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Polymers, Volume 9, Issue 7 (July 2017)

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Cover Story ABC star terpolymers are made of immiscible blocks and form vesicles with nanodomains that allow [...] Read more.
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Open AccessArticle CO2-Philic Thin Film Composite Membranes: Synthesis and Characterization of PAN-r-PEGMA Copolymer
Polymers 2017, 9(7), 219; doi:10.3390/polym9070219
Received: 7 May 2017 / Revised: 7 June 2017 / Accepted: 9 June 2017 / Published: 6 July 2017
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Abstract
In this work, we report the successful fabrication of CO2-philic polymer composite membranes using a polyacrylonitrile-r-poly(ethylene glycol) methyl ether methacrylate (PAN-r-PEGMA) copolymer. The series of PAN-r-PEGMA copolymers with various amounts of PEG content was synthesized
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In this work, we report the successful fabrication of CO2-philic polymer composite membranes using a polyacrylonitrile-r-poly(ethylene glycol) methyl ether methacrylate (PAN-r-PEGMA) copolymer. The series of PAN-r-PEGMA copolymers with various amounts of PEG content was synthesized by free radical polymerization in presence of AIBN initiator and the obtained copolymers were used for the fabrication of composite membranes. The synthesized copolymers show high molecular weights in the range of 44–56 kDa. We were able to fabricate thin film composite (TFC) membranes by dip coating procedure using PAN-r-PEGMA copolymers and the porous PAN support membrane. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were applied to analyze the surface morphology of the composite membranes. The microscopy analysis reveals the formation of the defect free skin selective layer of PAN-r-PEGMA copolymer over the porous PAN support membrane. Selective layer thickness of the composite membranes was in the range of 1.32–1.42 μm. The resulting composite membrane has CO2 a permeance of 1.37 × 10−1 m3/m2·h·bar and an ideal CO2/N2, selectivity of 65. The TFC membranes showed increasing ideal gas pair selectivities in the order CO2/N2 > CO2/CH4 > CO2/H2. In addition, the fabricated composite membranes were tested for long-term single gas permeation measurement and these membranes have remarkable stability, proving that they are good candidates for CO2 separation. Full article
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Open AccessArticle Direct Micromachining of Microfluidic Channels on Biodegradable Materials Using Laser Ablation
Polymers 2017, 9(7), 242; doi:10.3390/polym9070242
Received: 28 April 2017 / Revised: 12 June 2017 / Accepted: 15 June 2017 / Published: 23 June 2017
Cited by 2 | PDF Full-text (13126 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Laser patterning on polymeric materials is considered a green and rapid manufacturing process with low material selection barrier and high adjustability. Unlike microelectromechanical systems (MEMS), it is a highly flexible processing method, especially useful for prototyping. This study focuses on the development of
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Laser patterning on polymeric materials is considered a green and rapid manufacturing process with low material selection barrier and high adjustability. Unlike microelectromechanical systems (MEMS), it is a highly flexible processing method, especially useful for prototyping. This study focuses on the development of polymer surface modification method using a 193 nm excimer laser system for the design and fabrication of a microfluidic system similar to that of natural vasculatures. Besides from poly(dimethyl siloxane) (PDMS), laser ablation on biodegradable polymeric material, poly(glycerol sebacate) (PGS) and poly(1,3-diamino-2-hydroxypropane-co-polyol sebacate) (APS) are investigated. Parameters of laser ablation and fabrication techniques to create microchannels are discussed. The results show that nano/micro-sized fractures and cracks are generally observed across PDMS surface after laser ablation, but not on PGS and APS surfaces. The widths of channels are more precise on PGS and APS than those on PDMS. Laser beam size and channel depth are high correlation with a linear relationship. Repeated laser ablations on the same position of scaffolds reveal that the ablation efficiencies and edge quality on PGS and APS are higher than on PDMS, suggesting the high applicability of direct laser machining to PGS and APS. To ensure stable ablation efficiency, effects of defocus distance into polymer surfaces toward laser ablation stability are investigated. The depth of channel is related to the ratio of firing frequency and ablation progression speed. The hydrodynamic simulation of channels suggests that natural blood vessel is similar to the laser patterned U-shaped channels, and the resulting micro-patterns are highly applicable in the field of micro-fabrication and biomedical engineering. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessArticle Fracture Failure Mechanisms of Long Single PA6 Fibers
Polymers 2017, 9(7), 243; doi:10.3390/polym9070243
Received: 19 May 2017 / Revised: 19 June 2017 / Accepted: 20 June 2017 / Published: 23 June 2017
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Abstract
The present study investigates the failure mechanisms of industrial fiber materials, using a custom designed fiber cutting performance test bench. The fracture morphologies of single PA6 fibers are examined by scanning electron microscopy. The analysis reveals that fiber cutting can be distinguished according
[...] Read more.
The present study investigates the failure mechanisms of industrial fiber materials, using a custom designed fiber cutting performance test bench. The fracture morphologies of single PA6 fibers are examined by scanning electron microscopy. The analysis reveals that fiber cutting can be distinguished according to four distinct stages of fiber failure represented by shearing, cutting, brittle fracture, and tensile failure, which are the result of different mechanisms active during the processes of crack initiation, extension, and fracture. The results of fractographic analysis are further verified by an analysis of the blade assembly speed with respect to time over the entire fracture failure process based on high-speed camera data. The results of fractographic analysis and blade assembly speed are fully consistent. Full article
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Open AccessArticle The Combined Effects of Environmental Conditioning and Sustained Load on Mechanical Properties of Wet Lay-Up Fiber Reinforced Polymer
Polymers 2017, 9(7), 244; doi:10.3390/polym9070244
Received: 3 May 2017 / Revised: 19 June 2017 / Accepted: 20 June 2017 / Published: 23 June 2017
Cited by 2 | PDF Full-text (2541 KB) | HTML Full-text | XML Full-text
Abstract
The aim of this study was to investigate the combined effects of an aggressive environment and sustained load on the mechanical properties of wet lay-up fiber reinforced polymers (FRP). A total of 390 specimens, including 234 carbon fiber reinforced polymer (CFRP) specimens and
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The aim of this study was to investigate the combined effects of an aggressive environment and sustained load on the mechanical properties of wet lay-up fiber reinforced polymers (FRP). A total of 390 specimens, including 234 carbon fiber reinforced polymer (CFRP) specimens and 156 glass fiber reinforced polymer (GFRP) specimens, were exposed to freeze–thaw cycles, hygrothermal aging, and wet–dry cycles either in an unstressed state or loaded to about 30% or 60% of the initial ultimate load. Uniaxial tension tests were conducted on the samples after specific exposure time as well as on the control samples; and tensile properties were measured for each specimen. The results showed that the three environmental exposures, particularly hygrothermal aging, led to a significant decrease in tensile strength and elongation of the CFRP and GFRP specimens even for relatively short conditioning periods, and this decrease was markedly exacerbated by higher external loading levels. It was interesting to observe that the tensile modulus of the CFRP and GFRP specimens exhibited an excellent resistance and even appeared to increase slightly after exposure. Finally, predictive values of tensile strength based on the Arrhenius method were compared with the design values of ACI 440.2R-08 and GB 50608-2010. The results showed that both ACI 440.2R-08 and GB 50608-2010 were too conservative and significantly underestimated the tensile strength of FRP materials after an anticipated exposure period. Full article
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Open AccessArticle Dynamics of a Polymer Network Based on Dual Sierpinski Gasket and Dendrimer: A Theoretical Approach
Polymers 2017, 9(7), 245; doi:10.3390/polym9070245
Received: 30 May 2017 / Revised: 17 June 2017 / Accepted: 21 June 2017 / Published: 24 June 2017
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Abstract
In this paper we focus on the relaxation dynamics of a multihierarchical polymer network built through the replication of the dual Sierpinski gasket in the form of a regular dendrimer. The relaxation dynamics of this multihierarchical structure is investigated in the framework of
[...] Read more.
In this paper we focus on the relaxation dynamics of a multihierarchical polymer network built through the replication of the dual Sierpinski gasket in the form of a regular dendrimer. The relaxation dynamics of this multihierarchical structure is investigated in the framework of the generalized Gaussian structure model using both Rouse and Zimm approaches. In the Rouse-type approach, we show a method whereby the whole eigenvalue spectrum of the connectivity matrix of the multihierarchical structure can be determined iteratively, thereby rendering possible the analysis of the Rouse-dynamics at very large generations. Remarkably, the general picture that emerges from both approaches, even though we have a mixed growth algorithm and the monomers interactions are taken into account specifically to the adopted approach, is that the multihierarchical structure preserves the individual relaxation behaviors of its constituent components. The theoretical findings with respect to the splitting of the intermediate domain of the relaxation quantities are well supported by experimental results. Full article
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Open AccessArticle Photodeprotectable N-Alkoxybenzyl Aromatic Polyamides
Polymers 2017, 9(7), 246; doi:10.3390/polym9070246
Received: 22 May 2017 / Revised: 18 June 2017 / Accepted: 21 June 2017 / Published: 24 June 2017
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Abstract
N-alkoxybenzyl aromatic polyamides were synthesized by polycondensation of N-alkoxybenzyl aromatic diamine with equimolar dicarboxylic acid chloride in the presence of 2.2 equiv. of pyridine at room temperature for 2 days. The obtained polyamides were mainly cyclic polymers, as determined by means
[...] Read more.
N-alkoxybenzyl aromatic polyamides were synthesized by polycondensation of N-alkoxybenzyl aromatic diamine with equimolar dicarboxylic acid chloride in the presence of 2.2 equiv. of pyridine at room temperature for 2 days. The obtained polyamides were mainly cyclic polymers, as determined by means of matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and showed higher solubility in organic solvents than unprotected aromatic polyamides. Photodeprotection of N-alkoxybenzyl aromatic polyamide film containing photo acid generator (PAG) proceeded well under UV irradiation (5 J/cm2), followed by heating at 130 °C for 15 min. The nature of the polymer end groups of N-alkoxybenzyl aromatic polyamides was found to be crucial for photodeprotection reactivity. These polymers are promising candidates for photosensitive heat-resistant materials for fine Cu wiring formation by electroless Cu plating of high-density semiconductor packaging substrates. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessArticle Preparation and Characterization of Chitosan/Soy Protein Isolate Nanocomposite Film Reinforced by Cu Nanoclusters
Polymers 2017, 9(7), 247; doi:10.3390/polym9070247
Received: 26 May 2017 / Revised: 17 June 2017 / Accepted: 23 June 2017 / Published: 25 June 2017
Cited by 4 | PDF Full-text (6653 KB) | HTML Full-text | XML Full-text
Abstract
Soy protein isolate (SPI) based films have received considerable attention for use in packaging materials. However, SPI-based films exhibit relatively poor mechanical properties and water resistance ability. To tackle these challenges, chitosan (CS) and endogenous Cu nanoclusters (NCs) capped with protein were proposed
[...] Read more.
Soy protein isolate (SPI) based films have received considerable attention for use in packaging materials. However, SPI-based films exhibit relatively poor mechanical properties and water resistance ability. To tackle these challenges, chitosan (CS) and endogenous Cu nanoclusters (NCs) capped with protein were proposed and designed to modify SPI-based films. Attenuated total reflectance-Fourier transform infrared spectroscopy and X-ray diffraction patterns of composite films demonstrated that interactions, such as hydrogen bonds in the film forming process, promoted the cross-linking of composite films. The surface microstructure of CS/SPI films modified with Cu NCs was more uniform and transmission electron microscopy (TEM) showed that uniform and discrete clusters were formed. Compared with untreated SPI films, the tensile strength and elongation at break of composite films were simultaneously improved by 118.78% and 74.93%, respectively. Moreover, these composite films also exhibited higher water contact angle and degradation temperature than that of pure SPI film. The water vapor permeation of the modified film also decreased. These improved properties of functional bio-polymers show great potential as food packaging materials. Full article
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Open AccessArticle Chestnut Honey Impregnated Carboxymethyl Cellulose Hydrogel for Diabetic Ulcer Healing
Polymers 2017, 9(7), 248; doi:10.3390/polym9070248
Received: 5 May 2017 / Revised: 9 June 2017 / Accepted: 23 June 2017 / Published: 27 June 2017
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Abstract
Honey-based wound dressings have attracted a lot of attention from modern scientists owing to their anti-inflammatory and antibacterial effects without antibiotic resistance. Such dressings also promote moist wound healing, and have been considered natural, abundant, and cheap materials for folk marketing. This study
[...] Read more.
Honey-based wound dressings have attracted a lot of attention from modern scientists owing to their anti-inflammatory and antibacterial effects without antibiotic resistance. Such dressings also promote moist wound healing, and have been considered natural, abundant, and cheap materials for folk marketing. This study investigated the various behaviors and characteristics of chestnut honey-impregnated carboxymethyl cellulose sodium hydrogel paste (CH–CMC) as a therapeutic dressing, such as its moist retention, antibacterial activity for inhibiting the growth of Staphylococcus aureus and Escherichia coli, and the rate of wound healing in db/db mice. The results provide good evidence, suggesting that CH–CMC has potential as a competitive candidate for diabetic ulcer wound healing. Full article
(This article belongs to the Special Issue Hydrogels in Tissue Engineering and Regenerative Medicine)
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Open AccessArticle Facile Synthesis and Self-Assembly of Amphiphilic Polyether-Octafunctionalized Polyhedral Oligomeric Silsesquioxane via Thiol-Ene Click Reaction
Polymers 2017, 9(7), 251; doi:10.3390/polym9070251
Received: 17 May 2017 / Revised: 12 June 2017 / Accepted: 26 June 2017 / Published: 28 June 2017
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Abstract
We demonstrated here a facile and efficient synthesis of polyhedral oligomeric silsesquioxane-based amphiphilic polymer by thiol-ene click chemistry. The properties of polyhedral oligomeric silsesquioxane (POSS)–PEG amphiphilic polymers were studied in detail by a combination of 1H NMR, 13C NMR, 29Si
[...] Read more.
We demonstrated here a facile and efficient synthesis of polyhedral oligomeric silsesquioxane-based amphiphilic polymer by thiol-ene click chemistry. The properties of polyhedral oligomeric silsesquioxane (POSS)–PEG amphiphilic polymers were studied in detail by a combination of 1H NMR, 13C NMR, 29Si NMR FT-IR, GPC, and TG analysis. The newly-designed thiol-ene protocol obtains only anti-Markovnikov addition POSS-based amphiphilic polymers when compared with platinum-catalysed hydrosilylation method. The critical micelle concentration (CMC) of the resulting polymers are in the range of 0.011 to 0.050 mg/mL, and dynamic light scattering (DLS) results revealed that the obtained amphiphilic polymers can self-assemble into nanoparticles in aqueous solutions with a bimodal (two peaks) distribution. Furthermore, the specific polymer showed obvious thermo-sensitive behaviour at 45.5 °C. Full article
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Open AccessArticle Tailoring Drug Release Properties by Gradual Changes in the Particle Engineering of Polysaccharide Chitosan Based Powders
Polymers 2017, 9(7), 253; doi:10.3390/polym9070253
Received: 14 June 2017 / Revised: 22 June 2017 / Accepted: 24 June 2017 / Published: 29 June 2017
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Abstract
Chitosan is a natural copolymer generally available in pharmaceutical and food powders associated with drugs, vitamins, and nutraceuticals. This study focused on monitoring the effect of the morphology and structural features of the chitosan particles for controlling the release profile of the active
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Chitosan is a natural copolymer generally available in pharmaceutical and food powders associated with drugs, vitamins, and nutraceuticals. This study focused on monitoring the effect of the morphology and structural features of the chitosan particles for controlling the release profile of the active pharmaceutical ingredient (API) propranolol hydrochloride. Chitosan with distinct molecular mass (low and medium) were used in the formulations as crystalline and irregular particles from commercial raw material, or as spherical, uniform, and amorphous spray-dried particles. The API–copolymer interactions were assessed when adding the drug before (drug-loaded particles) or after the spray drying (only mixed with blank particles). The formulations were further compared with physical mixtures of the API with chitin and microcrystalline cellulose. The scanning electron microscopy (SEM) images, surface area, particle size measurements, X-ray diffraction (XRD) analysis and drug loading have supported the drug release behavior. The statistical analysis of experimental data demonstrated that it was possible to control the drug release behavior (immediate or slow drug release) from chitosan powders using different types of particles. Full article
(This article belongs to the Special Issue Polymers from Renewable Resources)
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Open AccessArticle In Vitro Response of Human Peripheral Blood Mononuclear Cells (PBMC) to Collagen Films Treated with Cold Plasma
Polymers 2017, 9(7), 254; doi:10.3390/polym9070254
Received: 30 May 2017 / Revised: 25 June 2017 / Accepted: 26 June 2017 / Published: 29 June 2017
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Abstract
The implantation of biomedical devices, including collagen-based implants, evokes an inflammatory response. Despite inflammation playing an important role in the early stages of wound healing, excessive and non-resolving inflammation may lead to the poor performance of biomaterial implants in some patients. Therefore, steps
[...] Read more.
The implantation of biomedical devices, including collagen-based implants, evokes an inflammatory response. Despite inflammation playing an important role in the early stages of wound healing, excessive and non-resolving inflammation may lead to the poor performance of biomaterial implants in some patients. Therefore, steps should be taken to control the level and duration of an inflammatory response. In this study, oxygen and nitrogen gas plasmas were employed to modify the surface of collagen film, with a view to modifying the surface properties of a substrate in order to induce changes to the inflammatory response, whilst maintaining the mechanical integrity of the underlying collagen film. The effects of cold plasma treatment and resultant changes to surface properties on the non-specific inflammatory response of the immune system was investigated in vitro in direct contact cell culture by the measurement of protein expression and cytokine production after one and four days of human peripheral blood mononuclear cell (PBMC) culture. The results indicated that compared to oxygen plasma, nitrogen plasma treatment produced an anti-inflammatory effect on the collagen film by reducing the initial activation of monocytes and macrophages, which led to a lower production of pro-inflammatory cytokines IL-1β and TNFα, and higher production of anti-inflammatory cytokine IL-10. This was attributed to the combination of the amino chemical group and the significant reduction in roughness associated with the introduction of the nitrogen plasma treatment, which had an effect on the levels of activation of the adherent cell population. Full article
(This article belongs to the Special Issue Advance of Polymers Applied to Biomedical Applications: Biointerface)
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Open AccessArticle Theoretical Analysis of Critical Flowable Physical Gel Cross-Linked by Metal Ions and Polyacrylamide-Derivative Associating Polymers Containing Imidazole Groups
Polymers 2017, 9(7), 256; doi:10.3390/polym9070256
Received: 19 May 2017 / Revised: 18 June 2017 / Accepted: 23 June 2017 / Published: 29 June 2017
Cited by 1 | PDF Full-text (6202 KB) | HTML Full-text | XML Full-text
Abstract
When the polymer chains are cross-linked by physical bonds having a finite lifetime, the relaxation time and viscosity do not diverge at the gel point though percolation occurs. These undivergent quantities are related to the finite-sized “largest relaxed cluster,” which can relax before
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When the polymer chains are cross-linked by physical bonds having a finite lifetime, the relaxation time and viscosity do not diverge at the gel point though percolation occurs. These undivergent quantities are related to the finite-sized “largest relaxed cluster,” which can relax before it breaks. Its size is the key rheological parameter characterizing of the critical physical gels. In order to evaluate this characteristic size, we propose here a generalized phenomenological model for the viscoelasticity of critical physical gels. We apply the theory to the previously reported experimental result for the physical gel consisting of polyacrylamide-derivative associating polymers containing imidazole groups cross-linked by coordination bonds with Ni ions. We successfully estimate the size of the largest relaxed cluster and the fractal dimension. The size is in good agreement with that estimated from the mean-square displacement of probe particles at the gel point by microrheological measurement. We also compare this system with the poly(vinyl alcohol) hydrogel cross-linked by borate ions, and show that the difference in the cluster structures is originating from the differences of precursor chain properties such as overlap concentration and radius of gyration and of the cross-linking states in these systems. Full article
(This article belongs to the Special Issue Complex Fluid Rheology)
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Open AccessArticle Forensic Engineering of Advanced Polymeric Materials—Part V: Prediction Studies of Aliphatic–Aromatic Copolyester and Polylactide Commercial Blends in View of Potential Applications as Compostable Cosmetic Packages
Polymers 2017, 9(7), 257; doi:10.3390/polym9070257
Received: 5 June 2017 / Revised: 23 June 2017 / Accepted: 26 June 2017 / Published: 29 June 2017
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Abstract
The main aim of the present study was to determine the behavior of the specimens from Ecovio, in the form of dumbbell-shaped samples and films, during degradation in selected cosmetic ingredients such as water and paraffin. The (bio)degradation test of the prototype cosmetic
[...] Read more.
The main aim of the present study was to determine the behavior of the specimens from Ecovio, in the form of dumbbell-shaped samples and films, during degradation in selected cosmetic ingredients such as water and paraffin. The (bio)degradation test of the prototype cosmetic package (sachet) made from a PBAT (poly[(1,4-butylene adipate)-co-(1,4-butylene terephthalate)]) and PLA (polylactide) blend was investigated under industrial composting conditions, and compared with the sample behavior during incubation in cosmetic media at 70 °C. During the degradation tests, the changes of the samples were evaluated using optical microscopy, 1H NMR (proton nuclear magnetic resonance) and GPC (gel permeation chromatography) techniques. The structures of the degradation products were investigated using ESI-MSn (mass spectrometry with electrospray ionization on positive and negative ions) analysis. The thermal properties of selected materials were determined by DSC (differential scanning calorimetry) and TGA (thermogravimetric analysis) analysis. It was concluded that the PBAT and PLA blend studied had a good stability during aging in cosmetic media, and could be recommended for long-shelf-life compostable packaging of cosmetics, especially with oily ingredients. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle Preparation and Characterization of Eco-Friendly Mg(OH)2/Lignin Hybrid Material and Its Use as a Functional Filler for Poly(Vinyl Chloride)
Polymers 2017, 9(7), 258; doi:10.3390/polym9070258
Received: 5 June 2017 / Revised: 23 June 2017 / Accepted: 28 June 2017 / Published: 30 June 2017
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Abstract
A functional magnesium hydroxide/lignin hybrid system was prepared by grinding and mixing the pure precursors using a planetary ball mill. In addition, the thermal stability was assessed based on the total mass loss of the hybrid system within the temperature range of 30–1000
[...] Read more.
A functional magnesium hydroxide/lignin hybrid system was prepared by grinding and mixing the pure precursors using a planetary ball mill. In addition, the thermal stability was assessed based on the total mass loss of the hybrid system within the temperature range of 30–1000 °C, which amounted to 38%. Moreover, the average particle size was at 4.9 μm as determined by the laser diffraction method. The effect of addition of the prepared and characterized Mg(OH)2/lignin hybrid filler at concentrations ranging from 2.5 wt % to 10 wt % on the processing as well as mechanical and thermal properties of composites on the matrix of the unplasticized PVC compound was also evaluated. The addition of a filler to the poly(vinyl chloride) matrix causes a significant improvement of its thermal stability, which is approximately three times higher compared to a polymer without a filler. Furthermore, the prepared composites are additionally characterized by advantageous mechanical properties, especially higher Young’s modulus. A 10% increase in the oxygen index of PVC composites upon addition of 10 wt % hybrid fillers has also been observed, which contributes to an extended range of their application under conditions that require notable fire resistance. Full article
(This article belongs to the Special Issue Bio-inspired and Bio-based Polymers)
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Open AccessArticle Preparation and Property Evaluation of Conductive Hydrogel Using Poly (Vinyl Alcohol)/Polyethylene Glycol/Graphene Oxide for Human Electrocardiogram Acquisition
Polymers 2017, 9(7), 259; doi:10.3390/polym9070259
Received: 25 May 2017 / Revised: 27 June 2017 / Accepted: 28 June 2017 / Published: 30 June 2017
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Abstract
Conductive hydrogel combined with Ag/AgCl electrode is widely used in the acquisition of bio-signals. However, the high adhesiveness of current commercial hydrogel causes human skin allergies and pruritus easily after wearing hydrogel for electrodes for a long time. In this paper, a novel
[...] Read more.
Conductive hydrogel combined with Ag/AgCl electrode is widely used in the acquisition of bio-signals. However, the high adhesiveness of current commercial hydrogel causes human skin allergies and pruritus easily after wearing hydrogel for electrodes for a long time. In this paper, a novel conductive hydrogel with good mechanical and conductive performance was prepared using polyvinyl alcohol (PVA), polyethylene glycol (PEG), and graphene oxide (GO) nanoparticles. A cyclic freezing–thawing method was employed under processing conditions of −40 °C (8 h) and 20 °C (4 h) separately for three cycles in sequence until a strong conductive hydrogel, namely, PVA/PEG/GO gel, was obtained. Characterization (Fourier transform infrared spectroscopy, nuclear magnetic resonance, scanning electron microscopy) results indicated that the assembled hydrogel was successfully prepared with a three-dimensional network structure and, thereafter, the high strength and elasticity due to the complete polymeric net formed by dense hydrogen bonds in the freezing process. The as-made PVA/PEG/GO hydrogel was then composited with nonwoven fabric for electrocardiogram (ECG) electrodes. The ECG acquisition data indicated that the prepared hydrogel has good electro-conductivity and can obtain stable ECG signals for humans in a static state and in motion (with a small amount of drift). A comparison of results indicated that the prepared PVA/PEG/GO gel obtained the same quality of ECG signals with commercial conductive gel with fewer cases of allergies and pruritus in volunteer after six hours of wear. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessArticle Improve Performance of Soy Flour-Based Adhesive with a Lignin-Based Resin
Polymers 2017, 9(7), 261; doi:10.3390/polym9070261
Received: 10 May 2017 / Revised: 26 June 2017 / Accepted: 27 June 2017 / Published: 3 July 2017
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Abstract
A lignin-based resin (LB) was used to improve the performance of soy flour-based adhesives. Soy flour (SF), polyamidoamine-epichlorohydrin (PAE), and LB were used to develop a plywood adhesive. The solid content and viscosity of the adhesive, the functional groups, the thermo-stability, and the
[...] Read more.
A lignin-based resin (LB) was used to improve the performance of soy flour-based adhesives. Soy flour (SF), polyamidoamine-epichlorohydrin (PAE), and LB were used to develop a plywood adhesive. The solid content and viscosity of the adhesive, the functional groups, the thermo-stability, and the crystallinity of the cured adhesives were characterized, and the performance of the resultant adhesive was evaluated by fabricating three-ply plywood. Results showed that the LB and PAE mixture used to modify the SF adhesive improved both dry and wet bond strength by 66.3% and 184.2%, respectively. Therefore, the PAE improved the wet bond strength, and the LB improved the dry bond strength. The improvement was attributed to: (1) the reaction of LB/PAE with the functions of the soy protein to form a cross-linking network; (2) a polycondensation reaction between the LB molecules improved the crosslinking density of the adhesive to form an interpenetration structure with cross-linked proteins; and (3) the easy penetration of the LB into the wood surface that enhanced interlocking between the wood and adhesive. Furthermore, the denser structure created by the LB and the PAE mixture improved thermal stability and decreased the crystallinity of the cured adhesive. The use of the LB and the PAE mixture increased the solid content by 35.5%, while still making its viscosity acceptable for industrial applications. Full article
(This article belongs to the collection Polymeric Adhesives)
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Open AccessArticle Homo- and Copolymerizations of Ethylene and Norbornene Using Bis(β-ketoamino) Titanium Catalysts Containing Pyrazolone Rings
Polymers 2017, 9(7), 262; doi:10.3390/polym9070262
Received: 14 June 2017 / Revised: 27 June 2017 / Accepted: 28 June 2017 / Published: 30 June 2017
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Abstract
A series of bis(β-ketoamino) titanium complexes containing pyrazolone rings (13) have been synthesized, characterized, and used as precursors for homo- and copolymerization of ethylene and norbornene. The titanium complexes activated with methylaluminoxane (MAO) exhibited good activities for homopolymerization of
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A series of bis(β-ketoamino) titanium complexes containing pyrazolone rings (13) have been synthesized, characterized, and used as precursors for homo- and copolymerization of ethylene and norbornene. The titanium complexes activated with methylaluminoxane (MAO) exhibited good activities for homopolymerization of ethylene (E) to produce linear polyethylenes (PEs). Ethylene–norbornene copolymers (E–N) were also prepared by these catalysts with moderate activities, and influences of ligand substituents and norbornene addition on copolymer microstructure were studied in detail. Microstructure analysis of the E–N copolymers by 13C NMR and differential scanning calorimetry (DSC) techniques showed that alternating (ENEN) and isolated (ENEE) norbornene predominately appeared in the copolymer chain, and the NN dyad and NNN triad sequences were also present in the copolymers obtained by the less bulky catalyst 1. Full article
(This article belongs to the Special Issue Olefin Polymerization and Polyolefin)
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Open AccessArticle Enhancement of Thermal Diffusivity in Phase-Separated Bismaleimide/Poly(ether imide) Composite Films Containing Needle-Shaped ZnO Particles
Polymers 2017, 9(7), 263; doi:10.3390/polym9070263
Received: 27 May 2017 / Revised: 25 June 2017 / Accepted: 27 June 2017 / Published: 2 July 2017
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Abstract
Phase-separated polymer blend composite films exhibiting high thermal diffusivity were prepared by blending a soluble polyimide (BPADA-MPD) and a bismaleimide (BMI) with needle-shaped zinc oxide (n-ZnO) particles followed by high-temperature curing at 250 °C. Images recorded with a field-emission scanning electron microscope (FE-SEM)
[...] Read more.
Phase-separated polymer blend composite films exhibiting high thermal diffusivity were prepared by blending a soluble polyimide (BPADA-MPD) and a bismaleimide (BMI) with needle-shaped zinc oxide (n-ZnO) particles followed by high-temperature curing at 250 °C. Images recorded with a field-emission scanning electron microscope (FE-SEM) equipped with wavelength-dispersive spectroscopy (WDS) demonstrated that the spontaneously separated phases in the composite films were aligned along the out-of-plane direction, and the n-ZnO particles were selectively incorporated into the BMI phase. The out-of-plane thermal diffusivity of the composite films was significantly higher than those of the previously reported composite films at lower filler contents. Based on wide-angle X-ray diffraction (WAXD) patterns and image analysis, the enhanced thermal diffusivity was attributed to the confinement of the anisotropically shaped particles and their nearly isotropic orientation in one phase of the composite films. Full article
(This article belongs to the Special Issue High Performance Polymers)
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Open AccessArticle The Impact of Polymer Grafting from a Graphene Oxide Surface on Its Compatibility with a PDMS Matrix and the Light-Induced Actuation of the Composites
Polymers 2017, 9(7), 264; doi:10.3390/polym9070264
Received: 12 May 2017 / Revised: 23 June 2017 / Accepted: 27 June 2017 / Published: 3 July 2017
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Abstract
Poly(dimethyl siloxane) (PDMS)-based materials with improved photoactuation properties were prepared by the incorporation of polymer-grafted graphene oxide particles. The modification of the graphene oxide (GO) surface was achieved via a surface initiated atom transfer radical polymerization (SI ATRP) of methyl methacrylate and butyl
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Poly(dimethyl siloxane) (PDMS)-based materials with improved photoactuation properties were prepared by the incorporation of polymer-grafted graphene oxide particles. The modification of the graphene oxide (GO) surface was achieved via a surface initiated atom transfer radical polymerization (SI ATRP) of methyl methacrylate and butyl methacrylate. The modification was confirmed by thermogravimetric analysis, infrared spectroscopy and electron microscopy. The GO surface reduction during the SI ATRP was investigated using Raman spectroscopy and conductivity measurements. Contact angle measurements, dielectric spectroscopy and dynamic mechanical analyses were used to investigate the compatibility of the GO filler with the PDMS matrix and the influence of the GO surface modification on its physical properties and the interactions with the matrix. Finally, the thermal conductivity and photoactuation properties of the PDMS matrix and composites were compared. The incorporation of GO with grafted polymer chains, especially poly(n-butyl methacrylate), into the PDMS matrix improved the compatibility of the GO filler with the matrix, increased the energy dissipation due to the improved flexibility of the PDMS chains, enhanced the damping behavior and increased the thermal conductivity. All the changes in the properties positively affected the photoactuation behavior of the PDMS composites containing polymer-grafted GO. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessCommunication Controlled Morphing of Microbubbles to Beaded Nanofibers via Electrically Forced Thin Film Stretching
Polymers 2017, 9(7), 265; doi:10.3390/polym9070265
Received: 22 May 2017 / Revised: 28 June 2017 / Accepted: 28 June 2017 / Published: 3 July 2017
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Abstract
Topography and microstructure engineering are rapidly evolving areas of importance for biomedical and pharmaceutical remits. Here, PVA (Polyvinyl alcohol) microbubbles (diameter range ~126 to 414 μm) were used to fabricate beaded (beads-on) nanofibers using an electrohydrodynamic atomization (EHDA) technique. Mean fiber diameter, inter-bead
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Topography and microstructure engineering are rapidly evolving areas of importance for biomedical and pharmaceutical remits. Here, PVA (Polyvinyl alcohol) microbubbles (diameter range ~126 to 414 μm) were used to fabricate beaded (beads-on) nanofibers using an electrohydrodynamic atomization (EHDA) technique. Mean fiber diameter, inter-bead distance, and aspect ratio (AR) were investigated by regulating EHDA process parameters. PVA fibers (diameter range ~233 to 737 nm) were obtained possessing bead ARs in the range of ~10 to 56%. AR was used to modulate hydrophilicity and active release. Full article
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Open AccessArticle Catalyzed Synthesis and Characterization of a Novel Lignin-Based Curing Agent for the Curing of High-Performance Epoxy Resin
Polymers 2017, 9(7), 266; doi:10.3390/polym9070266
Received: 19 June 2017 / Revised: 1 July 2017 / Accepted: 2 July 2017 / Published: 4 July 2017
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Abstract
In this study, lignin, an aromatic compound from the forestry industry, was used as a renewable material to synthesize a new aromatic amine curing agent for epoxy resin. Firstly, lignin was separated from black liquor and hydroxyl groups were converted to tosyl groups
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In this study, lignin, an aromatic compound from the forestry industry, was used as a renewable material to synthesize a new aromatic amine curing agent for epoxy resin. Firstly, lignin was separated from black liquor and hydroxyl groups were converted to tosyl groups as leaving groups. Then, primary amination was conducted using an ammonia solution at high pressure and temperature, in the presence of a nano-alumina-based catalyst. The structure of the nanocatalyst was confirmed by FT-IR, ICP, SEM, and XPS analyses. According to the FT-IR spectra, a demethylation reaction, the substitution of hydroxyl groups with tosyl groups, and then an amination reaction were successfully performed on lignin, which was further confirmed by the 13C NMR and CHNS analyses. The active hydrogen equivalent of aminated lignin was determined and three samples with 9.9 wt %, 12.9 wt %, and 15.9 wt % of aminated lignin, as curing agents, were prepared for curing the diglycidyl ether of bisphenol A (DGEBA). The thermal characteristics of the curing process of these epoxy samples were determined by DSC and TGA analyses. Moreover, the mechanical performance of the cured epoxy systems, e.g., the tensile strength and Izod impact strength, were measured, showing that in the presence of 12.9 wt % aminated lignin, the mechanical properties of the aminated lignin-epoxy system exhibited the best performance, which was competitive, compared to the epoxy systems cured by commercial aromatic curing agents. Full article
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Open AccessArticle A New Polymer-Based Fluorescent Chemosensor Incorporating Propane-1,3-Dione and 2,5-Diethynylbenzene Moieties for Detection of Copper(II) and Iron(III)
Polymers 2017, 9(7), 267; doi:10.3390/polym9070267
Received: 18 May 2017 / Revised: 27 June 2017 / Accepted: 3 July 2017 / Published: 6 July 2017
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Abstract
A novel conjugated polymer (PDBDBM) was developed by the polymerization of 1,4-dioctyloxy-2,5-diethynylbenzene with 1,3-bis(4-bromophenyl)propane-1,3-dione based on Pd-catalyzed Sonogashira-coupling reaction. The obtained polymer PDBDBM exhibited bright green photoluminescence under UV irradiation. According to the metal ion titration experiments, PDBDBM showed high sensitivity and selectivity
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A novel conjugated polymer (PDBDBM) was developed by the polymerization of 1,4-dioctyloxy-2,5-diethynylbenzene with 1,3-bis(4-bromophenyl)propane-1,3-dione based on Pd-catalyzed Sonogashira-coupling reaction. The obtained polymer PDBDBM exhibited bright green photoluminescence under UV irradiation. According to the metal ion titration experiments, PDBDBM showed high sensitivity and selectivity for detection of Cu2+ and Fe3+ over other metal ions. The fluorescent detection limits of PDBDBM were calculated to be 5 nM for Cu2+ and 0.4 μM for Fe3+ and the Stern–Volmer quenching constant for Cu2+ and Fe3+ were found to be 1.28 × 108 M−1 and 2.40 × 104 M−1, respectively. These results indicated that the polymer can be used as a potential probe for Cu2+ and Fe3+ detection. Full article
(This article belongs to the Special Issue Polymeric Membranes)
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Open AccessArticle Structure of Composite Based on Polyheteroarylene Matrix and ZrO2 Nanostars Investigated by Quantitative Nanomechanical Mapping
Polymers 2017, 9(7), 268; doi:10.3390/polym9070268
Received: 23 May 2017 / Revised: 30 June 2017 / Accepted: 2 July 2017 / Published: 6 July 2017
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Abstract
It is known that structure of the interface between inorganic nanoparticles and polymers significantly influences properties of a polymer–inorganic composite. At the same time, amount of experimental researches on the structure and properties of material near the inorganic-polymer interface is low. In this
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It is known that structure of the interface between inorganic nanoparticles and polymers significantly influences properties of a polymer–inorganic composite. At the same time, amount of experimental researches on the structure and properties of material near the inorganic-polymer interface is low. In this work, we report for the first time the investigation of nanomechanical properties and maps of adhesion of material near the inorganic-polymer interface for the polyheteroarylene nanocomposites based on semi-crystalline poly[4,4′-bis (4″-aminophenoxy)diphenyl]imide 1,3-bis (3′,4-dicarboxyphenoxy) benzene, modified by ZrO2 nanostars. Experiments were conducted using quantitative nanomechanical mapping (QNM) mode of atomic force microscopy (AFM) at the surface areas where holes were formed after falling out of inorganic particles. It was found that adhesion of AFM cantilever to the polymer surface is higher inside the hole than outside. This can be attributed to the presence of polar groups near ZrO2 nanoparticle. QNM measurements revealed that polymer matrix has increased rigidity in the vicinity of the nanoparticles. Influence of ZrO2 nanoparticles on the structure and thermal properties of semi-crystalline polyheteroarylene matrix was studied with wide-angle X-ray scattering, scanning electron microscopy, and differential scanning calorimetry. Full article
(This article belongs to the Special Issue Polymer Nanocomposites)
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Open AccessArticle Effect of Nanofibrillated Cellulose Content on the Temperature and Near Infrared Responses of Polyvinyl Butyral Nanofibers-Containing Bilayer Hydrogel System
Polymers 2017, 9(7), 270; doi:10.3390/polym9070270
Received: 30 May 2017 / Revised: 3 July 2017 / Accepted: 4 July 2017 / Published: 6 July 2017
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Abstract
A novel kind of nanofibrillated cellulose (NFC) reinforced polyvinyl butyral (PVB) nanofibers-containing bilayer hydrogel system was successfully fabricated via the combination of a one-step, in-situ, free radical polymerization and electrospinning. The hydrogel owned high mechanical strength, thermoresponsive, and near infrared bending/unbending properties. The
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A novel kind of nanofibrillated cellulose (NFC) reinforced polyvinyl butyral (PVB) nanofibers-containing bilayer hydrogel system was successfully fabricated via the combination of a one-step, in-situ, free radical polymerization and electrospinning. The hydrogel owned high mechanical strength, thermoresponsive, and near infrared bending/unbending properties. The cross-linking density of hydrogels enhanced along with the increase of NFC content. The addition of NFC and PVB nanofibers presented tiny influence on the variation of chemical bond and volume phase transition temperature. The combination between NFC and PVB nanofibers enhanced the mechanical strength and decreased the strain value, which built the base for high bonding strength of two layers and efficient thermoresponsive and near infrared responses. With the increase of NFC content, the bending degree became smaller. The bilayer hydrogel dimensions affected the deformation degree. Bilayer hydrogels with different NFC content own different deformation abilities, which can be designed as different parts of soft actuators and provide superior performance to satisfy various practical application demands. Full article
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Open AccessArticle Poly(3,3-dibenzyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)/Platinum Composite Films as Potential Counter Electrodes for Dye-Sensitized Solar Cells
Polymers 2017, 9(7), 271; doi:10.3390/polym9070271
Received: 28 April 2017 / Revised: 20 June 2017 / Accepted: 3 July 2017 / Published: 7 July 2017
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Abstract
In this study, poly(3,3-dibenzyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)/platinum composite films (PProDOT-Bz2/Pt) were used as counter electrodes (CEs) in dye-sensitized solar cells (DSSCs). The composite films were prepared on fluorine-doped tin oxide (FTO) glass by radio frequency (RF) sputtering to deposit platinum
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In this study, poly(3,3-dibenzyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)/platinum composite films (PProDOT-Bz2/Pt) were used as counter electrodes (CEs) in dye-sensitized solar cells (DSSCs). The composite films were prepared on fluorine-doped tin oxide (FTO) glass by radio frequency (RF) sputtering to deposit platinum (Pt) for 30 s. Afterwards, PProDOT-Bz2 was deposited on the Pt–FTO glass via electrochemical polymerization. The electron transfer process of DSSCs was investigated using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The DSSCs with 0.05 C/cm2 PProDOT-Bz2-Pt composite films showed an open circuit voltage (Voc) of 0.70 V, a short-circuit current density (Jsc) of 7.27 mA/cm2, and a fill factor (F.F.) of 68.74%. This corresponded to a photovoltaic conversion efficiency (η) of 3.50% under a light intensity of 100 mW/cm2. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessArticle Novel Two-Dimensional Conjugated Polymer Containing Fluorinated Bithiophene as Donor and Benzoselenodiazole as Acceptor Units with Vinyl-Terthiophene Pendants for Polymer Photovoltaic Cells
Polymers 2017, 9(7), 272; doi:10.3390/polym9070272
Received: 7 June 2017 / Revised: 29 June 2017 / Accepted: 3 July 2017 / Published: 7 July 2017
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Abstract
Novel two-dimensional conjugated copolymer, abbreviated as PDTBSeVTT-2TF, containing electron-deficient 4,7-di(thiophen-2-yl)benzo[c][1,2,5]selenodiazole (DTBSe) unit, conjugated vinyl-terthiophene (VTT) side chain and 3,3′-difluoro-2,2′-bithiophene (2TF) was designed and synthesized using microwave-assisted Stille cross-coupling polymerization. UV–visible absorption and cyclic voltammetry studies revealed that this copolymer possesses a
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Novel two-dimensional conjugated copolymer, abbreviated as PDTBSeVTT-2TF, containing electron-deficient 4,7-di(thiophen-2-yl)benzo[c][1,2,5]selenodiazole (DTBSe) unit, conjugated vinyl-terthiophene (VTT) side chain and 3,3′-difluoro-2,2′-bithiophene (2TF) was designed and synthesized using microwave-assisted Stille cross-coupling polymerization. UV–visible absorption and cyclic voltammetry studies revealed that this copolymer possesses a strong and broad absorption in the range of 300–800 nm and a narrow optical bandgap (Eg) of 1.57 eV with low-lying HOMO and LUMO energy levels. Further, the bulk heterojunction polymer solar cells (PSCs) were fabricated using PDTBSeVTT-2TF as donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as acceptor with an inverted device structure of ITO/ZnO/PDTBSeVTT-2TF:PC71BM/V2O5/Ag. The processing temperature of blend solution for preparing PDTBSeVTT-2TF:PC71BM active layer showed obvious impact on the photovoltaic performance of solar devices. The cell fabricated from the blend solution at 65 °C exhibited enhanced power conversion efficiencies (PCE) of 5.11% with a Jsc of 10.99 mA/cm−2 compared with the one at 50 °C, which had a PCE of 4.69% with a Jsc of 10.10 mA/cm−2. This enhancement is due to the dissolution of PDTBSeVTT-2TF clusters into single molecules and small aggregates, improving the miscibility between the polymer and PC71BM and thus increasing the donor/acceptor interface. Full article
(This article belongs to the Special Issue Polymer Solar Cells)
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Open AccessArticle Effective Removal of Chromium(III) from Low Concentration Aqueous Solution Using a Novel Diazene/Methoxy-Laced Coordination Polymer
Polymers 2017, 9(7), 273; doi:10.3390/polym9070273
Received: 6 June 2017 / Revised: 27 June 2017 / Accepted: 4 July 2017 / Published: 9 July 2017
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Abstract
In this study, a novel coordination polymer [CdL2(H2O)0.5]n (1), [HL = 4-(2-(4-((pyridin-3-yl)methoxy)phenyl)diazenyl)benzoic acid] was fabricated via an in situ ligand transformation reaction under solvothermal conditions. The as-prepared polymer exhibited a selectivity and efficiency for
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In this study, a novel coordination polymer [CdL2(H2O)0.5]n (1), [HL = 4-(2-(4-((pyridin-3-yl)methoxy)phenyl)diazenyl)benzoic acid] was fabricated via an in situ ligand transformation reaction under solvothermal conditions. The as-prepared polymer exhibited a selectivity and efficiency for Cr(III) removal with a high uptake capacity of 106.13 mg·g−1. Interestingly, even in the low concentration (0.02–0.20 ppm), it still performs a relatively high efficiency (≥ 92.5%) towards the removal of Cr(III) in aqueous solution. Remarkably, it also presents good selectivity and high efficiency (93.3%) for Cr(III) removal in the presences of interfering metal ions. The good removal performance for Cr(III) was demonstrated to be a structure-dependent chemical process between polymer and Cr(III) involving the diazene and methoxy groups in polymer 1, which happened not only on the surfaces of the adsorbent but also in the pores of polymer, giving rise to a strong affinity toward Cr(III) adsorption. The possible adsorption mechanism of Cr(III) was proposed and systematically verified by FT-IR, scanning electron microscope (SEM), atomic force microscope (AFM) and energy dispersive spectrometer (EDS) measurements. Full article
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Open AccessArticle A Rapid and Efficient Route to Preparation of Isocyanate Microcapsules
Polymers 2017, 9(7), 274; doi:10.3390/polym9070274
Received: 12 June 2017 / Revised: 1 July 2017 / Accepted: 6 July 2017 / Published: 9 July 2017
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Abstract
In this paper, polyaryl polymethylene isocyanates (PAPI) were used as an innovative alternative material to prepare isocyanate microcapsules. PAPI could be used as core materials, which would react with small molecules containing active hydrogen (1,4-butanediol, ethylene glycol, 1,2-diaminoethane etc.). The reaction products of
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In this paper, polyaryl polymethylene isocyanates (PAPI) were used as an innovative alternative material to prepare isocyanate microcapsules. PAPI could be used as core materials, which would react with small molecules containing active hydrogen (1,4-butanediol, ethylene glycol, 1,2-diaminoethane etc.). The reaction products of PAPI and active hydrogen would form a shell by interfacial polymerization reaction in an oil-in-water emulsion. Smooth spherical microcapsules of 70 ~ 180 μm in diameter were produced by controlling agitation rate (600 ~ 1200 rpm). High yields (~80%) of a free-flowing powder of PAPI/polyurethane and polyurea capsules were produced with a high isocyanate groups (–NCO) content of 23 wt % as determined by titration analysis. Structural analysis and quality assessments of each batch of microcapsules were performed by using thermogravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. Preliminary results indicated the microcapsules were stable with only about 20% loss of –NCO detected after one month storage under ambient conditions. This work showed the great potential of novel microencapsulation technique in development of protection of –NCO and in aspects of micro- and nano-structure construction materials. Full article
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Open AccessArticle Structure of Amphiphilic Terpolymer Raspberry Vesicles
Polymers 2017, 9(7), 275; doi:10.3390/polym9070275
Received: 14 June 2017 / Revised: 3 July 2017 / Accepted: 6 July 2017 / Published: 9 July 2017
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Abstract
Terpolymer raspberry vesicles contain domains of different chemical affinities. They are potential candidates as multi-compartment cargo carriers. Their efficacy depends on their stability and load capacity. Using a model star terpolymer system in an aqueous solution, a dissipative particle dynamic (DPD) simulation is
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Terpolymer raspberry vesicles contain domains of different chemical affinities. They are potential candidates as multi-compartment cargo carriers. Their efficacy depends on their stability and load capacity. Using a model star terpolymer system in an aqueous solution, a dissipative particle dynamic (DPD) simulation is employed to investigate how equilibrium aggregate structures are affected by polymer concentration and pairwise interaction energy in a solution. It is shown that a critical mass of polymer is necessary for vesicle formation. The free energy of the equilibrium aggregates are calculated and the results show that the transition from micelles to vesicles is governed by the interactions between the longest solvophobic block and the solvent. In addition, the ability of vesicles to encapsulate solvent is assessed. It is found that reducing the interaction energy favours solvent encapsulation, although solvent molecules can permeate through the vesicle’s shell when repulsive interactions among monomers are low. Thus, one can optimize the loading capacity and the release rate of the vesicles by turning pairwise interaction energies of the polymer and the solvent. The ability to predict and control these aspects of the vesicles is an essential step towards designing vesicles for specific purposes. Full article
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Open AccessArticle Smart Poly(imidazoyl-l-lysine): Synthesis and Reversible Helix-to-Coil Transition at Neutral pH
Polymers 2017, 9(7), 276; doi:10.3390/polym9070276
Received: 20 June 2017 / Revised: 3 July 2017 / Accepted: 6 July 2017 / Published: 11 July 2017
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Abstract
Polypeptide polymers can adopt natural protein secondary structures such as α-helices or β-sheets, and this unique feature is at the origin of some intriguing physico–chemical properties. In this work, we present how side chain imidazoylation of a poly(l-lysine) scaffold affords the
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Polypeptide polymers can adopt natural protein secondary structures such as α-helices or β-sheets, and this unique feature is at the origin of some intriguing physico–chemical properties. In this work, we present how side chain imidazoylation of a poly(l-lysine) scaffold affords the preparation of poly(histidine) counterparts exhibiting α-helix conformation. This structuring behavior is reversible and can be controlled by means of pH and or temperature changes. Full article
(This article belongs to the Special Issue Polypeptide Containing Polymers)
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Open AccessArticle Microporous Polyurethane Thin Layer as a Promising Scaffold for Tissue Engineering
Polymers 2017, 9(7), 277; doi:10.3390/polym9070277
Received: 16 June 2017 / Revised: 3 July 2017 / Accepted: 6 July 2017 / Published: 11 July 2017
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Abstract
The literature describes that the most efficient cell penetration takes place at 200–500 µm depth of the scaffold. Many different scaffold fabrication techniques were described to reach these guidelines. One such technique is solvent casting particulate leaching (SC/PL). The main advantage of this
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The literature describes that the most efficient cell penetration takes place at 200–500 µm depth of the scaffold. Many different scaffold fabrication techniques were described to reach these guidelines. One such technique is solvent casting particulate leaching (SC/PL). The main advantage of this technique is its simplicity and cost efficiency, while its main disadvantage is the scaffold thickness, which is usually not less than 3000 µm. Thus, the scaffold thickness is usually far from the requirements for functional tissue reconstruction. In this paper, we report a successful fabrication of the microporous polyurethane thin layer (MPTL) of 1 mm thick, which was produced using SC/PL technique combined with phase separation (PS). The obtained MPTL was highly porous (82%), had pore size in the range of 65–426 µm and scaffold average pore size was equal to 154 ± 3 µm. Thus, it can be considered a suitable scaffold for tissue engineering purpose, according to the morphology criterion. Polyurethane (PUR) processing into MPTL scaffold caused significant decrease of contact angle from 78 ± 4° to 56 ± 6° and obtained MPTL had suitable hydrophilic characteristic for mammalian cells growth and tissue regeneration. Mechanical properties of MPTL were comparable to the properties of native tissues. As evidenced by biotechnological examination the MPTL were highly biocompatible with no observed apparent toxicity on mouse embryonic NIH 3T3 fibroblast cells. Performed studies indicated that obtained MPTL may be suitable scaffold candidate for soft TE purposes such as blood vessels. Full article
(This article belongs to the Special Issue Advance of Polymers Applied to Biomedical Applications: Biointerface)
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Open AccessArticle Modeling Diffractive Lenses Recording in Environmentally Friendly Photopolymer
Polymers 2017, 9(7), 278; doi:10.3390/polym9070278
Received: 25 May 2017 / Revised: 29 June 2017 / Accepted: 6 July 2017 / Published: 12 July 2017
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Abstract
The improvements made in diffusion models simulating phase image recording in photopolymers enable the optimization of a wide range of complex diffractive optical elements (DOEs), while the miniaturization of spatial light modulators makes it possible to generate both symmetric and non-symmetric DOEs. In
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The improvements made in diffusion models simulating phase image recording in photopolymers enable the optimization of a wide range of complex diffractive optical elements (DOEs), while the miniaturization of spatial light modulators makes it possible to generate both symmetric and non-symmetric DOEs. In addition, there is increasing interest in the design of new friendly recording materials. In this respect, photopolymers are a promising material due to their optical properties. In this paper, we show a procedure to record diffractive spherical lenses using a nontoxic optimized photopolymer. To achieve this goal, we followed three steps: first, the chemical optimization for DOE recording; second, the recording material characterization to be simulated by a three-dimensional diffusion model; and third, the evaluation of the coverplating for the conservation of the DOE. Full article
(This article belongs to the Special Issue Photo-Responsive Polymers)
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Open AccessArticle Hydrogenolysis and Activation of Soda Lignin Using [BMIM]Cl as a Catalyst and Solvent
Polymers 2017, 9(7), 279; doi:10.3390/polym9070279
Received: 20 June 2017 / Revised: 7 July 2017 / Accepted: 8 July 2017 / Published: 12 July 2017
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Abstract
To improve the reactivity of the soda lignin, an acid ionic liquid 1-butyl-3-mthylimidazolium chloride ([BMIM]Cl) was used as the catalyst and solvent to degrade the soda lignin through hydrogenolysis. Structural elucidation of the lignin samples was conducted by using a combination of analytical
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To improve the reactivity of the soda lignin, an acid ionic liquid 1-butyl-3-mthylimidazolium chloride ([BMIM]Cl) was used as the catalyst and solvent to degrade the soda lignin through hydrogenolysis. Structural elucidation of the lignin samples was conducted by using a combination of analytical methods including chemical analysis, ultraviolet spectrophotometry (UV spectrophotometry), Fourier transform infrared spectroscopy (FT-IR spectra), two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR) techniques, and gel permeation chromatography (GPC). The antioxidant activities of the lignin samples were evaluated using the diammonium 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS+) radical scavenging and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging methods. The degradation mechanism was proposed based on the characterization results. The optimal reaction condition was as follows: the concentration of [BMIM]Cl in the solution was 10 wt %, the hydrogen initial pressure was 3 MPa, and the solution was heated for 4 h at 90 °C. After the reaction, the total hydroxyl content of the soda lignin increased by 81.3%, while the phenolic hydroxyl content increased by 23.1%. At the same time, the weight-average molar mass of the soda lignin sample decreased from 8220 to 6450 g/mol with an improved antioxidant activity. In addition, approximately 56.7% of the β-O-4 linkages were degraded in the lreaction. The main effect of the acid ionic liquid [BMIM]C1 was related to the cleavage of β-O-4 linkages. This study has shown the potential of using the catalyzed soda lignin as a natural polymer antioxidant. Full article
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Open AccessArticle PES/POSS Soluble Veils as Advanced Modifiers for Multifunctional Fiber Reinforced Composites
Polymers 2017, 9(7), 281; doi:10.3390/polym9070281
Received: 18 June 2017 / Revised: 8 July 2017 / Accepted: 10 July 2017 / Published: 13 July 2017
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Abstract
Novel polyhedral oligomeric silsesquioxanes (POSS)-filled thermoplastic electrospun veils were used to tailor the properties of the interlaminar region of epoxy-based composites. The veils were designed to be soluble upon curing in the epoxy matrix, so that POSS could be released within the interlaminar
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Novel polyhedral oligomeric silsesquioxanes (POSS)-filled thermoplastic electrospun veils were used to tailor the properties of the interlaminar region of epoxy-based composites. The veils were designed to be soluble upon curing in the epoxy matrix, so that POSS could be released within the interlaminar region. Three different POSS contents, varying from 1 to 10 wt %, were tested while the percentage of coPolyethersulphone (coPES) dissolved in the epoxy resin was kept to a fixed value of 10 wt %. Good quality veils could be obtained at up to 10 wt % of POSS addition, with the nanofibers’ diameters varying from 861 nm for the coPES to 428 nm upon POSS addition. The feasibility of the soluble veils to disperse POSS in the interlaminar region was proved, and the effect of POSS on phase morphology and viscoelastic properties studied. POSS was demonstrated to significantly affect the morphology and viscoelastic properties of epoxy composites, especially for the percentages 1% and 5%, which enabled the composites to avoid POSS segregates occurring. A dynamic mechanical analysis showed a significant improvement to the storage modulus, and a shift of more than 30 °C due to the POSS cages hindering the motion of the molecular chains and network junctions. Full article
(This article belongs to the Special Issue Polymer Nanocomposites)
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Open AccessFeature PaperArticle “Living” Polymerization of Ethylene and 1-Hexene Using Novel Binuclear Pd–Diimine Catalysts
Polymers 2017, 9(7), 282; doi:10.3390/polym9070282
Received: 26 June 2017 / Revised: 12 July 2017 / Accepted: 14 July 2017 / Published: 15 July 2017
PDF Full-text (4571 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
We report the synthesis of two novel binuclear Pd–diimine catalysts and their unique behaviors in initiating “living” polymerization of ethylene and 1-hexene. These two binuclear catalysts, [(N^N)Pd(CH2)3C(O)O(CH2)mO(O)C(CH2)3Pd(N^N)](SbF6)2 (
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We report the synthesis of two novel binuclear Pd–diimine catalysts and their unique behaviors in initiating “living” polymerization of ethylene and 1-hexene. These two binuclear catalysts, [(N^N)Pd(CH2)3C(O)O(CH2)mO(O)C(CH2)3Pd(N^N)](SbF6)2 (3a: m = 4, 3b: m = 6) (N^N≡ArN=C(Me)–(Me)C=NAr, Ar≡2,6–(iPr)2C6H3), were synthesized by simply reacting [(N^N)Pd(CH3)(N≡CMe)]SbF6 (1) with diacrylates, 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate, respectively. Their unique binuclear structure with two identical Pd–diimine acrylate chelates covalently linked together through an ester linkage was confirmed by NMR and single crystal XRD measurements. Ethylene “living” polymerizations were carried out at 5 °C and under ethylene pressure of 400 and 100 psi, respectively, with the binuclear catalysts, along with a mononuclear chelate catalyst, [(N^N)Pd(CH2)3C(O)OMe]SbF6 (2), for comparison. All the polyethylenes produced with both binuclear catalysts show bimodal molecular weight distribution with the number-average molecular weight of the higher molecular weight portion being approximately twice that of the lower molecular weight portion. The results demonstrate the presence of monofunctional chain growing species resembling catalyst 2, in addition to the expected bifunctional species leading to bifunctional “living” polymerization, in the polymerization systems. Both types of chain growing species exhibit “living” characteristics under the studied conditions, leading to the simultaneous linear increase of molecular weight in both portions. However, when applied for the “living” polymerization of 1-hexene, the binuclear catalyst 3a leads to polymers with only monomodal molecular weight distribution, indicating the sole presence of monofunctional chain growing species. These two binuclear catalysts are the first Pd–diimine catalysts capable of initiating bifunctional ethylene “living” polymerization. Full article
(This article belongs to the Special Issue Tailored Polymer Synthesis by Advanced Polymerization Techniques)
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Open AccessCommunication Fabrication and Test of an Inflated Circular Diaphragm Dielectric Elastomer Generator Based on PDMS Rubber Composite
Polymers 2017, 9(7), 283; doi:10.3390/polym9070283
Received: 26 May 2017 / Revised: 11 July 2017 / Accepted: 12 July 2017 / Published: 15 July 2017
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Abstract
This paper introduces a fabrication method and the experimental characterization of a soft polymeric energy converter manufactured using a combination of dielectric and conductive polydimethylsiloxane elastomers. The presented system is an inflated circular diaphragm dielectric elastomer generator; i.e., a deformable electrostatic transducer that
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This paper introduces a fabrication method and the experimental characterization of a soft polymeric energy converter manufactured using a combination of dielectric and conductive polydimethylsiloxane elastomers. The presented system is an inflated circular diaphragm dielectric elastomer generator; i.e., a deformable electrostatic transducer that converts the mechanical work done by a time-varying pressure into electricity. A prototype of the system is realized on the basis of a simple fabrication procedure that makes use of commercially available silicone dielectric elastomer films and custom-prepared deformable conductive electrodes. A test-bench is developed and employed to estimate the energy conversion performance. Remarkable results are obtained, such as an amount of energy converted per cycle of up to 0.3 J, converted power of up to 0.15 W, energy per unit of employed elastomer mass of up to 173 J/kg, and fraction of the input mechanical work converted into electricity of 30%. Full article
(This article belongs to the Special Issue Electroactive Polymers and Gels)
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Open AccessArticle Three Carbazole-Based Polymers as Potential Anodically Coloring Materials for High-Contrast Electrochromic Devices
Polymers 2017, 9(7), 284; doi:10.3390/polym9070284
Received: 8 June 2017 / Revised: 12 July 2017 / Accepted: 12 July 2017 / Published: 18 July 2017
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Abstract
Three carbazole-based conjugated polymers (poly(3,6-di(2-thienyl)carbazole) (PDTC), poly(2,7-bis(carbazol-9-yl)-9,9-spirobifluorene) (PS2CBP), and poly(3,6-bis(N-carbazole)-N-ethylcarbazole) (PCEC)) are synthesized using electrochemical polymerization. The spectroelectrochemical studies indicate that the PDTC, PS2CBP, and PCEC films show reversible electrochromic behaviors in their redox states, and the PS2CBP film
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Three carbazole-based conjugated polymers (poly(3,6-di(2-thienyl)carbazole) (PDTC), poly(2,7-bis(carbazol-9-yl)-9,9-spirobifluorene) (PS2CBP), and poly(3,6-bis(N-carbazole)-N-ethylcarbazole) (PCEC)) are synthesized using electrochemical polymerization. The spectroelectrochemical studies indicate that the PDTC, PS2CBP, and PCEC films show reversible electrochromic behaviors in their redox states, and the PS2CBP film shows a distinct color transition with four various colors (gray at 0 V, grayish-green at 1.0 V, moss green at 1.2 V, and foliage green at 1.4 V). The maximum optical contrast of the PS2CBP and PCEC films is 39.83% at 428 nm and 32.41% at 420 nm, respectively, in an ionic liquid solution. Dual-type electrochromic devices (ECDs) that employ PDTC, PS2CBP, or PCEC film as an anodic layer, and PProDOT-Et2 film as a cathodic layer, were constructed. The as-prepared PCEC/PProDOT-Et2 ECD shows high optical contrast (38.25% at 586 nm) and high coloration efficiency (369.85 cm2 C−1 at 586 nm), and the PS2CBP/PProDOT-Et2 ECD shows high optical contrast (34.45% at 590 nm), good optical memory, and good long-term cycling stability. Full article
(This article belongs to the Special Issue Polymeric Materials for Optical Applications)
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Open AccessArticle Dependency of Anion and Chain Length of Imidazolium Based Ionic Liquid on Micellization of the Block Copolymer F127 in Aqueous Solution: An Experimental Deep Insight
Polymers 2017, 9(7), 285; doi:10.3390/polym9070285
Received: 9 June 2017 / Revised: 8 July 2017 / Accepted: 15 July 2017 / Published: 19 July 2017
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Abstract
The non-ionic triblock copolymer, Pluronic® F127, has been selected to observe its interaction with ionic liquids (ILs) in aqueous solutions by using DLS, surface tension, and viscosity measurements. The Critical Micelle Concentration (CMC) of F127 increased with the addition of ILs, which
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The non-ionic triblock copolymer, Pluronic® F127, has been selected to observe its interaction with ionic liquids (ILs) in aqueous solutions by using DLS, surface tension, and viscosity measurements. The Critical Micelle Concentration (CMC) of F127 increased with the addition of ILs, which appeared logical since it increases the solubility of PPO (and PEO) moiety, making it behaves more like a hydrophilic block copolymer that is micellized at a higher copolymer concentration. The results from DLS data showed good agreement with those obtained from the surface tension measurements. Upon the addition of ILs, the tendency in micellar size reduction was demonstrated by viscosity results, and therefore, intrinsic viscosity decreased compared to pure F127 in aqueous solution. The results were discussed as a function of alkyl chain length and anions of imidazolium based ILs. Full article
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Open AccessArticle Effect of Drug Loading Method and Drug Physicochemical Properties on the Material and Drug Release Properties of Poly (Ethylene Oxide) Hydrogels for Transdermal Delivery
Polymers 2017, 9(7), 286; doi:10.3390/polym9070286
Received: 8 June 2017 / Revised: 10 July 2017 / Accepted: 13 July 2017 / Published: 19 July 2017
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Abstract
Novel poly (ethylene oxide) (PEO) hydrogel films were synthesized via UV cross-linking with pentaerythritol tetra-acrylate (PETRA) as cross-linking agent. The purpose of this work was to develop a novel hydrogel film suitable for passive transdermal drug delivery via skin application. Hydrogels were loaded
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Novel poly (ethylene oxide) (PEO) hydrogel films were synthesized via UV cross-linking with pentaerythritol tetra-acrylate (PETRA) as cross-linking agent. The purpose of this work was to develop a novel hydrogel film suitable for passive transdermal drug delivery via skin application. Hydrogels were loaded with model drugs (lidocaine hydrochloride (LID), diclofenac sodium (DIC) and ibuprofen (IBU)) via post-loading and in situ loading methods. The effect of loading method and drug physicochemical properties on the material and drug release properties of medicated film samples were characterized using scanning electron microscopy (SEM), swelling studies, differential scanning calorimetry (DSC), fourier transform infrared spectroscopy (FT-IR), tensile testing, rheometry, and drug release studies. In situ loaded films showed better drug entrapment within the hydrogel network and also better polymer crystallinity. High drug release was observed from all studied formulations. In situ loaded LID had a plasticizing effect on PEO hydrogel, and films showed excellent mechanical properties and prolonged drug release. The drug release mechanism for the majority of medicated PEO hydrogel formulations was determined as both drug diffusion and polymer chain relaxation, which is highly desirable for controlled release formulations. Full article
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Open AccessArticle A New Type of Photo-Thermo Staged-Responsive Shape-Memory Polyurethanes Network
Polymers 2017, 9(7), 287; doi:10.3390/polym9070287
Received: 2 July 2017 / Revised: 13 July 2017 / Accepted: 14 July 2017 / Published: 19 July 2017
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Abstract
In this paper, we developed a photo-thermo staged-responsive shape-memory polymer network which has a unique ability of being spontaneously photo-responsive deformable and thermo-responsive shape recovery. This new type of shape-memory polyurethane network (A-SMPUs) was successfully synthesized with 4,4-azodibenzoic acid (Azoa), hexamethylenediisocyanate (HDI) and
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In this paper, we developed a photo-thermo staged-responsive shape-memory polymer network which has a unique ability of being spontaneously photo-responsive deformable and thermo-responsive shape recovery. This new type of shape-memory polyurethane network (A-SMPUs) was successfully synthesized with 4,4-azodibenzoic acid (Azoa), hexamethylenediisocyanate (HDI) and polycaprolactone (PCL), followed by chemical cross-linking with glycerol (Gl). The structures, morphology, and shape-memory properties of A-SMPUs have been carefully investigated. The results demonstrate that the A-SMPUs form micro-phase separation structures consisting of a semi-crystallized PCL soft phase and an Azoa amorphous hard phase that could influence the crystallinity of PCL soft phases. The chemical cross-linking provided a stable network and good thermal stability to the A-SMPUs. All A-SMPUs exhibited good triple-shape-memory properties with higher than 97% shape fixity ratio and 95% shape recovery ratio. Additionally, the A-SMPUs with higher Azoa content exhibited interesting photo-thermo two-staged responsiveness. A pre-processed film with orientated Azoa structure exhibited spontaneous curling deformation upon exposing to ultraviolet (UV) light, and curling deformation is constant even under Vis light. Finally, the curling deformation can spontaneously recover to the original shape by applying a thermal stimulus. This work demonstrates new synergistically multi-responsive SMPUs that will have many applications in smart science and technology. Full article
(This article belongs to the Special Issue Shape Memory Polymers)
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Open AccessArticle Ultra High Electrical Performance of Nano Nickel Oxide and Polyaniline Composite Materials
Polymers 2017, 9(7), 288; doi:10.3390/polym9070288
Received: 7 June 2017 / Revised: 10 July 2017 / Accepted: 18 July 2017 / Published: 20 July 2017
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Abstract
The cooperative effects between the PANI (polyaniline)/nano-NiO (nano nickel oxide) composite electrode material and redox electrolytes (potassium iodide, KI) for supercapacitor applications was firstly discussed in this article, providing a novel method to prepare nano-NiO by using β-cyelodextrin (β-CD) as the template agent.
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The cooperative effects between the PANI (polyaniline)/nano-NiO (nano nickel oxide) composite electrode material and redox electrolytes (potassium iodide, KI) for supercapacitor applications was firstly discussed in this article, providing a novel method to prepare nano-NiO by using β-cyelodextrin (β-CD) as the template agent. The experimental results revealed that the composite electrode processed a high specific capacitance (2122.75 F·g−1 at 0.1 A·g−1 in 0.05 M KI electrolyte solution), superior energy density (64.05 Wh·kg−1 at 0.2 A·g−1 in the two-electrode system) and excellent cycle performance (86% capacitance retention after 1000 cycles at 1.5 A·g−1). All those ultra-high electrical performances owe to the KI active material in the electrolyte and the PANI coated nano-NiO structure. Full article
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Open AccessArticle Effect of Plasticizer Type on Tensile Property and In Vitro Indomethacin Release of Thin Films Based on Low-Methoxyl Pectin
Polymers 2017, 9(7), 289; doi:10.3390/polym9070289
Received: 7 June 2017 / Revised: 10 July 2017 / Accepted: 19 July 2017 / Published: 20 July 2017
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Abstract
This study developed the interests of low-methoxyl pectin (LMP) together with plasticizers for the preparation of elastic thin films. The effect of different plasticizer types (glycerol: Gly; sorbitol: Sor; propylene glycol: PG; and polyethylene glycol 300: PEG 300) and concentrations (20–40% w/w)
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This study developed the interests of low-methoxyl pectin (LMP) together with plasticizers for the preparation of elastic thin films. The effect of different plasticizer types (glycerol: Gly; sorbitol: Sor; propylene glycol: PG; and polyethylene glycol 300: PEG 300) and concentrations (20–40% w/w) on mechanical and thermal properties of LMP films as well as on in vitro release of indomethacin were evaluated. Without any plasticizer, a brittle LMP film with low tensile strength and % elongation at break was obtained. Addition of plasticizers from 20% to 40% caused reduction in the tensile strength and Young’s modulus values, whereas percent elongation was increased. Forty percent Gly-plasticized and PG-plasticized films were selected to deliver indomethacin in comparison with non-plasticized film. No significant difference in indomethacin release profiles was displayed between the films. The analysis of indomethacin release model indicated that more than one drug release mechanism from the film formulation was involved and possibly the combination of both diffusion and erosion. Even though indomethacin incorporated in non-plasticized film showed similar release profile, Gly or PG should be added to enhanced film flexibility and decrease film brittleness. Full article
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Open AccessArticle Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes
Polymers 2017, 9(7), 290; doi:10.3390/polym9070290
Received: 15 June 2017 / Revised: 14 July 2017 / Accepted: 17 July 2017 / Published: 20 July 2017
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Abstract
Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is
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Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC1), were successfully hybridized with heteropolyanions of [PW12O40]3− (PW12) to form inorganic-organic hybrid monomers of MAImC1-PW12. The synthetic procedure of MAImC1-PW12 was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC1-PW12 was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC1-PW12 was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10−4 S·cm−1 order under humidified conditions at 313 K. Full article
(This article belongs to the Special Issue Conductive Polymers 2017)
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Open AccessArticle Electronically Stabilized Copoly(Styrene-Acrylic Acid) Submicrocapsules Prepared by Miniemulsion Copolymerization
Polymers 2017, 9(7), 291; doi:10.3390/polym9070291
Received: 1 July 2017 / Revised: 17 July 2017 / Accepted: 20 July 2017 / Published: 20 July 2017
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Abstract
This work reports the preparation and characterization of poly(styrene-acrylic acid) (St/AA) submicrocapsules by using the miniemulsion copolymerization method. AA was introduced to miniemulsion polymerization of St to increase the zeta potential and the resulting electrostatic stability of St/AA submicrocapsules. Phytoncide oil was adopted
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This work reports the preparation and characterization of poly(styrene-acrylic acid) (St/AA) submicrocapsules by using the miniemulsion copolymerization method. AA was introduced to miniemulsion polymerization of St to increase the zeta potential and the resulting electrostatic stability of St/AA submicrocapsules. Phytoncide oil was adopted as the core model material. Miniemulsion copolymerization of St and AA was conducted at a fixed monomer concentration (0.172 mol) with a varying monomer feed ratio [AA]/[St] (0.2, 0.25, 0.33, 0.5, and 1.0). Concentrations of initiator (azobisisobutyronitrile; 1.0 × 10−3, 2.0 × 10−3, 3.0 × 10−3, and 4.0 × 10−3 mol/mol of monomer) and surfactant (sodium dodecyl sulfate; 0.6 × 10−3, 1.0 × 10−3, and 1.4 × 10−3 mol) were also controlled to optimize the miniemulsion copolymerization of St and AA. Dynamic light scattering and microscopic analyses confirmed the optimum condition of miniemulsion copolymerization of St and AA. Long-term colloidal stability of aqueous St/AA submicrocapsule suspension was evaluated by using TurbiscanTM Lab. In this work, the optimum condition for miniemulsion copolymerization of St and AA was determined ([AA]/[St] = 0.33; [SDS] = 1.0 × 10−3 mol; [AIBN] = 2.0 × 10−3 mol/mol of monomer). St/AA submicrocapsules prepared at the optimum condition (392.6 nm and −55.2 mV of mean particle size and zeta potential, respectively) showed almost no variations in backscattering intensity (stable colloids without aggregation). Full article
(This article belongs to the Special Issue Emulsion Polymerization)
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Open AccessArticle Preparation of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric Silica Nanocomposites Containing Gluconamide Units Possessing Highly Oleophobic/Superhydrophobic, Highly Oleophobic/Superhydrophilic, and Superoleophilic/Superhydrophobic Characteristics on the Modified Surfaces
Polymers 2017, 9(7), 292; doi:10.3390/polym9070292
Received: 2 June 2017 / Revised: 12 July 2017 / Accepted: 18 July 2017 / Published: 20 July 2017
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Abstract
Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2-CHSi(OMe)3)n-RF (RF-(VM)n-RF)] undergoes the sol-gel reaction in the presence of N-(3-triethoxysilylpropyl)gluconamide [Glu-Si(OEt)3] under alkaline conditions to afford the corresponding fluorinated oligomeric
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Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2-CHSi(OMe)3)n-RF (RF-(VM)n-RF)] undergoes the sol-gel reaction in the presence of N-(3-triethoxysilylpropyl)gluconamide [Glu-Si(OEt)3] under alkaline conditions to afford the corresponding fluorinated oligomeric silica nanocomposites containing gluconamide units [RF-(VM-SiO3/2)n-RF/Glu-SiO3/2]. These obtained nanocomposites were applied to the surface modification of glass to provide the unique wettability characteristics such as highly oleophobic/superhydrophobic and highly oleophobic/superhydrophilic on the modified surfaces under a variety of conditions. Such a highly oleophobic/superhydrophobic characteristic was also observed on the modified PET (polyethylene terephthalate) fabric swatch, which was prepared under similar conditions, and this modified PET fabric swatch was applied to the separation membrane for the separation of the mixture of fluorocarbon oil and hydrocarbon oil. The RF-(VM-SiO3/2)n-RF/Glu-SiO3/2 nanocomposites, which were prepared under lower feed amounts of basic catalyst (ammonia), were found to cause gelation in water. Interestingly, it was demonstrated that these gelling nanocomposites are also applied to the surface modification of the PET fabric swatch to give a highly oleophobic/superhydrophobic characteristic on the surface. On the other hand, the modified glass surfaces treated with the corresponding nanocomposite possessing no gelling ability were found to supply the usual hydrophobic characteristic with a highly oleophobic property. More interestingly, the wettability change on the modified PET fabric swatch from highly oleophobic to superoleophilic was observed, and remained superhydrophobic after immersing the modified PET fabric swatch into water. Full article
(This article belongs to the Special Issue Fluorinated Polymers)
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Open AccessArticle Self-Assembly of Double Hydrophilic Poly(2-ethyl-2-oxazoline)-b-poly(N-vinylpyrrolidone) Block Copolymers in Aqueous Solution
Polymers 2017, 9(7), 293; doi:10.3390/polym9070293
Received: 23 June 2017 / Revised: 14 July 2017 / Accepted: 16 July 2017 / Published: 20 July 2017
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Abstract
The self-assembly of a novel combination of hydrophilic blocks in water is presented, namely poly(2-ethyl-2-oxazoline)-b-poly(N-vinylpyrrolidone) (PEtOx-b-PVP). The completely water-soluble double hydrophilic block copolymer (DHBC) is formed via copper-catalyzed polymer conjugation, whereas the molecular weight of the PVP
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The self-assembly of a novel combination of hydrophilic blocks in water is presented, namely poly(2-ethyl-2-oxazoline)-b-poly(N-vinylpyrrolidone) (PEtOx-b-PVP). The completely water-soluble double hydrophilic block copolymer (DHBC) is formed via copper-catalyzed polymer conjugation, whereas the molecular weight of the PVP is varied in order to study the effect of block ratio on the self-assembly process. Studies via dynamic light scattering, static light scattering as well as microscopy techniques, e.g., cryo scanning electron microscopy or laser scanning confocal microscopy, show the formation of spherical particles in an aqueous solution with sizes between 300 and 400 nm. Particles of the DHBCs are formed without the influence of external stimuli. Moreover, the efficiency of self-assembly formation relies significantly on the molar ratio of the utilized blocks. The nature of the formed structures relies further on the concentration, and indications of particular and vesicular structures are found. Full article
(This article belongs to the Special Issue Polymers and Block Copolymers at Interfaces and Surfaces)
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Open AccessArticle Gas Barrier, Thermal, Mechanical and Rheological Properties of Highly Aligned Graphene-LDPE Nanocomposites
Polymers 2017, 9(7), 294; doi:10.3390/polym9070294
Received: 14 June 2017 / Revised: 17 July 2017 / Accepted: 18 July 2017 / Published: 21 July 2017
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Abstract
This contribution reports on properties of low-density polyethylene-based composites filled with different amounts of graphene nanoplatelets. The studied samples were prepared in the form of films by means of the precoating technique and single screw melt-extrusion, which yields a highly ordered arrangement of
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This contribution reports on properties of low-density polyethylene-based composites filled with different amounts of graphene nanoplatelets. The studied samples were prepared in the form of films by means of the precoating technique and single screw melt-extrusion, which yields a highly ordered arrangement of graphene flakes and results in a strong anisotropy of composites morphology. The performed tests of gas permeability reveal a drastic decrease of this property with increasing filler content. A clear correlation is found between permeability and free volume fraction in the material, the latter evaluated by means of positron annihilation spectroscopy. A strong anisotropy of the thermal conductivity is also achieved and the thermal conductivity along the extrusion direction for samples filled with 7.5 wt % of GnP (graphene nanoplatelets) reached 2.2 W/m·K. At the same time, when measured through a plane, a slight decrease of thermal conductivity is found. The use of GnP filler leads also to improvements of mechanical properties. The increase of Young’s modulus and tensile strength are reached as the composites become more brittle. Full article
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Open AccessArticle Light-Driven Rotation and Pitch Tuning of Self-Organized Cholesteric Gratings Formed in a Semi-Free Film
Polymers 2017, 9(7), 295; doi:10.3390/polym9070295
Received: 29 June 2017 / Revised: 18 July 2017 / Accepted: 19 July 2017 / Published: 21 July 2017
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Abstract
Cholesteric liquid crystal (CLC) has attracted intensive attention due to its ability to form a periodic helical structure with broad tunability. CLC gratings in open systems are especially promising in sensing and micromanipulation. However, there is still much to learn about the inherent
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Cholesteric liquid crystal (CLC) has attracted intensive attention due to its ability to form a periodic helical structure with broad tunability. CLC gratings in open systems are especially promising in sensing and micromanipulation. However, there is still much to learn about the inherent mechanism of such gratings. We investigate the light-driven rotation and pitch-tuning behaviors of CLC gratings in semi-free films which are formed by spin-coating the CLC mixtures onto planarly photoaligned substrates. The doped azobenzene chiral molecular switch supplies great flexibility to realize the continuous grating rotation. The maximum continuous rotational angle reaches 987.8°. Moreover, dependencies of light-driven rotation and pitch tuning on the dopant concentration and exposure are studied. The model of director configuration in the semi-free film is constructed. Precise beam steering and synchronous micromanipulation are also demonstrated. Our work may provide new opportunities for the CLC grating in applications of beam steering, micromanipulation, and sensing. Full article
(This article belongs to the Special Issue Photo-Responsive Polymers)
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Open AccessArticle Design and Study of a Novel Thermal-Resistant and Shear-Stable Amphoteric Polyacrylamide in High-Salinity Solution
Polymers 2017, 9(7), 296; doi:10.3390/polym9070296
Received: 2 June 2017 / Revised: 5 July 2017 / Accepted: 17 July 2017 / Published: 21 July 2017
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Abstract
Abstract: Water-soluble polymers are widely used in oilfields. The rheological behaviors of these polymers in high-salinity solution are very important for stimulation of high-salinity reservoirs. In this work, a novel thermal-resistant and shear-stable amphoteric polyacrylamide (PASD), prepared from acrylamide (AM), sodium styrene
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Abstract: Water-soluble polymers are widely used in oilfields. The rheological behaviors of these polymers in high-salinity solution are very important for stimulation of high-salinity reservoirs. In this work, a novel thermal-resistant and shear-stable amphoteric polyacrylamide (PASD), prepared from acrylamide (AM), sodium styrene sulfonate (SSS), and acryloxyethyl trimethylammonium chloride (DAC) monomers, was prepared by free-radical polymerization in high-salinity solution. The amphoteric polyacrylamide was characterized by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance spectroscopy (1H NMR), elemental analysis, thermogravimetric analysis (TG), and scanning electron microscopy (SEM). The amphoteric polyacrylamide exhibited excellent salinity tolerance. The slow increase in apparent viscosity of the polymer with increase in salinity was interesting. The amphoteric polyacrylamide showed perfect temperature resistance in high-salinity solution. The viscosity retention reached 38.9% at 120 °C and was restored to 87.8% of its initial viscosity when temperature was decreased to room temperature. The retention ratio of apparent viscosity reached 49.7% at 170 s−1 and could still retain it at 25.8% at 1000 s−1. All these results demonstrated that PASD had excellent thermal-resistance and shear-stability in high-salinity solution. We expect that this work could provide a new strategy to design polymers with excellent salinity-tolerance, thermal-resistance, and shear-stability performances. Full article
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Open AccessArticle Biphasic Calcium Phosphate (BCP)-Immobilized Porous Poly (d,l-Lactic-co-Glycolic Acid) Microspheres Enhance Osteogenic Activities of Osteoblasts
Polymers 2017, 9(7), 297; doi:10.3390/polym9070297
Received: 27 June 2017 / Revised: 11 July 2017 / Accepted: 18 July 2017 / Published: 21 July 2017
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Abstract
The purpose of this study was to evaluate the potential of porous poly (d,l-lactic-co-glycolic acid) (PLGA) microspheres (PMSs) immobilized on biphasic calcium phosphate nanoparticles (BCP NPs) (BCP-IM-PMSs) to enhance osteogenic activity. PMSs were fabricated using a fluidic device, and their surfaces
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The purpose of this study was to evaluate the potential of porous poly (d,l-lactic-co-glycolic acid) (PLGA) microspheres (PMSs) immobilized on biphasic calcium phosphate nanoparticles (BCP NPs) (BCP-IM-PMSs) to enhance osteogenic activity. PMSs were fabricated using a fluidic device, and their surfaces were modified with l-lysine (aminated-PMSs), whereas the BCP NPs were modified with heparin–dopamine (Hep-DOPA) to obtain heparinized–BCP (Hep-BCP) NPs. BCP-IM-PMSs were fabricated via electrostatic interactions between the Hep-BCP NPs and aminated-PMSs. The fabricated BCP-IM-PMSs showed an interconnected pore structure. In vitro studies showed that MG-63 cells cultured on BCP-IM-PMSs had increased alkaline phosphatase activity, calcium content, and mRNA expression of osteocalcin (OCN) and osteopontin (OPN) compared with cells cultured on PMSs. These data suggest that BCP NP-immobilized PMSs have the potential to enhance osteogenic activity. Full article
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Open AccessArticle Additives Type Schiff’s Base as Modifiers of the Optical Response in Holographic Polymer-Dispersed Liquid Crystals
Polymers 2017, 9(7), 298; doi:10.3390/polym9070298
Received: 9 June 2017 / Revised: 6 July 2017 / Accepted: 19 July 2017 / Published: 21 July 2017
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Abstract
Schiff’s bases with specific π-electron system have been synthesized and used as additives in holographic polymer-dispersed liquid crystals. It was observed that these substances modify different parameters such as current intensity, voltage, and diffracted light intensity. In addition, the maximum diffraction efficiency obtained
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Schiff’s bases with specific π-electron system have been synthesized and used as additives in holographic polymer-dispersed liquid crystals. It was observed that these substances modify different parameters such as current intensity, voltage, and diffracted light intensity. In addition, the maximum diffraction efficiency obtained in the reconstruction of the holograms is related to the additive molecule. We propose a relationship between this behavior and the molecular structure of these substances. Full article
(This article belongs to the Special Issue Photo-Responsive Polymers)
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Open AccessArticle Upconversion Nanophosphor-Involved Molecularly Imprinted Fluorescent Polymers for Sensitive and Specific Recognition of Sterigmatocystin
Polymers 2017, 9(7), 299; doi:10.3390/polym9070299
Received: 11 June 2017 / Revised: 19 July 2017 / Accepted: 19 July 2017 / Published: 22 July 2017
Cited by 1 | PDF Full-text (2414 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Originated from the bottom-up synthetic strategy, molecularly imprinted polymers (MIPs) possess the inherent ability of selective and specific recognition and binding of the target analytes, with their structural cavities that can match the target molecules in respect to size, shape, and functional groups.
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Originated from the bottom-up synthetic strategy, molecularly imprinted polymers (MIPs) possess the inherent ability of selective and specific recognition and binding of the target analytes, with their structural cavities that can match the target molecules in respect to size, shape, and functional groups. Herein, based on the high selectivity of MIPs and the fluorescence properties of the β-NaYF4:Yb3+, Er3+ upconversion nanoparticles, MIPs with both specificity and fluorescent signals are fabricated to recognize trace sterigmatocystin (ST) with high selectivity and sensitivity. The structure analogue of ST, 1,8-dihydroxyanthraquinone (DT), was employed as the template molecule, acrylamide as the functional monomer, 3-methacryloyloxypropyltrimethoxysilane as the crosslinking agent, and a new molecular imprinting technique of non-aqueous sol-gel method is used to synthesize a molecularly imprinted material with high selectivity to ST. Under optimal conditions, the fluorescence enhancement of fluorescent MIPs increased as the concentration of ST increased. In the range of 0.05–1.0 mg L−1, fluorescence enhancement and the concentration showed a good linear relationship with a detection limit of 0.013 mg L−1. Real sample analysis achieved the recoveries of 83.8–88.8% (RSD 5.1%) for rice, 82.1–87.5% (RSD 4.6%) for maize, and 80.6–89.2% (RSD 3.0%) for soybeans, respectively, revealing the feasibility of the developed method. Full article
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Open AccessArticle Enhancement of Wound Healing in Normal and Diabetic Mice by Topical Application of Amorphous Polyphosphate. Superior Effect of a Host–Guest Composite Material Composed of Collagen (Host) and Polyphosphate (Guest)
Polymers 2017, 9(7), 300; doi:10.3390/polym9070300
Received: 2 July 2017 / Revised: 16 July 2017 / Accepted: 20 July 2017 / Published: 22 July 2017
Cited by 2 | PDF Full-text (5377 KB) | HTML Full-text | XML Full-text
Abstract
The effect of polyphosphate (polyP) microparticles on wound healing was tested both in vitro and in a mice model in vivo. Two approaches were used: pure salts of polyphosphate, fabricated as amorphous microparticles (MPs, consisting of calcium and magnesium salts of polyP, “Ca–polyp-MPs”
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The effect of polyphosphate (polyP) microparticles on wound healing was tested both in vitro and in a mice model in vivo. Two approaches were used: pure salts of polyphosphate, fabricated as amorphous microparticles (MPs, consisting of calcium and magnesium salts of polyP, “Ca–polyp-MPs” and “Mg–polyp-MPs”), and host–guest composite particles, prepared from amorphous collagen (host) and polyphosphate (guest), termed “col/polyp-MPs”. Animal experiments with polyP on healing of excisional wounds were performed using both normal mice and diabetic mice. After a healing period of 7 days “Ca–polyp-MP” significantly improved re-epithelialization in normal mice from 31% (control) to 72% (polyP microparticle-treated). Importantly, in diabetic mice, particularly the host–guest particles “col/polyp-MP”, increased the rate of re-epithelialization to ≈40% (control, 23%). In addition, those particles increased the expression of COL-I and COL-III as well as the expression the α-smooth muscle actin and the plasminogen activator inhibitor-1. We propose that “Ca–polyp-MPs”, and particularly the host–guest “col/polyp-MPs” are useful for topical treatment of wounds. Full article
(This article belongs to the Special Issue Host-Guest Polymer Complexes)
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Open AccessArticle Synthesis and Phase Transition of Poly(N-isopropylacrylamide)-Based Thermo-Sensitive Cyclic Brush Polymer
Polymers 2017, 9(7), 301; doi:10.3390/polym9070301
Received: 24 June 2017 / Revised: 19 July 2017 / Accepted: 21 July 2017 / Published: 23 July 2017
Cited by 1 | PDF Full-text (2346 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Polymers with advanced topological architectures are promising materials for wide applications due to their structure-generated unique properties different from that of the linear analogues. The elegant integration of stimuli-responsive polymers with such advanced architectures can create novel materials with virtues from both moieties,
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Polymers with advanced topological architectures are promising materials for wide applications due to their structure-generated unique properties different from that of the linear analogues. The elegant integration of stimuli-responsive polymers with such advanced architectures can create novel materials with virtues from both moieties, are thus a hot subject of research for both fundamental and practical investigations. To fabricate cyclic brush polymer-based intelligent materials for biomedical applications, herein, we designed and synthesized thermo-sensitive cyclic brush polymers with poly(N-isopropylacrylamide) (PNIPAAm) brushes by controlled living radical polymerization using cyclic multimacroinitiator. The thermo-induced phase transition behaviors of the resultant cyclic brush polymers with different compositions were investigated in detail by temperature-dependent optical transmittance measurements, and compared with the properties of bottlebrush and linear counterparts. Interestingly, the cloud point transition temperature (Tcp) of cyclic brush PNIPAAm could be regulated by the chain length of PNIPAAm brush. Although the bottlebrush polymers with the same composition exhibited similarly structurally dependent Tcps behaviors to the cyclic brush polymers, the cyclic brush PNIPAAm did show higher critical aggregation concentration (CAC) and enhanced stability against dilution than the bottlebrush counterpart. The readily tailorable Tcps together with the ability to form highly stable nanoparticles makes thermo-sensitive cyclic brush PNIPAAm a promising candidate for controlled drug delivery. Full article
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Open AccessArticle Two-Photon-Induced Microstereolithography of Chitosan-g-Oligolactides as a Function of Their Stereochemical Composition
Polymers 2017, 9(7), 302; doi:10.3390/polym9070302
Received: 12 June 2017 / Revised: 20 July 2017 / Accepted: 21 July 2017 / Published: 24 July 2017
PDF Full-text (4898 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Chitosan-g-oligolactide copolymers with relatively long oligolactide grafted chains of various stereochemical compositions have been synthetized via a solvent-free mechanochemical technique and tailored to fabricate three-dimensional hydrogels using two-photon induced microstereolithography. An effect of the characteristics of chitosan and oligolactide used for
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Chitosan-g-oligolactide copolymers with relatively long oligolactide grafted chains of various stereochemical compositions have been synthetized via a solvent-free mechanochemical technique and tailored to fabricate three-dimensional hydrogels using two-photon induced microstereolithography. An effect of the characteristics of chitosan and oligolactide used for the synthesis on the grafting yield and copolymer’s behavior were evaluated using fractional analysis, FTIR-spectroscopy, dynamic light scattering, and UV-spectrophotometry. The lowest copolymer yield was found for the system based on chitosan with higher molecular weight, while the samples consisting of low-molecular weight chitosan showed higher grafting degrees, which were comparable in both the cases of l,l- or l,d-oligolactide grafting. The copolymer processability in the course of two-photon stereolithography was evaluated as a function of the copolymer’s characteristics and stereolithography conditions. The structure and mechanical properties of the model film samples and fabricated 3D hydrogels were studied using optical and scanning electron microscopy, as well as by using tensile and nanoindenter devices. The application of copolymer with oligo(l,d-lactide) side chains led to higher processability during two-photon stereolithography in terms of the response to the laser beam, reproduction of the digital model, and the mechanical properties of the fabricated hydrogels. Full article
(This article belongs to the Special Issue Three-Dimensional Structures: Fabrication and Application)
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Open AccessReview Sialic Acid-Targeted Biointerface Materials and Bio-Applications
Polymers 2017, 9(7), 249; doi:10.3390/polym9070249
Received: 6 June 2017 / Revised: 23 June 2017 / Accepted: 24 June 2017 / Published: 27 June 2017
Cited by 2 | PDF Full-text (6234 KB) | HTML Full-text | XML Full-text
Abstract
Sialic acids (SAs) are typically found as terminal monosaccharides attached to cell surface glycoconjugates, which play crucial roles in various biological processes, and aberrant sialylation is closely associated with many diseases, particularly cancers. As SAs are overexpressed in tumor-associated glycoproteins, the recognition and
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Sialic acids (SAs) are typically found as terminal monosaccharides attached to cell surface glycoconjugates, which play crucial roles in various biological processes, and aberrant sialylation is closely associated with many diseases, particularly cancers. As SAs are overexpressed in tumor-associated glycoproteins, the recognition and specific binding of SA are crucial for monitoring, analyzing and controlling cancer cells, which would have a considerable impact on diagnostic and therapeutic application. However, both effective and selective recognition of SA on the cancer cell surface remains challenging. In recent years, SA-targeted biointerface materials have attracted great attention in various bio-applications, including cancer detection and imaging, drug delivery for cancer therapy and sialylated glycopeptide separation or enrichment. This review provides an overview of recent advances in SA-targeted biointerface materials and related bio-applications. Full article
(This article belongs to the Special Issue Advance of Polymers Applied to Biomedical Applications: Biointerface)
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Open AccessReview Particle Distribution of Solid Flame Retardants in Infusion Moulded Composites
Polymers 2017, 9(7), 250; doi:10.3390/polym9070250
Received: 29 May 2017 / Revised: 23 June 2017 / Accepted: 23 June 2017 / Published: 28 June 2017
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Abstract
Resin transfer moulding (RTM) is commonly used for the production of high-performance fibre-reinforced polymer composites. In numerous application areas, the addition of fillers is necessary to enhance some properties of the polymer matrix or provide it with additional properties, such as flame retardancy.
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Resin transfer moulding (RTM) is commonly used for the production of high-performance fibre-reinforced polymer composites. In numerous application areas, the addition of fillers is necessary to enhance some properties of the polymer matrix or provide it with additional properties, such as flame retardancy. As many of the applied additives are solid phase, the reinforcement layers may filter the solid phase additive particles during RTM, resulting in a non-uniform distribution and uneven performance. Consequently, the proper distribution of the solid phase additives in composites is of key importance. This review primarily aims at facilitating the production of flame retarded structural composites by RTM in cases where the required fire performance can only be achieved with solid additives. First, the parameters influencing the particle distribution, along with the models describing it, are reviewed. Then, analytical methods for determining the particle distribution in composites manufactured by RTM are presented. Finally, the possible solutions to improve the particle distribution of solid phase additives are outlined. Full article
(This article belongs to the collection Featured Mini Reviews in Polymer Science)
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Open AccessReview Statistical and Dynamical Properties of Topological Polymers with Graphs and Ring Polymers with Knots
Polymers 2017, 9(7), 252; doi:10.3390/polym9070252
Received: 26 January 2017 / Revised: 22 June 2017 / Accepted: 23 June 2017 / Published: 28 June 2017
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Abstract
We review recent theoretical studies on the statistical and dynamical properties of polymers with nontrivial structures in chemical connectivity and those of polymers with a nontrivial topology, such as knotted ring polymers in solution. We call polymers with nontrivial structures in chemical connectivity
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We review recent theoretical studies on the statistical and dynamical properties of polymers with nontrivial structures in chemical connectivity and those of polymers with a nontrivial topology, such as knotted ring polymers in solution. We call polymers with nontrivial structures in chemical connectivity expressed by graphs “topological polymers”. Graphs with no loop have only trivial topology, while graphs with loops such as multiple-rings may have nontrivial topology of spatial graphs as embeddings in three dimensions, e.g., knots or links in some loops. We thus call also such polymers with nontrivial topology “topological polymers”, for simplicity. For various polymers with different structures in chemical connectivity, we numerically evaluate the mean-square radius of gyration and the hydrodynamic radius systematically through simulation. We evaluate the ratio of the gyration radius to the hydrodynamic radius, which we expect to be universal from the viewpoint of the renormalization group. Furthermore, we show that the short-distance intrachain correlation is much enhanced for real topological polymers (the Kremer–Grest model) expressed with complex graphs. We then address topological properties of ring polymers in solution. We define the knotting probability of a knot K by the probability that a given random polygon or self-avoiding polygon of N vertices has the knot K. We show a formula for expressing it as a function of the number of segments N, which gives good fitted curves to the data of the knotting probability versus N. We show numerically that the average size of self-avoiding polygons with a fixed knot can be much larger than that of no topological constraint if the excluded volume is small. We call it “topological swelling”. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessReview Glucose Oxidase-Based Glucose-Sensitive Drug Delivery for Diabetes Treatment
Polymers 2017, 9(7), 255; doi:10.3390/polym9070255
Received: 12 May 2017 / Revised: 19 June 2017 / Accepted: 25 June 2017 / Published: 29 June 2017
Cited by 1 | PDF Full-text (5539 KB) | HTML Full-text | XML Full-text
Abstract
The glucose-sensitive drug delivery systems based on glucose oxidase (GOD), which exhibit highly promising applications in diabetes therapy, have attracted much more interest in recent years. The self-regulated drug delivery systems regulate drug release by glucose concentration automatically and continuously to control the
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The glucose-sensitive drug delivery systems based on glucose oxidase (GOD), which exhibit highly promising applications in diabetes therapy, have attracted much more interest in recent years. The self-regulated drug delivery systems regulate drug release by glucose concentration automatically and continuously to control the blood glucose level (BGL) in normoglycemic state. This review covers the recent advances at the developments of GOD-based glucose-sensitive drug delivery systems and their in vivo applications for diabetes treatment. The applications of GOD-immobilized platforms, such as self-assembly layer-by-layer (LbL) films and polymer vesicles, cross-linking hydrogels and microgels, hybrid mesoporous silica nanoparticles, and microdevices fabricated with insulin reservoirs have been surveyed. The glucose-sensitive drug delivery systems based on GOD are expected to be a typical candidate for smart platforms for potential applications in diabetes therapy. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessReview Tissue Engineering Bionanocomposites Based on Poly(propylene fumarate)
Polymers 2017, 9(7), 260; doi:10.3390/polym9070260
Received: 13 June 2017 / Revised: 27 June 2017 / Accepted: 28 June 2017 / Published: 30 June 2017
Cited by 2 | PDF Full-text (6510 KB) | HTML Full-text | XML Full-text
Abstract
Poly(propylene fumarate) (PPF) is a linear and unsaturated copolyester based on fumaric acid that has been widely investigated for tissue engineering applications in recent years due to its tailorable mechanical performance, adjustable biodegradability and exceptional biocompatibility. In order to improve its mechanical properties
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Poly(propylene fumarate) (PPF) is a linear and unsaturated copolyester based on fumaric acid that has been widely investigated for tissue engineering applications in recent years due to its tailorable mechanical performance, adjustable biodegradability and exceptional biocompatibility. In order to improve its mechanical properties and spread its range of practical applications, novel approaches need to be developed such as the incorporation of fillers or polymer blending. Thus, PPF-based bionanocomposites reinforced with different amounts of single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT), graphene oxide nanoribbons (GONR), graphite oxide nanoplatelets (GONP), polyethylene glycol-functionalized graphene oxide (PEG-GO), polyethylene glycol-grafted boron nitride nanotubes (PEG-g-BNNTs) and hydroxyapatite (HA) nanoparticles were synthesized via sonication and thermal curing, and their morphology, biodegradability, cytotoxicity, thermal, rheological, mechanical and antibacterial properties were investigated. An increase in the level of hydrophilicity, biodegradation rate, stiffness and strength was found upon increasing nanofiller loading. The nanocomposites retained enough rigidity and strength under physiological conditions to provide effective support for bone tissue formation, showed antibacterial activity against Gram-positive and Gram-negative bacteria, and did not induce toxicity on human dermal fibroblasts. These novel biomaterials demonstrate great potential to be used for bone tissue engineering applications. Full article
(This article belongs to the Special Issue Advance of Polymers Applied to Biomedical Applications: Biointerface)
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Open AccessReview Poly(lactic acid) Composites Containing Carbon-Based Nanomaterials: A Review
Polymers 2017, 9(7), 269; doi:10.3390/polym9070269
Received: 15 June 2017 / Revised: 30 June 2017 / Accepted: 4 July 2017 / Published: 6 July 2017
Cited by 3 | PDF Full-text (3283 KB) | HTML Full-text | XML Full-text
Abstract
Poly(lactic acid) (PLA) is a green alternative to petrochemical commodity plastics, used in packaging, agricultural products, disposable materials, textiles, and automotive composites. It is also approved by regulatory authorities for several biomedical applications. However, for some uses it is required that some of
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Poly(lactic acid) (PLA) is a green alternative to petrochemical commodity plastics, used in packaging, agricultural products, disposable materials, textiles, and automotive composites. It is also approved by regulatory authorities for several biomedical applications. However, for some uses it is required that some of its properties be improved, namely in terms of thermo-mechanical and electrical performance. The incorporation of nanofillers is a common approach to attain this goal. The outstanding properties of carbon-based nanomaterials (CBN) have caused a surge in research works dealing with PLA/CBN composites. The available information is compiled and reviewed, focusing on PLA/CNT (carbon nanotubes) and PLA/GBM (graphene-based materials) composites. The production methods, and the effects of CBN loading on PLA properties, namely mechanical, thermal, electrical, and biological, are discussed. Full article
(This article belongs to the Special Issue Graphene-Polymer Composites)
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Open AccessReview Vesicles from Amphiphilic Dumbbells and Janus Dendrimers: Bioinspired Self-Assembled Structures for Biomedical Applications
Polymers 2017, 9(7), 280; doi:10.3390/polym9070280
Received: 17 May 2017 / Revised: 2 July 2017 / Accepted: 6 July 2017 / Published: 12 July 2017
Cited by 2 | PDF Full-text (10725 KB) | HTML Full-text | XML Full-text
Abstract
The current review focuses on vesicles obtained from the self-assembly of two types of dendritic macromolecules, namely amphiphilic Janus dendrimers (forming dendrimersomes) and amphiphilic dumbbells. In the first part, we will present some synthetic strategies and the various building blocks that can be
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The current review focuses on vesicles obtained from the self-assembly of two types of dendritic macromolecules, namely amphiphilic Janus dendrimers (forming dendrimersomes) and amphiphilic dumbbells. In the first part, we will present some synthetic strategies and the various building blocks that can be used to obtain dendritic-based macromolecules, thereby showing their structural versatility. We put our focus on amphiphilic Janus dendrimers and amphiphilic dumbbells that form vesicles in water but we also encompass vesicles formed thereof in organic solvents. The second part of this review deals with the production methods of these vesicles at the nanoscale but also at the microscale. Furthermore, the influence of various parameters (intrinsic to the amphiphilic JD and extrinsic—from the environment) on the type of vesicle formed will be discussed. In the third part, we will review the numerous biomedical applications of these vesicles of nano- or micron-size. Full article
(This article belongs to the Special Issue Bio-inspired and Bio-based Polymers)
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