Polymers

6700 KiB

Open AccessArticle

Immobilization of Platelet-Rich Plasma onto COOH Plasma-Coated PCL Nanofibers Boost Viability and Proliferation of Human Mesenchymal Stem Cells

by Anastasiya Solovieva, Svetlana Miroshnichenko, Andrey Kovalskii, Elizaveta Permyakova, Zakhar Popov, Eva Dvořáková, Philip Kiryukhantsev-Korneev, Aleksei Obrosov, Josef Polčak, Lenka Zajíčková, Dmitry V. Shtansky and Anton Manakhov

Polymers 2017, 9(12), 736; https://doi.org/10.3390/polym9120736 - 20 Dec 2017

Cited by 35 | Viewed by 7995

Abstract

The scaffolds made of polycaprolactone (PCL) are actively employed in different areas of biology and medicine, especially in tissue engineering. However, the usage of unmodified PCL is significantly restricted by the hydrophobicity of its surface, due to the fact that its inert surface [...] Read more.

The scaffolds made of polycaprolactone (PCL) are actively employed in different areas of biology and medicine, especially in tissue engineering. However, the usage of unmodified PCL is significantly restricted by the hydrophobicity of its surface, due to the fact that its inert surface hinders the adhesion of cells and the cell interactions on PCL surface. In this work, the surface of PCL nanofibers is modified by Ar/CO₂/C₂H₄ plasma depositing active COOH groups in the amount of 0.57 at % that were later used for the immobilization of platelet-rich plasma (PRP). The modification of PCL nanofibers significantly enhances the viability and proliferation (by hundred times) of human mesenchymal stem cells, and decreases apoptotic cell death to a normal level. According to X-ray photoelectron spectroscopy (XPS), after immobilization of PRP, up to 10.7 at % of nitrogen was incorporated into the nanofibers surface confirming the grafting of proteins. Active proliferation and sustaining the cell viability on nanofibers with immobilized PRP led to an average number of cells of 258 ± 12.9 and 364 ± 34.5 for nanofibers with ionic and covalent bonding of PRP, respectively. Hence, our new method for the modification of PCL nanofibers with PRP opens new possibilities for its application in tissue engineering. Full article

(This article belongs to the Special Issue Surface Modification and Functional Coatings for Polymers)

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16840 KiB

Open AccessArticle

Layer-by-Layer Assembly of Polyelectrolyte Multilayer onto PET Fabric for Highly Tunable Dyeing with Water Soluble Dyestuffs

by Shili Xiao, Pengjun Xu, Qingyan Peng, Jiali Chen, Jiankang Huang, Faming Wang and Nuruzzaman Noor

Polymers 2017, 9(12), 735; https://doi.org/10.3390/polym9120735 - 20 Dec 2017

Cited by 85 | Viewed by 7670

Abstract

Poly(ethyleneterephthalate) (PET) is a multi-purpose and widely used synthetic polymer in many industrial fields because of its remarkable advantages such as low cost, light weight, high toughness and resistance to chemicals, and high abrasion resistance. However, PET suffers from poor dyeability due to [...] Read more.

Poly(ethyleneterephthalate) (PET) is a multi-purpose and widely used synthetic polymer in many industrial fields because of its remarkable advantages such as low cost, light weight, high toughness and resistance to chemicals, and high abrasion resistance. However, PET suffers from poor dyeability due to its non-polar nature, benzene ring structure as well as high crystallinity. In this study, PET fabrics were firstly treated with an alkaline solution to produce carboxylic acid functional groups on the surface of the PET fabric, and then was modified by polyelectrolyte polymer through the electrostatic layer-by-layer self-assembly technology. The polyelectrolyte multilayer-deposited PET fabric was characterized using scanning electron microscopy SEM, contact angle, Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). The dyeability of PET fabrics before and after surface modification was systematically investigated. It showed that the dye-uptake of the polyelectrolyte multilayer-deposited PET fabric has been enhanced compared to that of the pristine PET fabric. In addition, its dyeability is strongly dependent on the surface property of the polyelectrolyte multilayer-deposited PET fabric and the properties of dyestuffs. Full article

(This article belongs to the Special Issue Textile and Textile-Based Materials)

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2946 KiB

Open AccessArticle

Preparation and Evaluation of a Polyimide-Coated Ultrafine Gilt Molybdenum Wire and Its Knitted Mesh Used for Electromagnetic Reflectors

by Huiqi Shao, Nanliang Chen, Shuang Li, Fangbing Lin, Jinhua Jiang and Xiaofei Ma

Polymers 2017, 9(12), 734; https://doi.org/10.3390/polym9120734 - 20 Dec 2017

Cited by 10 | Viewed by 6422

Abstract

In this work, polyimide (PI) was coated onto an ultrafine gilt molybdenum wire in order to protect the gilt surface and prepare an electrically stable wire mesh material which can be widely used in space. The surface of the PI-coated gilt molybdenum wires [...] Read more.

In this work, polyimide (PI) was coated onto an ultrafine gilt molybdenum wire in order to protect the gilt surface and prepare an electrically stable wire mesh material which can be widely used in space. The surface of the PI-coated gilt molybdenum wires was characterized using FTIR, SEM, and EDS. Factors such as temperature stability of the PI coating, mechanical properties of the PI-coated gilt molybdenum wires, contact resistance stability, and electromagnetic microwave reflectivity of the their knitted meshes were also investigated. The results indicate that the PI coating conformed uniformly to the surface of the gilt molybdenum wires. The prepared PI coating exhibited excellent temperature stability in the −196 to 300 °C range and could efficiently protect the gilt surface and improve the stability of contact resistance, while the reflection of its wire meshes showed only a slight decrease of 1.4% with the PI coating thickness of 3 μm for electromagnetic microwaves in the S band. Full article

(This article belongs to the Special Issue Textile and Textile-Based Materials)

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1537 KiB

Open AccessArticle

Microencapsulation of Lactobacillus Acidophilus by Xanthan-Chitosan and Its Stability in Yoghurt

by Guowei Shu, Yunxia He, Li Chen, Yajuan Song, Jiangpeng Meng and He Chen

Polymers 2017, 9(12), 733; https://doi.org/10.3390/polym9120733 - 20 Dec 2017

Cited by 18 | Viewed by 6443

Abstract

Microencapsulations of Lactobacillus acidophilus in xanthan-chitosan (XC) and xanthan-chitosan-xanthan (XCX) polyelectrolyte complex (PEC) gels were prepared in this study. The process of encapsulation was optimized with the aid of response surface methodology (RSM). The optimum condition was chitosan of 0.68%, xanthan of 0.76%, [...] Read more.

Microencapsulations of Lactobacillus acidophilus in xanthan-chitosan (XC) and xanthan-chitosan-xanthan (XCX) polyelectrolyte complex (PEC) gels were prepared in this study. The process of encapsulation was optimized with the aid of response surface methodology (RSM). The optimum condition was chitosan of 0.68%, xanthan of 0.76%, xanthan-L. acidophilus mixture (XLM)/chitosan of 1:2.56 corresponding to a high viable count (1.31 ± 0.14) × 10¹⁰ CFU·g⁻¹, and encapsulation yield 86 ± 0.99%, respectively. Additionally, the application of a new encapsulation system (XC and XCX) in yoghurt achieved great success in bacterial survival during the storage of 21 d at 4 °C and 25 °C, respectively. Specially, pH and acidity in yogurt were significantly influenced by the new encapsulation system in comparison to free suspension during 21 d storage. Our study provided a potential encapsulation system for probiotic application in dairy product which paving a new way for functional food development. Full article

(This article belongs to the Special Issue Polysaccharides)

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Open AccessArticle

Morphological and Structural Analysis of Polyaniline and Poly(o-anisidine) Layers Generated in a DC Glow Discharge Plasma by Using an Oblique Angle Electrode Deposition Configuration

by Bogdan Butoi, Andreea Groza, Paul Dinca, Adriana Balan and Valentin Barna

Polymers 2017, 9(12), 732; https://doi.org/10.3390/polym9120732 - 20 Dec 2017

Cited by 150 | Viewed by 8748

Abstract

This work is focused on the structural and morphological investigations of polyaniline and poly(o-anisidine) polymers generated in a direct current glow discharge plasma, in the vapors of the monomers, without a buffer gas, using an oblique angle-positioned substrate configuration. By atomic [...] Read more.

This work is focused on the structural and morphological investigations of polyaniline and poly(o-anisidine) polymers generated in a direct current glow discharge plasma, in the vapors of the monomers, without a buffer gas, using an oblique angle-positioned substrate configuration. By atomic force microscopy and scanning electron microscopy we identified the formation of worm-like interlinked structures on the surface of the polyaniline layers, the layers being compact in the bulk. The poly(o-anisidine) layers are flat with no kind of structures on their surfaces. By Fourier transform infrared spectroscopy we identified the main IR bands characteristic of polyaniline and poly(o-anisidine), confirming that the polyaniline chemical structure is in the emeraldine form. The IR band from 1070 cm⁻¹ was attributed to the emeraldine salt form of polyaniline as an indication of its doping with H⁺. The appearance of the IR band at 1155 cm⁻¹ also indicates the conducting protonated of polyaniline. The X-ray diffraction revealed the formation of crystalline domains embedded in an amorphous matrix within the polyaniline layers. The interchain separation length of 3.59 Å is also an indicator of the conductive character of the polymers. The X-ray diffraction pattern of poly(o-anisidine) highlights the semi-crystalline nature of the layers. The electrical conductivities of polyaniline and poly(o-anisidine) layers and their dependence with temperature are also investigated. Full article

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

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Open AccessArticle

Adhesives for Achieving Durable Bonds with Acetylated Wood

by Charles R. Frihart, Rishawn Brandon, James F. Beecher and Rebecca E. Ibach

Polymers 2017, 9(12), 731; https://doi.org/10.3390/polym9120731 - 20 Dec 2017

Cited by 23 | Viewed by 5861

Abstract

Acetylation of wood imparts moisture durability, decay resistance, and dimensional stability to wood; however, making durable adhesive bonds with acetylated wood can be more difficult than with unmodified wood. The usual explanation is that the acetylated surface has fewer hydroxyl groups, resulting in [...] Read more.

Acetylation of wood imparts moisture durability, decay resistance, and dimensional stability to wood; however, making durable adhesive bonds with acetylated wood can be more difficult than with unmodified wood. The usual explanation is that the acetylated surface has fewer hydroxyl groups, resulting in a harder-to-wet surface and in fewer hydrogen bonds between wood and adhesive. This concept was evaluated using four different adhesives (resorcinol–formaldehyde, emulsion polymer isocyanate, epoxy, and melamine–formaldehyde) with unmodified wood, acetylated wood, and acetylated wood that had been planed. Strikingly, acetylation did not hinder adhesive bonds with a waterborne resorcinol–formaldehyde adhesive that bonded equally well to both unmodified and acetylated yellow poplar. An epoxy adhesive bonded better to the acetylated wood than to the unmodified wood, in contrast to an emulsion polymer isocyanate, which gave less durable bonds to acetylated than to unmodified wood. Planing of the acetylated wood surface prior to bonding reduced bond durability for the epoxy adhesive and increased the amount of surface hydroxyl groups, as measured using X-ray photoelectron spectroscopic analysis of the trifluoroacetic anhydride-treated wood. These experiments showed that wood modification is useful in understanding wood-adhesive interactions, in addition to determining how to develop adhesives for acetylated woods. Full article

(This article belongs to the Collection Polymeric Adhesives)

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Open AccessArticle

Characterization of Chromatic Dispersion and Refractive Index of Polymer Optical Fibers

by Igor Ayesta, Joseba Zubia, Jon Arrue, María Asunción Illarramendi and Mikel Azkune

Polymers 2017, 9(12), 730; https://doi.org/10.3390/polym9120730 - 20 Dec 2017

Cited by 14 | Viewed by 6702

Abstract

The chromatic dispersion and the refractive index of poly(methyl methacrylate) polymer optical fibers (POFs) have been characterized in this work by using a tunable femtosecond laser and a Streak Camera. The characterization technique is based on the measurement of the time delays of [...] Read more.

The chromatic dispersion and the refractive index of poly(methyl methacrylate) polymer optical fibers (POFs) have been characterized in this work by using a tunable femtosecond laser and a Streak Camera. The characterization technique is based on the measurement of the time delays of light pulses propagating along POFs at different wavelengths. Polymer fibers of three different lengths made by two manufacturers have been employed for that purpose, and discrepancies lower than 3% have been obtained in all cases. Full article

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

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Open AccessReview

Preparation and Material Application of Amylose-Polymer Inclusion Complexes by Enzymatic Polymerization Approach

by Saya Orio, Kazuya Yamamoto and Jun-ichi Kadokawa

Polymers 2017, 9(12), 729; https://doi.org/10.3390/polym9120729 - 18 Dec 2017

Cited by 19 | Viewed by 6835

Abstract

This review presents our researches on the preparation and material application of inclusion complexes that comprises an amylose host and polymeric guests through phosphorylase-catalyzed enzymatic polymerization. Amylose is a well-known polysaccharide and forms inclusion complexes with various hydrophobic small molecules. Pure amylose is [...] Read more.

This review presents our researches on the preparation and material application of inclusion complexes that comprises an amylose host and polymeric guests through phosphorylase-catalyzed enzymatic polymerization. Amylose is a well-known polysaccharide and forms inclusion complexes with various hydrophobic small molecules. Pure amylose is produced by enzymatic polymerization by using α-d-glucose 1-phosphate as a monomer and maltooligosaccharide as a primer catalyzed by phosphorylase. We determined that a propagating chain of amylose during enzymatic polymerization wraps around hydrophobic polymers present in the reaction system to form inclusion complexes. We termed this polymerization “vine-twining polymerization” because it is similar to the way vines of a plant grow around a rod. Hierarchical structured amylosic materials, such as hydrogels and films, were fabricated by inclusion complexation through vine-twining polymerization by using copolymers covalently grafted with hydrophobic guest polymers. The enzymatically produced amyloses induced complexation with the guest polymers in the intermolecular graft copolymers, which acted as cross-linking points to form supramolecular hydrogels. By including a film-formable main-chain in the graft copolymer, a supramolecular film was obtained through hydrogelation. Supramolecular polymeric materials were successfully fabricated through vine-twining polymerization by using primer-guest conjugates. The products of vine-twining polymerization form polymeric continuums of inclusion complexes, where the enzymatically produced amylose chains elongate from the conjugates included in the guest segments of the other conjugates. Full article

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

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Open AccessArticle

The Effect of Carbon Nanotubes on the Mechanical Properties of Wood Plastic Composites by Selective Laser Sintering

by Yunhe Zhang, Jing Fang, Jian Li, Yanling Guo and Qingwen Wang

Polymers 2017, 9(12), 728; https://doi.org/10.3390/polym9120728 - 18 Dec 2017

Cited by 31 | Viewed by 5782

Abstract

Wood-plastic composites (WPCs) made by selective laser sintering (SLS) approach of 3D printing offer many advantages over single polymer materials, such as low cost, sustainability, and better sintering accuracy. However, WPCs made via SLS are too weak to have widespread applications. In order [...] Read more.

Wood-plastic composites (WPCs) made by selective laser sintering (SLS) approach of 3D printing offer many advantages over single polymer materials, such as low cost, sustainability, and better sintering accuracy. However, WPCs made via SLS are too weak to have widespread applications. In order to increase the mechanical properties of WPCs, a novel type of WPCs containing 0, 0.05, 0.1 and 0.15 wt % carbon nanotubes (CNT), 14 wt % wood fibers, 86 wt % polyether sulfone (PES) was manufactured via SLS. The experimental results showed that the addition of small amount of CNTs can significantly increase the mechanical properties of the wood/PES composite material. The tensile strength, bending strength, and elasticity modulus were 76.3%, 227.9%, and 128.7% higher with 0.1 wt % CNTs than those without CNTs. The mechanical properties of specimens first increased and then decreased with the addition of CNTs. The SEM results of the specimens’ fracture morphology indicate that the preferable bonding interfaces between wood flour grains and PES grains were achieved by adding CNTs to the composites. There are two reasons why the composites possessed superior mechanical properties: CNTs facilitate the laser sintering process of WPCs due to their thermal conductivities, and CNTs directly reinforce WPCs. Full article

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Open AccessArticle

Preparation and Characterization of Breathable Hemostatic Hydrogel Dressings and Determination of Their Effects on Full-Thickness Defects

by Hong Pan, Daidi Fan, Wei Cao, Chenhui Zhu, Zhiguang Duan, Rongzhan Fu, Xian Li and Xiaoxuan Ma

Polymers 2017, 9(12), 727; https://doi.org/10.3390/polym9120727 - 18 Dec 2017

Cited by 49 | Viewed by 8038

Abstract

Hydrogel-based wound dressings provide a cooling sensation, a moist environment, and act as a barrier to microbes for wounds. In this study, a series of soft, flexible, porous non-stick hydrogel dressings were prepared through the simple repeated freeze-thawing of a poly(vinyl alcohol), human-like [...] Read more.

Hydrogel-based wound dressings provide a cooling sensation, a moist environment, and act as a barrier to microbes for wounds. In this study, a series of soft, flexible, porous non-stick hydrogel dressings were prepared through the simple repeated freeze-thawing of a poly(vinyl alcohol), human-like collagen (or and carboxymethyl chitosan) mixed solution rather than chemical cross-linking and Tween80 was added as pore-forming agent for cutaneous wound healing. Some of their physical and chemical properties were characterized. Interestingly, hydrogel PVA-HLC-T80 and PVA-HLC-CS-T80 presented excellent swelling ratios, bacterial barrier activity, moisture vapor permeability, hemostasis activity and biocompatibility. Furthermore, in vivo evaluation of the healing capacity of these two hydrogels was checked by creating a full-thickness wound defect (1.3 cm × 1.3 cm) in rabbit. Macroscopic observation and subsequent hematoxylin eosin staining (H&E) staining and transmission electron microscopy (TEM) analysis at regular time intervals for 18 days revealed that the hydrogels significantly enhanced wound healing by reducing inflammation, promoting granulation tissue formation, collagen deposition and accelerating re-epithelialization. Taken together, the obtained data strongly encourage the use of these multifunctional hydrogels for skin wound dressings. Full article

(This article belongs to the Special Issue Hydrogels in Tissue Engineering and Regenerative Medicine)

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Open AccessArticle

Characterization of Wood-Plastic Composites Made with Different Lignocellulosic Materials that Vary in Their Morphology, Chemical Composition and Thermal Stability

by Ke-Chang Hung, Heng Yeh, Teng-Chun Yang, Tung-Lin Wu, Jin-Wei Xu and Jyh-Horng Wu

Polymers 2017, 9(12), 726; https://doi.org/10.3390/polym9120726 - 17 Dec 2017

Cited by 25 | Viewed by 7113

Abstract

In this study, four kinds of lignocellulosic fibers (LFs), namely, those from Chinese fir (Cunninghamia lanceolata), Taiwan red pine (Pinus taiwanensis), India-charcoal trema (Trema orientalis) and makino bamboo (Phyllostachys makinoi), were selected as reinforcements and incorporated into high-density polyethylene (HDPE) to manufacture wood-plastic [...] Read more.

In this study, four kinds of lignocellulosic fibers (LFs), namely, those from Chinese fir (Cunninghamia lanceolata), Taiwan red pine (Pinus taiwanensis), India-charcoal trema (Trema orientalis) and makino bamboo (Phyllostachys makinoi), were selected as reinforcements and incorporated into high-density polyethylene (HDPE) to manufacture wood-plastic composites (WPCs) by a flat platen pressing process. In addition to comparing the differences in the physico-mechanical properties of these composites, their chemical compositions were evaluated and their thermal decomposition kinetics were analyzed to investigate the effects of the lignocellulosic species on the properties of the WPCs. The results showed that the WPC made with Chinese fir displayed a typical M-shaped vertical density profile due to the high aspect ratio of its LFs, while a flat vertical density profile was observed for the WPCs made with other LFs. Thus, the WPC made with Chinese fir exhibited higher flexural properties and lower internal bond strength (IB) than other WPCs. In addition, the Taiwan red pine contained the lowest holocellulose content and the highest extractives and α-cellulose contents, which gave the resulting WPC lower water absorption and flexural properties. On the other hand, consistent with the flexural properties, the results of thermal decomposition kinetic analysis showed that the activation energy of the LFs at 10% of the conversion rate increased in the order of Taiwan red pine (146–161 kJ/mol), makino bamboo (158–175 kJ/mol), India-charcoal trema (185–194 kJ/mol) and Chinese fir (194–202 kJ/mol). These results indicate that the morphology, chemical composition and thermal stability of the LFs can have a substantial impact on the physico-mechanical properties of the resulting WPCs. Full article

(This article belongs to the Collection Polysaccharides)

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6668 KiB

Open AccessReview

Bio-Inspired Polymeric Structures with Special Wettability and Their Applications: An Overview

by Zihe Pan, Fangqin Cheng and Boxin Zhao

Polymers 2017, 9(12), 725; https://doi.org/10.3390/polym9120725 - 17 Dec 2017

Cited by 48 | Viewed by 15374

Abstract

It is not unusual for humans to be inspired by natural phenomena to develop new advanced materials; such materials are called bio-inspired materials. Interest in bio-inspired polymeric superhydrophilic, superhydrophobic, and superoleophobic materials has substantially increased over the last few decades, as has improvement [...] Read more.

It is not unusual for humans to be inspired by natural phenomena to develop new advanced materials; such materials are called bio-inspired materials. Interest in bio-inspired polymeric superhydrophilic, superhydrophobic, and superoleophobic materials has substantially increased over the last few decades, as has improvement in the related technologies. This review reports the latest developments in bio-inspired polymeric structures with desired wettability that have occurred by mimicking the structures of lotus leaf, rose petals, and the wings and shells of various creatures. The intrinsic role of surface chemistry and structure on delivering superhydrophilicity, superhydrophobicity, and superoleophobicity has been extensively explored. Typical polymers, commonly used structures, and techniques involved in developing bio-inspired surfaces with desired wettability are discussed. Additionally, the latest applications of bio-inspired structures with desired wettability in human activities are also introduced. Full article

(This article belongs to the Collection Polymeric Adhesives)

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1942 KiB

Open AccessArticle

Novel Random PBS-Based Copolymers Containing Aliphatic Side Chains for Sustainable Flexible Food Packaging

by Giulia Guidotti, Michelina Soccio, Valentina Siracusa, Massimo Gazzano, Elisabetta Salatelli, Andrea Munari and Nadia Lotti

Polymers 2017, 9(12), 724; https://doi.org/10.3390/polym9120724 - 16 Dec 2017

Cited by 58 | Viewed by 6978

Abstract

In the last decade, there has been an increased interest from the food packaging industry toward the development and application of biodegradable and biobased plastics, to contribute to the sustainable economy and to reduce the huge environmental problem afflicting the planet. In this [...] Read more.

In the last decade, there has been an increased interest from the food packaging industry toward the development and application of biodegradable and biobased plastics, to contribute to the sustainable economy and to reduce the huge environmental problem afflicting the planet. In this framework, the present paper describes the synthesis of novel PBS (poly(butylene succinate))-based random copolymers with different composition containing glycol sub-units characterized by alkyl pendant groups of different length. The prepared samples were subjected to molecular, thermal, diffractometric and mechanical characterization. The barrier performances to O₂, CO₂ and N₂ gases were also evaluated, envisioning for these new materials an application in food packaging. The presence of the side alkyl groups did not alter the thermal stability, whereas it significantly reduced the sample crystallinity degree, making these materials more flexible. The barrier properties were found to be worse than PBS; however, some of them were comparable to, or even better than, those of Low Density Polyethylene (LDPE), widely employed for flexible food packaging. The entity of variations in the final properties due to copolymerization were more modest in the case of the co-unit with short side methyl groups, which, when included in the PBS crystal lattice, causes a more modest decrement of crystallinity degree. Full article

(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)

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Open AccessArticle

Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate) via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

by Naoya Usuki, Kotaro Satoh and Masami Kamigaito

Polymers 2017, 9(12), 723; https://doi.org/10.3390/polym9120723 - 16 Dec 2017

Cited by 8 | Viewed by 9864

Abstract

Isotactic (it-) and syndiotactic (st-) poly(methyl methacrylate)s (PMMAs) form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b [...] Read more.

Isotactic (it-) and syndiotactic (st-) poly(methyl methacrylate)s (PMMAs) form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st-) PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl₄ as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN₃. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC) between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH₃CN and was affected by the block lengths and ratios. Full article

(This article belongs to the Special Issue Living Polymerization)

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Open AccessArticle

Aerogels from Chitosan Solutions in Ionic Liquids

by Gonzalo Santos-López, Waldo Argüelles-Monal, Elizabeth Carvajal-Millan, Yolanda L. López-Franco, Maricarmen T. Recillas-Mota and Jaime Lizardi-Mendoza

Polymers 2017, 9(12), 722; https://doi.org/10.3390/polym9120722 - 16 Dec 2017

Cited by 29 | Viewed by 6354

Abstract

Chitosan aerogels conjugates the characteristics of nanostructured porous materials, i.e., extended specific surface area and nano scale porosity, with the remarkable functional properties of chitosan. Aerogels were obtained from solutions of chitosan in ionic liquids (ILs), 1-butyl-3-methylimidazolium acetate (BMIMAc), and 1-ethyl-3-methyl-imidazolium acetate (EMIMAc), [...] Read more.

Chitosan aerogels conjugates the characteristics of nanostructured porous materials, i.e., extended specific surface area and nano scale porosity, with the remarkable functional properties of chitosan. Aerogels were obtained from solutions of chitosan in ionic liquids (ILs), 1-butyl-3-methylimidazolium acetate (BMIMAc), and 1-ethyl-3-methyl-imidazolium acetate (EMIMAc), in order to observe the effect of the solvent in the structural characteristics of this type of materials. The process of elaboration of aerogels comprised the formation of physical gels through anti-solvent vapor diffusion, liquid phase exchange, and supercritical CO₂ drying. The aerogels maintained the chemical identity of chitosan according to Fourier transform infrared spectrophotometer (FT-IR) spectroscopy, indicating the presence of their characteristic functional groups. The internal structure of the obtained aerogels appears as porous aggregated networks in microscopy images. The obtained materials have specific surface areas over 350 m²/g and can be considered mesoporous. According to swelling experiments, the chitosan aerogels could absorb between three and six times their weight of water. However, the swelling and diffusion coefficient decreased at higher temperatures. The structural characteristics of chitosan aerogels that are obtained from ionic liquids are distinctive and could be related to solvation dynamic at the initial state. Full article

(This article belongs to the Special Issue Advances in Chitin/Chitosan Characterization and Applications)

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Open AccessReview

Exploiting Microbial Polysaccharides for Biosorption of Trace Elements in Aqueous Environments—Scope for Expansion via Nanomaterial Intervention

by Manikandan Muthu, Hui-Fen Wu, Judy Gopal, Iyyakkannu Sivanesan and Sechul Chun

Polymers 2017, 9(12), 721; https://doi.org/10.3390/polym9120721 - 16 Dec 2017

Cited by 31 | Viewed by 7058

Abstract

With pollution sounding high alarms all around us, there is an immediate necessity for remediation. In most cases, the remediation measures require further remediation—the anti-pollutants themselves cause pollution. In this correspondence, the search deepens towards natural biogenic components that can be used for [...] Read more.

With pollution sounding high alarms all around us, there is an immediate necessity for remediation. In most cases, the remediation measures require further remediation—the anti-pollutants themselves cause pollution. In this correspondence, the search deepens towards natural biogenic components that can be used for bioremediation. Polysaccharide and biosorption have been themes in discussion for quite some time, where a slow decline in the enthusiasm in this area has been observed. This review revisits the importance of using polysaccharide based materials for biosorption. The need for polysaccharide-based nanocomposites, which hold better promise for greater deliverables, is emphasized as a means of rejuvenating the future perspectives in this area of application. Full article

(This article belongs to the Special Issue Polysaccharides)

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Open AccessCommunication

Individual Impact of Distinct Polysialic Acid Chain Lengths on the Cytotoxicity of Histone H1, H2A, H2B, H3 and H4

by Kristina Zlatina, Thomas Lütteke and Sebastian P. Galuska

Polymers 2017, 9(12), 720; https://doi.org/10.3390/polym9120720 - 16 Dec 2017

Cited by 23 | Viewed by 5354

Abstract

Neutrophils are able to neutralize pathogens by phagocytosis, by the release of antimicrobial components, as well as by the formation of neutrophil extracellular traps (NETs). The latter possibility is a DNA-meshwork mainly consisting of highly concentrated extracellular histones, which are not only toxic [...] Read more.

Neutrophils are able to neutralize pathogens by phagocytosis, by the release of antimicrobial components, as well as by the formation of neutrophil extracellular traps (NETs). The latter possibility is a DNA-meshwork mainly consisting of highly concentrated extracellular histones, which are not only toxic for pathogens, but also for endogenous cells triggering several diseases. To reduce the negative outcomes initiated by extracellular histones, different approaches like antibodies against histones, proteases, and the polysaccharide polysialic acid (polySia) were discussed. We examined whether each of the individual histones is a binding partner of polySia, and analyzed their respective cytotoxicity in the presence of this linear homopolymer. Interestingly, all of the histones (H1, H2A, H2B, H3, and H4) seem to interact with α2,8-linked sialic acids. However, we observed strong differences regarding the required chain length of polySia to bind histone H1, H2A, H2B, H3, and H4. Moreover, distinct degrees of polymerization were necessary to act as a cytoprotective agent in the presence of the individual histones. In sum, the outlined results described polySia-based strategies to bind and/or to reduce the cytotoxicity of individual histones using distinct polySia chain length settings. Full article

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Open AccessArticle

pH-Responsive Host–Guest Complexation in Pillar[6]arene-Containing Polyelectrolyte Multilayer Films

by Henning Nicolas, Bin Yuan, Jiangfei Xu, Xi Zhang and Monika Schönhoff

Polymers 2017, 9(12), 719; https://doi.org/10.3390/polym9120719 - 16 Dec 2017

Cited by 11 | Viewed by 6701

Abstract

A water-soluble, anionic pillar[6]arene derivative (WP6) is applied as monomeric building block for the layer-by-layer self-assembly of thin polyelectrolyte multilayer films, and its pH-dependent host–guest properties are employed for the reversible binding and release of a methylviologen guest molecule. The alternating assembly of [...] Read more.

A water-soluble, anionic pillar[6]arene derivative (WP6) is applied as monomeric building block for the layer-by-layer self-assembly of thin polyelectrolyte multilayer films, and its pH-dependent host–guest properties are employed for the reversible binding and release of a methylviologen guest molecule. The alternating assembly of anionic WP6 and cationic diazo resin (DAR) is monitored in-situ by a dissipative quartz crystal microbalance (QCM-D). In solution, the formation of a stoichiometric inclusion complex of WP6 and cationic methylviologen (MV) as guest molecule is investigated by isothermal titration calorimetry and UV-vis spectroscopy, respectively, and attributed to electrostatic interactions as primary driving force of the host–guest complexation. Exposure of WP6-containing multilayers to MV solution reveals a significant decrease of the resonance frequency, confirming MV binding. Subsequent release is achieved by pH lowering, decreasing the host–guest interactions. The dissociation of the host–guest complex, release of the guest from the film, as well as full reversibility of the binding event are identified by QCM-D. In addition, UV-vis data quantify the surface coverage of the guest molecule in the film after loading and release, respectively. These findings establish the pH-responsiveness of WP6 as a novel external stimulus for the reversible guest molecule recognition in thin films. Full article

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

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Open AccessArticle

PVDF Membrane Morphology—Influence of Polymer Molecular Weight and Preparation Temperature

by Monika Haponska, Anna Trojanowska, Adrianna Nogalska, Renata Jastrzab, Tania Gumi and Bartosz Tylkowski

Polymers 2017, 9(12), 718; https://doi.org/10.3390/polym9120718 - 15 Dec 2017

Cited by 54 | Viewed by 14456

Abstract

In this study, we successfully prepared nine non-woven, supported polyvinylidene fluoride (PVDF) membranes, using a phase inversion precipitation method, starting from a 15 wt % PVDF solution in N-methyl-2-pyrrolidone. Various membrane morphologies were obtained by using (1) PVDF polymers, with diverse molecular [...] Read more.

In this study, we successfully prepared nine non-woven, supported polyvinylidene fluoride (PVDF) membranes, using a phase inversion precipitation method, starting from a 15 wt % PVDF solution in N-methyl-2-pyrrolidone. Various membrane morphologies were obtained by using (1) PVDF polymers, with diverse molecular weights ranging from 300 to 700 kDa, and (2) different temperature coagulation baths (20, 40, and 60 ± 2 °C) used for the film precipitation. An environmental scanning electron microscope (ESEM) was used for surface and cross-section morphology characterization. An atomic force microscope (AFM) was employed to investigate surface roughness, while a contact angle (CA) instrument was used for membrane hydrophobicity studies. Fourier transform infrared spectroscopy (FTIR) results show that the fabricated membranes are formed by a mixture of TGTG’ chains, in α phase crystalline domains, and all-TTTT trans planar zigzag chains characteristic to β phase. Moreover, generated results indicate that the phases’ content and membrane morphologies depend on the polymer molecular weight and conditions used for the membranes’ preparation. The diversity of fabricated membranes could be applied by the End User Industries for different applications. Full article

(This article belongs to the Special Issue Polymeric Membranes)

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Open AccessArticle

Preparation of Copolymer-Based Nanoparticles with Broad-Spectrum Antimicrobial Activity

by Yang Li, Pingxiong Cai, Zhang-fa Tong, Huining Xiao and Yuanfeng Pan

Polymers 2017, 9(12), 717; https://doi.org/10.3390/polym9120717 - 15 Dec 2017

Cited by 7 | Viewed by 4728

Abstract

Polyacrylate and guanidine-based nanoparticles which involve acrylate monomers and glycidyl methacrylate modified oligo-guanidine were prepared by a seeded semi-continuous emulsion polymerization. The results from transmission electron microscope and dynamic light scattering measurements showed that the nanoparticles were spherical in shape and the particle [...] Read more.

Polyacrylate and guanidine-based nanoparticles which involve acrylate monomers and glycidyl methacrylate modified oligo-guanidine were prepared by a seeded semi-continuous emulsion polymerization. The results from transmission electron microscope and dynamic light scattering measurements showed that the nanoparticles were spherical in shape and the particle size was in the range of 80–130 nm. Antimicrobial experiments were performed with two types of bacteria, Gram-negative (Escherichia coli, ATCC 8739) and Gram-positive (Staphylococcus aureus, ATCC 6538). The as-synthesized cationic nanoparticles exhibited effective antimicrobial activities on Escherichia coli and Staphylococcus aureus with the minimal inhibitory concentrations at 8 μg/mL and 4 μg/mL, respectively. The mechanism of action of the resulted nanoparticles against these bacteria was revealed by the scanning electron microscopic observation. In addition, the films consisting of latex nanoparticles are non-leaching antimicrobial materials with excellent antimicrobial activity, which indicates the polymers could preserve their antimicrobial activity for long-term effectiveness. Full article

(This article belongs to the Special Issue Antimicrobial Polymers)

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Open AccessArticle

Ultra-Stretchable Piezoelectric Nanogenerators via Large-Scale Aligned Fractal Inspired Micro/Nanofibers

by Yongqing Duan, Yajiang Ding, Jing Bian, Zhoulong Xu, Zhouping Yin and Yongan Huang

Polymers 2017, 9(12), 714; https://doi.org/10.3390/polym9120714 - 15 Dec 2017

Cited by 25 | Viewed by 7864

Abstract

Stretchable nanogenerators that directly generate electricity are promising for a wide range of applications in wearable electronics. However, the stretchability of the devices has been a long-standing challenge. Here we present a newly-designed ultra-stretchable nanogenerator based on fractal-inspired piezoelectric nanofibers and liquid metal [...] Read more.

Stretchable nanogenerators that directly generate electricity are promising for a wide range of applications in wearable electronics. However, the stretchability of the devices has been a long-standing challenge. Here we present a newly-designed ultra-stretchable nanogenerator based on fractal-inspired piezoelectric nanofibers and liquid metal electrodes that can withstand strain as large as 200%. The large-scale fractal poly(vinylidene fluoride) (PVDF) micro/nanofibers are fabricated by combination of helix electrohydrodynamic printing (HE-Printing) and buckling-driven self-assembly. HE-Printing exploits “whipping/buckling” instability of electrospinning to deposit serpentine fibers with diverse geometries in a programmable, accurately positioned, and individually-controlled manner. Self-organized buckling utilizes the driven force from the prestrained elastomer to assemble serpentine fibers into ultra-stretchable fractal inspired architecture. The nanogenerator with embedded fractal PVDF fibers and liquid-metal microelectrodes demonstrates high stretchability (>200%) and electricity (currents >200 nA), it can harvest energy from all directions by arbitrary mechanical motion, and the rectified output has been applied to charge the commercial capacitor and drive LEDs, which enables wearable electronics applications in sensing and energy harvesting. Full article

(This article belongs to the Special Issue Soft Materials and Systems)

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Open AccessArticle

Presenting Precision Glycomacromolecules on Gold Nanoparticles for Increased Lectin Binding

by Sophia Boden, Kristina G. Wagner, Matthias Karg and Laura Hartmann

Polymers 2017, 9(12), 716; https://doi.org/10.3390/polym9120716 - 14 Dec 2017

Cited by 30 | Viewed by 8995 | Correction

Abstract

Glyco-functionalized gold nanoparticles have great potential as biosensors and as inhibitors due to their increased binding to carbohydrate-recognizing receptors such as the lectins. Here we apply previously developed solid phase polymer synthesis to obtain a series of precision glycomacromolecules that allows for straightforward [...] Read more.

Glyco-functionalized gold nanoparticles have great potential as biosensors and as inhibitors due to their increased binding to carbohydrate-recognizing receptors such as the lectins. Here we apply previously developed solid phase polymer synthesis to obtain a series of precision glycomacromolecules that allows for straightforward variation of their chemical structure as well as functionalization of gold nanoparticles by ligand exchange. A novel building block is introduced allowing for the change of spacer building blocks within the macromolecular scaffold going from an ethylene glycol unit to an aliphatic spacer. Furthermore, the valency and overall length of the glycomacromolecule is varied. All glyco-functionalized gold nanoparticles show high degree of functionalization along with high stability in buffer solution. Therefore, a series of measurements applying UV-Vis spectroscopy, dynamic light scattering (DLS) and surface plasmon resonance (SPR) were performed studying the aggregation behavior of the glyco-functionalized gold nanoparticles in presence of model lectin Concanavalin A. While the multivalent presentation of glycomacromolecules on gold nanoparticles (AuNPs) showed a strong increase in binding compared to the free ligands, we also observed an influence of the chemical structure of the ligand such as its valency or hydrophobicity on the resulting lectin interactions. The straightforward variation of the chemical structure of the precision glycomacromolecule thus gives access to tailor-made glyco-gold nanoparticles (glyco-AuNPs) and fine-tuning of their lectin binding properties. Full article

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

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Open AccessReview

Recent Advances in the Fabrication of Membranes Containing “Ion Pairs” for Nanofiltration Processes

by Yan-Li Ji, Bing-Xin Gu, Quan-Fu An and Cong-Jie Gao

Polymers 2017, 9(12), 715; https://doi.org/10.3390/polym9120715 - 14 Dec 2017

Cited by 44 | Viewed by 10456

Abstract

In the face of serious environmental pollution and water scarcity problems, the membrane separation technique, especially high efficiency, low energy consumption, and environmental friendly nanofiltration, has been quickly developed. Separation membranes with high permeability, good selectivity, and strong antifouling properties are critical for [...] Read more.

In the face of serious environmental pollution and water scarcity problems, the membrane separation technique, especially high efficiency, low energy consumption, and environmental friendly nanofiltration, has been quickly developed. Separation membranes with high permeability, good selectivity, and strong antifouling properties are critical for water treatment and green chemical processing. In recent years, researchers have paid more and more attention to the development of high performance nanofiltration membranes containing “ion pairs”. In this review, the effects of “ion pairs” characteristics, such as the super-hydrophilicity, controllable charge character, and antifouling property, on nanofiltration performances are discussed. A systematic survey was carried out on the various approaches and multiple regulation factors in the fabrication of polyelectrolyte complex membranes, zwitterionic membranes, and charged mosaic membranes, respectively. The mass transport behavior and antifouling mechanism of the membranes with “ion pairs” are also discussed. Finally, we present a brief perspective on the future development of advanced nanofiltration membranes with “ion pairs”. Full article

(This article belongs to the Special Issue Polymeric Membranes)

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Open AccessArticle

The Effect of Plasma Treated PLGA/MWCNTs-COOH Composite Nanofibers on Nerve Cell Behavior

by Jing Wang, Nuan Chen, Seeram Ramakrishna, Lingling Tian and Xiumei Mo

Polymers 2017, 9(12), 713; https://doi.org/10.3390/polym9120713 - 14 Dec 2017

Cited by 30 | Viewed by 5666

Abstract

Electrospun nanofibrous scaffolds which can mimic the architecture of the natural extracellular matrix (ECM) are potential candidates for peripheral nerve repair application. Multi-walled carbon nanotubes (MWCNTs) are used in peripheral nerve repair due to their ability to promote neurite extension and support neural [...] Read more.

Electrospun nanofibrous scaffolds which can mimic the architecture of the natural extracellular matrix (ECM) are potential candidates for peripheral nerve repair application. Multi-walled carbon nanotubes (MWCNTs) are used in peripheral nerve repair due to their ability to promote neurite extension and support neural network formation. In this study, surface-modified nanofibrous scaffolds composed of poly(lactic-co-glycolic acid) (PLGA) and various ratios of carboxyl-modified MWCNTs (MWCNTs-COOH) (PC0, PC2, PC4 and PC8) were fabricated by electrospinning. The effects of MWCNTs-COOH on the fibers’ morphology, diameter distribution, mechanical properties and surface hydrophilicity were characterized by Scanning Electron Microscopy (SEM), ImageJ software, tensile testing and water contact angle. Furthermore, air plasma treatment was applied to improve the surface hydrophilicity of the scaffolds, and the optimal treatment condition was determined in terms of surface morphology, water contact angle and PC12 cell adhesion. Plasma treated nanofibers (p-PC0, p-PC2, p-PC4 and p-PC8) under optimal treatment conditions were used for further study. PC12 cell proliferation and differentiation were both improved by the addition of MWCNTs-COOH in scaffolds. Additionally, the proliferation and maturation of Schwann cells were enhanced on scaffolds containing MWCNTs-COOH. The neurite outgrowth of rat dorsal root ganglia (DRG) neurons was promoted on MWCNTs-COOH-containing scaffolds, and those cultured on p-PC8 scaffolds showed elongated neurites with a length up to 78.27 μm after 3 days culture. Our results suggested that plasma treated nanofibers under appropriate conditions were able to improve cell attachment. They also demonstrated that plasma treated scaffolds containing MWCNTs-COOH, especially the p-PC8 nanofibrous scaffold could support the proliferation, differentiation, maturation and neurite extension of PC12 cells, Schwann cells and DRG neurons. Therefore, p-PC8 could be a potential candidate for peripheral nerve regeneration application. Full article

(This article belongs to the Special Issue Electrospinning of Nanofibres)

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6221 KiB

Open AccessArticle

Effects of Matrix Modification on the Mechanical Properties of Wood–Polypropylene Composites

by Shunmin Yi, Shihua Xu, Yiqun Fang, Haigang Wang and Qingwen Wang

Polymers 2017, 9(12), 712; https://doi.org/10.3390/polym9120712 - 14 Dec 2017

Cited by 18 | Viewed by 5534

Abstract

Polypropylene (PP) modified with two reactive monomers, divinyl benzene (DVB) and maleic anhydride (MAH), was used as the matrix to prepare wood–polypropylene composites to improve interfacial compatibility. The effects of the co-modified PP matrices with different DVB concentrations on the mechanical properties of [...] Read more.

Polypropylene (PP) modified with two reactive monomers, divinyl benzene (DVB) and maleic anhydride (MAH), was used as the matrix to prepare wood–polypropylene composites to improve interfacial compatibility. The effects of the co-modified PP matrices with different DVB concentrations on the mechanical properties of the composites were evaluated. Compared with unmodified composites and the composites containing a coupling agent, the composites modified with MAH only, and that with both MAH and DVB, improved the tensile, flexural, and impact strengths. Interestingly, adding a small amount of DVB (0.4%) resulted in significant increase in impact strength, relative to that of the composites modified with MAH only. Dynamic mechanical analysis and fracture morphology analysis of the modified composites also suggested an improvement in interfacial adhesion owing to the matrix modification. Full article

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Open AccessArticle

The Reaction between Furfuryl Alcohol and Model Compound of Protein

by Jiankun Liang, Zhigang Wu, Hong Lei, Xuedong Xi, Taohong Li and Guanben Du

Polymers 2017, 9(12), 711; https://doi.org/10.3390/polym9120711 - 14 Dec 2017

Cited by 18 | Viewed by 5720

Abstract

To guide the preparation of protein-based adhesive, especially the soy-based adhesive, the reaction between a simple dipeptide N-(2)-l-alanyl-l-glutamine (AG), being used as a model compound of protein, and its cross-linker furfuryl alcohol were studied in this paper. The [...] Read more.

To guide the preparation of protein-based adhesive, especially the soy-based adhesive, the reaction between a simple dipeptide N-(2)-l-alanyl-l-glutamine (AG), being used as a model compound of protein, and its cross-linker furfuryl alcohol were studied in this paper. The products that were prepared with furfuryl alcohol and AG under different pHs were analyzed by ESI-MS, ¹³C NMR, and FT-IR. It was found that the medium environment had great effects on the competition of the co-condensation reaction between furfuryl alcohol and AG and self-condensation reaction of furfuryl alcohol molecules in the mixing system with furfuryl alcohol and AG. Under alkaline conditions, both co- and self-condensation were not obviously detected. Only when the value of pH was higher than 11, were a few co-condensation reaction products gotten. The reaction occurred mainly between furfuryl alcohol and the primary amido groups of AG. Under acid conditions, both co- and self-condensation were observed. The more acid the preparation conditions were, the easier to be observed the self-condensation of furfuryl alcohol molecules would be than the co-condensation between furfuryl alcohol and AG. When the value of pH was higher than 5, both co- and self-condensation were not outstanding. In this study, under pH 3, the co- and self-condensation found equilibrium. There was a great possibility for the primary amido and aliphatic amino groups of AG molecules to react with furfuryl alcohol molecules. No reaction was detected between the secondary amido groups of AG and furfuryl alcohol. Full article

(This article belongs to the Collection Polymeric Adhesives)

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Open AccessFeature PaperArticle

Photo Irradiation-Induced Core Crosslinked Poly(ethylene glycol)-block-poly(aspartic acid) Micelles: Optimization of Block Copolymer Synthesis and Characterization of Core Crosslinked Micelles

by Kouichi Shiraishi, Shin-ichi Yusa, Masanori Ito, Keita Nakai and Masayuki Yokoyama

Polymers 2017, 9(12), 710; https://doi.org/10.3390/polym9120710 - 14 Dec 2017

Cited by 4 | Viewed by 4856

Abstract

We used photo irradiation to design core crosslinked polymeric micelles whose only significant physico-chemical change was in their physico-chemical stability, which helps elucidate poly(ethylene glycol) (PEG)-related immunogenicity. Synthetic routes and compositions of PEG-b-poly(aspartic acid) block copolymers were optimized with the control [...] Read more.

We used photo irradiation to design core crosslinked polymeric micelles whose only significant physico-chemical change was in their physico-chemical stability, which helps elucidate poly(ethylene glycol) (PEG)-related immunogenicity. Synthetic routes and compositions of PEG-b-poly(aspartic acid) block copolymers were optimized with the control of n-alkyl chain length and photo-sensitive chalcone moieties. The conjugation ratio between n-alkyl chain and the chalcone moieties was controlled, and upon the mild photo irradiation of polymeric micelles, permanent crosslink proceeded in the micelle cores. In the optimized condition, the core crosslinked (CCL) micelles exhibited no dissociation while the non-CCL micelles exhibited dissociation. These results indicate that the photo-crosslinking reactions in the inner core were successful. A gel-permeation chromatography (GPC) measurement revealed a difference between the micellar-formation stability of CCL micelles and that of the non-CCL micelles. GPC experiments revealed that the CCL micelles were more stable than the non-CCL micelles. Our research also revealed that photo-crosslinking reactions did not change the core property for drug encapsulation. In conclusion, the prepared CCL micelles exhibited the same diameter, the same formula, and the same inner-core properties for drug encapsulation as did the non-CCL micelles. Moreover, the CCL micelles exhibited non-dissociable micelle formation, while the non-CCL micelles exhibited dissociation into single block copolymers. Full article

(This article belongs to the Special Issue Polymer Micelles)

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Open AccessArticle

Proton Conductive Channel Optimization in Methanol Resistive Hybrid Hyperbranched Polyamide Proton Exchange Membrane

by Liying Ma, Jing Li, Jie Xiong, Guoxiao Xu, Zhao Liu and Weiwei Cai

Polymers 2017, 9(12), 703; https://doi.org/10.3390/polym9120703 - 14 Dec 2017

Cited by 7 | Viewed by 5439

Abstract

Based on a previously developed polyamide proton conductive macromolecule, the nano-scale structure of the self-assembled proton conductive channels (PCCs) is adjusted via enlarging the nano-scale pore size within the macromolecules. Hyperbranched polyamide macromolecules with different size are synthesized from different monomers to tune [...] Read more.

Based on a previously developed polyamide proton conductive macromolecule, the nano-scale structure of the self-assembled proton conductive channels (PCCs) is adjusted via enlarging the nano-scale pore size within the macromolecules. Hyperbranched polyamide macromolecules with different size are synthesized from different monomers to tune the nano-scale pore size within the macromolecules, and a series of hybrid membranes are prepared from these two micromoles to optimize the PCC structure in the proton exchange membrane. The optimized membrane exhibits methanol permeability low to 2.2 × 10⁻⁷ cm²/s, while the proton conductivity of the hybrid membrane can reach 0.25 S/cm at 80 °C, which was much higher than the value of the Nafion 117 membrane (0.192 S/cm). By considering the mechanical, dimensional, and the thermal properties, the hybrid hyperbranched polyamide proton exchange membrane (PEM) exhibits promising application potential in direct methanol fuel cells (DMFC). Full article

(This article belongs to the Special Issue Polymeric Membranes)

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11547 KiB

Open AccessArticle

Morphology, Nucleation, and Isothermal Crystallization Kinetics of Poly(ε-caprolactone) Mixed with a Polycarbonate/MWCNTs Masterbatch

by Thandi P. Gumede, Adriaan S. Luyt, Mohammad K. Hassan, Ricardo A. Pérez-Camargo, Agnieszka Tercjak and Alejandro J. Müller

Polymers 2017, 9(12), 709; https://doi.org/10.3390/polym9120709 - 13 Dec 2017

Cited by 23 | Viewed by 7095

Abstract

In this study, nanocomposites were prepared by melt blending poly (ε-caprolactone) (PCL) with a (polycarbonate (PC)/multi-wall carbon nanotubes (MWCNTs)) masterbatch in a twin-screw extruder. The nanocomposites contained 0.5, 1.0, 2.0, and 4.0 wt % MWCNTs. Even though PCL and PC have been reported [...] Read more.

In this study, nanocomposites were prepared by melt blending poly (ε-caprolactone) (PCL) with a (polycarbonate (PC)/multi-wall carbon nanotubes (MWCNTs)) masterbatch in a twin-screw extruder. The nanocomposites contained 0.5, 1.0, 2.0, and 4.0 wt % MWCNTs. Even though PCL and PC have been reported to be miscible, our DSC (Differential Scanning Calorimetry), SAXS (Small Angle X-ray Scattering), and WAXS (Wide Angle X-ray Scattering) results showed partial miscibility, where two phases were formed (PC-rich and PCL-rich phases). In the PC-rich phase, the small amount of PCL chains included within this phase plasticized the PC component and the PC-rich phase was therefore able to crystallize. In contrast, in the PCL-rich phase the amount of PC chains present generates changes in the glass transition temperature of the PCL phase that were much smaller than those predicted by the Fox equation. The presence of two phases was corroborated by SEM, TEM, and AFM observations where a fair number of MWCNTs diffused from the PC-rich phase to the PCL-rich phase, even though there were some MWCNTs agglomerates confined to PC-rich droplets. Standard DSC measurements demonstrated that the MWCNTs nucleation effects are saturated at a 1 wt % MWCNT concentration on the PCL-rich phase. This is consistent with the dielectric percolation threshold, which was found to be between 0.5 and 1 wt % MWCNTs. However, the nucleating efficiency was lower than literature reports for PCL/MWCNTs, due to limited phase mixing between the PC-rich and the PCL-rich phases. Isothermal crystallization experiments performed by DSC showed an increase in the overall crystallization kinetics of PCL with increases in MWCNTs as a result of their nucleating effect. Nevertheless, the crystallinity degree of the nanocomposite containing 4 wt % MWCNTs decreased by about 15% in comparison to neat PCL. This was attributed to the presence of the PC-rich phase, which was able to crystallize in view of the plasticization effect of the PCL component, since as the MWCNT content increases, the PC content in the blend also increases. The thermal conductivities (i.e., 4 wt % MWCNTs) were enhanced by 20% in comparison to the neat material. The nanocomposites prepared in this work could be employed in applications were electrical conductivity is required, as well as lightweight and tailored mechanical properties. Full article

(This article belongs to the Special Issue Polymer Nanocomposites)

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Open AccessArticle

Electrosynthesis of Aromatic Poly(amide-amine) Films from Triphenylamine-Based Electroactive Compounds for Electrochromic Applications

by Sheng-Huei Hsiao and Hsing-Yi Lu

Polymers 2017, 9(12), 708; https://doi.org/10.3390/polym9120708 - 13 Dec 2017

Cited by 32 | Viewed by 8214

Abstract

Two electropolymerizable monomers with a methoxytriphenylamine core linked via amide groups to two triphenylamine (TPA) or N-phenylcarbazole (NPC) terminal groups, namely 4,4′-bis(4-diphenylaminobenzamido)-4′′-methoxytriphenylamine (MeOTPA-(TPA)₂) and 4,4′-bis(4-(carbazol-9-yl)benzamido)-4′′-methoxytriphenylamine (MeOTPA-(NPC)₂), were synthesized and characterized by FTIR and ¹H NMR spectroscopy, mass [...] Read more.

Two electropolymerizable monomers with a methoxytriphenylamine core linked via amide groups to two triphenylamine (TPA) or N-phenylcarbazole (NPC) terminal groups, namely 4,4′-bis(4-diphenylaminobenzamido)-4′′-methoxytriphenylamine (MeOTPA-(TPA)₂) and 4,4′-bis(4-(carbazol-9-yl)benzamido)-4′′-methoxytriphenylamine (MeOTPA-(NPC)₂), were synthesized and characterized by FTIR and ¹H NMR spectroscopy, mass spectrometry, and cyclic voltammetry. The electrochemical polymerization reactions of these MeOTPA-cored monomers over indium tin oxide (ITO) electrode allow the generation of electroactive poly(amide-amine) films. The electro-generated polymer films exhibited reversible redox processes and multi-colored electrochromic behaviors upon electro-oxidation, together with moderate coloration efficiency and cycling stability. The optical density changes (ΔOD) were observed in the range of 0.18–0.68 at specific absorption maxima, with the calculated coloration efficiencies of 42–123 cm²/C. Single-layer electrochromic devices using the electrodeposited polymer films as active layers were fabricated for the preliminary investigation of their electrochromic applications. Full article

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

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