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  • Lignin modified by deep eutectic solvents as green, reusable, and bio-based catalysts for efficient chemical fixation of CO2
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-20
    Xingquan Xiong; Hui Zhang; Shi Lin Lai; Jinbin Gao; Lizhu Gao

    Lignin is a biodegradable, abundant and renewable natural polymer on earth. In this study, deep eutectic solvents (DESs)-modified lignin heterogeneous catalysts were prepared for the first time via a facile acid-base interaction between choline chloride (ChCl) and p-aminobenzoic acid (PABA) or its derivatives, which were used to efficiently catalyze the cycloaddition of CO2 and terminal epoxides under green and mild conditions. Among them, lignin-ChCl-PABA was found to exhibit the highest catalytic activity for the cycloaddition of epoxides in the presence of 1.0 MPa of CO2 while retaining high selectivity, which far outperformed those achieved on the homogeneous EDSs catalytic system. A series of cyclic carbonates could be obtained in high yields (90–99%), and lignin-ChCl-PABA was stable and reusable for the cycloaddition reaction (84% yield after 5 recycles). The attaching DES of ChCl/PABA onto the functional lignin increased the catalytic activity and also made the catalyst easier to recycle from the reaction mixture. The OH and NH2 groups on the surface of lignin-ChCl-PABA played a very important role in the acceleration of the cycloaddition reaction under solvent free conditions.

  • Response of photonic crystal hydrogels to carbohydrate and polyhydroxy alcohols
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-20
    Yongli Zhang; Jing Tang; Keke Feng; Huilin Zhao; Weiwei Yan; Zhiming Sun; Fuming Wu; Yu Sun; Jianping Gao
  • Recent advances in natural polymer-based drug delivery systems
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-18
    Xianqin Tong; Wenhao Pan; Ting Su; Mengying Zhang; Wei Dong; Xiaoliang Qi

    Natural polymers have been extensively explored as the vehicles for encapsulation and delivery of drugs and other bioactive molecules, which have attracted tremendous attention. Their inherent advantages in marvelous biocompatibility, controlled enzyme degradation, specific interactions with some biomolecules, and easy modification endow them with versatility in drug delivery. In this perspective, the drug delivery systems (DDS) constructed by representative natural polymers, polysaccharides (chitosan and hyaluronic acid) and proteins (silk fibroin and collagen), are generally summarized. Payloads mainly involve small molecular weight drug, proteins, and DNA for the applications of tissue engineering, wound healing or anticancer therapy. Moreover, the DDS constructed by their derivatives and with other materials also have been presented focusing on the chemical and morphological modifications, the addtions of smart stimuli-triggered or targeted motifs and so on, which evidently promoted the delivery and therapy efficiency. Obviously, more intelligent and specific delivery strategies will be developed and more multifunctional natural polymers based carriers will be expended in the future. We try to seek more insights into the evolution of delivery system so as to figure out what we will truly gain in the next few decades to come.

  • Effect of microwave on the synthesis of polyacrylamide-g-chitosan gel for azo dye removal
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-15
    Rodrigo C. da Silva; Samile B. de Aguiar; Pablyana Leila R. da Cunha; Regina Célia M. de Paula; Judith P.A. Feitosa

    Effective dye removal is of crucial importance for the well-being of the environment and human health, and hydrogels are top-players for this goal. In this work, hydrogels of polyacrylamide grafted onto chitosan, cross-linked with N,N′-methylenebisacrylamide, were synthesized by conventional (CM) and microwave-assisted methods (MWM). The products were characterized by Fourier transform infrared spectroscopy, elemental analysis, scanning electron microscopy and swelling capacity. The developed hydrogels were evaluated as an adsorbent for the azo dye Acid Blue 113. MWM provided higher yield of the product with reduced reaction time when compared to the CM. The dye removal efficiency by MWM was slightly lower than that observed by CM, but MWM showed a much higher maximum adsorption capacity than the conventional one. The adsorption behavior of conventional and MW hydrogels followed the Langmuir and Freundlich models, respectively. The MW hydrogel presented the best characteristics to be used as an adsorbent of the AB 113 dye.

  • Using chitosan to understand chitinases and the role of processivity in the degradation of recalcitrant polysaccharides
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-15
    Morten Sørlie; Svein Jarle Horn; Gustav Vaaje-Kolstad; Vincent G.H. Eijsink

    Enzymatic depolymerization of abundant polysaccharides such as chitin and cellulose is hampered by the recalcitrant, crystalline nature of these materials. Nature musters a large variety of hydrolytic and oxidative enzymes with varying properties that, together, manage the task of saccharifying chitin and cellulose. Processivity, i.e. the ability to carry out multiple hydrolytic reactions while sliding along the polysaccharide chain, is considered a key property of hydrolytic enzymes acting on the most recalcitrant parts of the substrate. Due to the insoluble nature of the substrate, this phenomenon is difficult to study. For family GH18 chitinases, the combination of a catalytic mechanism depending on acetyl groups in the substrate and the possibility to produce partially deacetylated soluble single chitin chains (chitosan) provides a unique tool for studying processivity. Here, we review how the use of well-defined chitosans has helped unraveling crucial and otherwise difficult to study properties of multiple chitinases, including well studied chitinases from Serratia marcescens and of human chitotriosidase (HCHT). These studies have yielded pioneering insights into the structural basis and functional implications of processivity that apply to both chitinases and cellulases. Recent studies of processive chitinases and cellulases confirm the insights originally derived from the work with chitosan and take this further, for example by providing kinetic and thermodynamic data for processive enzyme action.

  • Chitosan-coated nanocapsules ameliorates the effect of olanzapine in prepulse inhibition of startle response (PPI) in rats following oral administration
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-14
    Annelieke Veragten; Renata Vidor Contri; Andresa Heemann Betti; Vivian Herzfeldt; Luiza Abrahão Frank; Adriana Raffin Pohlmann; Stela Maris Kuze Rates; Silvia Stanisçuaski Guterres
  • Electrical cuing of chitosan's mesoscale organization
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-14
    Si Wu; Kun Yan; Jinyang Li; Ruby N. Huynh; Christopher B. Raub; Jana Shen; Xiaowen Shi; Gregory F. Payne

    Chitosan is a weak cationic polyelectrolyte that can be cued to undergo reversible pH-dependent self-assembly in which individual chains associate to form macroscopic hydrogels. Nearly 20 years ago it was observed that the high pH cues that induce chitosan's self-assembly can be imposed electrically to induce chitosan hydrogels to electrodeposit on cathode surfaces. These imposed electrical signals (< 5 V) have two components: the current (or rate of electron-transfer from the electrode) that quantifies the localized generation of OH– that is responsible for neutralizing chitosan chains and inducing their self-assembly; and the voltage (or field) that can provide a force on the charged chitosan chains to drive their migration toward the cathode and their alignment during electrodeposition. Five years ago, it was reported that an oscillatory ON-OFF electrical input cued the emergence of a segmented hydrogel structure: segments are formed during the ON-step while denser boundary regions are formed during the OFF-step. Later work extended the use of electrical signals to guide the emergence of structure from a dual-responsive chitosan-agarose interpenetrating network. In this short review, we summarize our understanding of the underlying phenomena, and the relevance to the transduction of electrical to structural information and the controllable introduction of hydrogel properties.

  • 更新日期:2020-01-14
  • Controllably coated graphene oxide particles with enhanced compatibility with poly(ethylene-co-propylene) thermoplastic elastomer for excellent photo-mechanical actuation capability
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-11
    Josef Osicka; Miroslav Mrlik; Marketa Ilcikova; Igor Krupa; Patrik Sobolčiak; Tomáš Plachý; Jaroslav Mosnáček
  • Cyclic and topological polymers: Ongoing innovations and upcoming breakthroughs
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-11
    Yasuyuki Tezuka

    The chain topology of polymer molecules arguably dictates their fundamental properties and functions. During the first two decades of this century a number of remarkable innovations have been observed in the field of polymer chemistry, to realize the precision designing of, in particular, a variety of cyclic and multicyclic polymer topologies. In this Perspective article, ongoing achievements and expectable breakthroughs in topological polymer chemistry are highlighted, by emphasizing the spectacular diversification of the choice of topologies in macromolecules beyond conventional linear or randomly branched forms.

  • Self-healing supramolecular waterborne polyurethane based on host–guest interactions and multiple hydrogen bonds
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-08
    Luqi Xiao; Jun Shi; Kun Wu; Mangeng Lu

    Polymers which contain 2-Amino-4-hydroxy-6-methylpyrimidine (UPy) usually show good self-healing capabilities under certain conditions. In this study, the UPy was grafted into the side chain of waterborne polyurethane (WBPU), which was synthesized from 4,4-diisocyanate dicyclohexylmethane (H12MDI) and polycarbonate diol (PCDL), for giving the function of self-healing to the polymer. Meanwhile, the methylated β-cyclodextrin (M-β-CD), which was able to enhance the mechanical properties of WBPU and realize the synergistic effect between M-β-CD and UPy to raise the performance of self-healing, was introduced onto the main chain of WBPU. The Tg (glass transition temperature) of the polymer can be observed from dynamic mechanical property analysis (DMA) below room temperature, which facilitated the movement of the chain in self-healing process. From the tensile test, it showed that the cut polymer spline displayed a self-healing efficiency of 92.29% at 100 °C within 36 h. Furthermore, the disappearance of surface scratch of polymer film was observed by heating under a polarized microscope (POM) with a heating table. The results manifested that SWBPU exhibited great application as an intelligent response-type material.

  • Polylactide with improved optical property by introducing natural functional substance: Aloe-emodin
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-08
    Yanfeng Shen; Yun Huang; Long Jiang; Yi Dan

    The PLA materials with improved optical property and derived from renewable resources were synthesized through ring-opening polymerization using natural aloe-emodin, having anthraquinone structure and alcoholic hydroxyl group, as initiator. The chemical bonding of the aloe-emodin unit on PLA backbone provided the PLA with the function of absorbing UV light and would avoid the migration of aloe-emodin during the lifetime of PLA materials. The chemical structure of the new PLA was confirmed by NMR and the content of aloe-emodin was evaluated by UV–Vis absorption spectra. By investigating the structural changes and the variation of average molecular weight (Mn) during the UV-irradiation test, it was found that the aloe-emodin unit could enhance the UV-stability of the polylactide. The molecular weight remained about 80% for aloe-emodin capped PLA after UV irradiation (PLA-E400), while it was only 50% for PLA-C400 without aloe-emodin. A small amount of aloe-emodin could enhance the UV block effect of PLA film. When covered with aloe-emodin functionalized PLA film, the optical damage rate of β-carotene decreased to one-fifth of that for the uncovered one. In addition, aloe-emodin showed little influence on the biodegradation of PLA.

  • Improved flame retardancy of epoxy resin composites modified with a low additive content of silica-microencapsulated phosphazene flame retardant
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-07
    Lijie Qu; Yanlong Sui; Chunling Zhang; Xueyan Dai; Peihong Li; Guoen Sun; Baosheng Xu; Daining Fang
  • Cysteine conjugated chitosan based green nanohybrid hydrogel embedded with zinc oxide nanoparticles towards enhanced therapeutic potential of naringenin
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-07
    Dhanya George; P. Uma Maheswari; K.M. Meera Sheriffa Begum

    This article reports the role of l-Cysteine (CYS) conjugated nanohybrid hydrogel carrier for the enhanced therapeutic delivery of the Naringenin (NRG). CYS was effectively conjugated with chitosan through the amidation reaction followed by the incorporation of phyto-synthesised zinc oxide nanoparticles (ZNPs). Dialdehyde cellulose (DAC), a green crosslinker derived from Sugarcane Bagasse (SCB) crosslinked the modified chitosan. Taguchi method optimised the NRG loading in the hydrogel carrier. The hybrid material was characterized using 1H and 13C NMR, FTIR, XRD, SEM and swelling studies. The hybrid hydrogel, loaded with 86.09% of NRG was further subjected to drug release studies at varying pH and NRG loading concentrations. Maximum release of 72.78% was obtained for 1 mg/mL of initial drug concentration at pH 5. CYS conjugation with chitosan stabilized the hydrogel and enabled a sustained release of NRG drug. Kinetic modelling predicted the NRG release to follow a non-Fickian diffusion along with polymer erosion. The antimicrobial activity was studied against the Staphylococcus aureus and Trichophyton rubrum strains. Biocompatibility assay of the materials with L929 cells revealed significant cell viability. The NRG delivery using the developed nanohybrid hydrogel exhibited a two-fold increase in cytotoxicity towards A431 human skin carcinoma cells compared to NRG delivery without carrier.

  • Increased power conversion efficiency of dye-sensitized solar cells with counter electrodes based on porous polypyrrole
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-07
    Shahzad Ahmad Khan; Ligui Li; Dengke Zhao; Shaowei Chen

    The porous polypyrrole (PPPy) was synthesized with zeolitic imidazolate framework-8 (ZIF-8) used as template by simple hydrothermal. The resultant PPPy was employed as counter electrode (CE) in dye-sensitized solar cell (DSSC). The 5% Cu(ClO4)2 and 2% ZIF-8 ratio in PPPy at 100 °C by simple hydrothermal method demonstrates comparable performance with traditional Pt in DSSC as CE, 8.63% and 9.05% energy conversion efficiency (η), respectively. The electrochemical and photo-electrochemical as well as impedance spectra measurements revealed that ZIF-8 as template by simple hydrothermal method is a effective way for preparing PPPy at 100 °C as CE in DSSC, which may open up an alternative choice for the future industrial application. In DSSC, PPPy at 100 °C is one of the most promising material used for nano-porous thin film when, it serves as CE due to its appropriate low cost, and easy preparation method. The template polymerization of PPPy on zeolytes is interesting method for DSSC and as electro-catalyst, it can be big perspective in polymer membrane fuel cells, Zn air battery, Li ion battery and also useful for hydrogen production from water. So, this article will broaden the application of conductive polymers in DSSCs as well as above described fields.

  • A type of silicone modified styrene-acrylate latex for weatherable coatings with improved mechanical strength and anticorrosive properties
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-07
    Yumin Wu; Chuancong Zhu; Zhengzhe Yanchen; Hui Qiu; Haoyuan Ma; Chuanhui Gao; Yuetao Liu

    In this study, a type of silicone modified styrene-acrylate latex (SSA) was synthesized by styrene (St), vinyl trimethoxysilane (VTMS) and isooctyl acrylate (IA) through RAFT emulsion polymerization. The molecular weight and distribution (PDI) of SSA increased with VTMS contents ranging from 0 to 4%. It also enhanced the tensile strength of SSA coatings from 3.6 to 5.8 MPa. Furthermore, SSA coatings possessed the good self-healing properties. TGA and DMA indicated the thermal stability of SSA coatings increased with the increasing of VTMS contents. It also increased the water contact angle (CA) from 85 to 105° and reduced the water absorption from 3.75 to 0.8%. The open circuit potential (Eocp)-time and anodic polarization (Tafel) curves indicated the corrosion resistance enhanced with the increase of the VTMS contents. The all obtained results indicated the SSA would have great potential as weatherable and anticorrosive coatings.

  • Structural and magnetic characteristics of carboxymethyl dextran coated magnetic nanoparticles: From characterization to immobilization application
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-07
    Katja Vasić; Željko Knez; Elizaveta A. Konstantinova; Alexander I. Kokorin; Sašo Gyergyek; Maja Leitgeb
  • Bis(phenyl)fluorene-based polymer of intrinsic microporosity/functionalized multi-walled carbon nanotubes mixed matrix membranes for enhanced CO2 separation performance
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-03
    Haixiang Sun; Wen Gao; Yanwei Zhang; Xingzhong Cao; Shanshan Bao; Peng Li; Zixi Kang; Q. Jason Niu

    Polymers of intrinsic microporosity (PIM) as one of potential next generation membrane materials for gas separation has attracted great interests due to its ultra-permeable characteristics. Herein, a novel bis(phenyl)fluorene-based PIMs (Cardo-PIM-1) based on 9,9-bis(3,4-dihydroxyphenyl) fluorene (BDPF), 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN) and spirocyclic 5,5′,6,6′-tetrahydroxy-3,3′,3,3′-tetramethylspirobisindane (TTSBI) were prepared vis dibenzodioxane polymerization reaction, and then the functionalized multi-walled carbon nanotubes (f-MWCNTs) were incorporated into Cardo-PIM-1 to fabricate mixed matrix membranes (MMMs) with solution mixing method for CO2 separation. The structure analysis indicated that the MWCNTs were cut into short ropes and the amino groups were incorporated into the nanotubes surface after treated with acid mixtures followed by ethylenediamine modification. FTIR spectroscopy and nuclear magnetic resonance (NMR) measurement confirmed the formation of Cardo-PIM-1 macromolecule. BET and positron annihilation lifetime spectroscopy (PALS) analysis exhibited that Cardo-PIM-1 contained larger pore-size distribution and fractional free volume (FFV), and preferential CO2 adsorption capacity over N2 compared with that of PIM-1. This work investigated the structure of polymer as well as the effect of nanofillers in the gas separation performance. High CO2 permeability of 2.9 × 104 Barrer with a desirable CO2/N2 separation factor of 24.2 was achieved using the MMMs with 7.5 wt% f-MWCNTs loading, which were among the best performance for CO2 separation. The Cardo-PIM-1/f-MWCNTs MMMs will provide a promising alternative in industrial flue gas separation and CO2 capture process.

  • Phosphoric acid modified kenaf fiber (K-PA) as green adsorbent for the removal of copper (II) ions towards industrial waste water effluents
    React. Funct. Polym. (IF 3.074) Pub Date : 2020-01-02
    Muhammad Raznisyafiq Razak; Nor Azah Yusof; Ahmad Zaharin Aris; Hanisah Mohmad Nasir; Md. Jelas Haron; Nor Azowa Ibrahim; Ili Syazana Johari; Sazlinda Kamaruzaman

    A novel and simple chemically modified kenaf fiber functionalized with phosphoric acid was prepared to remove copper (II) ions from waste water water samples. Combination of kenaf fiber and phosphoric acid possess renewable, green and rapid removal for waste waters treatment. In the present study, the green adsorbent was thoroughly characterized with Fourier Transform Infrared Spectroscopy (FTIR), chemical composition analysis (CHNS), Brunauer-Emmett-Teller (BET) and Scanning Electron Microscopy (SEM). Moreover, the maximum adsorption capacity towards copper (II) ions were 57.14 mg/g. The adsorption isotherm follows Langmuir model and fitted with pseudo-second-order kinetics model. The enthalpy, entropy Gibbs free energy values show the adsorption fitted with non-spontaneous and endothermic reaction. The optimal desorption process was determined during the exposure with 1 M of hydrochloric acid (95.41%) followed by sulphuric acid (82.31%) and nitric acid (81.25%). After the 2nd cycle of reusability study, the adsorption capacity slightly dropped suggesting the adsorbent only can be used for once to continue its efficiency. Hence, the K-PA was confirmed to be highly adsorptive material and having promising applications in water purification application by the encounter with real waste water matrices obtained from the electroplating (88.2% removal) and wood treatment industries (61.5% removal).

  • 更新日期:2020-01-02
  • Synthesis of zwitterionic redox-responsive nanogels by one-pot amine-thiol-ene reaction for anticancer drug release application
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-30
    Quoc Thang Phan; Maheshkumar Prakash Patil; Trang T.K. Tu; Gun-Do Kim; Kwon Taek Lim

    Zwitterionic polymers with high biocompatibility and extremely low fouling properties have attracted interest as promising nanocarriers for drug delivery. In this work, novel zwitterionic nano-gels were prepared via the facile one-pot “click” reaction of α, ω-functionalized poly(sulfobetaine)s (FPSBs) and cystamine. FPSBs were first synthesized by atom transfer radical polymerization with initiators having furan-maleimide adducts followed by the end-capping reaction with thiolactone derivatives. Subsequently, the thiolactone rings of PSBs could be opened by aminolysis of cystamine crosslinkers and the released thiol-groups reacted with the double-bonds of furan-maleimide moieties to form PSB nanogel networks through the thiol-ene “click” reaction. The nanogels were readily degraded in the presence of glutathione (GSH) as a reducing agent, which was confirmed by the changes in particle size. Doxorubicin (DOX), could be loaded in the core of the nanogels with a high drug loading content of 24.3%. Moreover, the in vitro drug release profile showed a low release (24.8%) of DOX at a physiological environment, whereas there were burst releases of 74.4% and 89.9% in the presence of 5 mM and 10 mM GSH similar to a tumor cytoplasm environment. Cell viability assays demonstrated that the nanogel showed low cytotoxicity against the normal HEK293 cell, while exhibited a high cytotoxic activity towards HeLa cancer cells. These evidences revealed the effective redox responsive characteristics of the PSB nanogels.

  • Synthesis and sorption properties of heparin imprinted zeolite beta/polydopamine composite nanoparticles
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-30
    Somaye Seraj; Mohammad Nader Lotfollahi; Ali Nematollahzadeh

    Heparin-specific molecularly imprinted polymer (MIP) using a nano-layer of polydopamine was synthesized at the surface of zeolite Beta nanoparticles. The Brunauer–Emmett–Teller (BET) surface area of MIP is about 347.23 m2/g with a mean pore diameter of nearly 8 nm, while the corresponding features for the non-imprinted polymers (NIP) are 255.50 m2/g and 10.17 nm, respectively. The transmission electron microscope (TEM) results revealed that the thickness of the polydopamine shell in NIP is less than that of MIP. The static and selective sorption of heparin along with its sorption kinetics were investigated at physiological pH. The results demonstrated that the sorption isotherm of heparin using NIP follows the Langmuir isotherm model, suggesting the monolayer sorption. However, the Freundlich model presented a better description of heparin sorption by MIP, which indicates the presence of high-affinity binding sites and surface heterogeneity. The pseudo-second-order model demonstrated satisfactorily the kinetic data, indicating the secondary reaction of heparin with imprinting sites through chemical sorption. The selectivity of MIP was assessed using sodium alginate as a similar compound, providing imprinting factor and selectivity coefficient of ca. 10.37 and 9.66, respectively. Finally, the reusability of MIP was studied in three sequential sorption-desorption cycles. Interestingly, after 3 cycles, MIP did not exhibit a significant reduction in binding capacity.

  • Controlled release of testosterone by polymer-polymer interaction enriched organogel as a novel transdermal drug delivery system: Effect of limonene/PG and carbon-chain length on drug permeability
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-28
    Preeyarad Charoensumran; Hiroharu Ajiro

    The aim of this research is to develop a transdermal drug delivery system (TDDS) for testosterone by novel physical chain entanglement organogels in propylene glycol. The organogels have been widely studied for TDDS, due to their good interactive properties with skin. The physical gel with amphiphilic polymers was studied and evaluated in this study, in order to fabricate the controllable release and sufficient permeability through the skin barrier of transdermal testosterone. The novel sugar amine-derived gel, that is poly(vinyl benzyl-N-methyl-D-glucamine) gel (poly(VbNMDG) gel), was obtained by the subsequent polymerization of the neutral form (VbNMDG) and cationic form (VbNMDG-H) with an organic base as a promotor. The gel showed electrostatic interactions as indicated by FTIR, and responsive behavior under alkali conditions. The network structure is generated from multi-interaction of linear polymer chain, confirmed by in situ polymerization. This was evidenced by the rheological measurement, which confirmed a gradual change from sol to gel-like behavior. Regarding the drug release, we set the target release time at 24 h, which is an effective treatment condition for hypogonadism. For the permeation, it was studied by using abdominal rat skin as a membrane. The d-limonene/PG synergistic activity enhanced the permeability, resulting in the highest coefficient (KD/L) at 8.80 ± 1.95 cm/h at 10% Limonene/PG. Furthermore, we evaluated the carbon chain length effect by copolymerizing of benzalkonium chloride. The dodecyl (C-12) group showed significant penetration enhancement, indicated by the coefficient which was 13.76 ± 5.45 cm/h.

  • Process optimization for the preparation of thiamethoxam microspheres by response surface methodology
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-25
    Yu Zhang; Changyou Li; Dong Chu; Guangyao Yan; Meiqi Zhu; Xin Zhao; Juncheng Gu; Gongqiang Li; Jintian Wang; Baohua Zhang

    4A zeolite has reasonable adsorption and frame support properties thanks to its special pore structure and large surface area. This paper aims at improving the properties of microspheres by introducing zeolite as structural modifier. Therefore, the 4A zeolite/sodium alginate (SA)/Chitosan (CS) thiamethoxam microspheres (4A/SA/CS MCs) were hereby prepared and optimized through Response Surface Methodology. The Box-Behnken design was used to build the model and to analyze the effects of the concentration of sodium alginate, calcium chloride and 4A zeolite on the response value-loading efficiency. Furthermore, the fabricated 4A/SA/CS MCs were characterized by fourier transform infrared spectroscopy, scanning electron microscope, X-ray diffraction, differential scanning calorimetry. The performances of 4A/SA/CS TMCs such as the swelling rate, particle size, slow-release behaviors were systematically investigated. The phytotoxicity and insect activity of 4A/SA/CS MCs were also evaluated. The experimental results illustrated that the relationship between the response value and three independent variables were corresponded with the quadratic model. The properties of microspheres indicated that microspheres containing 4A zeolite had better LE and EE, displayed good sustained-release property and thermal stability, possessed persistent insecticidal activity as well as high biosafety.

  • Research on a kind of biocompatible molecularly imprinted materials with silybin controlled release based on pH/temperature dual responses
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-25
    Ni Tan; Kang Ji; Dianxiong He; Sen Liao; Leqing He; Jingwen Han; Can Chen; Yaqing Liu

    Silybin, a hepatoprotective active natural ingredient, was used as the template, methyl acrylic acid (MAA) as the functional monomer, n-isopropyl acrylamide (NIPAm) as the thermal response monomer, magnetic core Fe3O4@[email protected]@BiBB coated by biocompatible chitosan as the carrier, and a kind of silybin molecularly imprinted materials (MMIPs) based on pH/temperature dual responses were prepared by electron transfer activation regenerative catalyst atom transfer radical polymerization (ARGET ATRP). The synthesized material was characterized by FT-IR, TGA, SEM, XRD, VSM, and XPS, and the loading behavior of silybin in MMIPs could be explained by the pseudo-second-order kinetic model. The selectivity factor α (2.636) and the relative selectivity factor β (2.468) indicated MMIPs had good specific recognition ability for silybin. In addition, a series of experimental data displayed MMIPs had many other excellent characteristics such as adsorption property, swelling performance, biocompatibility, degradability, stability, reproducibility and so on. The cumulative release rates of MMIPs could reach 29%, 23% and 25% in the media of pH 1.0, 7.4 and 8.2 at 37.5 °C, resepectively, and when the temperature was raised to 43 °C, the release rate of MMIPs in solution (pH 7.4) reached 49%, which indicated that the carrier material had good pH/temperature dual responses.

  • Development of BSA gel/Pectin/Chitosan polyelectrolyte complex microcapsules for Berberine delivery and evaluation of their inhibitory effect on Cutibacterium acnes
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-24
    Violeta Paşcalău; Cătălina Bogdan; Emoke Pall; Luminiţa Matroş; Stanca-Lucia Pandrea; Maria Suciu; Gheorghe Borodi; Cristina Adela Iuga; Rareş Ştiufiuc; Tamara Topală; Codruţa Pavel; Cătălin Popa; Mirela Liliana Moldovan

    The aim of this work was to develop a novel fully natural drug delivery system for the treatment of acne, based on core-shell microcapsules that contain Berberine (Brb). The two main objectives of the work were: a) the synthesis and the characterization of complex microcapsules (ms), ms encapsulating Berberine (ms-Brb), and b) in vitro evaluation of the release of Brb, of the cytotoxicity on normal skin cells and of the antimicrobial effect on Cutibacterium acnes (formerly Propionibacterium acnes) (C. acnes). For a), bovine serum albumine (BSA) gel-core microcapsules with alternating multilayer shells of calcium cross-linked Pectin (P) hydrogel and the polyelectrolyte complex formed by P and Chitosan (Chi) (BSA gel/P/Chi/P) were synthesized. The BSA gel-core microcapsules were obtained using a sacrificial CaCO3 template method, while the multilayer shell was formed through a technique consisting in the layer-by-layer (Lbl) deposition of polyelectrolyte complex formed by P and Chi. Brb was encapsulated into the resulting microcapsules, by a process of diffusion from solution. The structure characterization of ms/ms-Brb was performed by FTIR and UV–Vis spectroscopy, X-ray diffraction, confocal laser scanning microscopy, and scanning electron microscopy. The in vitro assessment of ms/ms-Brb cytotoxicity on skin cells was performed using keratinocyte (HaCaT) cell line. Results of physicochemical analyses confirm the successful encapsulation of Brb in ms, and the in vitro biological study recommends ms-Brb as a candidate for future in vivo research targeting anti-acne treatment.

  • Physical and chemical modifications of poly(vinyl chloride) materials to prevent plasticizer migration - Still on the run
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-24
    Yufeng Ma; Shengliang Liao; Qiaoguang Li; Qian Guan; Puyou Jia; Yonghong Zhou

    Poly (vinyl chloride)(PVC), as the second general plastic just following the product of polyethylene (PE), has been widely applied in building, electrical parts, automobile, package and other fields of our common life. PVC products have accounted for about 80% of all plasticizers consumed. Phthalates, as the mostly used plasticizers, have gradually been restricted because of their migration and reproductive toxicity. This paper is an overview of current understanding in the areas of issues caused by migration of plasticizers from flexible PVC products and the current bans in dealing with these issues. The countermeasures and the recent scientific strategies to prevent plasticizer migration from PVC materials are comprehensibly reviewed. The advantages and disadvantages of various strategies are compared to conduct more in-depth research and find more scientific and effective solutions.

  • Chitosan as a coating material for nanoparticles intended for biomedical applications
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-24
    L.A. Frank; G.R. Onzi; A.S. Morawski; A.R. Pohlmann; S.S. Guterres; R.V. Contri

    This review provides a comprehensive and updated overview of the state of the art related to the biomedical applications of nanoparticles coated with chitosan. Discussions were based on selected literature in the field. Here, we discussed nanoparticles constituted by polymer, lipid and metal materials, which have been coated with chitosan. In addition, the methodological aspects of the coating process, which is performed by the addition of a chitosan solution into previously prepared nanoparticles or during nanoparticle formation, was reviewed, as well as the techniques employed to confirm an efficient coating process, such as determinations of particle size and zeta potential. Special attention is given to physicochemical and biological advantages brought by the chitosan-coating, such as increase in physicochemical stability, controlled release, improvement of tissue/cells interaction, and increase in the bioavailability of drugs (or active substances) and drug efficacy. We also pointed out safety concerns regarding chitosan-coated nanoparticles based on the results presented so far in the literature.

  • As(V) removal from water using the La(III)- Montmorillonite hydrogel beads
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-17
    Shengjin Yan; Qing An; Ling Xia; Shuang Liu; Shaoxian Song; Jose René Rangel Méndez

    The porous La(III)- montmorillonite hydrogel beads (La-MMT_hb) with stable structure were fabricated via hydrogen-bond and electrostatic interactions for arsenic removal from water. The structural characteristics of La-MMT_hb and its sorption performances for As(V) were evaluated. The results showed that porous La-MMT_hb were clearly observed by scanning electron microscopy, and the addition of lanthanum significantly increased the specific surface area. The maximum adsorption capacity of La-MMT_hb for As(V) was 58.75 mg/g, reached within 4 h, at the optimum pH of 4 with optimum La dosage of 1%. The mechanism of adsorption can be attributed to the electrostatic forces between La(III) and H2AsO4− at pH 4, ion exchange of OH groups on the surface of adsorbent with H2AsO4− and complex chelate formation as.-NH3-H2AsO4 and -La-O-As.

  • Synthesis optimization and X-ray absorption spectroscopy investigation of polymeric anion exchanger supported binary Fe/Mn oxides nanoparticles for enhanced As(III) removal
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-10
    Antika Pranudta, Wantana Klysubun, Medhat Mohamed El-Moselhy, Surapol Padungthon

    A macroporous anion exchange resin containing high density of positively-charged quaternary ammonium functional groups and supporting binary Fe/Mn oxides nanoparticles (HA502P-Fe/Mn) was synthesized for simultaneous As(III)oxidation and As(V) adsorption within a single bead. Various preparation parameters were investigated and optimized to achieve the highest As(III) removal efficiency, including metal oxides type, supporting materials, preparation solvents, and number of loading cycles. The results from five imaging techniques (SEM-EDX, TEM, XRD, XANES, EXAFS) confirmed that amorphous ferric and manganese oxides nanoparticles were successfully dispersed throughout the matrix of the parent macroporous anion exchanger. The changes in oxidation state of the Mn oxides from +4 to +2 and + 2 to +4 were observed by XANES during As(III) removal and regeneration runs, respectively. The EXAFS was used to investigate the neighborhood atoms surrounding arsenic during As(III) removal by HA502P-Fe/Mn. The bond distance between AsFe and AsMn of HA502P-Fe/Mn are 3.35 and 2.94 Å, respectively, suggesting that As(III) was oxidized to As(V) and adsorbed on the surface of Fe(III) and Mn(IV) oxide nanoparticles by formation of inner-sphere complex. As(III) was oxidized by MnO2 nanoparticles under the absence of oxygen environment and only As(V) was observed after adsorption. The equilibrium As(III) sorption isotherms, effect of pH, competing ions, and NOM were also evaluated. Fixed-bed column experiments using NSF challenge water standard 53 (300 μg As(III)/L, pH 6.5) were carried out and found that the material can remove As(III) equivalent to 4300 bed volumes (BVs) compared with 2000 BVs using commercial arsenic selective material (Layne-RT). The exhausted material can be regenerated using 10 BVs of regeneration solution and 98% of adsorbed arsenic can be recovered.

  • 更新日期:2019-12-09
  • Grafting high content of imidazolium polymer brushes on graphene oxide for nanocomposite membranes with enhanced anion transport
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-09
    Jianshe Wang, Huiling Chen, Yingying Ma, Huijuan Bai, Benbing Shi, Chunli Hou, Jingtao Wang, Yifan Li
  • Direct functionalizing of acrylonitrile-butadiene rubber surfaces through different peroxide curing
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-06
    Jing Sang, Sumio Aisawa, Hiroki Muraoka, Kunio Mori, Hidetoshi Hirahara

    This study focuses on the influence of peroxide type on the chemical composition, curing properties, and free-radical reactions of peroxide cured acrylonitrile-butadiene rubber (NBR). A novel perspective regarding peroxide curing as a surface modification method to control the formation of functional groups on cured rubber surfaces via the primary curing process is provided. During curing, the peroxide acts as a useful curing agent and as an efficient controller of functional group formation on rubber surfaces. Surface functionalization of NBR cured using peroxides containing structures such as alkyl, phenyl, and both groups was examined by X-ray photoelectron spectroscopy (XPS). The effects of different curing temperatures were also studied. Oxygen-containing functional groups were obtained on the cured NBR surfaces. Notably, NBR surfaces cured by the peroxide containing phenyl groups showed an increased abundance of oxygen-containing functional groups compared to those cured by the peroxide containing alkyl groups. The functional group formation mechanism on rubber surfaces is also discussed herein. This strategy offers opportunities for large-scale fabrication of versatile functional surfaces and thin films on rubber for various applications.

  • 3D printable Polycaprolactone-gelatin blends characterized for in vitro osteogenic potency
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-05
    Raja S. Azarudeen, Mohamad Nageeb Hassan, Mohammed Ahmed Yassin, M. Thirumarimurugan, N. Muthukumarasamy, Dhayalan Velauthapillai, Kamal Mustafa

    Synthetic polycaprolactone (PCL) was modified with various concentrations of gelatin (GL) to enhance its physical properties and biological activity for bone regeneration. A novel trisolvent mixture has been used to mix PCL and GL that were fabricated as scaffolds using 3D plotting. The scaffolds were characterized for their mechanical properties, hydrophilicity and swelling ability. In addition, the structure and morphology of the printed scaffolds were analyzed by Fourier-Transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and microcomputed tomography (μCT). Attachment, proliferation and osteogenic differentiation of rat bone marrow stromal cells (BMSC) cultured on the printed scaffolds were evaluated within 21 days. Increasing GL content in the scaffolds led to an enhanced hydrophilic nature, better pore size distribution and interconnected micro-pores. This resulted in better cellular attachment, proliferation and osteogenic differentiation. Although the multiple reactive sites and biochemical compatibility provided by GL improved the scaffolds'osteogenic potency, the tensile strength and elasticity of the printed scaffolds are yet challenging with increasing GL contents.

  • Poly(butylene succinate) biocomposite modified by amino functionalized ramie fiber fabric towards exceptional mechanical performance and biodegradability
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-05
    Qianqian Han, Liang Zhao, Panlong Lin, Zhongmin Zhu, Kun Nie, Feihua Yang, Luoxin Wang

    This work reports a poly(butylene succinate) (PBS) biocomposite modified by amino functionalized ramie fiber fabric (RFF) via a facile thermal-compressive method. Different from other methods, we introduced PBS nonwoven as matrix raw material, whose three-dimensional network structure can effectively anchor RFF, resulting in excellent infiltration. Results show that the mechanical performance, wettability, crystallization behavior, thermal performance, rheological behavior as well as biodegradability of PBS biocomposite are competitive with the introduction of amino functionalized RFF. Compared with RFF/PBS biocomposites fabricated in other researches, there is a significant promotion in mechanical performance. For RFF/PBS-50 wt% biocomposite, the tensile strength, elongation at break, flexural strength, flexural modulus, interlaminar shear strength (ILSS) and impact strength reach to 72.4 MPa, 19.4%, 100.5 MPa, 4.9 GPa, 3.3 MPa and 67.5 KJ/m2, respectively. They are mainly ascribed to observed excellent interfacial bonding, typical plastic deformation of PBS and riveting effect of RFFs. Furthermore, the RFF/PBS biocomposite shows favorable biodegradability in the compost test. The biodegradable function of RFF/PBS biocomposite enables it to become a desirable substitute of conventional nondegradable composite.

  • The dynamic chain effect on healing performance and thermo-mechanical properties of a polyurethane network
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-05
    Lei Zhang, Haiqing Wang, Zenghui Dai, Zhongxiang Zhao, Feiya Fu, Xiangdong Liu

    Dynamic covalent chains that composed of three or five dynamic polyurea bonds are introduced into cross-linked polyurethane to overcome the classical dilemma between healing rate and thermo-mechanical properties. Comparing with dynamic urea bond, the incorporation of the dynamic polyurea chains with multiple leads to significantly improved thermo-mechanical performance and healing rate/efficiency on the network. Remarkably, several folds' increases in tensile and adhesion shear strength as well as 53 °C enhancement in glass transition temperature are achieved without sacrificing the material properties of the polyurethane network. We attribute the improvements to the decomposed polyurea chain segments, which have higher diffusivity and larger quantity than the dynamic urea bond that tied in the control network. This study provides a concept of dynamic covalent chain to address the classical dilemma between healing performances and thermo-mechanical properties among healable thermosets.

  • Bio-phenol formaldehyde (BPF) resoles prepared using phenolic extracts from the biocrude oils derived from hydrothermal liquefaction of hydrolysis lignin
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-03
    Hooman Paysepar, Yulin Hu, Shanghuan Feng, Zhongshun Yuan, Hengfu Shui, Chunbao Xu

    In this work, hydrolysis lignin, as a low-value feedstock, was liquefied in ethanol/water co-solvents (50:50, v/v) at 350 °C for 30 min, with or without the use of hematite ore as the catalyst. Following this, the resulting bio-crude oil was applied as the feedstock for the preparation of neat phenol formaldehyde (PF) resole and bio-phenol formaldehyde (BPF) resoles. The net PF resole was prepared by using the whole bio-crude oil, while, the phenolic extracts from the crude oil together with 50% of phenol were employed for the preparation of BPF resoles. The results displayed that although the BPF resole contained a higher free formaldehyde and less thermally stable than neat PF resole, a lower curing temperature was adopted for BPF resole compared to neat PF resole. By analyzing their physical properties, it was observed that the dry bonding strength of BPF resoles was higher than that of neat PF resole. Most importantly, the dry and wet strengths of BPF resole met the requirements for using as an adhesive for plywood bonding. Overall, it can be concluded that the bio-crude oil-derived phenolic extracts from HTL of hydrolysis lignin is a suitable feedstock for producing value-added BPF with potential use as a wood adhesive.

  • Fluorophenylboronic acid substituted chitosan for insulin loading and release
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-12-02
    Lei Luo, Rijian Song, Jiajie Chen, Benyu Zhou, Xuan Mao, Shunqing Tang

    Phenylboronic acid (PBA) can form dynamical reversible chemical bonds with sugars, and has potential in glucose response and controlling insulin delivery. In this paper, 4-fluorophenylboronic acid (FPBA) was employed which could work better than normal PBA in physiological environment. Herein, FPBA-substituted chitosans (CS-FPBA) with three different molecular weights were prepared, and affecting factors on preparation, including solvent, pH, raw materials ratio, activation time and reaction time, were discussed. The glucose responsiveness and controlling insulin release properties of CS-FPBA were also determined. Results showed that the substitution of FPBA onto CS could decrease the zeta potential of CS to negative values, which was favorable for CS-FPBA to react with hydroxyl groups in biological environments. They could effectively load with insulin with approximately 50% (wt%) encapsulation efficiency in 0.5 mg/mL insulin. Also, CS-FPBA particles had significant binding efficiency to glucose, which was dramatically higher by over 6 folds compared to chitosan. The maximum releasing amount of insulin was >90% in 9 h in 3 mg/mL of glucose solution when the molecular weight of CS was 50 kDa. In summary, CS-FPBA has potential to control the release of insulin, and can regulate the release rate by controlling the molecular weight of CS.

  • Heat driven self-healing isocyanate-based crosslinked three-arm Star-shaped polyglycolide based on dynamic transesterification
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-30
    Qi Fu, Qiming Yan, Xiang Jiang, Heqing Fu

    Dynamic combinatorial chemistry (DCC) involves reversible reactions which can be controlled by thermodynamics method. Transesterification is one of the most widely explored DCC reactions. In this paper, transesterification was used to synthesize self-healing network. First, a three-arm star-shaped hydroxyl-terminated polyglycolide (HTPG) was fabricated though the ring-opening polymerization (ROP) of glycolide by using triethanolamine (TEA) as initiator and tetrabutyl titanate (TBT) as catalyst. Then the self-healing network i.e. isocyanate-based crosslinked star-shaped polyglycolide (ICSPG) was prepared through the crosslink between hexamethylene diisocyanate trimer (HDIT) and HTPG. In order to explore the mechanism of the self-healing, a polyurethane based on a tri-functional polyether polyol (PPPU)was synthesized. The structures of HTPG, ICSPG and PPPU were characterized by fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (1H NMR). The mechanical properties and self-healing properties were characterized by dynamic mechanical thermal analysis (DMTA) and polarizing optical microscopy (POM). And the welding test was used to further characterize the self-healing properties of ICSPG. It was found that mechanical recovery is about 70%. The POM results showed that ICSPG exhibited self-healing properties at high temperature.

  • Preparation of a novel mixed non-covalent and semi-covalent molecularly imprinted membrane with hierarchical pores for separation of genistein in Radix Puerariae Lobatae
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-29
    Jie-Ping Fan, Yu-Tong Cheng, Xue-Hong Zhang, Zhou-Peng Xiao, Dan-Dan Liao, Hui-Ping Chen, Kuan Huang, Hai-Long Peng

    In this work, a novel mixed non-covalent and semi-covalent molecularly imprinted membrane (MIM) with hierarchical pores was prepared by cryopolymerization at −18 °C and using PEG2000 and dimethyl sulfoxide ice crystals as the pore templates. The free-standing MIM was characterized by scanning electron microscope and nitrogen adsorption-desorption isotherms, and the results confirmed the formation of the hierarchical pore structure. In the static adsorption, membrane permeation and dead-end filtration experiments, the results indicated that the mixed non-covalent and semi-covalent molecular imprinting was a good method to improve the performance of MIM which had a good adsorption selectivity toward genistein due to the presence of the imprinted sites in MIM and possessed strong imprinting efficiency toward genistein even in some similar compound mixture or extract of Radix Puerariae Lobatae.

  • Self-assembled nano-vesicles based on mPEG-NH2 modified carboxymethyl chitosan-graft-eleostearic acid conjugates for delivery of spinosad for Helicoverpa armigera
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-27
    Chuang Zhou, Ziming Yang, Li Zhang, Enming Dong, Zuyu He, Xianwu Liu, Chao Wang, Yan Yang, Jing Jiao, Yunhao Liu, Yu Chen, Puwang Li

    In this work, carboxymethyl chitosan-graft-eleostearic acid (CMCS-g-EA) was synthesized via the amide reaction between the amino groups of carboxymethyl chitosan and the carboxyl group of eleostearic acid, and then mPEG-NH2 was grafted to CMCS-g-EA to prepare amphiphilic polymers (mPEG-CMCS-g-EA). The chemical structures of the above conjugates were characterized by FT-IR and 1H NMR. Both CMCS-g-EA and mPEG-CMCS-g-EA based nano-vesicles were prepared by ultrasonic self-assembly method and they exhibited a low critical aggregation concentration (CAC) of 14.97 μg/mL, 16.82 μg/mL, respectively. The spinosad-loaded mPEG-CMCS-g-EA nano-vesicles (SSD@mPEG-CMCS-g-EA NVs) were spherical in shape with an average diameter of 502.8 nm and the zeta potential of −25.60 mV. The encapsulation efficiency (EE) and drug loading content (LC) of SSD@mPEG-CMCS-g-EA nano-vesicles were 42.00%, 23.07%, respectively. In vitro release revealed that the SSD@mPEG-CMCS-g-EA nano-vesicles exhibited a sustained and pH-responsive drug release property, and could significantly enhance the photostability of spinosad. Furthermore, the toxicological tests demonstrated that the SSD@mPEG-CMCS-g-EA nano-vesicles could efficiently inhibit the growth and development of Helicoverpa armigera. These results indicated that the SSD@mPEG-CMCS-g-EA nano-vesicles were highly potential for the treatment of Helicoverpa armigera.

  • Poly(p-phenylenediamine)/maghemite composite as highly effective adsorbent for anionic dye removal
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-26
    Islam M. Minisy, Beata A. Zasońska, Eduard Petrovský, Pavel Veverka, Ivana Šeděnková, Jiřina Hromádková, Patrycja Bober

    Poly(p-phenylenediamine)/maghemite (PPDA/γ-Fe2O3) composites were prepared by the oxidative polymerization of p-phenylenediamine with ammonium peroxodisulfate as an oxidizing agent in the presence of γ-Fe2O3 nanoparticles. Morphology of the prepared composites was examined by the scanning and transmission electron microscopies. X-ray diffraction and EDX were used to study crystallinity and chemical composition, respectively. TGA demonstrated that only 7 and 45 wt% of γ-Fe2O3 were incorporated into PPDA prepared with 25 and 50 wt% of γ-Fe2O3, respectively. Adsorption property of the composites was examined towards the anionic dye, Reactive Black 5. The adsorption results were fitted to different kinetics and isotherm models. The highest adsorption capacity (Qmax) was estimated to be 223 mg g−1 in case of PPDA with the highest specific surface area (70.6 m2 g–1) prepared with 25 wt% of γ-Fe2O3. Qmax of neat PPDA was estimated to be 185.2 mg g−1 and 123.2 mg g−1 for PPDA prepared with 50 wt% of γ-Fe2O3. In addition to the enhancing of the adsorption capacity, the incorporation of γ-Fe2O3 particles provided an easy separation of the composites from the adsorption medium.

  • Covalent modification of graphene oxide and applications in polystyrene composites
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-24
    Ming Jin, Wenjun He, Chuanming Wang, Fengping Yu, Weimin Yang

    p-Methylstyrene groups were covalently grafted onto graphene oxide (GO) via esterification reactions and confirmed by Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and Thermogravimetric analysis (TGA). The as-prepared functionalized graphene oxide (FGO) exhibits good dispersibility in many organic solvents and monomer such as ethanol, dichloromethane and styrene. The high dispersibility and accessible reactive groups enable the preparation of reduced FGO (FrGO)/cross-linked polystyrene (PS) microsphere nanocomposites with improved thermal and anti-swelling properties. The thermal degradation temperature of the nanocomposites at 1.0 wt% addition increased by 27 °C, while the glass transition temperature improved by 8 °C; the swelling capacity in water and methanol decreased by 66% and 37%, respectively. Such enhanced properties could effectively improve the catalysis performance of nanocomposite-based ion-exchange resins (IERs). The IERs demonstrated high ethylene oxide (EO) conversion and monoethylene glycol (MEG) selectivity in the hydration of EO, even after a long run of 1800 h.

  • Graphene oxide grafted hyperbranched poly (vinyl imidazole) with ionic liquid components as a potential carbon dioxide scrubber
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-21
    Tamalika Das, Srijoni Sengupta, Animesh Jana, Abhijit Pal, Indranil Roy, Soumen Sardar, Nayan Ranjan Saha, Sourja Ghosh, Abhijit Bandyopadhyay

    The present work focuses on the design of a CO2 scavenger, capable of adsorbing a low concentration of CO2 from a mixed gas composition. Typically, vinyl imidazole and an ionic liquid brancher were copolymerized by “Strathclyde methodology” and grafted from graphene oxide; GO-g-(HB) PVIm-co-PIL (Cl). The chain transfer agent maintained short chains and developed hyperbranched architecture in GO-g-(HB) PVIm-co-PIL (Cl). The structure and the properties of GO-g-(HB) PVIm-co-PIL (Cl) was established from FTIR, 1HNMR, Raman, XRD and rheology. A metathesis reaction was carried out to exchange chloride anions with hexafluorophosphate anions; GO-g-(HB) PVIm-co-PIL (PF6). GO-g-(HB) PVIm-co-PIL (PF6) selectively captured a low concentration of CO2 from a mixed gas. The surface functionalities/ properties of GO, hyperbranched architecture, porosity, nitrogen content and surface charge distribution together played a significant role in efficient and selective CO2 capture.

  • Synthesis and characterization of magnetic glycocyamine-modified chitosan as a biosupport for the copper immobilization and its catalytic activity investigation
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-21
    F. Rafiee, F. Rezaie Karder

    Trichloro-1,3,5-triazine agent was used for chitosan functionalization and as a bridge between the functionalized chitosan and glycocyamine to form a bio ligand for the copper coordination. The magnetization of modified chitosan was done using of Fe3O4 nanoparticles. In the presence of coordinated groups of glycocyamine containing amidino and carboxylate, copper ions were immobilized on this magnetic biopolymer. This new nanocomposite (Fe3O4@CSC@AG@Cu) was characterized by FT-IR, FE-SEM, EDX, XRD, VSM, DRS and ICP analysis. After which, its catalytic activity was examined in the three coupling reactions of aliphatic and aromatic aldehydes, secondary cyclic amines and phenyl acetylene for the synthesis of propargylamine derivatives.

  • Facile fabrication of dual-crosslinked single network heterostructural polyurethane hydrogels with superior mechanical and fluorescent performance
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-21
    Jie Wen, Mingwang Pan, Jinfeng Yuan, Jiaxi Wang, Lei Zhu, Zhanyu Jia, Shaofeng Song
  • Chitosan-based nanomedicine for brain delivery: Where are we heading?
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-21
    Catarina Pacheco, Flávia Sousa, Bruno Sarmento

    Neurological disorders have been increased in the last years, affecting over one billion people globally. The lack of successful treatments is related to the low brain bioavailability of potent drugs to reach the brain due to the blood-brain-barrier (BBB) crossing. To overcome this limitation, high concentrations of drugs are administered to patient in order to reach brain more efficiently, leading consequently to off-target organ toxicity. For that reason, there is an urgent need to improve neurological disorders with powerful treatments. Drug delivery nanosystems have been explored due to their targeting properties. Chitosan is a natural polymer widely used to formulate drug delivery nanosystems, allowing a targeted therapy with no toxicity due to its unique properties, such as biocompatibility, biodegradability and mucoadhesive properties. Drug delivery nanosystems, hydrogels and scaffolds composed chitosan have recently been used for brain delivery, targeting different neurological disorders. Besides intravenous administration of chitosan-based nanocarriers for brain delivery, intranasal administration has been an alternative due to its mucoadhesive properties, improving the patient adhesion to therapy. This review will focus on most recent approaches of chitosan-based nanomedicine for brain delivery, from drug delivery systems to scaffolds for brain regeneration.

  • Highly selective removal of cationic dyes from water by acid-base regulated anionic functionalized polyacrylonitrile fiber: Fast adsorption, low detection limit, reusability
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-18
    Jian Xiao, Lu Wang, Jiaoru Ran, Jingyan Zhao, Minli Tao, Wenqin Zhang

    A series of anionic functionalized polyacrylonitrile fibers were prepared and used to remove cationic dyes from water. The phenolate immobilized fiber (PANP(−)F) exhibited excellent adsorption capacities for cationic dyes, among which the best results was obtained for Brilliant cresyl blue (BCB) with color changing of the solution from sapphire to light yellow. Additionally, PANP(−)F can selectively remove cationic dyes from dye mixtures containing both anionic and cationic dyes. After acid-base regulating, the highest adsorption capacity of PANP(−)F was obtained at pH 10. Moreover, adsorption kinetic illustrated that PANP(−)F can achieve half adsorption capacity within 10 mins and follow pseudo-second-order model. The maximum adsorption capacity calculated from isotherms experiments reached 2.306 mmol/g (890.1 mg/g) at 25 °C. The activation energy of the adsorption process was 30.74 kJ/mol indicating that the BCB adsorption process occurs via chemical adsorption. Furthermore, the PANP(−)F can be readily separated from solution and reused 10 cycles. Under a continuous flow condition, the BCB concentration can be reduced to 20 ppb at first and remained below 1.69 ppm during the 825 mins adsorption process. At the same time, the removal ratio kept above 98.31%. In general, this novel PANP(−)F adsorbent is eco-friendly, highly efficient, selective, reusable, and has great potential for the removal of dyes from industrial wastewaters.

  • Chitosan-based hydrogel for magnetic particle coating
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-16
    Vanessa A. de Pereira, Irisvan S. Ribeiro, Haroldo C.B. Paula, Regina C.M. de Paula, Rubem Luis Sommer, Ruben Jesus Sanchez Rodriguez, Flavia O.M.S. Abreu

    Magnetic particles coated with chitosan-based hydrogel were prepared and characterized by infrared spectroscopy, thermal analysis, atomic force microscopy (AFM), energy dispersive X-ray (EDX), wide angle X-ray diffraction (WAXD) and by vibrating sample magnetometry. A polyelectrolyte complex of chitosan (CH) and Sterculia striata gum (CHG) was employed as a coating. FT-IR analysis of the hydrogel obtained revealed the presence of main characteristic bands of CH, CHG and magnetite (Fe3O4). The thermograms showed a moderate efficiency of magnetite incorporation (26.0%) in the hydrogel, as well as evidence of interactions between functional groups of magnetite and biopolymers. Patterns of X-ray diffraction showed the presence of magnetite in the hydrogel with saturation magnetization of 36.5 emu g−1 and crystal average size of 20.8 nm. The hydrogel was found to present a negatively charged outer surface. EDX and AFM revealed that Fe3O4 nanoparticles were aggregated, forming large clusters. The CH /CHG hydrogel was shown to be suitable for magnetite coating, enabling its future application such as a drug carrier and a water remediation agent.

  • Mushroom-derived chitosan-glucan nanopaper filters for the treatment of water
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-15
    Jan Janesch, Mitchell Jones, Markus Bacher, Eero Kontturi, Alexander Bismarck, Andreas Mautner

    Contaminated water represents a significant threat to public health, with heavy metals present in industrial effluents constituting a particular hazard. Conventional heavy metal removal processes are often expensive and rely on synthetic materials. Renewable adsorbents or filters, such as chitosan, provide a low-cost, simple alternative for treatment of water. Fungal chitin and hence fungal chitosan is a cheap, renewable, easily isolated, and abundant alternative to crustacean chitin. This study investigated the water treatment potential of chitosan-glucan nanopapers derived from common white-button mushroom (A. bisporus) extract as adsorptive filter. These nanopapers completely rejected 10 nm gold nanoparticles, indicating potential for virus filtration. They had copper ion (2 mM) adsorption capacities (up to 120 mg g−1) increasing with degree of deacetylation of fungal chitin on par with or even outperforming current chitosan membranes with the advantage of simpler production, not requiring further crosslinking. In order to improve the performance of fungal chitosan-glucan filters, hybrid filters with cellulose microfibres from fibre sludge were prepared. Hybrid nanopapers exhibited significantly increased copper ion adsorption (162 mg g−1) in conjunction with high water permeances (63,000 to 121,000 L h−1 m−2 MPa−1). The simple manufacturing process and impressive filtration/adsorbent properties of these renewable filters make them a viable option for water treatment helping to reduce the ecological impact of traditional water treatment processes.

  • Polyurethane-based thiomers: A new multifunctional copolymer platform for biomedical applications
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-15
    Rossella Laurano, Claudio Cassino, Gianluca Ciardelli, Valeria Chiono, Monica Boffito
  • Development of zirconia nanoparticle-loaded hydrogel for arsenic adsorption and sensing
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-14
    Hideaki Tokuyama, Eri Kitamura, Yoshimi Seida

    A novel zirconia nanoparticle-loaded synthetic polymeric hydrogel was developed as an adsorbent and quartz crystal microbalance (QCM) sensor for arsenic in an aqueous solution. The bulk composite hydrogel was prepared by polymerizing a pre-gel aqueous solution containing N,N-dimethylacrylamide as the primary monomer, a crosslinking monomer, an initiator, and commercially available zirconia nanoparticles. The hydrogel-coated QCM sensor was simply fabricated by polymerizing the pre-gel aqueous solution onto the surface of a gold electrode on a quartz crystal. The hydrogel selectively adsorbed As(III) and As(V), and the adsorption equilibrium followed the Langmuir-type isotherm. The amount of arsenic adsorbed was higher in acidic and neutral solutions and decreased with an increase in pH. Moreover, the hydrogel adsorbed/desorbed arsenic repeatedly via the regeneration process using a NaOH aqueous solution. Furthermore, the investigation of the oscillation behavior of the hydrogel-coated QCM sensor revealed that the resonance frequency shift increases with an increase in arsenic concentration, which indicates that the adsorption of arsenic onto the sensor follows a Langmuir-type isotherm. The hydrogel-coated QCM sensor could detect arsenic with high selectivity and sensitivity even in the presence of Na(I), Mg(II), and Ca(II) ions. Thus, we successfully developed the world's first QCM sensor for arsenic.

  • A super long-acting and anti-photolysis pesticide release platform through self-assembled natural polymer-based polyelectrolyte
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-14
    Guohuan Huang, Guangfu Qian, Yuping Yan, Danxia Xu, Chuanhui Xu, Lihua Fu, Baofeng Lin
  • 更新日期:2019-11-13
  • Chitosan as a potential alternative to collagen for the development of genipin-crosslinked scaffolds
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-12
    V. Perez-Puyana, J.F. Rubio-Valle, M. Jiménez-Rosado, A. Guerrero, A. Romero

    Tissue Engineering emerged as a research field to solve problems derived from the loss of tissue and organ failure, specifically through the development of scaffolds. In this work, scaffolds were manufactured using collagen and chitosan as raw materials, evaluating the potential use of the latter as a substitute for collagen. Throughout this work, different proportions of these raw materials were used, and the influence of genipin (crosslinking agent) was evaluated, studying the variations in the mechanical and morphological properties of the scaffolds. The results obtained show that the properties of the scaffolds were strongly dependent on the biopolymer concentration used and on the concentrations of crosslinking agent. According to the results, the best mechanical properties were obtained for hybrid systems with high biopolymer concentrations (2 wt%), especially chitosan. Furthermore, the addition of a small amount of crosslinking agent (genipin) improved low biopolymer concentration systems (1 wt%), showing an improvement in the critical strain.

  • Zinc heterocyclic vinyl complexes and their gamma-irradiated derivatives: From the metal to antimicrobial materials
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-09
    Felipe López-Saucedo, Noé Zúñiga-Villarreal, Guadalupe G. Flores-Rojas, Diego Martínez-Otero, Beatríz Magariños, Emilio Bucio
  • Aminobenzothiazole-substituted cyclotriphosphazene derivative as reactive flame retardant for epoxy resin
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-09
    Jianwen Cheng, Jun Wang, Shuang Yang, Qianqian Zhang, Yefa Hu, Guoping Ding, Siqi Huo

    Aminobenzothiazole-substituted cyclotriphosphazene derivative (ABCP) was successfully synthesized and used as reactive flame retardant to improve the fire safety of epoxy resin (EP). The chemical structure of ABCP was confirmed by Fourier transform infrared spectroscopy (FTIR), 1H and 31P nuclear magnetic resonance (NMR), high-resolution mass spectroscopy (HR-MS) and elemental analysis (EA). The curing behavior, thermal stability, thermo-mechanical property and flame retardancy of the prepared EP systems were studied. The differential scanning calorimeter (DSC) results indicated that ABCP induced the anionic polymerization of EP and facilitated the addition reaction between EP and 4,4′-diamino-diphenyl sulfone (DDS). The thermogravimetric analysis (TGA) results indicated that ABCP accelerated the thermal degradation of EP matrix and contributed to the formation of more residual chars with better thermo-oxidative stability. The dynamic mechanical analysis (DMA) results indicated that EP/DDS/ABCP thermosets exhibited higher storage modulus at 50 °C and their glass transition temperature (Tg) values were slightly reduced by 6–10 °C, in comparison with EP/DDS thermoset. The combustion test results revealed the fire hazards of EP/DDS/ABCP thermosets were effectively reduced. Compared with EP/DDS thermoset, the limiting oxygen index (LOI) value of EP/DDS/ABCP-1.2 thermoset was increased to 31.2% and the sample passed UL94 V-0 rating; the average of heat release rate (av-HRR), peak of heat release rate (pk-HRR) and total heat release (THR) values of EP/DDS/ABCP-1.2 thermoset were reduced by 36.5%, 53.7% and 34.5%, respectively; particularly, the fire growth rate (FIGRA) of EP/DDS/ABCP-0.6 thermoset was reduced by half. The research on flame retardant mechanism disclosed that ABCP played dominated flame retardant effect in condensed phase.

  • Tri-functional phthalonitrile monomer as stiffness increasing additive for easy processable high performance resins
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-09
    M.V. Yakovlev, O.S. Morozov, E.S. Afanaseva, B.A. Bulgakov, A.V. Babkin, A.V. Kepman

    A new tri-functional phthalonitrile monomer tris(3-(3,4-dicyanophenoxy)phenyl) phosphate (TPP) was first synthesized and characterized with the intent of increasing the cross-linking rate of phthalonitrile resins. By combining TTP and di-functional phthalonitrile with aromatic diamine easy-processable formulations (η < 200 mPa·s at 150 °C) were developed. Thermosets were derived from the formulations by curing at 330 and 375 °C. The polymers that were post-cured at 375 °C demonstrated Young's moduli up to 7.2 GPa — which is the highest value reported for phthalonitriles. Thermal stability of these materials was on the high level featured to phthalonitriles (Tg > 450 °C, T5% > 500 °C, TOS5% > 500 °C, Yc at 900 °C > 80%). TPP, the introduced monomer, can be used as a stiffness increasing additive with common di-functional phthalonitriles, and easy-processable formulations for cost-effective techniques of composites manufacturing.

  • Semi-aromatic thermosetting polyimide resins containing alicyclic units for achieving low melt viscosity and low dielectric constant
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-09
    Zhen-he Wang, Guang-Qiang Fang, Jian-jun He, Hai-xia Yang, Shi-yong Yang

    Semi-aromatic thermosetting polyimide resins containing alicyclic units were prepared by the polymerization of 1,2,4,5- cyclohexanetetrcarboxylic dianhydride (HPMDA), aromatic diamines and nadic anhydride (NA) served as reactive capping agent. To obtain the homogeneous poly (amic ester) (PAE) matrix resins, the 2-methoxyethanol (EGME) was used to esterify HPMDA. The chemical structure of PAE resins dried at different temperatures were characterized in detail by FT-IR, 1H NMR and TGA-GCMS. Compared with the full-aromatic API-1, the alicyclic units with less Pi(π) bonds and twisted structure endow the semi-aromatic PI resins with loose polymer chains packing and weak intermolecular forces, which contribute to low melt viscosities, good solubility and excellent dielectric properties. The cured semi-aromatic PI resins show low dielectric constants ranging from 2.8 to 3.0 and dielectric loss of <0.01 at a range of frequencies from 1GHz to 12GHz. The results indicate the semi-aromatic thermosetting PI resins are promising dielectric interlayer materials for high frequency substrates.

  • Triptycene based fluorescent polymers with azo motif pendants: Effect of alkyl chain on fluorescence, morphology and picric acid sensing
    React. Funct. Polym. (IF 3.074) Pub Date : 2019-11-06
    Mosim Ansari, Atikur Hassan, Akhtar Alam, Achintya Jana, Neeladri Das

    A design and synthesis of three unique triptycene based polymers containing azo linkages in the side chain of polymer backbone is being reported herein for the first time. These triptycene based azo-polymers (TBAPs) have high solubility in common organic solvents due to presence of pendent alkyl chains as well as triptycene motif. TBAPs are well characterized by GPC, TGA, 1H NMR, FTIR, PXRD, FESEM, UV and fluorescence spectroscopy. Polymers with azo-linkage are generally non-fluorescent. However, TBAPS are fluorescent in nature which makes them unique. It was observed that TBAFP3 having the longest pendent alkyl chain is most fluorescent when compared with TBAP1 and TBAP2 (which have smaller pendent alkyl chains). Furthermore, TBAPS have been applied for the detection of trace quantities of PA in THF. The binding constants of TBAPS with PA are in the order of 105 M−1 and the PA can be detected even in nanomolar concentrations. It was observed that TBAP1 having the smallest pendent alkyl chain has the highest binding affinity for PA relative to TBAP2 and TBAP3 (having longer pendent alkyl chains). Further, the effect of the chain length on the supramolecular assembly of these polymers was observed using FESEM. The size of domains present in polymer films was found to increase with increasing chain length of alkyl group.

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上海纽约大学William Glover