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Mn-catalyzed hydroarylation polyaddition of 1-(2-pyrimidinyl)pyrrole (1a) with aromatic diynes is investigated. The use of commercially available MnBr(CO) 5 as a precatalyst under the optimized reaction conditions resulted in a site- and regioselective hydroarylation polyaddition, affording the corresponding poly(arylenevinylene)s (PAVs) with excellent vinylene selectivity. The reaction protocol eliminates the production of stoichiometric amounts of byproducts from the monomers. The nonstoichiometric polyaddition of an excess amount of 1a with aromatic diynes is also demonstrated. The 2-pyrimidinyl substituent promoted the intramolecular transfer of the Mn catalyst walking through the 1a moiety., (© 2024 Wiley‐VCH GmbH.)

This work aims at synthesizing tailor-made poly(vinyl alcohol- co -vinyl acetate) (PVA) amphiphilic copolymers, obtained by alcoholysis of poly(vinyl acetate) (PVAc) that could display improved properties as stabilizers compared to commercially available PVAs. Well-defined PVAs with different alcoholysis degrees were produced from a library of PVAc homopolymers synthesized by macromolecular design via interchange of xanthate polymerization and exhibiting different degrees of polymerization degrees. Subsequently, these PVAs were evaluated as stabilizers in the emulsion copolymerization of VAc and vinyl neodecanoate (VERSA 10, referred to as V10) and compared to a commercially available reference PVA obtained by alcoholysis of PVAc formed by conventional radical polymerization. In all cases, stable latexes were obtained and compared in terms of their colloidal characteristics. To identify the best stabilizer candidate, the amount of PVA remaining in water and not participating to the particle stabilization was evaluated in each case.

This study focuses on the development of regiospecific hydroarylation polyaddition of naphthalene- and carbazole-based monomers with diynes under mild reaction conditions at room temperature. A 1-pyrazole substituent serves as an appropriate directing group for a Co-catalyst to efficiently activate the C-H bonds of generally inactive six-membered aromatic hydrocarbons. The 1-pyrazole groups in 2,6-di(1-pyrazolyl)naphthalene adopt planar conformations and act as directing groups, resulting in a smooth hydroarylation reaction. In contrast, the reaction with 1,5-di(1-pyrazolyl)naphthalene do not proceed. The polyaddition reaction of 2,6-di(1-pyrazolyl)naphthalene selectively proceeds at 3,7-positions under mild reaction conditions at 30 °C, and yields corresponding poly(arylenevinylene) (PAV) with high molecular weight. This molecular design is also applicable to the hydroarylation polyaddition of carbazole; the polyaddition reaction of 9-(2-ethylhexyl)-3,6-di(1-pyrazolyl)carbazole selectively occurred at 2,7-positions. The optical and electronic properties of the synthesized compounds are evaluated. The obtained PAVs serve as an emitting material in organic light-emitting diode (OLED). This study aims to develop a Co-catalyzed hydroarylation polyaddition via C-H activation of generally inactive polyaromatic hydrocarbons (PAHs) under mild conditions., (© 2024 Wiley‐VCH GmbH.)

Inspired by living organisms, soft robots are developed from intrinsically compliant materials, enabling continuous motions that mimic animal and vegetal movement 1 . In soft robots, the canonical hinges and bolts are replaced by elastomers assembled into actuators programmed to change shape following the application of stimuli, for example pneumatic inflation 2-5 . The morphing information is typically directly embedded within the shape of these actuators, whose assembly is facilitated by recent advances in rapid prototyping techniques 6-11 . Yet, these manufacturing processes have limitations in scalability, design flexibility and robustness. Here we demonstrate a new all-in-one methodology for the fabrication and the programming of soft machines. Instead of relying on the assembly of individual parts, our approach harnesses interfacial flows in elastomers that progressively cure to robustly produce monolithic pneumatic actuators whose shape can easily be tailored to suit applications ranging from artificial muscles to grippers. We rationalize the fluid mechanics at play in the assembly of our actuators and model their subsequent morphing. We leverage this quantitative knowledge to program these soft machines and produce complex functionalities, for example sequential motion obtained from a monotonic stimulus. We expect that the flexibility, robustness and predictive nature of our methodology will accelerate the proliferation of soft robotics by enabling the assembly of complex actuators, for example long, tortuous or vascular structures, thereby paving the way towards new functionalities stemming from geometric and material nonlinearities., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

Disinfecting pathogenic contaminated water rapidly and effectively on sites is one of the critical challenges at point-of-use (POU) situations. Currently available technologies are still suffering from irreversible depletion of disinfectants, generation of toxic by-products, and potential biofouling problems. Herein, we developed a chlorine rechargeable biocidal nanofibrous membrane, poly(acrylonitrile- co -5-methyl-5-(4'-vinylphenyl)imidazolidine-2,4-dione) (P(AN-VAPH)), via a combination of a free radical copolymerization reaction and electrospun technology. The copolymer exhibits good electrospinnability and desirable mechanical properties. Also, the 5-methyl-5-(4'-vinylphenyl)imidazolidine-2,4-dione (VAPH) moieties containing unique hydantoin structures are able to be chlorinated and converted to halamine structures, enabling the P(AN-VAPH) nanofibrous membrane with rapid and durable biocidal activity. The chlorinated P(AN-VAPH) nanofibrous membranes showed intriguing features of unique 3D morphological structures with large specific surface area, good mechanical performance, rechargeable chlorination capacity (>5000 ppm), long-term durability, and desirable biocidal activity against both bacteria and viruses (>99.9999% within 2 min of contact). With these attributes, the chlorinated P(AN-VAPH) membranes demonstrated promising disinfecting efficiency against concentrated bacteria-contaminated water during direct filtration applications with superior killing capacity and high flowing flux (5000 L m -2 h -1 ).

Butyrate has been attracting attention for the suppression of inflammatory bowel disease (IBD). However, clinical trials of butyrate for IBD treatment have resulted in controversial outcomes, likely owing to the adverse effect of butyrate on the intestinal epithelium that was observed at high butyrate concentrations. Herein, we propose polyvinyl butyrate (PVBu) nanoparticles (NPs) as butyrate donors for delivery to the lower part of the intestine for the treatment of colitis. The PVBu NPs suppressed the inflammatory activation of macrophages in vitro , although sodium butyrate inversely further activated macrophages. Oral administration of NPs did not change the luminal concentration of free butyrate; however, NPs showed a therapeutic effect on a colitis mouse model. In addition, incorporation of vitamin D 3 into the NPs enhanced the therapeutic effect on colitis. Hence, PVBu NPs are a promising therapeutic for IBD treatment, not only as a butyrate donor but also as a carrier for hydrophobic drugs like vitamin D 3 .

The development of a novel molecularly imprinted solid-phase extraction (MISPE) method for simultaneous preconcentration of imazapyr (IMP), imazapic (IMZ) and imazethapyr (IMT) with determination by HPLC-PAD (High performance liquid chromatography - photodiode-array detector) is proposed. The polymer synthesis was performed using imazethapyr as template molecule and 1-vinylimidazole as functional monomer. The method is based on preconcentration of 100.0 mL of sample through 200.0 mg of molecularly imprinted poly(vinylimidazole-TRIM) (MIP-1VN) at pH 4.0, followed by elution with 2.0 mL of MeOH:CH 2 Cl 2 :HAc (34:62:4, v/v). The range of analytical curve (0.29-200.0, 0.21-200.0 and 0.15-200.0 µg L -1 ), limits of detection (0.09, 0.06 and 0.04 µg L -1 ) and preconcentration factors (92, 96 and 98) determined for the herbicides, IMP, IMZ and IMT, respectively, were greatly superior when compared with those ones obtained with commercial adsorbents. The analytical method was successfully applied to spiked surface water and rice samples with good results of recovery values (86-107%)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Herein, electrospun zinc oxide nanoparticle/poly (vinylidene fluoride) (ZnONP/PVDF) composite fiber membranes were designed, fabricated, and tested for improved orthopedic applications. A single factor screening study was conducted to determine the optimal ZnONP/PVDF formulation based on osteoblast (bone forming cells) proliferation and antibacterial properties. Further, ZnONP/PVDF materials were characterized for their morphology, crystallinity, roughness, piezoelectric properties, and chemistry to understand such cell results. The optimal concentration of high molecular weight PVDF (18%, w/v) and a low concentration of ZnONPs (1 mg/ml) were identified for electrospinning at room temperature in order to inhibit bacterial colonization (without resorting to antibiotic use) and promote osteoblast proliferation. Compared to no ZnO/PVDF scaffold without Piezo-excited group,the study showed that on the 1 mg/ml ZnO/PVDF scaffolds with piezo-excitation, the density of SA and E.coli decreased by 68% and 56%.The density of osteoblasts doubled within three days(compared to the control). In summary, ZnONP/PVDF composite fiber membranes were formulated by electrospinning showing an exceptional ability to eliminate bacteria colonization while at the same time promote osteoblast functions and, thus, they should be further studied for a wide range of orthopedic applications.

To date, amphiphilic block copolymers (BCPs) containing poly(vinylidene fluoride- co -hexafluoropropene) (P(VDF- co -HFP)) copolymers are rare. At moderate content of HFP, this fluorocopolymer remains semicrystalline and is able to crystallize. Amphiphilic BCPs, containing a P(VDF-co-HFP) segment could, thus be appealing for the preparation of self-assembled block copolymer morphologies through crystallization-driven self-assembly (CDSA) in selective solvents. Here the synthesis, characterization by 1 H and 19 F NMR spectroscopies, GPC, TGA, DSC, and XRD; and the self-assembly behavior of a P(VDF- co -HFP)- b -PEG- b -P(VDF- co -HFP) triblock copolymer were studied. The well-defined ABA amphiphilic fluorinated triblock copolymer was self-assembled into nano-objects by varying a series of key parameters such as the solvent and the non -solvent, the self-assembly protocols, and the temperature. A large range of morphologies such as spherical, square, rectangular, fiber-like, and platelet structures with sizes ranging from a few nanometers to micrometers was obtained depending on the self-assembly protocols and solvents systems used. The temperature-induced crystallization-driven self-assembly (TI-CDSA) protocol allowed some control over the shape and size of some of the morphologies.

In nanoimprint lithography (NIL), a pattern is created by mechanical deformation of an imprint resist via embossing with a stamp, where the adhesion behavior during the filling of the imprint stamp and its subsequent detachment may impose some practical challenges. Here we explored thermal and reverse NIL patterning of polyvinylferrocene and vinylferrocene-methyl methacrylate copolymers to prepare complex non-spherical objects and patterns. While neat polyvinylferrocene was found to be unsuitable for NIL, freshly-prepared vinylferrocene-methyl methacrylate copolymers, for which identity and purity were established, have been structured into 3D-micro/nano-patterns using NIL. The cross-, square-, and circle-shaped columnar structures form a 3 × 3 mm arrangement with periodicity of 3 µm, 1 µm, 542 nm, and 506 nm. According to our findings, vinylferrocene-methyl methacrylate copolymers can be imprinted without further additives in NIL processes, which opens the way for redox-responsive 3D-nano/micro-objects and patterns via NIL to be explored in the future.

Adverse effects of pharmaceutical emerging contaminants (PECs), including antibiotics, in water supplies has been a global concern in recent years as they threaten fresh water security and lead to serious health problems to human, wildlife and the environment. However, detection of these contaminants in water sources, as well as food products, is difficult due to their low concentration. Here, we prepared a new family of magnetic molecular imprinted polymer (MMIP) networks for binding antibiotics via a microemulsion polymerization technique using vinyl silane modified Fe 3 O 4 magnetic nanoparticles. The cross-linked polymer backbone successfully integrated with 20-30 nm magnetic nanoparticles and generated a novel porous polymeric network structure. These networks showed a high binding capacity for both templates, erythromycin and ciprofloxacin at 70 and 32 mg/g. Both MMIPs were also recyclable, retaining 75 % and 68 % of the binding capacity after 4 cycles. These MMIPs have showed a clear preference for binding the template molecules, with a binding capacity 4- to 7-fold higher than the other antibiotics in the same matrix. These results demonstrate our MMIP networks, which offered high binding capacity and selectivity as well as recyclability, can be used for both removal and monitoring hazardous antibiotic pollutants in different sources/samples and food products., Competing Interests: Declaration of Competing Interest There is no conflict of interest to declare., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Numerous emerging and re-emerging advanced materials have been successful in capturing iodine pollutants that pose an unprecedented global challenge to public health. However, little attention has been paid to the reutilization of the captured iodine. Herein, we report on a pyrrolidone-based polymer capable of reversible iodine capture for reutilization in antibacterial applications. The pyrrolidone-based polymer poly(N-vinyl-2-pyrrolidone-co-vinyl acetate), denoted as P(VAc-NVP), was synthesized facilely via a one-step radical copolymerization strategy, and the synthesis was regulated by step-by-step optimization, specifically by tuning the feed ratio of NVP to VAc. The as-synthesized P(VAc-NVP) copolymer functioned as an adsorbent for iodine in various solutions, including water/ethanol, cyclohexane, and petroleum ether, in addition to having the special capability of releasing iodine in the presence of starch or bacteria. This opens up a new horizon for its functional practical use as a flexible adsorbent to capture iodine for safe disposal. Interestingly, the P(VAc-NVP) copolymer, after adsorbing iodine, showed antibacterial ability against pathogenic bacteria, including Staphylococcus aureus and Escherichia coli, when a series of simulated and practical antibacterial assays were conducted. It is believed that this proposed strategy based on the synergism of iodine capture and antibacterial use should have great potential for environmental remediation and public healthcare., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Fenugreek gum is modified using two different techniques: microwave-assisted and thermal synthesis technique of graft copolymerization. The synthesis was done by varying the concentration of acrylamide monomer and CAN initiator to get the best-grafted product. The physicochemical characteristics were determined by elemental analysis, FTIR spectroscopy, SEM, XRD, DSC, TGA, number-average molecular weight and intrinsic viscosity. All the grafted materials were tested by flocculation of different synthetic suspension media as well as river water. The process of deflocculation and refloccculation was also carried out and it was observed that refloccculation process has a good potential as the flocculation efficacy increased to a considerable extent. The flocculation efficacy increased from 92.05% to 94.32% upto a maximum of 95.98% in refloccculation process. The flocculation efficacy was found out to be 95.98%, 40.52% and 68.94% respectively kaolin, coal fine and iron ore suspensions. Flocculation was done in kaolin suspension of pH 2, 4, 7 and 10 and at different temperature range of 10 0 , 25 0 , 40 0 and 55 0 C. It is expected that this material can be used as a highly efficient flocculant in future., (Copyright © 2019. Published by Elsevier B.V.)

A simple and effective strategy to simultaneously enhance the permeability and antifouling properties of ethylene vinyl alcohol (EVAL) membrane was developed based on the bioinspired natural cleaner, cilia. Taking clue from the self-cleaning effect of cilia, supramolecular polyrotaxanes (PRs) with sliding and rotating cyclic molecules along linear chains were synthesized using azide-alkyne click chemistry. Cilia-like PRs were incorporated into EVAL matrix in the fabrication of modified EVAL membranes. Cilia-like structures protruding from the membrane surface have been observed by SEM, TEM and AFM. By imitating natural ciliary movements, these structures provided a proactive self-cleaning system to remove the foulants. The introduction of cilia-like PRs enhanced the surface roughness and hydrophilicity, and significantly enhanced permeability by 55.3% compared to raw EVAL membrane. Moreover, the membrane modified with cilia-like PRs showed an excellent antifouling property with a lower water flux decline (12.6%) and higher water flux recovery (94%) in dynamic fouling tests. Furthermore, this modified membrane develops the scope of bioinspired membranes, inspiring more attractive potential applications in self-cleaning materials, dynamic membranes and supramolecular machines., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, a novel poly(ionic liquid) with 1-vinyl-3-aminopropyl imidazolium cations was designed and used to modify cellulose aerogels via Schiff base reaction. The poly(ionic liquid) modified cellulose aerogels (PIL-CA) exhibited a well-interconnected porous structure and a high porosity of 86.2%. A zeta potential study showed the PIL-CA had a strong positive potential of more than 65 mV when its pH was below 6. Furthermore, after 350 min of adsorption experiments, the PIL-CA showed a superior adsorption capacity of 918 ± 8 mg g -1 towards bovine serum albumin (BSA) at pH 6 when its concentration was 1.5 mg m L -1 . Finally, the PIL-CA was employed for the selective separation of target protein from a real serum sample, obtaining the BSA with high purity of over 98%., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

According to the molecular properties of non-steroidal anti-inflammatory drugs (NSADs), a new adsorbent for magnetic solid phase extraction (MSPE) was designed and synthesized. Triethyl-(4-vinylbenzyl)aminium chloride and 4-vinylbenzeneboronic acid were utilized as dual functional monomers to copolymerize with divinylbenzene on the surface of pre-modified Fe 3 O 4 nanoparticles. The prepared magnetic adsorbent (Fe 3 O 4 @TCVA) was characterized by elemental analysis, Fourier transform infrared, scanning electron microscopy, transmission electron microscopy and vibrating sample magnetometer. Due to the abundant boronic acid, quaternary amine and phenyl groups, the Fe 3 O 4 @TCVA displayed satisfactory extraction performance for target NSADs (diclofenac acid, ibuprofen and mefenamic acid) by means of B-N coordination, anion-exchange, π-π and hydrophobic interactions. Under the optimized conditions, the Fe 3 O 4 @TCVA/MSPE was combined with high-performance liquid chromatography with diode array detection (HPLC-DAD) to sensitively analyze NSADs in water and human urine samples. Results indicated that the limits of detection for water and urine samples were in the ranges of 0.014-0.031 μg/L and 0.029-0.11 μg/L, respectively. The relative standard deviations for the intra-day and inter-day assay variability were below 10%. The applicability of the proposed Fe 3 O 4 @TCVA/MSPE-HPLC-DAD method was demonstrated by the successful extraction and quantification of trace levels of NSADs in real water and human urine samples. Satisfactory spiked recovery and reproducibility were achieved., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Owing to their multiscale pore size regimes and unique properties, the materials with hierarchically porous structures have become an important family of functional materials in recent years. They have been applied from energy conversion and storage, catalysis, separation to drug delivery, etc. The synthesis of them is difficult by the need to employ multiple templates and take complicated steps. Herein, we successfully prepared epoxy-functionalized hierarchically porous hybrid monoliths (HPHMs) with micro/meso/macro-structures in an easy way. Firstly, a bulk monolithic material was formed via free radical polymerization between polyhedral oligomeric vinylsilsesquioxanes (vinylPOSS) and allyl glycidyl ether (AGE) in the presence of polycaprolactone (PCL). Then PCL was degraded with hydrochloric acid solution, and the epoxy-functionalized HPHM was obtained. This approach was very simple and suitable for large-scale preparation. Hybrid monoliths with different specific surface area (from 5.4 to 636.7 m 2 /g) were prepared by adjusting the mole ratio of vinylPOSS to AGE and the content of PCL. The results of several characterization methods, including nitrogen adsorption/desorption measurements, scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP), showed that these materials contained not only micropores and mesopores but also macropores. The materials were further modified with penicillamine to be used as hydrophilic interaction chromatography (HILIC) adsorbents for enriching N-glycopeptides in IgG and serum protein tryptic digests. Up to 23 N-glycopeptides were identified from IgG digest, and 385 N-glycopeptides and 283 N-glycosylation sites were identified from human serum digest., (Copyright © 2019 Elsevier B.V. All rights reserved.)

During the last number of years a variety of crystallization-driven self-assembly (CDSA) processes based on semicrystalline block copolymers have been developed to prepare a number of different nanomorphologies in solution (micelles). We herein present a convenient synthetic methodology combining: (i) The anionic polymerization of 2-vinylpyridine initiated by organolithium functionalized phosphane initiators; (ii) the cationic polymerization of iminophosphoranes initiated by -PR 2 Cl 2 ; and (iii) a macromolecular nucleophilic substitution step, to prepare the novel block copolymers poly(bistrifluoroethoxy phosphazene)- b -poly(2-vinylpyridine) (PTFEP- b -P2VP), having semicrystalline PTFEP core forming blocks. The self-assembly of these materials in mixtures of THF (tetrahydrofuran) and 2-propanol (selective solvent to P2VP), lead to a variety of cylindrical micelles of different lengths depending on the amount of 2-propanol added. We demonstrated that the crystallization of the PTFEP at the core of the micelles is the main factor controlling the self-assembly processes. The presence of pyridinyl moieties at the corona of the micelles was exploited to stabilize gold nanoparticles (AuNPs).

This study proposed a novel strategy to improve performance of inherently hydrophobic poly(vinylidene fluoride) (PVDF) membrane. The proposed strategy combined radiation grafting of poly(acrylic acid) (PAA) and electroless nickel plating. After a 5 min plating by using this modification strategy, the water contact angle of the modified membrane decreased from 75.5° to 47.1°, and water content ratio increased from 61.4% to 109.9%. The modified PVDF-g-PAA-Ag@Ni membrane presented 100% flux recovery and reduced fouling propensity when filtrating 0.1 g/L sodium alginate (SA) solution. Moreover, involvement of silver in this strategy provided evident antibacterial activity of the modified membranes. The ease and high efficiency of this strategy point towards the potential widespread applications of this strategy and the modified membranes., (Copyright © 2019 Elsevier Inc. All rights reserved.)

A novel polymer monolith based on the dicationic crosslinker 3,3'-(hexane-1,6-diyl)bis(1-vinylimidazolium) bromide, the monomer 1-vinylimidazole and a ternary porogen mixture (1-propanol, decan-1-ol and water) was developed and optimized for capillary electrochromatography. This aim was accomplished by adjusting the composition of individual constituents in the polymerization mixture and monitored based on several relevant parameters (e.g. pore structure by scanning electron microscopy, generation of electroosmotic flow, or permeability of material). The ultimately selected composition yielded a monolithic phase which excellently resolved six methylxanthines (including caffeine, theobromine and theophylline) in 15 min. Key requirements concerning the utilized buffer were an acidic pH of 3 and the addition of 50% acetonitrile; additionally, a negative voltage (-25 kV) had to be applied during analyses. The proposed separation mechanism was mixed mode, i.e. the combination of electrostatic repulsion and hydrophobic interaction. Monolith fabrication as well as separation efficiency were found to be highly repeatable, the material was mechanically stable and useable for at least 150 injections. Thus the presented stationary phase is definitely a very promising option for CEC., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Surface topography has a profound effect on the development of the nervous system, such as neuronal differentiation and morphogenesis. While the interaction of neurons and the surface topography of their local environment is well characterized, the neuron-topography interaction during the regeneration process remains largely unknown. To address this question, an anisotropic surface topography resembling linear grooves made from poly(ethylene-vinyl acetate) (EVA), a soft and biocompatible polymer, using nanoimprinting, is established. It is found that neurons from both the central and peripheral nervous system can survive and grow on this grooved surface. Additionally, it is observed that axons but not dendrites specifically align with these grooves. Furthermore, it is demonstrated that neurons on the grooved surface are capable of regeneration after an on-site injury. More importantly, these injured neurons have an accelerated and enhanced regeneration. Together, the data demonstrate that this anisotropic topography guides axon growth and improves axon regeneration. This opens up the possibility to study the effect of surface topography on regenerating axons and has the potential to be developed into a medical device for treating peripheral nerve injuries., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Solid dispersions of spironolactone with Soluplus ® and polyvinylpyrrolidone were prepared by spray drying according to a mixture experimental design and evaluated for moisture content, particle size, drug solubility, crystallinity (powder X-ray diffraction and differential scanning calorimetry), and physicochemical interactions (Fourier-transform infrared spectroscopy, Raman). In vitro dissolution was evaluated for the spray dried product itself and after compression into tablets, and prediction models were derived using multiple linear regression analysis. The spray dried products consisted of amorphous drug, indicated by the absence of crystalline powder X-ray diffraction peaks. Amorphization and interactions impacted changes in the Fourier-transform infrared spectroscopy spectra in the ranges 2900-3000 cm -1 (C-H) and 1600-1800 cm -1 (C=O) and caused merging at 1690 cm -1 (C=O of lactone) and 1670 cm -1 (C=O of thioacetyl group). In the Raman spectra, amorphization and interactions resulted in disappearance of peak at 1690 cm -1 (C=O) and merging of peaks at 582 and 600 cm -1 (C-S). Hydrogen bonding between the thioacetyl group of the drug with the hydroxyl groups of Soluplus ® caused marked suppression of the peak at 1190 cm -1 (R-C(=O)-S vibration). Amorphization and interactions resulted in improved solubility and dissolution which was greatest for drug/Soluplus ® ratio 1:4 and was also demonstrated in the corresponding tablets., (Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.)

In this study, π-conjugated poly(arylenevinylene)s are synthesized via the Pd-catalyzed dehydrogenative direct alkenylation of polyfluoroarenes with diethenyl aromatic monomer. The introduction of a fluoro group promotes the cross-coupling reaction, and the formation of the undesired homocoupling byproduct is minimized by optimizing the reaction conditions. The polycondensation reactions lead to the formation of poly(arylenevinylene)s with a well-defined trans-configuration. The obtained polymers are evaluated as emitting materials for organic light-emitting diodes., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Conjugated polymer nanoparticle systems have gained significant momentum in the bioimaging field on account of their biocompatibility and outstanding spectroscopic properties. Recently, new control procedures have spawned custom-built functional poly(p-phenylene vinylene) (PPV). These facilitate the one-pot synthesis of semiconducting polymer NPs with incorporated surface functional groups, an essential feature for advanced biomedical applications. In this work, nanoparticles (NPs) of different sizes are synthesized consisting of the statistical copolymer CPM-co-MDMO-PPV with monomer units 2-(5'-methoxycarbonylpentyloxy)-5-methoxy-1,4-phenylenevinylene (CPM-PPV) and poly(2-methoxy-5-(3',7'-dimethoxyoctyloxy)-1,4-phenylenevinylene) (MDMO-PPV). To monitor potential implications of switching from a commonly used homopolymer to copolymer system, MDMO-PPV NPs were prepared as a control. The versatile combination of the miniemulsion and solvent evaporation method allowed for an easy adaptation of the NP size. Decreasing the diameter of functional PPV-based NPs up to 20 nm did not significantly affect their optical properties nor the biocompatibility of the bioimaging probe, as cell viability never dropped below 90%. The quantum yield and molar extinction coefficient remained stable at values of 1-2% and 10 6  M -1  cm -1 respectively, indicating an excellent fluorescence brightness. However, a threshold was observed to which the size could be lowered without causing irreversible changes to the system. Cell uptake varied drastically depended on size and material choice, as switching from homo- to copolymer system and lowering the size significantly increased NP uptake. These results clearly demonstrate that adjusting the size of functional PPV-based NPs can be achieved easily to a lower limit of 20 nm without adversely affecting their performance in bioimaging applications., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Amorphous solid dispersions (ASDs) are inherently unstable because of high internal energy. Evaluating physical and chemical stability during the process and storage is essential. Numerous researches have demonstrated how polymers influence the drug precipitation and physical stability of ASDs, while the influence of polymers on the chemical stability of ASDs is often overlooked. Therefore, this study aimed to investigate the effect of polymers on the physical and chemical stability of spray-dried ASDs using dipyridamole (DP) as a model drug. Proper polymers were selected by assessing their abilities to inhibit drug recrystallization in supersaturated solutions. HPMC E5, Soluplus®, HPMCP-55, and HPMCAS-LP were shown to be effective stabilizers. The optimized formulations were further stored at a high temperature (60 °C) and high humidity (40 °C, 75% RH) for 2 months, and their physical and chemical stability was evaluated using polarizing optical microscopy, FTIR, HPLC, and mass spectrometry (MS). In general, crystallization was observed in all samples, which indicated the physical instability under stressed storage conditions. Also, it was noted that the polymers in ASDs rather than physical mixtures, induced a dramatic drug degradation after being exposed to a high temperature (HPMCP-55 > 80% and HPMCAS-LP > 50%) and high humidity (HPMCP-55 > 40% and HPMCAS-LP > 10%). The MS analysis further confirmed the degradation products, which might be generated from the reaction between dipyridamole and phthalic anhydride decomposed from HPMCP-55 and HPMCAS-LP. Overall, the exposure of ASDs to stressed conditions resulted in recrystallization and even the chemical degradation induced by polymers.

The synthesis and self-assembly in thin-film configuration of linear ABC triblock terpolymer chains consisting of polystyrene (PS), poly(2-vinylpyridine) (P2VP), and polyisoprene (PI) are described. For that purpose, a hydroxyl-terminated PS-b-P2VP (45 kg mol -1 ) building block and a carboxyl-terminated PI (9 kg mol -1 ) are first separately prepared by anionic polymerization, and then are coupled via a Steglich esterification reaction. This quantitative and metal-free catalyst synthesis route reveals to be very interesting since functionalization and purification steps are straightforward, and well-defined terpolymers are produced. A solvent vapor annealing (SVA) process is used to promote the self-assembly of frustrated PS-b-P2VP-b-PI chains into a thin-film core-shell double gyroid (Q 230 , space group: Ia3¯d) structure. As terraces are formed within PS-b-P2VP-b-PI thin films during the SVA process under a CHCl 3 vapor, different plane orientations of the Q 230 structure ((211), (110), (111), and (100)) are observed at the polymer-air interface depending on the film thickness., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first copper(0) mediated controlled radical polymerization (CRP) of methyl methacrylate (MMA) toward CF bonds onto poly(vinylidene fluoride) (PVDF) is reported with rather high activity. By avoiding the halogen exchange, Cu 0 instead of Cu I complexes utilized as catalyst is responsible for the significantly improved polymerization activity. Using FH decoupled nuclear magnetic resonance technique, the grafting sites onto PVDF are finely located. From this, detailed topologic information including the grafting density, average length of each side chain, along with the overall grafted content of PMMA, is detected by tracking the polymerization as a function of time. This work offers not only a facile CRP strategy based on inactive CF bonds but also a deep insight into the cleavage of F-bearing compounds in organic chemistry., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

It is well known that high-pressure carbon dioxide (CO 2 ) lowers the glass transition temperature (T g ) of polymers. We therefore investigated whether T g depression of high-pressure CO 2 results in interparticle bridging of a polymer and the tablet characteristics that makes the manufacture of an orally disintegrating tablet (ODT) possible. Copolyvidone (Kollidon ® ) and polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (Soluplus ® ) were examined and found to exhibit a large T g depression. Placebo ODTs were prepared and hardness, disintegration rate, porosity, and change in thickness and appearance were evaluated before and after the high-pressure CO 2 treatment. This enabled the establishment of the optimal conditions for pressure, temperature, and treatment time under pressure. Experimental results showed that it was possible to manufacture ODTs comprising Kollidon ® as a water-soluble polymer with CO 2 treatment under the suitable conditions such as temperature at 45°C, pressure lower than 8 MPa, and a treatment time shorter than 30 min, which is a new ODT manufacturing process called "Carbon Dioxide Assisted Tablet Formation Scheme" (CATS). In comparison to the conventional processes, which require high temperatures or humidity, CATS is expected to be applicable to drugs that are unstable at high temperature and humidity, and to functional drug particles used for bitter taste masking, sustained release, and other uses.

To address the challenge of metal contamination, a "graft from" approach via organocatalyzed atom transfer radical polymerization (O-ATRP) is developed to synthesize poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-co-CTFE)) graft copolymers. N-phenylphenothiazine is utilized as a model organic photoredox catalyst for catalyzing the (co)polymerization of methyl methacrylate (MMA), methacrylate (MA), and n-butyl acrylate (BA). By employing this technique, high temporal control of polymerization and graft content are achieved. A series of P(VDF-co-CTFE)-g-PMMA, P(VDF-co-CTFE)-g-PMA, and P(VDF-co-CTFE)-g-PBA is prepared under mild conditions. The resultant graft copolymer can be used as macroinitiator to re-initiate O-ATRP to synthesize P(VDF-co-CTFE)-g-(PMMA-b-PMA), which might exhibit the potential application as novel dielectric material., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Block copolymer (BCP) self-assembly is a versatile technique in the preparation of polymeric aggregates with varieties of morphologies. However, its morphology library is limited. Here, the discovery of pincushion of tubules is reported for the first time, via BCP self-assembly of poly(4-vinylpyridine)-b-polystyrene (P4VP-b-PS) with very high molecular weight (500 kDa) and asymmetry (2 mol% P4VP). The investigation confirms the importance of core-forming block length on morphology control of BCP self-assemblies, especially with respect to tubular structures. The morphology landscape of tubular structures is successfully established, where dumbbell of tubule, tubule, loose clew of tubules, tight clew of tubules, and pincushion of tubules can be prepared by adjusting the core-forming block length. This work therefore expands the structure library of BCP self-assemblies and opens up a new avenue for the further applications of these tubular materials., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A promising approach to improve the solubility of poorly water-soluble drugs and to overcome the stability issues related to the plain amorphous form of the drugs, is the formulation of drugs as co-amorphous systems. Although polymer coatings have been proven very useful with regard to tablet stability and modifying drug release, there is little known on coating co-amorphous formulations. Hence, the aim of the present study was to investigate whether polymer coating of co-amorphous formulations is possible without inducing recrystallization. Tablets containing either a physical mixture of crystalline indomethacin and arginine or co-amorphous indomethacin-arginine were coated with a water soluble polyvinyl alcohol-polyethylene glycol graft copolymer (Kollicoat® Protect) and stored at 23°C/0% RH and 23°C/75% RH. The solid state properties of the coated tablets were analyzed by XRPD and FTIR and the drug release behavior was tested for up to 4h in phosphate buffer pH 4.5. The results showed that the co-amorphous formulation did not recrystallize during the coating process or during storage at both storage conditions for up to three months, which confirmed the high physical stability of this co-amorphous system. Furthermore, the applied coating could partially inhibit recrystallization of indomethacin during drug release testing, as coated tablets reached a higher level of supersaturation compared to the respective uncoated formulations and showed a lower decrease of the dissolved indomethacin concentration upon precipitation. Thus, the applied coating enhanced the AUC of the dissolution curve of the co-amorphous tablets by about 30%. In conclusion, coatings might improve the bioavailability of co-amorphous formulations., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Recent developments in scanning probe block copolymer lithography (SPBCL) enable the confinement of multiple metal precursors in a polymer nanoreactor and their subsequent transformation into a single multimetallic heterostructured nanoparticle through thermal annealing. However, the process by which multimetallic nanoparticles form in SPBCL-patterned nanoreactors remains unclear. Here, we utilize the combination of PEO-b-P2VP and Au, Ag, and Cu salts as a model three-component system to investigate this process. The data suggest that the formation of single-component Au, Ag, or Cu nanoparticles within polymer nanoreactors consists of two stages: (I) nucleation, growth, and coarsening of the particles to yield a single particle in each reactor; (II) continued particle growth by depletion of the remaining precursor in the reactor until the particle reaches a stable size. Also, different aggregation rates are observed for single-component particle formation (Au > Ag > Cu). This behavior is also observed for two-component systems, where nucleation sites have greater Au content than the other metals. This information can be used to trap nanoparticles with kinetic structures. High-temperature treatment ultimately facilitates the structural evolution of the kinetic particle into a particle with a fixed structure. Therefore, with multicomponent systems, a third stage that involves elemental redistribution within the particle must be part of the description of the synthetic process. This work not only provides a glimpse at the mechanism underlying multicomponent nanoparticle formation in SPBCL-generated nanoreactors but also illustrates, for the first time, the utility of SPBCL as a platform for controlling the architectural evolution of multimetallic nanoparticles in general.

Self-healing materials are of interest for drug delivery, cell and gene therapy, tissue engineering, and other biomedical applications. In this work, on the base of biocompatible polymer poly(methyl vinyl ether-alt-maleic acid) (P(MVE-alt-MA)), host polymer β-cyclodextrin-grafted P(MVE-alt-MA) (P(MVE-alt-MA)-g-β-CD) and guest polymer adamantane-grafted P(MVE-alt-MA) (P(MVE-alt-MA)-g-Ad) were first prepared. Then through taking advantage of the traditional host-guest interaction of β-cyclodextrin and adamantane, a novel self-healing pH-sensitive physical P(MVE-alt-MA)-g-β-CD/P(MVE-alt-MA)-g-Ad supramolecular hydrogels were obtained after simply mixing the aqueous solution of host polymer and guest polymer. This kind of supramolecular hydrogels not only possess pH-sensitivity, but also possess the ability to repair themselves after being damaged., (Copyright © 2016 Elsevier B.V. All rights reserved.)

This study reports on gold nanoparticles (AuNPs) immobilized in a sponge made of short electrospun fibers (Au-sponge), which show surprisingly high reaction rates at extremely low gold amount. Au-sponges are made by freeze-drying of dispersions of short electrospun fibers with preimmobilization of AuNPs. The resulting Au-sponges show very low densities around 7 mg cm -3 corresponding to a pore volume of about 150 mL g -1 , but low surface area and very low amount of AuNPs in the range of 0.29-3.56 wt%. In general, catalysts with immobilized AuNPs show much low reaction rates compared to systems with dispersed AuNPs. By contrast, the Au-sponge catalyst with immobilized AuNPs is discerned here as an extremely efficient catalyst even superior to other systems with dispersed AuNPs. The fidelity of the Au-sponges after reactions is good enough for manifold use and thereby provides a sustainable catalyst design as well., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study presents the synthesis and characterization of zwitterionic core-shell hybrid nanoparticles consisting of a core of iron oxide multicore nanoparticles (MCNPs, γ-Fe 2 O 3 ) and a shell of sultonated poly(2-vinylpyridine-grad-acrylic acid) copolymers. The gradient copolymers are prepared by reversible addition fragmentation chain transfer polymerization of 2-vinylpyridine (2VP), followed by the addition of tert-butyl acrylate and subsequent hydrolysis. Grafting of P(2VP-grad-AA) onto MCNP results in P(2VP-grad-AA)@MCNP, followed by quaternization using 1,3-propanesultone-leading to P(2VP S -grad-AA)@MCNP with a zwitterionic shell. The resulting particles are characterized by transmission electron microscopy, dynamic light scattering, and thermogravimetric analysis measurements, showing particle diameters of ≈70-90 nm and an overall content of the copolymer shell of ≈10%. Turbidity measurements indicate increased stability toward secondary aggregation after coating if compared to the pristine MCNP and additional cytotoxicity tests do not reveal any significant influence on cell viability., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this study, polyvinylidene fluoride (PVDF) hollow fiber membranes (HFMs) were modified by coating with polyvinyl alcohol (PVA) and chitosan. The influences of PVA and chitosan amount on PVDF membrane mechanical and separation performance were investigated. The results showed that the modified PVDF membranes had better mechanical and separation performance when the amount of PVA and chitosan was 20 mg/m2. At the same time, the biocompatibility of PVDF membranes was also investigated. Compared with virgin PVDF membranes, the modified PVDF membranes showed better anticoagulation, hydrophilicity, less bovine serum albumin (BSA) adsorption, and lower hemolytic ratio. The anticoagulation behavior of modified PVDF membranes coating with PVA had been obviously improved. Prothrombin time (PT) and activated partial thromboplastin time (APTT) of the modified PVDF membrane are 44.8 s and 72.5 s while the PT and APTT of virgin PVDF membrane are 15.6 s and 37.3 s. The advancing water contact angle (WCA) and BSA adsorption of the modified PVDF membrane coating with PVA are 24° and 23 mg/m2 while virgin PVDF membrane is 52° and 49 mg/m2. However, further biocompatibility evaluation is needed to obtain a more comprehensive conclusion.

Binary polystyrene and poly(4-vinylpyridine) mixed grafted silica nanoparticles (PSt/P4VP-g-SNPs) are fabricated using Cu I -catalyzed azide-alkyne Huisgen cycloaddition (CuAAC) via grafting-to method. Azide-terminated PSt and P4VP are synthesized via post- and pre-atom transfer radical polymerization modification, respectively. Then, the polymers are simultaneously anchored onto alkyne-modified SNPs by CuAAC yielding mixed brushes as shown by Raman spectroscopy, dynamic light scattering, and thermogravimetric analysis. To the best of our knowledge, this is the first report of simultaneously grafting two distinct polymer chains to synthesize mixed grafted silica nanoparticles using CuAAC technique via grafting-to method., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Efavirenz (EFV), a first-line anti-HIV drug largely used as part of antiretroviral therapies, is practically insoluble in water and belongs to BCS class II (low solubility/high permeability). The aim of this study was to improve the solubility and dissolution performances of EFV by formulating an amorphous solid dispersion of the drug in polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (Soluplus ® ) using spray-drying technique. To this purpose, spray-dried dispersions of EFV in Soluplus ® at different mass ratios (1:1.25, 1:7, 1:10) were prepared and characterized using particle size measurements, SEM, XRD, DSC, FTIR and Raman microscopy mapping. Solubility and dissolution were determined in different media. Stability was studied at accelerated conditions (40 °C/75% RH) and ambient conditions for 12 months. DSC and XRD analyses confirmed the EFV amorphous state. FTIR spectroscopy analyses revealed possible drug-polymer molecular interaction. Solubility and dissolution rate of EFV was enhanced remarkably in the developed spray-dried solid dispersions, as a function of the polymer concentration. Spray-drying was concluded to be a proper technique to formulate a physically stable dispersion of amorphous EFV in Soluplus ® , when protected from moisture.

Surface modification of magnetic nanoparticle (MNP) with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) (PEO-b-PVDM) diblock copolymers and its application as recyclable magnetic nano-support for adsorption with antibody were reported herein. PEO-b-PVDM copolymers were first synthesized via a reversible addition-fragmentation chain-transfer (RAFT) polymerization using poly(ethylene oxide) chain-transfer agent as a macromolecular chain transfer agent to mediate the RAFT polymerization of VDM. They were then grafted on amino-functionalized MNP by coupling with some azlactone rings of the PVDM block to form magnetic nanoclusters with tunable cluster size. The nanocluster size could be tuned by adjusting the chain length of the PVDM block. The nanoclusters were successfully used as efficient and recyclable nano-supports for adsorption with anti-rabbit IgG antibody. They retained higher than 95% adsorption of the antibody during eight adsorption-separation-desorption cycles, indicating the potential feasibility in using this novel hybrid nanocluster as recyclable support in cell separation applications., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Linear poly(4-tert-butoxystyrene)-b-poly(4-vinylpyridine) (PtBOS-b-P4VP) diblock copolymers are synthesized using reversible addition-fragmentation chain transfer polymerization. The self-assembly of four different PtBOS-b-P4VP diblock copolymers is studied using small-angle X-ray scattering and transmission electron microscopy and a number of interesting observations are made. A tBOS62 -b-4VP28 diblock copolymer with a weight fraction P4VP of 0.21 shows a disordered morphology of P4VP spheres with liquid-like short-range order despite an estimated value of χN of the order of 50. Increasing the length of the 4VP block to tBOS62 -b-4VP199 results in a diblock copolymer with a weight fraction P4VP of 0.66. It forms a remarkably well-ordered lamellar structure. Likewise, a tBOS146 -b-4VP120 diblock copolymer with a weight fraction P4VP of 0.33 forms an extremely well-ordered hexagonal structure of P4VP cylinders. Increasing the P4VP block of this block copolymer to tBOS146 -b-4VP190 with a weight fraction P4VP of 0.44 results in a bicontinuous gyroid morphology despite the estimated strong segregation of χN≅150. These results are discussed in terms of the architectural dissimilarity of the two monomers, characterized by the presence of the large side group of PtBOS, and the previously reported value of the interaction parameter, χ≅0.39, for this polymer pair., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

For the first time, the successful Gilch synthesis of poly(ortho-phenylene vinylenes) (ortho-PPVs) is reported. The molar mass of the constitutionally homogeneous ortho-PPVs reaches values as high as Mw ≈ 300 000 Da. The ortho-connectivity of the repeating units forces the chains to assume closely packed conformations even in good solvents. Significant perturbation of the π-electron systems and considerable shortening of the conjugation lengths are the consequences. UV-vis absorption and photoluminescence maxima consequently are shifted clearly toward shorter wavelengths compared to, e.g., classic para-PPVs., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel procedure has been developed for the Gilch reaction leading to poly(p-phenylene vinylenes) (PPVs). In the first step, selective activation of the starting material is achieved at low temperature. Subsequently, controlled chain growth is induced by lighting the α-halo-p-quinodimethane monomer. In contrast to the thermal Gilch polymerization, the photoinduced process allows adjusting crucial parameters such as intensity and energy of light. The progress of PPV formation can be followed visually or by in situ UV-vis spectroscopy. If the polymers are formed under appropriate conditions, they show very high molar masses, polydispersities in the common range, and higher constitutional homogeneity than thermally grown PPVs., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study for the first time demonstrates combined application of mixture experimental design and artificial neural networks (ANNs) in the solid dispersions (SDs) development. Ternary carbamazepine-Soluplus®-poloxamer 188 SDs were prepared by solvent casting method to improve carbamazepine dissolution rate. The influence of the composition of prepared SDs on carbamazepine dissolution rate was evaluated using d-optimal mixture experimental design and multilayer perceptron ANNs. Physicochemical characterization proved the presence of the most stable carbamazepine polymorph III within the SD matrix. Ternary carbamazepine-Soluplus®-poloxamer 188 SDs significantly improved carbamazepine dissolution rate compared to pure drug. Models developed by ANNs and mixture experimental design well described the relationship between proportions of SD components and percentage of carbamazepine released after 10 (Q10) and 20 (Q20) min, wherein ANN model exhibit better predictability on test data set. Proportions of carbamazepine and poloxamer 188 exhibited the highest influence on carbamazepine release rate. The highest carbamazepine release rate was observed for SDs with the lowest proportions of carbamazepine and the highest proportions of poloxamer 188. ANNs and mixture experimental design can be used as powerful data modeling tools in the systematic development of SDs. Taking into account advantages and disadvantages of both techniques, their combined application should be encouraged.

Statistical experimental design was employed to optimize the preparation conditions of polyvinylidenefluoride (PVDF) membranes. Three variables considered were polymer concentration, dissolving temperature, and casting thickness, whereby the response variable was membrane-protein binding. The optimum preparation for the PVDF membrane was a polymer concentration of 16.55 wt%, a dissolving temperature of 27.5°C, and a casting thickness of 450 µm. The statistical model exhibits a deviation between the predicted and actual responses of less than 5%. Further characterization of the formed PVDF membrane showed that the morphology of the membrane was in line with the membrane-protein binding performance.

Vinyl acetate is polymerized in the living way under the irradiation of blue light-emitting diodes (LEDs) or sunlight without photocatalyst at ambient temperature. 2-(Ethoxycarbonothioyl)sulfanyl propanoate is exclusively added and acts as initiator and chain transfer agent simultaneously in the current system. Poly(vinyl acetate) with well-regulated molecular weight and narrow molecular weight distribution (Đ < 1.30) is synthesized. Near quantitative end group fidelity of polymer is demonstrated by nuclear magnetic resonance (NMR) and matrix-assisteed laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS)., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new class of rod-coil block copolymers is synthesized by chemoenzymatic polymerization. In the first step, maltoheptaose, which acts as a primer for the synthesis of amylose, is attached to poly(2-vinyl pyridine) (P2 VP). The enzymatic polymerization of maltoheptaose is carried out by phosphorylase to obtain amylose-b-P2 VP block copolymers. The block copolymer is characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, and wide-angle X-ray scattering techniques. The designed molecules combine the inclusion complexation ability of amylose with the supramolecular complexation ability of P2 VP and therefore this kind of rod-coil block copolymers can be used to generate well-organized novel self-assembled structures., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new ion-selective cross-linked poly(vinylimidazole-co-ethylene glycol dimethacrylate) prepared via a double-imprinting process was developed for the recognition and preconcentration of Pb(2+) from water samples. The sorbent was characterized by FT-IR, SEM, TGA and textural data. The maximum dynamic sorption capacity of Pb(2+) was 42.04 mg Pb(2+) g(-1) of the double-imprinted polymer. The sorption kinetics data were described by a pseudo-second-order model. The double-imprinted polymer exhibited a higher sorption efficiency of Pb(2+) than the blank polymer (non-imprinted polymer). The preconcentration procedure involved the loading of a Pb(2+) solution at pH 7.25 through 40.0 mg of the double-imprinted polymer packed in a mini-column at 5.0 mL min(-1). The selective efficiency of proposed method for the Pb(2+) preconcentration was assured by competitive sorption using different proportions of Pb(2+)/cations and Pb(2+)/anions. An analytical curve was obtained in the range 0.0-300.0 μg L(-1) (r=0.999) and a limit of detection of 2.46 μg L(-1) was obtained. The preconcentration factor was found to be 21, the consumptive index 0.95 mL and the concentration efficiency 5.25 min(-1). The preconcentration method was successfully applied to the Pb(2+) ions determination in different kinds of water samples with high recovery values (91.3-108.9%)., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Polymer light-emitting diodes (PLEDs) have attracted much attention from academia and industry field because of their various applications such as large area flat-panel displays and lightings. In this paper, we suggest new blue emitting polymer based on anthracene, Poly(9-(3-Vinyl-phenyl)-anthracene) (PVPA). From NMR data, vinyl group protons were disappeared and aromatic protons showed broad proton peaks because of polymer characteristics. PVPA had film property well and it exhibited vivid PL maximum values of 431, 455, 482 nm and broad PL spectrum. Three dopants for green, red, yellow were used to PVPA, all energy transfer was happened well. By using rubrene dopant of yellow emission, doped film provided white PL.

A bioinspired geometric templating of an electrospun PVDF substrate with hexagonal platelets of Mg-Al layered double hydroxide (LDH), an intrinsic anion conductor, is presented. The distinctive morphology restructures the internal pore geometry and modulates the dynamic wetting profile of PVDF, transforming it into a highly functional substrate for SAFC anion conducting membranes. The membrane fabricated with PVDF-LDH substrate exhibited exceptionally high durability (>140 °C), high anionic conductivity, ion exchange capacity (IEC), restricted swelling, and improved tensile strength, overcoming critical challenges associated with PVDF electrospun substrates and validating its immense potential as a high-temperature-stable and durable substrate for advanced fuel cell membrane applications.

In this work, a simple and sensitive multiplexed immunoassay protocol for simultaneous electrochemical determination of alpha-fetoprotein (AFP) and carcinoembryonic antigen (CEA) was designed using redox-active nanocomposites. As the redox-active species, the poly(o-phenylenediamine) (POPD)/Au nanocomposite and poly(vinyl ferrocene-2-aminothiophenol) (poly(VFc-ATP))/Au nanocomposite were obtained by one-step method which HAuCl4 was used as the oxidant. With Au nanoparticles (AuNPs), the nanocomposites were successful to immobilize labeled anti-CEA and anti-AFP as the immunosensing probes. The proposed electrochemical immunoassay enabled the simultaneous monitoring of AFP and CEA in a wide range of 0.01-100ngmL(-1). The detection limits was 0.006ngmL(-1) for CEA and 0.003ngmL(-1) for AFP (S/N=3). The assay results of serum samples with the proposed method were well consistent with the reference values from standard ELISA method. And the negligible cross-reactivity between the two analytes makes it possesses potential promise in clinical diagnosis., (Copyright © 2014 Elsevier B.V. All rights reserved.)