Acetoacetoxy functionalized natural rubber latex capable of forming cross-linkable film under ambient conditions

This work demonstrates that natural rubber (NR) latex particles containing acetoacetoxy (AcAc) groups are able to undergo cross-linking upon film formation at ambient temperature by reaction with glutaraldehyde (GTA). Natural rubber latex grafted with poly(acetoacetoxyethyl methacrylate) (NR-g-PAAEM) was synthesized by seeded emulsion polymerization, using benzoyl peroxide (BPO) as an initiator in free radical polymerization. The degree of grafting of PAAEM in the graft copolymers was evaluated by ¹H NMR technique. Transmission electron microscope (TEM) was used for investigation the particle morphology of the grafted NR latex. Since the AcAc groups are intentionally attached to the NR particles providing sites of cross-linking at ambient temperature, the cross-linking ability of these sites by reaction with GTA was then investigated. The results revealed that the latex film of NR-g-PAAEM with the addition of GTA had a much higher tensile strength in comparison with the film without GTA. The surface morphology of the NR-g-PAAEM latex film formed in the absence and presence of the GTA cross-linker was also investigated using atomic force microscopy (AFM). By GTA addition into the NR-g-PAAEM latex before film formation, an increase in the root-mean-square (RMS) roughness of the surface of the latex film was observed. Moreover, it was also observed that the NR-g-PAAEM films with the addition of GTA had higher activation energy for thermal degradation than that without the cross-linker. This confirms that the cross-linking reaction took place in the NR-g-PAAEM latex film as a result of its reaction with the GTA.     

Influence of ether bond on degradation property of PBS-based copolymers at molecular level using molecular simulations

In order to understand the relationship between enzymatic degradation and the structure of PBS-based copolyesters PBS-co-DEGS and PBS-co-BDGA modified with monomers (diethylene glycol and diglycolic acid) were synthesized and the enzymatic degradation property was studied. Pseudomonas cepacia lipase was selected as the catalyst, while the chloroform was used as solvent. The results indicated that both PBS-co-DEGS and PBS-co-BDGA can be catalytically degraded by PC lipase but they were different. The hydrolysis of PBS-co-BDGA improved greatly and the degree of hydrolysis of PBS-co-BDGA was almost consistent with the degree of degradation due to the introduction of DGA. Similarly, thermal property changes were also observed with a decrease of the decomposition temperature of 5 and 50% sample in most cases. The enzymatic degradation of PBS-based copolymers produced not only linear segments, but also cyclic oligomers. Furthermore, PBS-co-BDGA generated more oligomers than PBS-co-DEGS. According to the results of molecular docking, the free energy of binding between PCL and the substrate in chloroform was in the order BDGAB > DEGSDEG > BSB. That is, the docking of the substrate containing BDGA in the active site of PCL was more stable than any other ones.     

Swelling and auramine-<Emphasis Type="Italic">O</Emphasis> adsorption of carboxymethyl cellulose grafted poly(methyl methacrylate)/Cloisite 30B nanocomposite hydrogels

Carboxymethyl cellulose (CMC) grafted poly(methyl methacrylate)/Cloisite 30B nanocomposite hydrogels were prepared for adsorptive removal of auramine-O (as a cationic dye model) from wastewater. For the synthesis of nanocomposite hydrogel by free radical polymerization method, potassium persulfate (KPS), methyl methacrylate (MMA), N,N′-methylene bisacrylamide (MBA) and Cloisite 30B were used as initiator, monomer, cross-linker and nano-filler, respectively. The nanocomposite hydrogels were characterized by FTIR, TGA, SEM and XRD techniques. The FTIR results showed that the monomer was grafted onto carboxymethyl cellulose chains successfully. Swelling behavior of nanocomposite hydrogel as a function of KPS, MBA, MMA concentration and CMC/Cloisite 30B weight ratio was studied by Taguchi method using Minitab 16 software. According to ANOVA results, the most effective factor of equilibrium swelling of nanocomposite hydrogel was CMC/Cloisite 30B weight ratio. Addition of Cloisite 30B to hydrogel up to a certain amount improved swelling, though its high amount decreased swelling. The effects of pH and ionic strength on swelling of optimum hydrogels were investigated. Maximum swelling of nanocomposite hydrogel occurred at pH 7.0. The kinetic data of adsorption fitted well to pseudo-second-order model. The best isotherm for investigation of adsorption mechanism was Langmuir model suggesting the formation of a monolayer on the adsorbent surface. FTIR results, before and after auramine-O adsorption, showed that complexation is the main mechanism of adsorption. High adsorption capacity of nanocomposite hydrogels made them more efficient in wastewater treatment application.     

Novel amphiphilic temperature responsive graft copolymers PCL-<Emphasis Type="Italic">g</Emphasis>-P(MEO<Subscript>2</Subscript>MA-<Emphasis Type="Italic">co</Emphasis>-OEGMA) via a combination of ROP and ATRP: synthesis,characterization, and sol-gel transition

A series of well-defined novel amphiphilic temperature-responsive graft copolymers containing PCL analogues P(αClεCL-co-εCL) as the hydrophobic backbone, and the hydrophilic side-chain PEG analogues P(MEO₂MA-co-OEGMA), designated as P(αClεCL-co-εCL)-g-P(MEO₂MA-co-OEGMA) have been prepared via a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The composition and structure of these copolymers were characterized by ¹H NMR and GPC analyses. The self-assembly behaviors of these amphiphilic graft copolymers were investigated by UV transmittance, a fluorescence probe method, dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses. The results showed that the graft copolymers exhibited the good solubility in water, and was given the low critical temperature (LCST) at 35(±1) °C, which closed to human physiological temperature. The critical micelle concentrations (CMC) of P(αClεCL-co-εCL)-g-P(MEO₂MA-co-OEGMA) in aqueous solution were investigated to be 2.0 × 10^?3, 9.1 × 10^?4 and 1.5 × 10^?3 mg·mL^?1, respectively. The copolymer could self-assemble into sphere-like aggregates in aqueous solution with diverse sizes when changing the environmental temperature. The vial inversion test demonstrated that the graft copolymers could trigger the sol-gel transition which also depended on the temperature.     

Synthesis,characterization and adsorption of cationic dyes by CS/P(AMPS-<Emphasis Type="Italic">co</Emphasis>-AM) hydrogel initiated by glow-discharge-electrolysis plasma

In this work, a novel chitosan/P(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylic amide) (CS/P(AMPS-co-AM)) hydrogel was successfully prepared by a simple one-step method using glow-discharge-electrolysis plasma (GDEP) initiated copolymerization, in which N,N′-methylenebisacrylamide was used as a cross-linking agent. A copolymerization mechanism of AMPS and AM onto CS initiated by GDEP was proposed. The structure, thermal stability and morphology of CS/P(AMPS-co-AM) hydrogel were characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD), TG/DTG, and scanning electron microscope (SEM). This hydrogel was employed as an absorbent for the removal of methylene blue (MB) and malachite green (MG) from aqueous solutions. The effects of pH, contact time and equilibrium concentration on the dye adsorption were investigated batchwise. FTIR and XRD indicated that AM and AMPS were grafted onto the CS backbone successfully, forming copolymer. TG/DTG suggested that grafted AMPS and AM onto CS could change the thermal stability of the CS. SEM showed a unique three-dimensional porous structure for the CS/P(AMPS-co-AM) hydrogel. The optimum pH for the removal of cationic dyes was 5.8, and time of adsorption equilibrium was achieved in 90 min. The CS/P(AMPS-co-AM) hydrogel exhibited a very high adsorption potential, and its adsorption capacities calculated based on the Langmuir isotherm for MB and MG were 1,538.5 and 917.4 mg g^?1, respectively. The dye adsorption data fitted well to the pseudo-second-order model and Langmuir model at 25 °C with pH 5.8.     

Properties of Thermoresponsive N-maleyl gelatin-co-P(N-isopropylacrylamide) hydrogel with ultrahigh mechanical strength and self-recovery

Thermo-responsive polymer hydrogels with superior strength and toughness are potential candidate materials in biomedical field, such as drug delivery system and tissue engineering. By introducing maleylgelatin (MAGEL) into the conventional PNIPAAm hydrogel, a series of composite P(NIPAAm-co-MAGEL) hydrogels with combined features were fabricated. Thermo-responsive behaviors, equilibrium swelling ratio (ESR), compression strength, tensile strength (TS) and elongation at-break (E), cyclic compression tests, and thermal stability properties of hydrogels with different amount of MAGEL were investigated. Experimental data indicated that the amount of MAGEL could modulate the mechanical property of the composite hydrogel. With the increase of the MAGEL contents from 0 to 50%, the composite hydrogel with relatively high water content possessed good compressive strength, tensile strength and stretrability. Only when the weight ratio of MAGEL/NIPAAm was 30:70, did the P(NIPAAm-co-MAGEL) have a homogeneous distribution and stable 3D networks which played a significant role in the properties of the hydrogels. Cyclic compression tests results indicated that P(NIPAAm-co-MAGEL) hydrogel had an excellent thermo-reversible ability. This research would expand the scope of the PNIPAAm hydrogel applications.     

Synthesis of all-acrylic graft copolymers by grafting-through strategy in emulsion

In this paper, PnBA-g-PMMA brush-like and centipede multigraft copolymers were synthesized via DPE seeded emulsion polymerization and miniemulsion polymerization. PMMA macromonomers with single tail and double tails were prepared by DPE-technique in emulsion and Steglich esterification. Then PnBA-g-PMMA multigraft copolymers were obtained by miniemulsion copolymerization. The molecular weight and polydispersity indices of PMMA macromonomers and graft copolymers were characterized by GPC. The structural characteristics, weight content of PMMA and the number of grafting sites in brush-like and centipede multigraft copolymers were determined by ¹H NMR. The thermal performance of graft copolymers were analyzed by DSC and TGA. AFM confirmed microphase separation between PnBA block and PMMA block.     

A new method in designing compatibility and adhesion of EVA/PMMA blend by using EVA-<Emphasis Type="Italic">g</Emphasis>-PMMA with controlled graft chain length

Atom transfer free radical polymerization (ATRP) was employed in a synthesis of graft polymer EVA-g-PMMA with controlled length of side PMMA chains. Three steps of synthesis: partial hydrolysis of EVA, esterification with chloroacetyl chloride and ATRP grafting were performed to produce EVAOH, macroinitiator EVACl and grafted polymers G8020 (EVA/PMMA?=?80/20 wt%) and G6040 (EVA/PMMA?=?60/40 wt%). FTIR, Raman and NMR spectroscopy were used in the determination of the chemical structure and modification of EVA. Transmitted light and dark field microscopy showed higher affinity for coil formation of EVA-g-PMMA with longer PMMA side chains, i.e. G6040 compatibilizer. Morphological, thermal and adhesive properties of optical fiber adhesives of graft polymers and polymer blends poly(ethylene-co-vinyl acetate)-blend-poly(methyl methacrylate) (EVA/PMMA) compatibilized with 1 wt% of EVA-g-PMMA, were studied. Image analysis of SEM micrographs showed effective compatibilization with short grafted chains (G8020) that was indicated by lower porosity characteristics. TG/DTG analysis enabled determination of degree of hydrolysis and amount of chloro-functionalized groups. DSC analysis showed higher thermal stability of G8020 polymer. Single lap joint of adhesives/optical fibers were subjected to adhesive testing and obtained results for maximal force applied and adhesive failure suggested the visible influence of the length of graft chains on adhesion.     

Development of natural and synthetic polymer-based semi-interpenetrating polymer network for controlled drug delivery: optimization and in vitro evaluation studies

This research paper describes the development, optimization and in vitro characterization of chemically cross-linked pectin–polyvinyl alcohol-co-poly(2-Acrylamido-2-methylpropane sulfonic acid) semi-interpenetrating polymer network hydrogel [pectin–PVA-co-poly(AMPS) semi-IPN hydrogel] for controlled delivery of model drug tramadol HCl. Response surface methodology based on 3² factorial design was used for optimization and investigating the effect of independent factors: polymer-blend ratio (pectin:PVA = X ₁) and monomer (AMPS = X ₂) concentration on the dependent variables, swelling ratio (q _18th), percent drug release (R _18th, %), time required for 80 % drug release (t _{80 %}, h), drug encapsulation efficiency (DEE, %) and drug loaded contents (DLC, mg/g) in pectin-PVA-co-poly(AMPS) gels prepared by free radical polymerization. The optimized semi-IPN gel (FPP-10) showed controlled in vitro drug release (R _18th) of 56.34 % in 18 h, t _{80 %} of 30 h, and DEE of 23.40 %. These semi-IPN hydrogels were also characterized through SEM, FTIR, sol–gel analysis, swelling studies and drug release characteristics. Therefore, this newly synthesized polymeric network could be a potential polymeric system for controlled drug delivery of tramadol HCl for prolonged drug release.     

Specific rebinding of protein imprinted polyethylene glycol grafted calcium alginate hydrogel with different crosslinking degree

Bovine serum albumin imprinted polyethylene glycol 600 (PEG600) grafted Calcium alginate (CaA) hydrogel microspheres were prepared and characterized. The adsorption and recognition properties of PEG600 grafted calcium alginate (CaA-g-PEG600) microspheres were evaluated and the results showed that the crosslinking structure of CaA-g-PEG600 microspheres exerted an obvious effect on the adsorption capacity and imprinting properties for bovine serum albumin. The adsorption isotherms and recognition properties indicated that the imprinted modified microspheres had excellent rebinding affinity toward target proteins and the imprinting efficiency varied according to PEG600 grafting degree. The adsorption capacity and the imprinting factor were 5.5 mg g^?1 and 3.6, respectively. Adsorption kinetics of CaA-g-PEG600 microspheres in accordance with the molecular weight between crosslinks (Mc) was investigated and the structural influence on protein selective rebinding was discussed. Furthermore, the binary solution separation performance of CaA-g-PEG600 microspheres with different Mc was investigated by selective binding bovine serum albumin from protein mixture solution.     

Synthesis of novel polymer brushes of poly(acrylonitrile-<Emphasis Type="Italic">g</Emphasis>-<Emphasis Type="Italic">N,N</Emphasis>ʹ-dimethylaminoethyl methacrylate) by nitrile modification

Functional polymer brushes of poly(acrylonitrile-g-N,N?-dimethylaminoethyl methacrylate) were efficiently synthesized by a novel approach of combining Cu(0)-mediated controlled/“living” radical polymerization and nitrile click chemistry. The poly(acrylonitrile-g-N,N?-dimethylaminoethyl methacrylate) as a promising material exhibited excellent hydrophile–lipohile balance in the process of self-assembly and could autonomously develop the orderly structure micelle in N,N?-dimethylformamide/water mixture solvent for the potential application of a new drug delivery carrier. In the process of self-assembly, polyacrylonitrile acted as a backbone of the functional polymer brushes due to its hydrophobic feature and poly(N,N?-dimethylaminoethyl methacrylate) as the branch of functional polymer brushes due to its hydrophilic characteristic, which both were prepared by Cu(0)-mediated controlled/“living” radical polymerization with ethyl-bromoisobutyrate as initiator. Poly(N,N?-dimethylaminoethyl methacrylate) containing azide end group was synthesized by substitution reaction of poly(N,N?-dimethylaminoethyl methacrylate) containing bromine end groups with sodium azide in N,N?-dimethylformamide. The click reaction between the nitrile of polyacrylonitrile and the azide group of poly(N,N?-dimethylaminoethyl methacrylate) was carried out under ammonium chloride as catalyst in N,N?-dimethylformamide. The polymer was further confirmed by GPC, FTIR, ¹H NMR and TGA. Meanwhile, the micelles with different morphologies were observed by TEM, and the particle diameter distribution of self-assembled micelle from the PAN-g-PDMAEMA brushes was determined by DLS.     

Chemical structure and remarkably enhanced mechanical properties of chitosan-graft-poly(acrylic acid)/polyacrylamide double-network hydrogels

The novel double-network (DN) hydrogels were prepared using the chitosan-g-poly(acrylic acid) as the first network, and polyacrylamide as the second. The effects of the concentrations of the second network on chemical structure, intermolecular interactions and mechanical properties for the DN gels were investigated. The DN hydrogels had decreased swelling capacities and significantly improved glassy modulus and strength with the increase of the acrylamide concentration, owing to the enhanced intermolecular interaction and physical entanglement, and reduced molecular motion. It is worth noting that DN hydrogels with 5.50 mol/L acrylamide content had the greatest mechanical strength and still relatively high water content (~82 wt%), resulting from the effectiveness of the intermolecular penetration and intermolecular interactions between two independent polymer networks. Therefore, the reported novel chitosan-based DN hydrogels exhibit good potentials in some applications, for example biomedical engineering applications.     

Synthesis and self-assembly behavior of POSS tethered amphiphilic polymer based on poly(caprolactone) (PCL) grafted with poly(acrylic acid) (PAA) via ROP,ATRP, and CuAAC reaction

This investigation reports the preparation and self-assembly behavior of polyhedral oligomeric silsesquioxane (POSS) containing poly(caprolactone)-graft-poly(acrylic acid) (POSS-PCL-graft-PAA) polymer. This article focuses on the self-assembly behavior of POSS tethered amphiphilic graft copolymer. In this investigation, POSS tethered alkyne functionalized polycaprolactone (PCL) was prepared by strategic ring opening polymerization (ROP) of ε-caprolactone and α-propargyl-ε-caprolactone using hydroxyl-terminated POSS as an initiator. Azide-terminated poly(tert-butyl acrylate) (P ^t BA) was grafted onto functional PCL via Cu-catalyzed azide-alkyne “click” (CuAAC) reaction. Finally, hydrolysis of the tert-butyl ester group into acid furnished the POSS tethered PCL-graft-PAA polymer. This amphiphilic graft copolymer was characterized by GPC, NMR, and FT-IR analyses and the morphology of the graft copolymer analyzed by HRTEM and FESEM analyses. On changing the graft copolymer concentration (low to high) in water, the morphology of the final graft copolymer changed from micelles to worm-like and core-shell. The structural motif of POSS plays an important role in this morphological transformation. The pH sensitivity was studied using DLS analysis as well as via release profile of rhodamine B as a model compound.     

Synthesis and swelling behavior of metal-chelating superabsorbent hydrogels based on sodium alginate-<Emphasis Type="Italic">g</Emphasis>-poly(AMPS-<Emphasis Type="Italic">co</Emphasis>-AA-<Emphasis Type="Italic">co</Emphasis>-AM) obtained under microwave irradiation

A metal-chelating superabsorbent hydrogel based on poly(2-acrylamido-2-methylpropanesulfonic acid-co-acrylic acid-co-acrylamide) grafted onto sodium alginate backbone, NaAlg-g-poly(AMPS-co-AA-co-AM) is prepared under microwave irradiation. The Taguchi method is used for the optimization of synthetic parameters of the hydrogel based on water absorbency. The Taguchi L₉ (3⁴) orthogonal array is chosen for experimental design. Mass concentrations of crosslinker MBA \(C_{\text{MBA}}\) initiator KPS \(C_{\text{KPS}}\), sodium alginate \(C_{\text{NaAlg}}\) and mass ratio of monomers \(C_{\text{AM/AA/AMPS}}\) are chosen as four factors. The analysis of variance of the test results indicates the following optimal conditions: 0.8 g L^?1 of MBA, 0.9 g L^?1 of KPS, 8 g L^?1 of NaAlg and \(R_{\text{AM/AA/AMPS}}\) equals to 1:1.1:1.1. The maximum water absorbency of the optimized final hydrogel is found to be 822 g g^?1. The relative thermal stability of the optimized hydrogel in comparison with sodium alginate is demonstrated via thermogravimetric analysis. The prepared hydrogel is characterized by FTIR spectroscopy and scanning electron microscopy. The influence of the environmental parameters on water absorbency such as the pH and the ionic force is also investigated. The optimized hydrogel is used as adsorbent for hazardous heavy metal ions Pb(II), Cd(II), Ni(II) and Cu(II) and their competitive adsorption is also discussed. Isotherm of adsorption and effect of pH, adsorption dosage and recyclability are investigated. The results show that the maximum adsorption capacities of lead and cadmium ions on the hydrogel are 628.93 and 456.62 mg g^?1, respectively. The adsorption is well described by Langmuir isotherm model. The hydrogel is also utilized for the loading of potassium nitrate as an active agrochemical agent and the release of this active agent has also been investigated.     

Micellization and sol-gel transition of novel thermo- and pH-responsive ABC triblock copolymer synthesized by RAFT

A well-defined thermo- and pH-responsive ABC-type triblock copolymer monomethoxy poly(ethylene glycol)-b-poly(2-(2-methoxyethoxy) ethyl methacrylate-co-N-hydroxymethyl acrylamide)-b-poly(2-(diethylamino) ethyl methacrylate), mPEG-b-P(MEO₂MA-co-HMAM)-b-PDEAEMA, was synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT). The ABC-type triblock copolymer was endowed thermo- and pH-responsive, corresponding to the thermosensitive properties of P(MEO₂MA-co-HMAM) and pH-responsive properties PDEAEMA segments, respectively. The thermo- and pH-responsive properties of copolymer aqueous solutions were studied by UV transmittance measurements, dynamic light scattering (DLS), transmission electron microscopy (TEM). The results showed that the N-hydroxymethyl acrylamide (HMAM) content in triblock copolymer affected the lower critical solution temperature (LCST) of the triblock copolymer aqueous solution. The copolymer self-assembled into core-shell micelles, with the thermoresponsive P(MEO₂MA-co-HMAM) block and the hydrophilic PEG block as the shell, the hydrophobic PDEAEMA block as the core, in alkaline solution at room temperature. While in acidic media, when the temperature above the lower critical solution temperature (LCST) of the triblock copolymer aqueous solution, the copolymer self-assembled into P(MEO₂MA-co-HMAM)-core micelles with mixed hydrophilic PEG and pH-responsive PDEAEMA coronas. Sol-gel transition temperature (T_sol-gel) for the triblock copolymer determined by vial inversion test further indicated that it is dependent on the concentration of the triblock copolymers and solution pH. Copolymer hydrogel loaded with bovine serum albumin (BSA) were used for the sustained release study. The results indicated that the hydrogel was a promising candidate for controlling protein drug delivery.     

New hybrid agarose/Cu-Bioglass® biomaterials for antibacterial coatings

Agarose hydrogels, combined with 45S5 Bioglass®, were elaborated to serve as copper delivery systems. Our aim was to study the antibacterial properties of these hydrogels. The results show that the amount of glass does not influence the stiffness properties, but it improves the hydrophilicity and the swelling profile of agarose hydrogel. Two bacterial strains, Bacillus sp. 4J6 and Pseudomonas aeruginosa sp. PAO1, were chosen. Their retention on the substrates was analyzed by confocal laser scanning microscopy. The mechanical characteristics and the release of copper have an effect on the bacterial adhesion and the biofilm formation. All the obtained results indicate that these hydrogels could be adapted to a potential application to the antibacterial coatings     

Effect of epoxidized soybean oil grafted poly(12-hydroxy stearate) on mechanical and thermal properties of microcrystalline cellulose fibers/polypropylene composites

A new green compatibilizer named epoxidized soybean oil grafted poly(12-hydroxy stearate) (ESO-g-PHS) was successfully synthesized using 12-hydroxy stearic acid and epoxidized soybean oil (ESO). The chemical structure of ESO-g-PHS was investigated through Fourier transformed infrared spectroscopy, thermogravimetric analysis, and gel permeation chromatography. ESO-g-PHS was used as a compatibilizer to enhance the interfacial compatibility between polypropylene (PP) and microcrystalline cellulose fibers (MCF). The results showed that the impact strength and tensile strength were 33.55 and 27.57 MPa when the content loading of MCF reached 10 wt% and ESO-g-PHS was 4 wt%, which enhanced by 75.4 and 30.04 %, respectively, compared to that of composites without ESO-g-PHS. In addition, the SEM images of the fracture surfaces display that PP was highly bonded to MCF with ESO-g-PHS treated. In addition, the wide angle X-ray diffraction measurement revealed that the addition of ESO-g-PHS did not change the crystal structure of PP. Moreover, there was a slight improvement in thermal properties for PP composites with the addition of ESO-g-PHS.     

Synthesis and electrospinning of well-defined polymer brushes by modification of polyacrylonitrile

As one of the most important precursors, polyacrylonitrile (PAN) and its functionality gained extensive attention but faced challenges in the preparation of nanofiber by electrospinning technology. Herein, poly(acrylonitrile-g-ethylene alcohol) (PAN-g-PEG) were succussfuly synthesized by the modification of PAN, using the methods of Click Chemistry and Mitsunobu reaction sequentially. Firstly, well-defined PAN was prepared by Cu(0)-mediated controlled/living radical polymerization with a molar ratio of [AN]₀:[EBiB]₀:[Cu]₀:[TEMED]₀?=?500:1:1:2. Tetrazole-containing PAN was then successfully modified by nitrile-Click Chemistry, which sodium azide and ammonium chloride was used as substrate and catalyst, respectively. Using Mitsunobu reaction, PAN-g-PEG was obtained from tetrazole-containing PAN and poly(ethyl alcohol) with the catalyst of diethyl azodicarboxylate and triphenylphosphine. After typical characterization, PAN-g-PEG nanofiber with the average diameter around 90 nm, was successfully prepared by electrospinning. The obtained PAN-g-PEG nanofiber has a smoother surface than PAN nanofiber, which suggests that a new modification approach of PAN nanofiber is successfully achieved.     

Biocompatibility and adsorption properties of hydrogels obtained by graft polymerization of acrylic acid on cellulose from rice hulls

Hydrogels constitute a group of cross-linked polymeric materials with the capability of swelling and retaining large amounts of water without dissolving. In this work, the hydrogels were obtained by grafting the acrylic acid on cellulose from rice hulls and cross-linking it with glycerol, ethylene glycol, and polyethylene glycol (M_w?=?200 and 10,000 g mol^?1). The samples were characterized using IR and Raman spectroscopy, the absence of the bands at 1636 and 1614 cm^?1 (in IR) and at 1659 and 1637 cm^?1 (in Raman), in the spectra of grafted cellulose and assigned to ν(C=C), indicated the polymerization process and the absence of the monomer residual. The cross-linking process was verified by the appearance of bands at 1090 cm^?1 (IR) and 996 cm^?1 (Raman), attributed to ν(C–O–C). Thermogravimetric analysis showed that the cross-linked sample with glycerol presented the lowest thermal stability. The molecular mass of CDClCC-g-AA was 55.56?±?5.21 kDa with an R² of 0.9741 and the CDClCC average particle size of 694 nm. The topography and the average roughness of the samples were obtained by atomic force microscopy and the samples that were cross-linked with the polyethylene glycol presented greater roughness. The degree of swelling was lower in the sample cross-linked with ethylene glycol, which was related to its higher degree of cross-linking. Finally, the biocompatibility of the samples was studied by analyzing the toxic effect of the samples on human embryonic kidney cells, where results showed that samples cross-linked with ethylene glycol were non-toxic.     

Investigation of the fast relaxation in glass-forming selenium by low-frequency Raman spectroscopy

The low-frequency Raman spectra of liquid and vitreous selenium are investigated. It is demonstrated that the temperature dependence of the intensity of the fast relaxation at the glass transition temperature (T _g = 308 K) exhibits a specific feature. This feature manifests itself in a sharper increase in the intensity at temperatures T > T _g as compared to that observed at lower temperatures. The intensities of the fast relaxation at the critical temperature T _c are evaluated by the extrapolation of the linear dependence to the temperature range T > T _g in the framework of the mode-coupling theory. The new results obtained for selenium are compared with the available data for other glass-forming materials (boron oxide, toluene, arsenic sulfide). It is shown that, for all the glasses under investigation, the parameter describing the contribution of the fast relaxation to the Raman spectrum takes on the same value at the critical temperature T _c and is approximately equal to 0.3.