Polymers

11 pages, 5614 KiB

Open AccessArticle

Chemical Oxidative Polymerization of 2-Aminothiazole in Aqueous Solution: Synthesis, Characterization and Kinetics Study

by Hua Zou, Lu Wang, Xia Wang, Pengfei Lv and Yaozu Liao

Polymers 2016, 8(11), 407; https://doi.org/10.3390/polym8110407 - 23 Nov 2016

Cited by 18 | Viewed by 7351

Abstract

The chemical oxidative polymerization of 2-aminothiazole (AT) was studied in aqueous solution using copper chloride (CuCl₂) as an oxidant. The effect of varying the reaction temperature, reaction time and oxidant/monomer molar ratio on the polymer yield was investigated. The resulting poly(2-aminothiazole)s [...] Read more.

The chemical oxidative polymerization of 2-aminothiazole (AT) was studied in aqueous solution using copper chloride (CuCl₂) as an oxidant. The effect of varying the reaction temperature, reaction time and oxidant/monomer molar ratio on the polymer yield was investigated. The resulting poly(2-aminothiazole)s (PATs) were characterized by FTIR, ¹H NMR, UV-vis, gel permeation chromatography, scanning electron microscopy, thermogravimetric analysis and four-point probe electrical conductivity measurements. Compared with a previous study, PATs with higher yield (81%) and better thermal stability could be synthesized. The chemical oxidative polymerization kinetics of AT were studied for the first time. The orders of the polymerization reaction with respect to monomer concentration and oxidant concentration were found to be 1.14 and 0.97, respectively, and the apparent activation energy of the polymerization reaction was determined to be 21.57 kJ/mol. Full article

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14 pages, 30526 KiB

Open AccessArticle

Physical and Mechanical Evaluation of Silicone-Based Double-Layer Adhesive Patch Intended for Keloids and Scar Treatment Therapy

by Barbara Mikolaszek, Marzena Jamrógiewicz, Krystyna Mojsiewicz-Pieńkowska, Maria Żebrowska, Małgorzata Sznitowska and Justyna Strankowska

Polymers 2016, 8(11), 398; https://doi.org/10.3390/polym8110398 - 22 Nov 2016

Cited by 8 | Viewed by 7820

Abstract

Growing interest in silicone elastomers for pharmaceutical purposes is due to both their beneficial material effect for scar treatment and their potential as drug carriers. Regarding their morphological structure, silicone polymers possess unique properties, which enable a wide range of applicability possibilities. The [...] Read more.

Growing interest in silicone elastomers for pharmaceutical purposes is due to both their beneficial material effect for scar treatment and their potential as drug carriers. Regarding their morphological structure, silicone polymers possess unique properties, which enable a wide range of applicability possibilities. The present study focused on developing a double-layer adhesive silicone film (DLASil) by evaluating its physical and mechanical properties, morphology, and stability. DLASil suitability for treatment of scars and keloids was evaluated by measurement of tensile strength, elasticity modulus, and elongation. The results indicated that mechanical and physical properties of the developed product were satisfying. Full article

(This article belongs to the Collection Silicon-Containing Polymeric Materials)

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12 pages, 3779 KiB

Open AccessArticle

Enhanced Transdermal Permeability via Constructing the Porous Structure of Poloxamer-Based Hydrogel

by Wen-Yi Wang, Patrick C. L. Hui, Elaine Wat, Frency S. F. Ng, Chi-Wai Kan, Clara B. S. Lau and Ping-Chung Leung

Polymers 2016, 8(11), 406; https://doi.org/10.3390/polym8110406 - 21 Nov 2016

Cited by 36 | Viewed by 8541

Abstract

A major concern for transdermal drug delivery systems is the low bioavailability of targeted drugs primarily caused by the skin’s barrier function. The resistance to the carrier matrix for the diffusion and transport of drugs, however, is routinely ignored. This study reports a [...] Read more.

A major concern for transdermal drug delivery systems is the low bioavailability of targeted drugs primarily caused by the skin’s barrier function. The resistance to the carrier matrix for the diffusion and transport of drugs, however, is routinely ignored. This study reports a promising and attractive approach to reducing the resistance to drug transport in the carrier matrix, to enhance drug permeability and bioavailability via enhanced concentration-gradient of the driving force for transdermal purposes. This approach simply optimizes and reconstructs the porous channel structure of the carrier matrix, namely, poloxamer 407 (P407)-based hydrogel matrix blended with carboxymethyl cellulose sodium (CMCs). Addition of CMCs was found to distinctly improve the porous structure of the P407 matrix. The pore size approximated to normal distribution as CMCs were added and the fraction of pore number was increased by over tenfold. Transdermal studies showed that P407/CMCs saw a significant increase in drug permeability across the skin. This suggests that P407/CMC with improved porous structure exhibits a feasible and promising way for the development of transdermal therapy with high permeability and bioavailability, thereby avoiding or reducing use of any chemical enhancers. Full article

(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)

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12 pages, 5203 KiB

Open AccessReview

Olefin–Styrene Copolymers

by Nunzia Galdi, Antonio Buonerba and Leone Oliva

Polymers 2016, 8(11), 405; https://doi.org/10.3390/polym8110405 - 19 Nov 2016

Cited by 19 | Viewed by 10930

Abstract

In this review are reported some of the most relevant achievements in the chemistry of the ethylene–styrene copolymerization and in the characterization of the copolymer materials. Focus is put on the relationship between the structure of the catalyst and that of the obtained [...] Read more.

In this review are reported some of the most relevant achievements in the chemistry of the ethylene–styrene copolymerization and in the characterization of the copolymer materials. Focus is put on the relationship between the structure of the catalyst and that of the obtained copolymer. On the other hand, the wide variety of copolymer architecture is related to the properties of the material and to the potential utility. Full article

(This article belongs to the Collection Featured Mini Reviews in Polymer Science)

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12 pages, 5008 KiB

Open AccessArticle

Thixotropic Supramolecular Pectin-Poly(Ethylene Glycol) Methacrylate (PEGMA) Hydrogels

by Siew Yin Chan, Wee Sim Choo, David James Young and Xian Jun Loh

Polymers 2016, 8(11), 404; https://doi.org/10.3390/polym8110404 - 18 Nov 2016

Cited by 33 | Viewed by 10799

Abstract

Pectin is an anionic, water-soluble polymer predominantly consisting of covalently 1,4-linked α-d-galacturonic acid units. This naturally occurring, renewable and biodegradable polymer is underutilized in polymer science due to its insolubility in organic solvents, which renders conventional polymerization methods impractical. To circumvent [...] Read more.

Pectin is an anionic, water-soluble polymer predominantly consisting of covalently 1,4-linked α-d-galacturonic acid units. This naturally occurring, renewable and biodegradable polymer is underutilized in polymer science due to its insolubility in organic solvents, which renders conventional polymerization methods impractical. To circumvent this problem, cerium-initiated radical polymerization was utilized to graft methoxy-poly(ethylene glycol) methacrylate (mPEGMA) onto pectin in water. The copolymers were characterized by ¹H nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA), and used in the formation of supramolecular hydrogels through the addition of α-cyclodextrin (α-CD) to induce crosslinking. These hydrogels possessed thixotropic properties; shear-thinning to liquid upon agitation but settling into gels at rest. In contrast to most of the other hydrogels produced through the use of poly(ethylene glycol) (PEG)-grafted polymers, the pectin-PEGMA/α-CD hydrogels were unaffected by temperature changes. Full article

(This article belongs to the Collection Polysaccharides)

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14 pages, 5812 KiB

Open AccessArticle

Structure and Transport Properties of Mixed-Matrix Membranes Based on Polyimides with ZrO₂ Nanostars

by Maria P. Sokolova, Michael A. Smirnov, Pavel Geydt, Alexander N. Bugrov, Sami-Seppo Ovaska, Erkki Lahderanta and Alexander M. Toikka

Polymers 2016, 8(11), 403; https://doi.org/10.3390/polym8110403 - 18 Nov 2016

Cited by 22 | Viewed by 6598

Abstract

Mixed-matrix membranes based on amorphous and semi-crystalline polyimides with zirconium dioxide (ZrO₂) nanostars were synthesized. Amorphous poly(4,4′-oxydiphenylenepyromellitimide) and semi-crystalline polyimide prepared from 1,4-bis(4-aminophenoxy)benzene and 4,4’-oxydiphthalic anhydride were used. The effect of ZrO₂ nanostars on the structure and morphology of nanocomposite [...] Read more.

Mixed-matrix membranes based on amorphous and semi-crystalline polyimides with zirconium dioxide (ZrO₂) nanostars were synthesized. Amorphous poly(4,4′-oxydiphenylenepyromellitimide) and semi-crystalline polyimide prepared from 1,4-bis(4-aminophenoxy)benzene and 4,4’-oxydiphthalic anhydride were used. The effect of ZrO₂ nanostars on the structure and morphology of nanocomposite membranes was studied by wide-angle X-ray scattering, scanning electron microscopy, atomic force microscopy, and contact angle measurements. Thermal properties and stability were investigated by thermogravimetric analysis and differential scanning calorimetry. Transport properties of hybrid membranes containing 5 wt % ZrO₂ were tested for pervaporation of a mixture of butanol–water with 10 wt % H₂O content. It was found that a significant amount of the ZrO₂ added to the semi-crystalline polyimide is encapsulated inside spherulites. Therefore, the beneficial influence of inorganic filler on the selectivity of mixed-matrix membrane with respect to water was hampered. Mixed-matrix membranes based on amorphous polymer demonstrated the best performance, because water molecules had higher access to inorganic particles. Full article

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17 pages, 13426 KiB

Open AccessArticle

Polycaprolactone/Amino-β-Cyclodextrin Inclusion Complex Prepared by an Electrospinning Technique

by Edgar Moyers-Montoya, Perla García-Casillas, Claudia Vargas-Requena, René Escobedo-González, Santos-Adriana Martel-Estrada and Carlos A. Martínez-Pérez

Polymers 2016, 8(11), 395; https://doi.org/10.3390/polym8110395 - 18 Nov 2016

Cited by 31 | Viewed by 9739

Abstract

Electrospun scaffolds of neat poly-ε-caprolactone (PCL), poly-ε-caprolactone/β-cyclodextrin inclusion complex (PCL/β-CD) and poly-ε-caprolactone amino derivative inclusion complex (PCL/β-CD-NH₂) were prepared by the electrospinning technique. The obtained mats were analyzed by a theoretical model using the Hartree–Fock method with an STO-3G basis set, [...] Read more.

Electrospun scaffolds of neat poly-ε-caprolactone (PCL), poly-ε-caprolactone/β-cyclodextrin inclusion complex (PCL/β-CD) and poly-ε-caprolactone amino derivative inclusion complex (PCL/β-CD-NH₂) were prepared by the electrospinning technique. The obtained mats were analyzed by a theoretical model using the Hartree–Fock method with an STO-3G basis set, and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR), differential scanning calorimetry (DSC), confocal-Raman spectroscopy, proton nuclear magnetic resonance (¹HNMR) and contact angle measure (CA). Different mixtures of solvents, such as dimethylformamide (DMF)-tetrahydrofuran (THF), dichlormethane (DCM)-dimethyl sulfoxide (DMSO) and 2,2,2-Trifluoroethanol (TFE), were tested in the fiber preparation. The results indicate that electrospun nanofibers have a pseudorotaxane structure and when it was prepared using a 2,2,2-Trifluoroethanol (TFE) as solvent, the nanofibers were electrospun well and, with the other solvents, fibers present defects such as molten fibers and bead-like defects into the fiber structure. This work provides insights into the design of PCL/β-CD-NH₂ based scaffolds that could have applications in the biomedical field. Full article

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

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16 pages, 3099 KiB

Open AccessArticle

Patterned Fibers Embedded Microfluidic Chips Based on PLA and PDMS for Ag Nanoparticle Safety Testing

by Yaowen Liu, Shuyao Wang and Yihao Wang

Polymers 2016, 8(11), 402; https://doi.org/10.3390/polym8110402 - 16 Nov 2016

Cited by 20 | Viewed by 8645

Abstract

A new method to integrate poly-dl-lactide (PLA) patterned electrospun fibers with a polydimethylsiloxane (PDMS) microfluidic chip was successfully developed via lithography. Hepatocyte behavior under static and dynamic conditions was investigated. Immunohistochemical analyses indicated good hepatocyte survival under the dynamic culture system [...] Read more.

A new method to integrate poly-dl-lactide (PLA) patterned electrospun fibers with a polydimethylsiloxane (PDMS) microfluidic chip was successfully developed via lithography. Hepatocyte behavior under static and dynamic conditions was investigated. Immunohistochemical analyses indicated good hepatocyte survival under the dynamic culture system with effective hepatocyte spheroid formation in the patterned microfluidic chip vs. static culture conditions and tissue culture plate (TCP). In particular, hepatocytes seeded in this microfluidic chip under a flow rate of 10 μL/min could re-establish hepatocyte polarity to support biliary excretion and were able to maintain high levels of albumin and urea secretion over 15 days. Furthermore, the optimized system could produce sensitive and consistent responses to nano-Ag-induced hepatotoxicity during culture. Thus, this microfluidic chip device provides a new means of fabricating complex liver tissue-engineered scaffolds, and may be of considerable utility in the toxicity screening of nanoparticles. Full article

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14 pages, 6901 KiB

Open AccessArticle

Effect of Microwave Treatment of Graphite on the Electrical Conductivity and Electrochemical Properties of Polyaniline/Graphene Oxide Composites

by Yanjun Tang, Xiulan Hu, Dongdong Liu, Daliang Guo and Junhua Zhang

Polymers 2016, 8(11), 399; https://doi.org/10.3390/polym8110399 - 16 Nov 2016

Cited by 21 | Viewed by 8398

Abstract

Polyaniline (PANI)/graphene oxide (GO) composites were synthesized via in situ polymerization of aniline in the presence of GO. The effect of microwave treatment of graphite on the electrical conductivity and electrochemical properties of PANI/GO composites was highlighted, and the morphology and microstructure were [...] Read more.

Polyaniline (PANI)/graphene oxide (GO) composites were synthesized via in situ polymerization of aniline in the presence of GO. The effect of microwave treatment of graphite on the electrical conductivity and electrochemical properties of PANI/GO composites was highlighted, and the morphology and microstructure were subsequently characterized using transmission electron microscopy, scanning electron microscopy, Fourier-transformed infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. The results demonstrated that microwave treatment of graphite imparted a well-dispersed, highly ordered layered structure to the as-prepared GO, and in turn facilitated strong bonding between the GO and PANI nanosheets, which may be responsible for the improved electrical conductivity and electrochemical properties of the resulting PANI/GO composites. The desired PANI/GO composites possessed an electrical conductivity of 508 S/m, an areal capacitance of 172.8 mF/cm², and a retained capacitance of 87.4% after cycling, representing percentage increases of 102, 232, and 112, respectively, as a result of the microwave treatment of graphite. The resulting composites are promising electrode materials for high-performance and ecofriendly electrical energy storage devices. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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17 pages, 11343 KiB

Open AccessArticle

Co-Delivery of Imiquimod and Plasmid DNA via an Amphiphilic pH-Responsive Star Polymer that Forms Unimolecular Micelles in Water

by Wenjing Lin, Na Yao, Hongru Li, Samuel Hanson, Wenqing Han, Chun Wang and Lijuan Zhang

Polymers 2016, 8(11), 397; https://doi.org/10.3390/polym8110397 - 16 Nov 2016

Cited by 25 | Viewed by 10694

Abstract

Dual functional unimolecular micelles based on a pH-responsive amphiphilic star polymer β-CD-(PLA-b-PDMAEMA-b-PEtOxMA)₂₁ have been developed for the co-delivery of imiquimod and plasmid DNA to dendritic cells. The star polymer with well-defined triblock arms was synthesized by combining activator [...] Read more.

Dual functional unimolecular micelles based on a pH-responsive amphiphilic star polymer β-CD-(PLA-b-PDMAEMA-b-PEtOxMA)₂₁ have been developed for the co-delivery of imiquimod and plasmid DNA to dendritic cells. The star polymer with well-defined triblock arms was synthesized by combining activator regenerated by electron-transfer atom-transfer radical polymerization with ring-opening polymerization. Dissipative particle dynamics simulation showed that core-mesophere-shell-type unimolecular micelles could be formed. Imiquimod-loaded micelles had a drug loading of 1.6 wt % and a larger average size (28 nm) than blank micelles (19 nm). The release of imiquimod in vitro was accelerated at the mildly acidic endolysosomal pH (5.0) in comparison to physiologic pH (7.4). Compared with blank micelles, a higher N:P ratio was required for imiquimod-loaded micelles to fully condense DNA into micelleplexes averaging 200–400 nm in size. In comparison to blank micelleplexes, imiquimod-loaded micelleplexes of the same N:P ratio displayed similar or slightly higher efficiency of gene transfection in a mouse dendritic cell line (DC2.4) without cytotoxicity. These results suggest that such pH-responsive unimolecular micelles formed by the well-defined amphiphilic star polymer may serve as promising nano-scale carriers for combined delivery of hydrophobic immunostimulatory drugs (such as imiquimod) and plasmid DNA with potential application in gene-based immunotherapy. Full article

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

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11 pages, 2359 KiB

Open AccessArticle

Characterization of Aniline Tetramer by MALDI TOF Mass Spectrometry upon Oxidative and Reductive Cycling

by Rebecca L. Li, Cheng-Wei Lin, Yuanlong Shao, Che Wei Chang, Fu-Kai Yao, Matthew D. Kowal, Haosen Wang, Michael T. Yeung, Shu-Chuan Huang and Richard B. Kaner

Polymers 2016, 8(11), 401; https://doi.org/10.3390/polym8110401 - 15 Nov 2016

Cited by 24 | Viewed by 8697

Abstract

By combining electrochemical experiments with mass spectrometric analysis, it is found that using short chain oligomers to improve the cycling stability of conducting polymers in supercapacitors is still problematic. Cycling tests via cyclic voltammetry over a potential window of 0 to 1.0 V [...] Read more.

By combining electrochemical experiments with mass spectrometric analysis, it is found that using short chain oligomers to improve the cycling stability of conducting polymers in supercapacitors is still problematic. Cycling tests via cyclic voltammetry over a potential window of 0 to 1.0 V or 0 to 1.2 V in a two-electrode device configuration resulted in solid-state electropolymerization and chain scission. Electropolymerization of the aniline tetramer to generate long chain oligomers is shown to be possible despite the suggested decrease in reactivity and increase in intermediate stability with longer oligomers. Because aniline oligomers are more stable towards reductive cycling when compared to oxidative cycling, future conducting polymer/oligomer-based pseudocapacitors should consider using an asymmetric electrode configuration. Full article

(This article belongs to the Special Issue Conjugated Polymers 2016)

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23 pages, 2991 KiB

Open AccessArticle

Fabrication of a Miniature Paper-Based Electroosmotic Actuator

by Deepa Sritharan and Elisabeth Smela

Polymers 2016, 8(11), 400; https://doi.org/10.3390/polym8110400 - 15 Nov 2016

Cited by 10 | Viewed by 10293

Abstract

A voltage-controlled hydraulic actuator is presented that employs electroosmotic fluid flow (EOF) in paper microchannels within an elastomeric structure. The microfluidic device was fabricated using a new benchtop lamination process. Flexible embedded electrodes were formed from a conductive carbon-silicone composite. The pores in [...] Read more.

A voltage-controlled hydraulic actuator is presented that employs electroosmotic fluid flow (EOF) in paper microchannels within an elastomeric structure. The microfluidic device was fabricated using a new benchtop lamination process. Flexible embedded electrodes were formed from a conductive carbon-silicone composite. The pores in the layer of paper placed between the electrodes served as the microchannels for EOF, and the pumping fluid was propylene carbonate. A sealed fluid-filled chamber was formed by film-casting silicone to lay an actuating membrane over the pumping liquid. Hydraulic force generated by EOF caused the membrane to bulge by hundreds of micrometers within fractions of a second. Potential applications of these actuators include soft robots and biomedical devices. Full article

(This article belongs to the Special Issue Polymeric Soft Actuators)

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15 pages, 2898 KiB

Open AccessArticle

Sustainable Phenolic Fractions as Basis for Furfuryl Alcohol-Based Co-Polymers and Their Use as Wood Adhesives

by Paul Luckeneder, Johannes Gavino, Robert Kuchernig, Alexander Petutschnigg and Gianluca Tondi

Polymers 2016, 8(11), 396; https://doi.org/10.3390/polym8110396 - 14 Nov 2016

Cited by 39 | Viewed by 7584

Abstract

Furfuryl alcohol is a very interesting green molecule used in the production of biopolymers. In the present paper, the copolymerization in acid environment with natural, easily-available, phenolic derivatives is investigated. The processes of polymerization of the furfuryl alcohol with: (i) spent-liquor from the [...] Read more.

Furfuryl alcohol is a very interesting green molecule used in the production of biopolymers. In the present paper, the copolymerization in acid environment with natural, easily-available, phenolic derivatives is investigated. The processes of polymerization of the furfuryl alcohol with: (i) spent-liquor from the pulping industry and (ii) commercial tannin from acacia mimosa were investigated though viscometry and IR-spectroscopy. The curing kinetics of the formulations highlighted the importance of the amount of furfuryl alcohol and catalyst as well as the effect of temperature for both phenolic-furanic polymers. Evidence of covalent copolymerization has been observed through infrared spectrometry (FT-IR) combined with principal component analysis (PCA) and confirmed with additional solubility tests. These bio-based formulations were applied as adhesives for solid wood and particleboards with interesting results: at 180 °C, the spent-liquor furanic formulations allow wood bonding slightly with lower performance than PVA in dry conditions, while mixed formulations allow the gluing of particleboard with only satisfactory internal bonding tests. Full article

(This article belongs to the Special Issue Renewable Polymeric Adhesives)

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17 pages, 4141 KiB

Open AccessArticle

Synthesis of Novel Temperature- and pH-Sensitive ABA Triblock Copolymers P(DEAEMA-co-MEO₂MA-co-OEGMA)-b-PEG-b-P(DEAEMA-co-MEO₂MA-co-OEGMA): Micellization, Sol–Gel Transitions, and Sustained BSA Release

by Yanan Han, Shouxin Liu, Hongguang Mao, Lei Tian and Wenyan Ning

Polymers 2016, 8(11), 367; https://doi.org/10.3390/polym8110367 - 11 Nov 2016

Cited by 13 | Viewed by 10414

Abstract

Novel temperature- and pH-responsive ABA-type triblock copolymers, P(DEAEMA-co-MEO₂MA-co-OEGMA)-b-PEG-b-P(DEAEMA-co-MEO₂MA-co-OEGMA), composed of a poly(ethylene glycol) (PEG) middle block and temperature- and pH-sensitive outer blocks, were synthesized by atom transfer [...] Read more.

Novel temperature- and pH-responsive ABA-type triblock copolymers, P(DEAEMA-co-MEO₂MA-co-OEGMA)-b-PEG-b-P(DEAEMA-co-MEO₂MA-co-OEGMA), composed of a poly(ethylene glycol) (PEG) middle block and temperature- and pH-sensitive outer blocks, were synthesized by atom transfer radical polymerization (ATRP). The composition and structure of the copolymer were characterized by ¹H NMR and gel permeation chromatography (GPC). The temperature- and pH-sensitivity, micellization, and the sol–gel transitions of the triblock copolymers in aqueous solutions were studied using transmittance measurements, surface tension, viscosity, fluorescence probe technique, dynamic light scattering (DLS), zeta-potential measurements, and transmission electron microscopy (TEM). The lower critical solution temperature (LCST) of the triblock copolymer, which contains a small amount of a weak base group, (N,N-diethylamino) ethyl methacrylate (DEAEMA), can be tuned precisely and reversibly by changing the solution pH. When the copolymer concentration was sufficiently high, increasing temperature resulted in the free-flowing solution transformation into a micellar gel. The sol-to-gel transition temperature (T_sol–gel) in aqueous solution will continue to decrease as solution concentration increases. Full article

(This article belongs to the Special Issue Responsive Polymers for Drug Delivery, Imaging and Theranostic Functions)

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12 pages, 10590 KiB

Open AccessArticle

Core/Shell Structure of Ni/NiO Encapsulated in Carbon Nanosphere Coated with Few- and Multi-Layered Graphene: Synthesis, Mechanism and Application

by Ferial Ghaemi, Luqman Chuah Abdullah and Paridah Tahir

Polymers 2016, 8(11), 381; https://doi.org/10.3390/polym8110381 - 9 Nov 2016

Cited by 8 | Viewed by 7342

Abstract

This paper focuses on the synthesis and mechanism of carbon nanospheres (CNS) coated with few- and multi-layered graphene (FLG, MLG). The graphitic carbon encapsulates the core/shell structure of the Ni/NiO nanoparticles via the chemical vapor deposition (CVD) method. The application of the resulting [...] Read more.

This paper focuses on the synthesis and mechanism of carbon nanospheres (CNS) coated with few- and multi-layered graphene (FLG, MLG). The graphitic carbon encapsulates the core/shell structure of the Ni/NiO nanoparticles via the chemical vapor deposition (CVD) method. The application of the resulting CNS and hybrids of CNS-FLG and CNS-MLG as reinforcement nanofillers in a polypropylene (PP) matrix were studied from the aspects of mechanical and thermal characteristics. In this research, to synthesize carbon nanostructures, nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O) and acetylene (C₂H₂) were used as the catalyst source and carbon source, respectively. Besides, the morphology, structure and graphitization of the resulting carbon nanostructures were investigated. On the other hand, the mechanisms of CNS growth and the synthesis of graphene sheets on the CNS surface were studied. Finally, the mechanical and thermal properties of the CNS/PP, CNS-FLG/PP, and CNS-MLG/PP composites were analyzed by applying tensile test and thermogravimetric analysis (TGA), respectively. Full article

(This article belongs to the Special Issue Polymeric Fibers)

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10 pages, 1143 KiB

Open AccessArticle

High Bonding Temperatures Greatly Improve Soy Adhesive Wet Strength

by Charles R. Frihart, Thomas Coolidge, Chera Mock and Eder Valle

Polymers 2016, 8(11), 394; https://doi.org/10.3390/polym8110394 - 8 Nov 2016

Cited by 24 | Viewed by 6337

Abstract

Soy wood adhesive bond strengths reported in different literature studies are difficult to compare because a variety of temperatures and other conditions have been used for the bonding and testing step. Some reports have indicated bond strengths are sensitive to bonding temperature, but [...] Read more.

Soy wood adhesive bond strengths reported in different literature studies are difficult to compare because a variety of temperatures and other conditions have been used for the bonding and testing step. Some reports have indicated bond strengths are sensitive to bonding temperature, but the reason(s) for this has not been intensively investigated. Although these prior studies differ in other ways (such as type of soy, wood species, and test method), the effect of bonding temperature has not been clearly examined, which is important for focusing commercial applications. A tensile shear test using two-parallel-ply veneer specimens with smooth maple was used to measure both the dry and wet cohesive strength of soy adhesives. Although the soy adhesives gave very good strengths and dry wood failure, they often have low wood failure and shear strengths under wet conditions when bonded at 120 °C. However, wet strength greatly increased as the bonding temperature increased (120, 150 and 180 °C) for these two-ply tests with. This study examined the use of different types of soys (flours, concentrates and isolates) and different bonding temperatures and bonding conditions to evacuate several possible mechanisms for this temperature sensitivity, with coalescence being the most likely. Full article

(This article belongs to the Special Issue Renewable Polymeric Adhesives)

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12 pages, 2219 KiB

Open AccessArticle

Mechanical and Electrochemical Performance of Carbon Fiber Reinforced Polymer in Oxygen Evolution Environment

by Ji-Hua Zhu, Liangliang Wei, Guanping Guo and Aizhu Zhu

Polymers 2016, 8(11), 393; https://doi.org/10.3390/polym8110393 - 8 Nov 2016

Cited by 24 | Viewed by 7726

Abstract

Carbon fiber-reinforced polymer (CFRP) is recognized as a promising anode material to prevent steel corrosion in reinforced concrete. However, the electrochemical performance of CFRP itself is unclear. This paper focuses on the understanding of electrochemical and mechanical properties of CFRP in an oxygen [...] Read more.

Carbon fiber-reinforced polymer (CFRP) is recognized as a promising anode material to prevent steel corrosion in reinforced concrete. However, the electrochemical performance of CFRP itself is unclear. This paper focuses on the understanding of electrochemical and mechanical properties of CFRP in an oxygen evolution environment by conducting accelerated polarization tests. Different amounts of current density were applied in polarization tests with various test durations, and feeding voltage and potential were measured. Afterwards, tensile tests were carried out to investigate the failure modes for the post-polarization CFRP specimens. Results show that CFRP specimens had two typical tensile-failure modes and had a stable anodic performance in an oxygen evolution environment. As such, CFRP can be potentially used as an anode material for impressed current cathodic protection (ICCP) of reinforced concrete structures, besides the fact that CFRP can strengthen the structural properties of reinforced concrete. Full article

(This article belongs to the Special Issue Polymeric Fibers)

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16 pages, 3759 KiB

Open AccessArticle

Preparation of Magnetic Iron Oxide Nanoparticles (MIONs) with Improved Saturation Magnetization Using Multifunctional Polymer Ligand

by Muhammad Irfan Majeed, Jiaojiao Guo, Wei Yan and Bien Tan

Polymers 2016, 8(11), 392; https://doi.org/10.3390/polym8110392 - 8 Nov 2016

Cited by 50 | Viewed by 10782

Abstract

This paper describes the preparation of ultra-small magnetic iron oxide (Fe₃O₄) nanoparticles (MIONs) coated with water-soluble thioether end-functionalized polymer ligand pentaerythritol tetrakis 3-mercaptopropionate-polymethacrylic acid (PTMP-PMAA). The MIONs were prepared by co-precipitation of aqueous iron precursor solution at a high [...] Read more.

This paper describes the preparation of ultra-small magnetic iron oxide (Fe₃O₄) nanoparticles (MIONs) coated with water-soluble thioether end-functionalized polymer ligand pentaerythritol tetrakis 3-mercaptopropionate-polymethacrylic acid (PTMP-PMAA). The MIONs were prepared by co-precipitation of aqueous iron precursor solution at a high temperature. The polymer modified MIONs were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and vibrating sample magnetometery (VSM). It was found that these MIONs were successfully modified by this water-soluble polymer ligand with a fairly uniform size and narrow size distribution. The dried powder of MIONs could be stored for a long time and re-dispersed well in water without any significant change. Additionally, the polymer concentration showed a significant effect on size and magnetic properties of the MIONs. The saturation magnetization was increased by optimizing the polymer concentration. Furthermore, the 3-(4,5-dimethylthiazol-2-yl)-2-5-diphenyltetrazolium bromide (MTT)-assay demonstrated that these MIONs were highly biocompatible and they could be successfully coupled with fluorescent dye Rhodamine due to the formation of amide bond between carboxylic acid groups of MIONs and amine groups of dye. The obtained results indicated that these multifunctional MIONs with rich surface chemistry exhibit admirable potential in biomedical applications. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials)

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15 pages, 1608 KiB

Open AccessArticle

A ¹³C-NMR Study on the 1,3-Dimethylolurea-Phenol Co-Condensation Reaction: A Model for Amino-Phenolic Co-Condensed Resin Synthesis

by Ming Cao, Taohong Li, Jiankun Liang, Zhigang Wu, Xiaojian Zhou and Guanben Du

Polymers 2016, 8(11), 391; https://doi.org/10.3390/polym8110391 - 8 Nov 2016

Cited by 15 | Viewed by 9510

Abstract

The reactions of di-hydroxymethylurea with phenol under alkaline (pH = 10), weak (pH = 6) and strong acidic (pH = 2) conditions were investigated via the ¹³C-NMR method. Based on the proposed reaction mechanisms, the variations of the structures of different condensed [...] Read more.

The reactions of di-hydroxymethylurea with phenol under alkaline (pH = 10), weak (pH = 6) and strong acidic (pH = 2) conditions were investigated via the ¹³C-NMR method. Based on the proposed reaction mechanisms, the variations of the structures of different condensed products were analyzed and the competitive relationship between self- and co-condensation reactions was elucidated. The required experimental conditions for co-condensations were clearly pointed out. The main conclusions include: (1) the self-condensation between urea formaldehyde (UF) or phenol formaldehyde (PF) monomers were dominant while the co-condensations were very limited under alkaline conditions. This is because the intermediates produced from urea, methylolurea and phenol are less reactive in co-condensations with respect to self-condensations; (2) under weak acidic conditions, the self-condensations occurred exclusively among the UF monomers. The co-condensation structures were not observed; and (3) the co-condensations became much more competitive under strong acidic conditions as the relative content of the co-condensed methylenic carbon accounts for 53.3%. This result can be rationalized by the high reactivity of the methylolphenol carbocation intermediate toward urea and methylolurea. The revealed reaction selectivity and mechanisms may also be applied to the synthesis of those more complex co-condensed adhesives based on natural phenolic and amino compounds. Full article

(This article belongs to the Special Issue Renewable Polymeric Adhesives)

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19 pages, 2737 KiB

Open AccessArticle

Accurate Cure Modeling for Isothermal Processing of Fast Curing Epoxy Resins

by Alexander Bernath, Luise Kärger and Frank Henning

Polymers 2016, 8(11), 390; https://doi.org/10.3390/polym8110390 - 3 Nov 2016

Cited by 62 | Viewed by 11365

Abstract

In this work a holistic approach for the characterization and mathematical modeling of the reaction kinetics of a fast epoxy resin is shown. Major composite manufacturing processes like resin transfer molding involve isothermal curing at temperatures far below the ultimate glass transition temperature. [...] Read more.

In this work a holistic approach for the characterization and mathematical modeling of the reaction kinetics of a fast epoxy resin is shown. Major composite manufacturing processes like resin transfer molding involve isothermal curing at temperatures far below the ultimate glass transition temperature. Hence, premature vitrification occurs during curing and consequently has to be taken into account by the kinetic model. In order to show the benefit of using a complex kinetic model, the Kamal-Malkin kinetic model is compared to the Grindling kinetic model in terms of prediction quality for isothermal processing. From the selected models, only the Grindling kinetic is capable of taking into account vitrification. Non-isothermal, isothermal and combined differential scanning calorimetry (DSC) measurements are conducted and processed for subsequent use for model parametrization. In order to demonstrate which DSC measurements are vital for proper cure modeling, both models are fitted to varying sets of measurements. Special attention is given to the evaluation of isothermal DSC measurements which are subject to deviations arising from unrecorded cross-linking prior to the beginning of the measurement as well as from physical aging effects. It is found that isothermal measurements are vital for accurate modeling of isothermal cure and cannot be neglected. Accurate cure predictions are achieved using the Grindling kinetic model. Full article

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12 pages, 1650 KiB

Open AccessArticle

Influences of Alkyl and Aryl Substituents on Iminopyridine Fe(II)- and Co(II)-Catalyzed Isoprene Polymerization

by Lihua Guo, Xinyu Jing, Shuoyan Xiong, Wenjing Liu, Yanlan Liu, Zhe Liu and Changle Chen

Polymers 2016, 8(11), 389; https://doi.org/10.3390/polym8110389 - 3 Nov 2016

Cited by 52 | Viewed by 7611

Abstract

A series of alkyl- and aryl-substituted iminopyridine Fe(II) complexes 1a–7a and Co(II) complexes 2b, 3b, 5b, and 6b were synthesized. The activator effect, influence of temperature, and, particularly, the alkyl and aryl substituents’ effect on catalytic activity, polymer [...] Read more.

A series of alkyl- and aryl-substituted iminopyridine Fe(II) complexes 1a–7a and Co(II) complexes 2b, 3b, 5b, and 6b were synthesized. The activator effect, influence of temperature, and, particularly, the alkyl and aryl substituents’ effect on catalytic activity, polymer molecular weight, and regio-/stereoselectivity were investigated when these complexes were applied in isoprene polymerization. All of the Fe(II) complexes afforded polyisoprene with high molecular weight and moderate cis-1,4 selectivity. In contrast, the Co(II) complexes produced polymers with low molecular weight and relatively high cis-1,4 selectivity. In the iminopyridine Fe(II) system, the alkyl and aryl substituents’ effect exhibits significant variation on the isoprene polymerization. In the iminopyridine Co(II) system, there is little influence observed on isoprene polymerization by alkyl and aryl substituents. Full article

(This article belongs to the Special Issue Young Talents in Polymer Science)

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13 pages, 3364 KiB

Open AccessArticle

Understanding the Structural Evolution of Single Conjugated Polymer Chain Conformers

by Adam J. Wise and John K. Grey

Polymers 2016, 8(11), 388; https://doi.org/10.3390/polym8110388 - 3 Nov 2016

Cited by 7 | Viewed by 6224

Abstract

Single molecule photoluminescence (PL) spectroscopy of conjugated polymers has shed new light on the complex structure–function relationships of these materials. Although extensive work has been carried out using polarization and excitation intensity modulated experiments to elucidate conformation-dependent photophysics, surprisingly little attention has been [...] Read more.

Single molecule photoluminescence (PL) spectroscopy of conjugated polymers has shed new light on the complex structure–function relationships of these materials. Although extensive work has been carried out using polarization and excitation intensity modulated experiments to elucidate conformation-dependent photophysics, surprisingly little attention has been given to information contained in the PL spectral line shapes. We investigate single molecule PL spectra of the prototypical conjugated polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) which exists in at least two emissive conformers and can only be observed at dilute levels. Using a model based on the well-known “Missing Mode Effect” (MIME), we show that vibronic progression intervals for MEH-PPV conformers can be explained by relative contributions from particular skeletal vibrational modes. Here, observed progression intervals do not match any ground state Raman active vibrational frequency and instead represent a coalescence of multiple modes in the frequency domain. For example, the higher energy emitting “blue” MEH-PPV form exhibits PL maxima at ~18,200 cm⁻¹ with characteristic MIME progression intervals of ~1200–1350 cm⁻¹, whereas the lower energy emitting “red” form peaks at ~17,100 cm⁻¹ with intervals in the range of ~1350–1450 cm⁻¹. The main differences in blue and red MEH-PPV chromophores lie in the intra-chain order, or, planarity of monomers within a chromophore segment. We demonstrate that the Raman-active out-of-plane C–H wag of the MEH-PPV vinylene group (~966 cm⁻¹) has the greatest influence in determining the observed vibronic progression MIME interval. Namely, larger displacements (intensities)—indicating lower intra-chain order—lower the effective MIME interval. This simple model provides useful insights into the conformational characteristics of the heterogeneous chromophore landscape without requiring costly and time-consuming low temperature or single molecule Raman capabilities. Full article

(This article belongs to the Special Issue Conjugated Polymers 2016)

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36 pages, 10732 KiB

Open AccessReview

Composite Polymer Electrolytes: Nanoparticles Affect Structure and Properties

by Wei Wang and Paschalis Alexandridis

Polymers 2016, 8(11), 387; https://doi.org/10.3390/polym8110387 - 3 Nov 2016

Cited by 129 | Viewed by 18098

Abstract

Composite polymer electrolytes (CPEs) can significantly improve the performance in electrochemical devices such as lithium-ion batteries. This review summarizes property/performance relationships in the case where nanoparticles are introduced to polymer electrolytes. It is the aim of this review to provide a knowledge network [...] Read more.

Composite polymer electrolytes (CPEs) can significantly improve the performance in electrochemical devices such as lithium-ion batteries. This review summarizes property/performance relationships in the case where nanoparticles are introduced to polymer electrolytes. It is the aim of this review to provide a knowledge network that elucidates the role of nano-additives in the CPEs. Central to the discussion is the impact on the CPE performance of properties such as crystalline/amorphous structure, dielectric behavior, and interactions within the CPE. The amorphous domains of semi-crystalline polymer facilitate the ion transport, while an enhanced mobility of polymer chains contributes to high ionic conductivity. Dielectric properties reflect the relaxation behavior of polymer chains as an important factor in ion conduction. Further, the dielectric constant (ε) determines the capability of the polymer to dissolve salt. The atom/ion/nanoparticle interactions within CPEs suggest ways to enhance the CPE conductivity by generating more free lithium ions. Certain properties can be improved simultaneously by nanoparticle addition in order to optimize the overall performance of the electrolyte. The effects of nano-additives on thermal and mechanical properties of CPEs are also presented in order to evaluate the electrolyte competence for lithium-ion battery applications. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials)

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1 pages, 424 KiB

Open AccessErratum

Erratum: RAFT-Mediated Polymerization-Induced Self-Assembly of Poly(Acrylic Acid)-b-Poly(Hexafluorobutyl Acrylate): Effect of the pH on the Synthesis of Self-Stabilized Particles. Polymers, 2016, 8, 207

by Jianhua Zhou, Renyan He and Jianzhong Ma

Polymers 2016, 8(11), 384; https://doi.org/10.3390/polym8110384 - 1 Nov 2016

Cited by 2 | Viewed by 4219

Abstract

n/a Full article

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15 pages, 6593 KiB

Open AccessArticle

Influence of Organically-Modified Montmorillonite and Synthesized Layered Silica Nanoparticles on the Properties of Polypropylene and Polyamide-6 Nanocomposites

by Moisés Gómez, Humberto Palza and Raúl Quijada

Polymers 2016, 8(11), 386; https://doi.org/10.3390/polym8110386 - 31 Oct 2016

Cited by 23 | Viewed by 5889

Abstract

Nanocomposites of layered silica nanoparticles (LSN) obtained by the sol–gel method, and commercial montmorillonite clay Cloisite^®20A with polypropylene (PP) and Cloisite^®30B with polyamide-6 (PA6) were prepared by melt blending in order to study their effects on barrier, mechanical properties, [...] Read more.

Nanocomposites of layered silica nanoparticles (LSN) obtained by the sol–gel method, and commercial montmorillonite clay Cloisite^®20A with polypropylene (PP) and Cloisite^®30B with polyamide-6 (PA6) were prepared by melt blending in order to study their effects on barrier, mechanical properties, and thermal stability. Transmission electron microscopy (TEM) showed that all of the nanocomposites present agglomerated nanoparticles with some degree of individual particles. In barrier properties, LSN dramatically increased the oxygen and water vapor permeability of PP at low loadings (<5 wt %) due to the percolation effect. However, in PP and PA6 nanocomposites with clays, the permeability showed increases and decreases depending on the solubility of the permeating gases with the clays and the polymers. Tensile stress-strain tests otherwise showed that the nanocomposites with clays present an enhancement in the elastic modulus. Meanwhile, with the LSN, a decrease was found due to the formation of agglomerations and voids. Finally, thermogravimetric analysis under inert conditions showed the nanoparticles do not have a significant effect on the thermal stability of the nanocomposites. These results expose the relevance of the type of layered nanoparticle and polymer matrix on the barrier, mechanical, and thermal behaviors of the resulting nanocomposites. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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10 pages, 2557 KiB

Open AccessArticle

Fluorescence Imaging in Genipin Crosslinked Chitosan–Poly(vinyl pyrrolidone) Hydrogels

by Simon Matcham and Katarina Novakovic

Polymers 2016, 8(11), 385; https://doi.org/10.3390/polym8110385 - 28 Oct 2016

Cited by 21 | Viewed by 7297

Abstract

Recent research has identified genipin as a promising natural crosslinking agent for biocompatible hydrogels as genipin is significantly less cytotoxic than current synthetic crosslinking agents, such as glutaraldehyde. Conveniently, fluorophores can be produced when genipin crosslinks. In this study, fluorescence intensity measurements of [...] Read more.

Recent research has identified genipin as a promising natural crosslinking agent for biocompatible hydrogels as genipin is significantly less cytotoxic than current synthetic crosslinking agents, such as glutaraldehyde. Conveniently, fluorophores can be produced when genipin crosslinks. In this study, fluorescence intensity measurements of genipin crosslinked chitosan-poly(vinyl pyrrolidone) hydrogels have been explored as a dynamic, in situ method for tracing sol-gel transition. These pH-responsive smart materials have a future in medical applications, in particular in tissue engineering and drug delivery, where methods to follow the process in situ and in real-time are crucial for future advancement. Samples were prepared using deionised water, pH 4, and pH 10 solutions, and studied at 24 and 37 °C over a 24 h period. Both temperature and pH have been found to affect sol-gel transition in the hydrogels studied. The transition from acidic (pH 4) to basic (pH 10) solution resulted in reduced fluorescence intensity suggesting that, under more basic conditions, genipin molecules self-polymerise, reducing the number of molecules available for reaction with the amino groups of chitosan. Three-dimensional representations of the fluorescence present in a hydrogel sample have also been produced from the data, enabling the visualisation of variation in fluorescence with time at the surface of the hydrogel. Full article

(This article belongs to the Collection Polysaccharides)

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16 pages, 9864 KiB

Open AccessArticle

Processing of Syndiotactic Polystyrene to Microspheres for Part Manufacturing through Selective Laser Sintering

by Nicolas Mys, An Verberckmoes and Ludwig Cardon

Polymers 2016, 8(11), 383; https://doi.org/10.3390/polym8110383 - 28 Oct 2016

Cited by 37 | Viewed by 7389

Abstract

Syndiotactic polystyrene pellets were processed into powder form using mechanical (ball milling, rotor milling) and physicochemical (spray drying) techniques with the intention of using it as feed material for selective laser sintering. New materials are an important component in broadening the application window [...] Read more.

Syndiotactic polystyrene pellets were processed into powder form using mechanical (ball milling, rotor milling) and physicochemical (spray drying) techniques with the intention of using it as feed material for selective laser sintering. New materials are an important component in broadening the application window for selective laser sintering but must meet strict requirements to be used. Particles obtained were characterized in size and shape using SEM imaging, analyzed by software, and compared to the product obtained by conventional ball milling. Rotor milling and spray drying proved capable of making spherical powders, yet only rotor milling achieved particles with a mean diameter within the desired range of 45–97 µm. Subsequently, the obtained powders were examined for the effect each processing technique imparts on the intrinsic properties of the material. Differential scanning calorimetry analysis revealed amorphization for all methods and a reduction in crystallinity after processing, however, the reduction in crystallinity was acceptably low for the spray-dried and rotor-milled powders. Ball milling displayed an exceptional reduction in crystallinity, suggesting severe degradation. As a final test, the rotor-milled powder was subjected to single-layer test and displayed good coalescence and smooth morphology, albeit with a large amount of warpage. Full article

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14 pages, 2604 KiB

Open AccessArticle

Synthesis and Characterization of Two-Dimensional Conjugated Polymers Incorporating Electron-Deficient Moieties for Application in Organic Photovoltaics

by Chuen-Yo Hsiow, Han-Ying Wang, Yu-Hsiang Lin, Rathinam Raja, Syang-Peng Rwei, Wen-Yen Chiu, Chi-An Dai and Leeyih Wang

Polymers 2016, 8(11), 382; https://doi.org/10.3390/polym8110382 - 27 Oct 2016

Cited by 4 | Viewed by 6453

Abstract

A series of novel p-type conjugated copolymers, PTTVBDT, PTTVBDT-TPD, and PTTVBDT-DPP, cooperating benzo[1,2-b:4,5-b′]dithiophene (BDT) and terthiophene-vinylene (TTV) units with/without thieno[3,4-c]pyrrole-4,6-dione (TPD) or pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) via Stille polymerization were synthesized and characterized. Copolymer PTTVBDT shows a low-lying HOMO energy level [...] Read more.

A series of novel p-type conjugated copolymers, PTTVBDT, PTTVBDT-TPD, and PTTVBDT-DPP, cooperating benzo[1,2-b:4,5-b′]dithiophene (BDT) and terthiophene-vinylene (TTV) units with/without thieno[3,4-c]pyrrole-4,6-dione (TPD) or pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) via Stille polymerization were synthesized and characterized. Copolymer PTTVBDT shows a low-lying HOMO energy level and ordered molecular-packing behavior. Furthermore, two terpolymers, PTTVBDT-TPD and PTTVBDT-DPP, display stronger absorption ability, alower-lying HOMO energy level, and preferred molecular orientation, due to the replacement TTV-monomer units with electron-deficient groups. Furthermore, bulk-heterojunction organic solar cells were fabricated using blends of the PTTVBDT-TPD, and PC₆₁BM gave the best power conversion efficiency of 5.01% under the illumination of AM 1.5G, 100 mW·cm⁻²; the short circuit current (J_sc) was 11.65 mA·cm⁻² which displayed a 43.8% improvement in comparison with the PTTVBDT/PC₆₁BM device. These results demonstrate a valid strategy combining the two-dimensional molecular structure with random copolymerization strikes promising conjugated polymers to achieve highly efficient organic photovoltaics. Full article

(This article belongs to the Special Issue Conjugated Polymers 2016)

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25 pages, 6199 KiB

Open AccessReview

Recent Advances in Dual Temperature Responsive Block Copolymers and Their Potential as Biomedical Applications

by Yohei Kotsuchibashi, Mitsuhiro Ebara, Takao Aoyagi and Ravin Narain

Polymers 2016, 8(11), 380; https://doi.org/10.3390/polym8110380 - 27 Oct 2016

Cited by 118 | Viewed by 16872

Abstract

The development of stimuli responsive polymers has progressed significantly with novel preparation techniques, which has allowed access to new materials with unique properties. Dual thermoresponsive (double temperature responsive) block copolymers are particularly of interest as their properties can change depending on the lower [...] Read more.

The development of stimuli responsive polymers has progressed significantly with novel preparation techniques, which has allowed access to new materials with unique properties. Dual thermoresponsive (double temperature responsive) block copolymers are particularly of interest as their properties can change depending on the lower critical solution temperature (LCST) or upper critical solution temperature (UCST) of each segment. For instance, these block copolymers can change from being hydrophilic, to amphiphilic or to hydrophobic simply by changing the solution temperature without any additional chemicals and the block copolymers can change from being fully solubilized to self-assembled structures to macroscopic aggregation/precipitation. Based on the unique solution properties, these dual thermo-responsive block copolymers are expected to be suitable for biomedical applications. This review is divided into three parts; LCST-LCST types of block copolymers, UCST-LCST types of block copolymers, and their potential as biomedical applications. Full article

(This article belongs to the Special Issue Responsive Polymers for Drug Delivery, Imaging and Theranostic Functions)

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15 pages, 2813 KiB

Open AccessArticle

Conjugation of Lectin to Poly(ε-caprolactone)-block-glycopolymer Micelles for In Vitro Intravesical Drug Delivery

by Ning Ning Li, Xiao Yan Cai, Jiu Cun Chen, Xue Feng Hu and Li Qun Xu

Polymers 2016, 8(11), 379; https://doi.org/10.3390/polym8110379 - 26 Oct 2016

Cited by 15 | Viewed by 6469

Abstract

Amphiphilic poly(ε-caprolactone)-block-poly[2-(α-d-mannopyranosyloxy) ethyl acrylamide] (PCL-b-PManEA) block copolymers were synthesized via a combination of ring-opening polymerization (ROP), reversible addition-fragmentation chain transfer (RAFT) polymerization and reactive ester-amine reaction. The PCL-b-PManEA block copolymers can self-assemble into micelles and [...] Read more.

Amphiphilic poly(ε-caprolactone)-block-poly[2-(α-d-mannopyranosyloxy) ethyl acrylamide] (PCL-b-PManEA) block copolymers were synthesized via a combination of ring-opening polymerization (ROP), reversible addition-fragmentation chain transfer (RAFT) polymerization and reactive ester-amine reaction. The PCL-b-PManEA block copolymers can self-assemble into micelles and encapsulate anticancer drug doxorubicin (DOX). To enhance mucoadhesive property of the resulting DOX-loaded PCL-b-PManEA micelles, Concanavalin A (ConA) lectin was further conjugated with the micelles. Turbidimetric assay using mucin shows that the DOX-loaded PCL-b-PManEA@ConA micelles are mucoadhesive. DOX release from the DOX-loaded PCL-b-PManEA@ConA micelles in artificial urine at 37 °C exhibits an initial burst release, followed by a sustained and slow release over three days. Confocal laser scanning microscope (CLSM) images indicate that the DOX-loaded PCL-b-PManEA@ConA micelles can be effectively internalized by UMUC3 human urothelial carcinoma cells. The DOX-loaded PCL-b-PManEA@ConA micelles exhibit significant cytotoxicity to these cells. Full article

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