interfaces and Surfaces)

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20796 KiB

Open AccessArticle

Preparation of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric Silica Nanocomposites Containing Gluconamide Units Possessing Highly Oleophobic/Superhydrophobic, Highly Oleophobic/Superhydrophilic, and Superoleophilic/Superhydrophobic Characteristics on the Modified Surfaces

by Shinsuke Katayama, Shogo Fujii, Tomoya Saito, Shohei Yamazaki and Hideo Sawada

Polymers 2017, 9(7), 292; https://doi.org/10.3390/polym9070292 - 20 Jul 2017

Cited by 5 | Viewed by 5174

Abstract

Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [R_F-(CH₂-CHSi(OMe)₃)_n-R_F (R_F-(VM)_n-R_F)] undergoes the sol-gel reaction in the presence of N-(3-triethoxysilylpropyl)gluconamide [Glu-Si(OEt)₃] under alkaline conditions to afford the corresponding fluorinated oligomeric [...] Read more.

Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [R_F-(CH₂-CHSi(OMe)₃)_n-R_F (R_F-(VM)_n-R_F)] undergoes the sol-gel reaction in the presence of N-(3-triethoxysilylpropyl)gluconamide [Glu-Si(OEt)₃] under alkaline conditions to afford the corresponding fluorinated oligomeric silica nanocomposites containing gluconamide units [R_F-(VM-SiO_3/2)_n-R_F/Glu-SiO_3/2]. These obtained nanocomposites were applied to the surface modification of glass to provide the unique wettability characteristics such as highly oleophobic/superhydrophobic and highly oleophobic/superhydrophilic on the modified surfaces under a variety of conditions. Such a highly oleophobic/superhydrophobic characteristic was also observed on the modified PET (polyethylene terephthalate) fabric swatch, which was prepared under similar conditions, and this modified PET fabric swatch was applied to the separation membrane for the separation of the mixture of fluorocarbon oil and hydrocarbon oil. The R_F-(VM-SiO_3/2)_n-R_F/Glu-SiO_3/2 nanocomposites, which were prepared under lower feed amounts of basic catalyst (ammonia), were found to cause gelation in water. Interestingly, it was demonstrated that these gelling nanocomposites are also applied to the surface modification of the PET fabric swatch to give a highly oleophobic/superhydrophobic characteristic on the surface. On the other hand, the modified glass surfaces treated with the corresponding nanocomposite possessing no gelling ability were found to supply the usual hydrophobic characteristic with a highly oleophobic property. More interestingly, the wettability change on the modified PET fabric swatch from highly oleophobic to superoleophilic was observed, and remained superhydrophobic after immersing the modified PET fabric swatch into water. Full article

(This article belongs to the Special Issue Fluorinated Polymers)

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2541 KiB

Open AccessArticle

Electronically Stabilized Copoly(Styrene-Acrylic Acid) Submicrocapsules Prepared by Miniemulsion Copolymerization

by Minkwan Kim, Yura Hwang and Han Do Ghim

Polymers 2017, 9(7), 291; https://doi.org/10.3390/polym9070291 - 20 Jul 2017

Cited by 5 | Viewed by 4594

Abstract

This work reports the preparation and characterization of poly(styrene-acrylic acid) (St/AA) submicrocapsules by using the miniemulsion copolymerization method. AA was introduced to miniemulsion polymerization of St to increase the zeta potential and the resulting electrostatic stability of St/AA submicrocapsules. Phytoncide oil was adopted [...] Read more.

This work reports the preparation and characterization of poly(styrene-acrylic acid) (St/AA) submicrocapsules by using the miniemulsion copolymerization method. AA was introduced to miniemulsion polymerization of St to increase the zeta potential and the resulting electrostatic stability of St/AA submicrocapsules. Phytoncide oil was adopted as the core model material. Miniemulsion copolymerization of St and AA was conducted at a fixed monomer concentration (0.172 mol) with a varying monomer feed ratio [AA]/[St] (0.2, 0.25, 0.33, 0.5, and 1.0). Concentrations of initiator (azobisisobutyronitrile; 1.0 × 10⁻³, 2.0 × 10⁻³, 3.0 × 10⁻³, and 4.0 × 10⁻³ mol/mol of monomer) and surfactant (sodium dodecyl sulfate; 0.6 × 10⁻³, 1.0 × 10⁻³, and 1.4 × 10⁻³ mol) were also controlled to optimize the miniemulsion copolymerization of St and AA. Dynamic light scattering and microscopic analyses confirmed the optimum condition of miniemulsion copolymerization of St and AA. Long-term colloidal stability of aqueous St/AA submicrocapsule suspension was evaluated by using Turbiscan^TM Lab. In this work, the optimum condition for miniemulsion copolymerization of St and AA was determined ([AA]/[St] = 0.33; [SDS] = 1.0 × 10⁻³ mol; [AIBN] = 2.0 × 10⁻³ mol/mol of monomer). St/AA submicrocapsules prepared at the optimum condition (392.6 nm and −55.2 mV of mean particle size and zeta potential, respectively) showed almost no variations in backscattering intensity (stable colloids without aggregation). Full article

(This article belongs to the Special Issue Emulsion Polymerization)

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3229 KiB

Open AccessArticle

Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes

by Takeru Ito, Saki Otobe, Tatsuma Oda, Tatsuhiro Kojima, Seiji Ono, Masayuki Watanabe, Yoshiki Kiyota, Toshiyuki Misawa, Shinichi Koguchi, Masashi Higuchi, Masaki Kawano and Yu Nagase

Polymers 2017, 9(7), 290; https://doi.org/10.3390/polym9070290 - 20 Jul 2017

Cited by 18 | Viewed by 7743

Abstract

Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is [...] Read more.

Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC₁), were successfully hybridized with heteropolyanions of [PW₁₂O₄₀]³⁻ (PW₁₂) to form inorganic-organic hybrid monomers of MAImC₁-PW₁₂. The synthetic procedure of MAImC₁-PW₁₂ was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC₁-PW₁₂ was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC₁-PW₁₂ was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10⁻⁴ S·cm⁻¹ order under humidified conditions at 313 K. Full article

(This article belongs to the Special Issue Conductive Polymers 2017)

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1540 KiB

Open AccessArticle

Effect of Plasticizer Type on Tensile Property and In Vitro Indomethacin Release of Thin Films Based on Low-Methoxyl Pectin

by Pensak Jantrawut, Tanpong Chaiwarit, Kittisak Jantanasakulwong, Claire Hélène Brachais and Odile Chambin

Polymers 2017, 9(7), 289; https://doi.org/10.3390/polym9070289 - 20 Jul 2017

Cited by 89 | Viewed by 8090

Abstract

This study developed the interests of low-methoxyl pectin (LMP) together with plasticizers for the preparation of elastic thin films. The effect of different plasticizer types (glycerol: Gly; sorbitol: Sor; propylene glycol: PG; and polyethylene glycol 300: PEG 300) and concentrations (20–40% w/w) [...] Read more.

This study developed the interests of low-methoxyl pectin (LMP) together with plasticizers for the preparation of elastic thin films. The effect of different plasticizer types (glycerol: Gly; sorbitol: Sor; propylene glycol: PG; and polyethylene glycol 300: PEG 300) and concentrations (20–40% w/w) on mechanical and thermal properties of LMP films as well as on in vitro release of indomethacin were evaluated. Without any plasticizer, a brittle LMP film with low tensile strength and % elongation at break was obtained. Addition of plasticizers from 20% to 40% caused reduction in the tensile strength and Young’s modulus values, whereas percent elongation was increased. Forty percent Gly-plasticized and PG-plasticized films were selected to deliver indomethacin in comparison with non-plasticized film. No significant difference in indomethacin release profiles was displayed between the films. The analysis of indomethacin release model indicated that more than one drug release mechanism from the film formulation was involved and possibly the combination of both diffusion and erosion. Even though indomethacin incorporated in non-plasticized film showed similar release profile, Gly or PG should be added to enhanced film flexibility and decrease film brittleness. Full article

(This article belongs to the Collection Polysaccharides)

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3588 KiB

Open AccessArticle

Ultra High Electrical Performance of Nano Nickel Oxide and Polyaniline Composite Materials

by Xiaomin Cai, Xiuguo Cui, Lei Zu, You Zhang, Xing Gao, Huiqin Lian, Yang Liu and Xiaodong Wang

Polymers 2017, 9(7), 288; https://doi.org/10.3390/polym9070288 - 20 Jul 2017

Cited by 33 | Viewed by 7192

Abstract

The cooperative effects between the PANI (polyaniline)/nano-NiO (nano nickel oxide) composite electrode material and redox electrolytes (potassium iodide, KI) for supercapacitor applications was firstly discussed in this article, providing a novel method to prepare nano-NiO by using β-cyelodextrin (β-CD) as the template agent. [...] Read more.

The cooperative effects between the PANI (polyaniline)/nano-NiO (nano nickel oxide) composite electrode material and redox electrolytes (potassium iodide, KI) for supercapacitor applications was firstly discussed in this article, providing a novel method to prepare nano-NiO by using β-cyelodextrin (β-CD) as the template agent. The experimental results revealed that the composite electrode processed a high specific capacitance (2122.75 F·g⁻¹ at 0.1 A·g⁻¹ in 0.05 M KI electrolyte solution), superior energy density (64.05 Wh·kg⁻¹ at 0.2 A·g⁻¹ in the two-electrode system) and excellent cycle performance (86% capacitance retention after 1000 cycles at 1.5 A·g⁻¹). All those ultra-high electrical performances owe to the KI active material in the electrolyte and the PANI coated nano-NiO structure. Full article

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4631 KiB

Open AccessArticle

A New Type of Photo-Thermo Staged-Responsive Shape-Memory Polyurethanes Network

by Jinghao Yang, Hao Wen, Haitao Zhuo, Shaojun Chen and Jianfeng Ban

Polymers 2017, 9(7), 287; https://doi.org/10.3390/polym9070287 - 19 Jul 2017

Cited by 22 | Viewed by 5463

Abstract

In this paper, we developed a photo-thermo staged-responsive shape-memory polymer network which has a unique ability of being spontaneously photo-responsive deformable and thermo-responsive shape recovery. This new type of shape-memory polyurethane network (A-SMPUs) was successfully synthesized with 4,4-azodibenzoic acid (Azoa), hexamethylenediisocyanate (HDI) and [...] Read more.

In this paper, we developed a photo-thermo staged-responsive shape-memory polymer network which has a unique ability of being spontaneously photo-responsive deformable and thermo-responsive shape recovery. This new type of shape-memory polyurethane network (A-SMPUs) was successfully synthesized with 4,4-azodibenzoic acid (Azoa), hexamethylenediisocyanate (HDI) and polycaprolactone (PCL), followed by chemical cross-linking with glycerol (Gl). The structures, morphology, and shape-memory properties of A-SMPUs have been carefully investigated. The results demonstrate that the A-SMPUs form micro-phase separation structures consisting of a semi-crystallized PCL soft phase and an Azoa amorphous hard phase that could influence the crystallinity of PCL soft phases. The chemical cross-linking provided a stable network and good thermal stability to the A-SMPUs. All A-SMPUs exhibited good triple-shape-memory properties with higher than 97% shape fixity ratio and 95% shape recovery ratio. Additionally, the A-SMPUs with higher Azoa content exhibited interesting photo-thermo two-staged responsiveness. A pre-processed film with orientated Azoa structure exhibited spontaneous curling deformation upon exposing to ultraviolet (UV) light, and curling deformation is constant even under Vis light. Finally, the curling deformation can spontaneously recover to the original shape by applying a thermal stimulus. This work demonstrates new synergistically multi-responsive SMPUs that will have many applications in smart science and technology. Full article

(This article belongs to the Special Issue Shape Memory Polymers)

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Open AccessArticle

Effect of Drug Loading Method and Drug Physicochemical Properties on the Material and Drug Release Properties of Poly (Ethylene Oxide) Hydrogels for Transdermal Delivery

by Rachel Shet Hui Wong and Kalliopi Dodou

Polymers 2017, 9(7), 286; https://doi.org/10.3390/polym9070286 - 19 Jul 2017

Cited by 56 | Viewed by 7818

Abstract

Novel poly (ethylene oxide) (PEO) hydrogel films were synthesized via UV cross-linking with pentaerythritol tetra-acrylate (PETRA) as cross-linking agent. The purpose of this work was to develop a novel hydrogel film suitable for passive transdermal drug delivery via skin application. Hydrogels were loaded [...] Read more.

Novel poly (ethylene oxide) (PEO) hydrogel films were synthesized via UV cross-linking with pentaerythritol tetra-acrylate (PETRA) as cross-linking agent. The purpose of this work was to develop a novel hydrogel film suitable for passive transdermal drug delivery via skin application. Hydrogels were loaded with model drugs (lidocaine hydrochloride (LID), diclofenac sodium (DIC) and ibuprofen (IBU)) via post-loading and in situ loading methods. The effect of loading method and drug physicochemical properties on the material and drug release properties of medicated film samples were characterized using scanning electron microscopy (SEM), swelling studies, differential scanning calorimetry (DSC), fourier transform infrared spectroscopy (FT-IR), tensile testing, rheometry, and drug release studies. In situ loaded films showed better drug entrapment within the hydrogel network and also better polymer crystallinity. High drug release was observed from all studied formulations. In situ loaded LID had a plasticizing effect on PEO hydrogel, and films showed excellent mechanical properties and prolonged drug release. The drug release mechanism for the majority of medicated PEO hydrogel formulations was determined as both drug diffusion and polymer chain relaxation, which is highly desirable for controlled release formulations. Full article

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Open AccessArticle

Dependency of Anion and Chain Length of Imidazolium Based Ionic Liquid on Micellization of the Block Copolymer F127 in Aqueous Solution: An Experimental Deep Insight

by Jignesh Lunagariya, Nadavala Siva Kumar, Mohammad Asif, Abhishek Dhar and Rohit L. Vekariya

Polymers 2017, 9(7), 285; https://doi.org/10.3390/polym9070285 - 19 Jul 2017

Cited by 15 | Viewed by 6922

Abstract

The non-ionic triblock copolymer, Pluronic^® F127, has been selected to observe its interaction with ionic liquids (ILs) in aqueous solutions by using DLS, surface tension, and viscosity measurements. The Critical Micelle Concentration (CMC) of F127 increased with the addition of ILs, which [...] Read more.

The non-ionic triblock copolymer, Pluronic^® F127, has been selected to observe its interaction with ionic liquids (ILs) in aqueous solutions by using DLS, surface tension, and viscosity measurements. The Critical Micelle Concentration (CMC) of F127 increased with the addition of ILs, which appeared logical since it increases the solubility of PPO (and PEO) moiety, making it behaves more like a hydrophilic block copolymer that is micellized at a higher copolymer concentration. The results from DLS data showed good agreement with those obtained from the surface tension measurements. Upon the addition of ILs, the tendency in micellar size reduction was demonstrated by viscosity results, and therefore, intrinsic viscosity decreased compared to pure F127 in aqueous solution. The results were discussed as a function of alkyl chain length and anions of imidazolium based ILs. Full article

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Open AccessArticle

Three Carbazole-Based Polymers as Potential Anodically Coloring Materials for High-Contrast Electrochromic Devices

by Yuh-Shan Su and Tzi-Yi Wu

Polymers 2017, 9(7), 284; https://doi.org/10.3390/polym9070284 - 18 Jul 2017

Cited by 23 | Viewed by 5486

Abstract

Three carbazole-based conjugated polymers (poly(3,6-di(2-thienyl)carbazole) (PDTC), poly(2,7-bis(carbazol-9-yl)-9,9-spirobifluorene) (PS2CBP), and poly(3,6-bis(N-carbazole)-N-ethylcarbazole) (PCEC)) are synthesized using electrochemical polymerization. The spectroelectrochemical studies indicate that the PDTC, PS2CBP, and PCEC films show reversible electrochromic behaviors in their redox states, and the PS2CBP film [...] Read more.

Three carbazole-based conjugated polymers (poly(3,6-di(2-thienyl)carbazole) (PDTC), poly(2,7-bis(carbazol-9-yl)-9,9-spirobifluorene) (PS2CBP), and poly(3,6-bis(N-carbazole)-N-ethylcarbazole) (PCEC)) are synthesized using electrochemical polymerization. The spectroelectrochemical studies indicate that the PDTC, PS2CBP, and PCEC films show reversible electrochromic behaviors in their redox states, and the PS2CBP film shows a distinct color transition with four various colors (gray at 0 V, grayish-green at 1.0 V, moss green at 1.2 V, and foliage green at 1.4 V). The maximum optical contrast of the PS2CBP and PCEC films is 39.83% at 428 nm and 32.41% at 420 nm, respectively, in an ionic liquid solution. Dual-type electrochromic devices (ECDs) that employ PDTC, PS2CBP, or PCEC film as an anodic layer, and PProDOT-Et₂ film as a cathodic layer, were constructed. The as-prepared PCEC/PProDOT-Et₂ ECD shows high optical contrast (38.25% at 586 nm) and high coloration efficiency (369.85 cm² C⁻¹ at 586 nm), and the PS2CBP/PProDOT-Et₂ ECD shows high optical contrast (34.45% at 590 nm), good optical memory, and good long-term cycling stability. Full article

(This article belongs to the Special Issue Polymeric Materials for Optical Applications)

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24576 KiB

Open AccessCommunication

Fabrication and Test of an Inflated Circular Diaphragm Dielectric Elastomer Generator Based on PDMS Rubber Composite

by Giacomo Moretti, Michele Righi, Rocco Vertechy and Marco Fontana

Polymers 2017, 9(7), 283; https://doi.org/10.3390/polym9070283 - 15 Jul 2017

Cited by 38 | Viewed by 9014

Abstract

This paper introduces a fabrication method and the experimental characterization of a soft polymeric energy converter manufactured using a combination of dielectric and conductive polydimethylsiloxane elastomers. The presented system is an inflated circular diaphragm dielectric elastomer generator; i.e., a deformable electrostatic transducer that [...] Read more.

This paper introduces a fabrication method and the experimental characterization of a soft polymeric energy converter manufactured using a combination of dielectric and conductive polydimethylsiloxane elastomers. The presented system is an inflated circular diaphragm dielectric elastomer generator; i.e., a deformable electrostatic transducer that converts the mechanical work done by a time-varying pressure into electricity. A prototype of the system is realized on the basis of a simple fabrication procedure that makes use of commercially available silicone dielectric elastomer films and custom-prepared deformable conductive electrodes. A test-bench is developed and employed to estimate the energy conversion performance. Remarkable results are obtained, such as an amount of energy converted per cycle of up to 0.3 J, converted power of up to 0.15 W, energy per unit of employed elastomer mass of up to 173 J/kg, and fraction of the input mechanical work converted into electricity of 30%. Full article

(This article belongs to the Special Issue Electroactive Polymers and Gels)

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Open AccessFeature PaperArticle

“Living” Polymerization of Ethylene and 1-Hexene Using Novel Binuclear Pd–Diimine Catalysts

by Jianding Ye and Zhibin Ye

Polymers 2017, 9(7), 282; https://doi.org/10.3390/polym9070282 - 15 Jul 2017

Cited by 3 | Viewed by 7103

Abstract

We report the synthesis of two novel binuclear Pd–diimine catalysts and their unique behaviors in initiating “living” polymerization of ethylene and 1-hexene. These two binuclear catalysts, [(N^N)Pd(CH₂)₃C(O)O(CH₂)_mO(O)C(CH₂)₃Pd(N^N)](SbF₆)₂ ( [...] Read more.

We report the synthesis of two novel binuclear Pd–diimine catalysts and their unique behaviors in initiating “living” polymerization of ethylene and 1-hexene. These two binuclear catalysts, [(N^N)Pd(CH₂)₃C(O)O(CH₂)_mO(O)C(CH₂)₃Pd(N^N)](SbF₆)₂ (3a: m = 4, 3b: m = 6) (N^N≡ArN=C(Me)–(Me)C=NAr, Ar≡2,6–(iPr)₂C₆H₃), were synthesized by simply reacting [(N^N)Pd(CH₃)(N≡CMe)]SbF₆ (1) with diacrylates, 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate, respectively. Their unique binuclear structure with two identical Pd–diimine acrylate chelates covalently linked together through an ester linkage was confirmed by NMR and single crystal XRD measurements. Ethylene “living” polymerizations were carried out at 5 °C and under ethylene pressure of 400 and 100 psi, respectively, with the binuclear catalysts, along with a mononuclear chelate catalyst, [(N^N)Pd(CH₂)₃C(O)OMe]SbF₆ (2), for comparison. All the polyethylenes produced with both binuclear catalysts show bimodal molecular weight distribution with the number-average molecular weight of the higher molecular weight portion being approximately twice that of the lower molecular weight portion. The results demonstrate the presence of monofunctional chain growing species resembling catalyst 2, in addition to the expected bifunctional species leading to bifunctional “living” polymerization, in the polymerization systems. Both types of chain growing species exhibit “living” characteristics under the studied conditions, leading to the simultaneous linear increase of molecular weight in both portions. However, when applied for the “living” polymerization of 1-hexene, the binuclear catalyst 3a leads to polymers with only monomodal molecular weight distribution, indicating the sole presence of monofunctional chain growing species. These two binuclear catalysts are the first Pd–diimine catalysts capable of initiating bifunctional ethylene “living” polymerization. Full article

(This article belongs to the Special Issue Tailored Polymer Synthesis by Advanced Polymerization Techniques)

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9601 KiB

Open AccessArticle

PES/POSS Soluble Veils as Advanced Modifiers for Multifunctional Fiber Reinforced Composites

by Gianluca Cicala, Ignazio Blanco, Alberta Latteri, Giulia Ognibene, Francesco Agatino Bottino and Maria Elena Fragalà

Polymers 2017, 9(7), 281; https://doi.org/10.3390/polym9070281 - 13 Jul 2017

Cited by 19 | Viewed by 6155

Abstract

Novel polyhedral oligomeric silsesquioxanes (POSS)-filled thermoplastic electrospun veils were used to tailor the properties of the interlaminar region of epoxy-based composites. The veils were designed to be soluble upon curing in the epoxy matrix, so that POSS could be released within the interlaminar [...] Read more.

Novel polyhedral oligomeric silsesquioxanes (POSS)-filled thermoplastic electrospun veils were used to tailor the properties of the interlaminar region of epoxy-based composites. The veils were designed to be soluble upon curing in the epoxy matrix, so that POSS could be released within the interlaminar region. Three different POSS contents, varying from 1 to 10 wt %, were tested while the percentage of coPolyethersulphone (coPES) dissolved in the epoxy resin was kept to a fixed value of 10 wt %. Good quality veils could be obtained at up to 10 wt % of POSS addition, with the nanofibers’ diameters varying from 861 nm for the coPES to 428 nm upon POSS addition. The feasibility of the soluble veils to disperse POSS in the interlaminar region was proved, and the effect of POSS on phase morphology and viscoelastic properties studied. POSS was demonstrated to significantly affect the morphology and viscoelastic properties of epoxy composites, especially for the percentages 1% and 5%, which enabled the composites to avoid POSS segregates occurring. A dynamic mechanical analysis showed a significant improvement to the storage modulus, and a shift of more than 30 °C due to the POSS cages hindering the motion of the molecular chains and network junctions. Full article

(This article belongs to the Special Issue Polymer Nanocomposites)

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10725 KiB

Open AccessReview

Vesicles from Amphiphilic Dumbbells and Janus Dendrimers: Bioinspired Self-Assembled Structures for Biomedical Applications

by Soraya Taabache and Annabelle Bertin

Polymers 2017, 9(7), 280; https://doi.org/10.3390/polym9070280 - 12 Jul 2017

Cited by 20 | Viewed by 10985

Abstract

The current review focuses on vesicles obtained from the self-assembly of two types of dendritic macromolecules, namely amphiphilic Janus dendrimers (forming dendrimersomes) and amphiphilic dumbbells. In the first part, we will present some synthetic strategies and the various building blocks that can be [...] Read more.

The current review focuses on vesicles obtained from the self-assembly of two types of dendritic macromolecules, namely amphiphilic Janus dendrimers (forming dendrimersomes) and amphiphilic dumbbells. In the first part, we will present some synthetic strategies and the various building blocks that can be used to obtain dendritic-based macromolecules, thereby showing their structural versatility. We put our focus on amphiphilic Janus dendrimers and amphiphilic dumbbells that form vesicles in water but we also encompass vesicles formed thereof in organic solvents. The second part of this review deals with the production methods of these vesicles at the nanoscale but also at the microscale. Furthermore, the influence of various parameters (intrinsic to the amphiphilic JD and extrinsic—from the environment) on the type of vesicle formed will be discussed. In the third part, we will review the numerous biomedical applications of these vesicles of nano- or micron-size. Full article

(This article belongs to the Special Issue Bio-inspired and Bio-based Polymers)

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1782 KiB

Open AccessArticle

Hydrogenolysis and Activation of Soda Lignin Using [BMIM]Cl as a Catalyst and Solvent

by Shengming Zhang, Liang Liu, Guizhen Fang, Ning Yan, Shixue Ren and Yanli Ma

Polymers 2017, 9(7), 279; https://doi.org/10.3390/polym9070279 - 12 Jul 2017

Cited by 14 | Viewed by 4681

Abstract

To improve the reactivity of the soda lignin, an acid ionic liquid 1-butyl-3-mthylimidazolium chloride ([BMIM]Cl) was used as the catalyst and solvent to degrade the soda lignin through hydrogenolysis. Structural elucidation of the lignin samples was conducted by using a combination of analytical [...] Read more.

To improve the reactivity of the soda lignin, an acid ionic liquid 1-butyl-3-mthylimidazolium chloride ([BMIM]Cl) was used as the catalyst and solvent to degrade the soda lignin through hydrogenolysis. Structural elucidation of the lignin samples was conducted by using a combination of analytical methods including chemical analysis, ultraviolet spectrophotometry (UV spectrophotometry), Fourier transform infrared spectroscopy (FT-IR spectra), two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR) techniques, and gel permeation chromatography (GPC). The antioxidant activities of the lignin samples were evaluated using the diammonium 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS⁺) radical scavenging and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging methods. The degradation mechanism was proposed based on the characterization results. The optimal reaction condition was as follows: the concentration of [BMIM]Cl in the solution was 10 wt %, the hydrogen initial pressure was 3 MPa, and the solution was heated for 4 h at 90 °C. After the reaction, the total hydroxyl content of the soda lignin increased by 81.3%, while the phenolic hydroxyl content increased by 23.1%. At the same time, the weight-average molar mass of the soda lignin sample decreased from 8220 to 6450 g/mol with an improved antioxidant activity. In addition, approximately 56.7% of the β-O-4 linkages were degraded in the lreaction. The main effect of the acid ionic liquid [BMIM]C1 was related to the cleavage of β-O-4 linkages. This study has shown the potential of using the catalyzed soda lignin as a natural polymer antioxidant. Full article

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Open AccessArticle

Modeling Diffractive Lenses Recording in Environmentally Friendly Photopolymer

by Roberto Fernández, Víctor Navarro-Fuster, Francisco Javier Martínez, Sergi Gallego, Andrés Márquez, Inmaculada Pascual and Augusto Beléndez

Polymers 2017, 9(7), 278; https://doi.org/10.3390/polym9070278 - 12 Jul 2017

Cited by 4 | Viewed by 4723

Abstract

The improvements made in diffusion models simulating phase image recording in photopolymers enable the optimization of a wide range of complex diffractive optical elements (DOEs), while the miniaturization of spatial light modulators makes it possible to generate both symmetric and non-symmetric DOEs. In [...] Read more.

The improvements made in diffusion models simulating phase image recording in photopolymers enable the optimization of a wide range of complex diffractive optical elements (DOEs), while the miniaturization of spatial light modulators makes it possible to generate both symmetric and non-symmetric DOEs. In addition, there is increasing interest in the design of new friendly recording materials. In this respect, photopolymers are a promising material due to their optical properties. In this paper, we show a procedure to record diffractive spherical lenses using a nontoxic optimized photopolymer. To achieve this goal, we followed three steps: first, the chemical optimization for DOE recording; second, the recording material characterization to be simulated by a three-dimensional diffusion model; and third, the evaluation of the coverplating for the conservation of the DOE. Full article

(This article belongs to the Special Issue Photo-Responsive Polymers)

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Open AccessArticle

Microporous Polyurethane Thin Layer as a Promising Scaffold for Tissue Engineering

by Justyna Kucińska-Lipka, Iga Gubanska and Anna Skwarska

Polymers 2017, 9(7), 277; https://doi.org/10.3390/polym9070277 - 11 Jul 2017

Cited by 19 | Viewed by 6085

Abstract

The literature describes that the most efficient cell penetration takes place at 200–500 µm depth of the scaffold. Many different scaffold fabrication techniques were described to reach these guidelines. One such technique is solvent casting particulate leaching (SC/PL). The main advantage of this [...] Read more.

The literature describes that the most efficient cell penetration takes place at 200–500 µm depth of the scaffold. Many different scaffold fabrication techniques were described to reach these guidelines. One such technique is solvent casting particulate leaching (SC/PL). The main advantage of this technique is its simplicity and cost efficiency, while its main disadvantage is the scaffold thickness, which is usually not less than 3000 µm. Thus, the scaffold thickness is usually far from the requirements for functional tissue reconstruction. In this paper, we report a successful fabrication of the microporous polyurethane thin layer (MPTL) of 1 mm thick, which was produced using SC/PL technique combined with phase separation (PS). The obtained MPTL was highly porous (82%), had pore size in the range of 65–426 µm and scaffold average pore size was equal to 154 ± 3 µm. Thus, it can be considered a suitable scaffold for tissue engineering purpose, according to the morphology criterion. Polyurethane (PUR) processing into MPTL scaffold caused significant decrease of contact angle from 78 ± 4° to 56 ± 6° and obtained MPTL had suitable hydrophilic characteristic for mammalian cells growth and tissue regeneration. Mechanical properties of MPTL were comparable to the properties of native tissues. As evidenced by biotechnological examination the MPTL were highly biocompatible with no observed apparent toxicity on mouse embryonic NIH 3T3 fibroblast cells. Performed studies indicated that obtained MPTL may be suitable scaffold candidate for soft TE purposes such as blood vessels. Full article

(This article belongs to the Special Issue Advance of Polymers Applied to Biomedical Applications: Biointerface)

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3143 KiB

Open AccessArticle

Smart Poly(imidazoyl-l-lysine): Synthesis and Reversible Helix-to-Coil Transition at Neutral pH

by Estefania Piedra-Arroni, Fatma Makni, Laura Severac, Jean-Luc Stigliani, Geneviève Pratviel and Colin Bonduelle

Polymers 2017, 9(7), 276; https://doi.org/10.3390/polym9070276 - 11 Jul 2017

Cited by 12 | Viewed by 9263

Abstract

Polypeptide polymers can adopt natural protein secondary structures such as α-helices or β-sheets, and this unique feature is at the origin of some intriguing physico–chemical properties. In this work, we present how side chain imidazoylation of a poly(l-lysine) scaffold affords the [...] Read more.

Polypeptide polymers can adopt natural protein secondary structures such as α-helices or β-sheets, and this unique feature is at the origin of some intriguing physico–chemical properties. In this work, we present how side chain imidazoylation of a poly(l-lysine) scaffold affords the preparation of poly(histidine) counterparts exhibiting α-helix conformation. This structuring behavior is reversible and can be controlled by means of pH and or temperature changes. Full article

(This article belongs to the Special Issue Polypeptide Containing Polymers)

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2901 KiB

Open AccessArticle

Structure of Amphiphilic Terpolymer Raspberry Vesicles

by Yingying Guo, Luca Di Mare, Robert K. Y. Li and Janet S. S. Wong

Polymers 2017, 9(7), 275; https://doi.org/10.3390/polym9070275 - 09 Jul 2017

Cited by 4 | Viewed by 5749

Abstract

Terpolymer raspberry vesicles contain domains of different chemical affinities. They are potential candidates as multi-compartment cargo carriers. Their efficacy depends on their stability and load capacity. Using a model star terpolymer system in an aqueous solution, a dissipative particle dynamic (DPD) simulation is [...] Read more.

Terpolymer raspberry vesicles contain domains of different chemical affinities. They are potential candidates as multi-compartment cargo carriers. Their efficacy depends on their stability and load capacity. Using a model star terpolymer system in an aqueous solution, a dissipative particle dynamic (DPD) simulation is employed to investigate how equilibrium aggregate structures are affected by polymer concentration and pairwise interaction energy in a solution. It is shown that a critical mass of polymer is necessary for vesicle formation. The free energy of the equilibrium aggregates are calculated and the results show that the transition from micelles to vesicles is governed by the interactions between the longest solvophobic block and the solvent. In addition, the ability of vesicles to encapsulate solvent is assessed. It is found that reducing the interaction energy favours solvent encapsulation, although solvent molecules can permeate through the vesicle’s shell when repulsive interactions among monomers are low. Thus, one can optimize the loading capacity and the release rate of the vesicles by turning pairwise interaction energies of the polymer and the solvent. The ability to predict and control these aspects of the vesicles is an essential step towards designing vesicles for specific purposes. Full article

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2857 KiB

Open AccessArticle

A Rapid and Efficient Route to Preparation of Isocyanate Microcapsules

by Yangbao Ma, Yang Jiang, Haiyan Tan, Yanhua Zhang and Jiyou Gu

Polymers 2017, 9(7), 274; https://doi.org/10.3390/polym9070274 - 09 Jul 2017

Cited by 24 | Viewed by 7173

Abstract

In this paper, polyaryl polymethylene isocyanates (PAPI) were used as an innovative alternative material to prepare isocyanate microcapsules. PAPI could be used as core materials, which would react with small molecules containing active hydrogen (1,4-butanediol, ethylene glycol, 1,2-diaminoethane etc.). The reaction products of [...] Read more.

In this paper, polyaryl polymethylene isocyanates (PAPI) were used as an innovative alternative material to prepare isocyanate microcapsules. PAPI could be used as core materials, which would react with small molecules containing active hydrogen (1,4-butanediol, ethylene glycol, 1,2-diaminoethane etc.). The reaction products of PAPI and active hydrogen would form a shell by interfacial polymerization reaction in an oil-in-water emulsion. Smooth spherical microcapsules of 70 ~ 180 μm in diameter were produced by controlling agitation rate (600 ~ 1200 rpm). High yields (~80%) of a free-flowing powder of PAPI/polyurethane and polyurea capsules were produced with a high isocyanate groups (–NCO) content of 23 wt % as determined by titration analysis. Structural analysis and quality assessments of each batch of microcapsules were performed by using thermogravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. Preliminary results indicated the microcapsules were stable with only about 20% loss of –NCO detected after one month storage under ambient conditions. This work showed the great potential of novel microencapsulation technique in development of protection of –NCO and in aspects of micro- and nano-structure construction materials. Full article

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Open AccessArticle

Effective Removal of Chromium(III) from Low Concentration Aqueous Solution Using a Novel Diazene/Methoxy-Laced Coordination Polymer

by Lei-Lei Liu, Yun Xing, Hui-Ying Yu, Cai-Wen Zhang, Meng-Qi Ye, Ming-Zhen Miao and Cai-Xia Yu

Polymers 2017, 9(7), 273; https://doi.org/10.3390/polym9070273 - 09 Jul 2017

Cited by 9 | Viewed by 4782

Abstract

In this study, a novel coordination polymer [CdL₂(H₂O)_0.5]_n (1), [HL = 4-(2-(4-((pyridin-3-yl)methoxy)phenyl)diazenyl)benzoic acid] was fabricated via an in situ ligand transformation reaction under solvothermal conditions. The as-prepared polymer exhibited a selectivity and efficiency for [...] Read more.

In this study, a novel coordination polymer [CdL₂(H₂O)_0.5]_n (1), [HL = 4-(2-(4-((pyridin-3-yl)methoxy)phenyl)diazenyl)benzoic acid] was fabricated via an in situ ligand transformation reaction under solvothermal conditions. The as-prepared polymer exhibited a selectivity and efficiency for Cr(III) removal with a high uptake capacity of 106.13 mg·g⁻¹. Interestingly, even in the low concentration (0.02–0.20 ppm), it still performs a relatively high efficiency (≥ 92.5%) towards the removal of Cr(III) in aqueous solution. Remarkably, it also presents good selectivity and high efficiency (93.3%) for Cr(III) removal in the presences of interfering metal ions. The good removal performance for Cr(III) was demonstrated to be a structure-dependent chemical process between polymer and Cr(III) involving the diazene and methoxy groups in polymer 1, which happened not only on the surfaces of the adsorbent but also in the pores of polymer, giving rise to a strong affinity toward Cr(III) adsorption. The possible adsorption mechanism of Cr(III) was proposed and systematically verified by FT-IR, scanning electron microscope (SEM), atomic force microscope (AFM) and energy dispersive spectrometer (EDS) measurements. Full article

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Polymers, Volume 9, Issue 7 (July 2017) – 62 articles

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