Kappa carrageenan-g-poly (acrylic acid)/SPION nanocomposite as a novel stimuli-sensitive drug delivery system

In this article, a novel triple-stimuli hydrogel was prepared by simultaneous formation of super paramagnetic iron oxide nanoparticles (SPION) and crosslinking of poly (acrylic acid) grafted onto kappa carrageenan (κC-g-PAA). The structure, thermal stability, surface morphology, and magnetic property of the κC-g-PAA/SPION hydrogel were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy with energy dispersive X-ray analysis (SEM–EDAX), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM). Moreover, swelling capacity of the obtained hydrogel was measured at different temperature, pH, and magnetic-field to assess the sensitivity of κC-g-PAA/SPION hydrogel. This synthetic hydrogel was also examined as a controlled drug delivery system and defrasirox release was investigated at different temperature, pH, and magnetic-field. The in vitro antibacterial activity of κC-g-PAA/SPION hydrogel was studied against Escherichia coli and Staphylococcus aureus bacteria where the results showed no antibacterial activity of this new hydrogel. In vitro biocompatibility experiments were undertaken using human bladder epithelial cell line HTB 5637. These results indicated the synthesized κC-g-PAA/SPION hydrogel are nontoxic that will be useful for biomedical applications.

Full polysaccharide chitosan‐CMC membrane and silver nanocomposite: synthesis,characterization, and antibacterial behaviors

Chitosan‐carboxymethyl cellulose (CMC) full polysaccharide membrane was prepared by cross‐linking of chitosan with CMC dialdehyde and subsequent reductive amination. CMC dialdehyde molecule was prepared by periodate oxidation of CMC and then applied as a cross‐linking agent to form a new membrane network. The properties of oxidized CMC were investigated by various methods such as Fourier transform infrared (FT‐IR) spectroscopy, ¹H NMR spectroscopy, and viscosity test. Then, novel chitosan‐CMC silver nanocomposite was prepared using chitosan‐CMC as a carrier. The structure of the chitosan‐CMC membrane and the silver nanocomposite were confirmed by FT‐IR spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). TEM images indicate that the chitosan‐CMC nanocomposite comprises silver nanoparticles with diameters in the range of about 5–20 nm. The antibacterial studies of the nanocomposite were also evaluated. The chitosan‐CMC silver nanocomposite demonstrates good antibacterial activity against Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli. Copyright © 2016 John Wiley & Sons, Ltd.     

Colloidal nanocomposite hydrogel particles

Quaternary ammonium salt, (3-acrylamidopropyl)-trimethylammonium chloride was used to synthesize nanohydrogel and composite particles such as inorganic–organic hybrid composites and hydrogel nanoparticles with magnetic properties utilizing a water-in-oil microemulsion system. The positively charged cationic monomer was chosen to promote silica hydrolysis and condensation to prepare silica-hydrogel nanocomposite particles with interesting morphologies. It was shown that highly monodisperse, completely charged nanohydrogel can be used to encapsulate ferrite particles. Furthermore, it was also confirmed that cationic nanohydrogel particles with variant morphology can be prepared by employing suitable silica precursor. Morphology, structure, properties, and size of nanocomposite materials were explored utilizing transmission electron microscopy, atomic force microscopy, and vibrating sample magnetometer.     

An eco-friendly synthesis,characterization and antibacterial applications of novel almond gum – poly(acrylamide) based hydrogel silver nanocomposite

Polysaccharide based semi interpenetrating hydrogel (SIH) networks of cross-linked poly(acrylamide) was synthesised through an redox initiating free radical polymerization utilizing almond gum as a grafting backbone, N,N′– methylenebisacrylamide (MBA) as the cross-linker and ammonium persulphate (APS) – N,N,N′,N′-tetramethyl ethylenediamine (TEMED) as the redox initiator pair. Silver ions were introduced into the hydrogel matrix and silver nanoparticles of invariable size were developed insitu of the swollen hydrogel by the reduction of silver ions (Ag⁺) using azadirachta indica (neem) leaf extract. The prepared hydrogel - silver nanocomposite (HSN) was characterized by UV–visible diffused reflectance spectroscopy (DRS), fourier transform infrared spectroscopy (FT-IR), high resolution scanning electron microscopy (HR-SEM), energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA). The influence of pH on the swelling behavior of HSN was studied and the antibacterial activity of the developed nanocomposite was evaluated.     

Embedding magnetic nanoparticles into polysaccharide-based hydrogels for magnetically assisted bioseparation.

Based on the preparation of biocompatible polysaccharide-based hydrogels with stimuli-responsive properties by the copolymerization of maleilated carboxymethyl chitosan with N-isopropylacrylamide, novel magnetic hybrid hydrogels were fabricated by the in situ embedding of magnetic iron oxide nanoparticles into the porous hydrogel networks. Scanning electron microscopy (SEM) and thermogravimetric (TG) analyses showed that the size, morphology, and content of the iron oxide nanoparticles formed could be modulated by controlling the amount of maleilated carboxymethyl chitosan. As confirmed by X-ray diffractometry (XRD), equilibrium swelling ratio, and differential scanning calorimetry (DSC) measurements, the embedding process did not induce a phase change of the magnetic iron oxide nanoparticles, and the resultant hybrid hydrogels could retain the pH- and temperature-responsive characteristics of their hydrogel precursors. By investigating the partition coefficients of bovine serum albumin as a model protein, this magnetic hydrogel material was found to hold a potential application in magnetically assisted bioseparation.     

Preparation of thermoresponsive and pH-sensitivity polymer magnetic hydrogel nanospheres as anticancer drug carriers

In this work, a novel thermo and pH responsive magnetic hydrogel nanosphere poly(N-isopropylacrylamide-co-acrylic acid)/Fe(3)O(4) (poly(NIPAAm-co-AA)/Fe(3)O(4)) has been successfully prepared. The magnetic hydrogel nanospheres with thermo and pH-sensitivity were characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS), Fourier transform infrared-spectrometer (FT-IR), UV-vis absorption spectroscopy, and vibrating sample magnetometer (VSM). The magnetic hydrogel nanospheres exhibited uniform sphere structures and superparamagnetic property. Finally, the drug loading capacities and the releasing behavior of the magnetic hydrogel nanospheres were investigated with doxorubicin hydrochloride (DOX) as an anticancer drug model. The resulting magnetic hydrogel nanospheres exhibited high encapsulation efficiency (95%) to DOX under an appropriate condition. In vitro release experiments revealed that release was faster at pH 5.3 (37°C) than at pH 7.4 (25°C) or pH 7.4 (37°C). The DOX-loaded magnetic hydrogel nanospheres also showed enhanced anticancer effect compared with the free drug in vitro. These presented results suggested that the magnetic hydrogel nanospheres have a potential as tumor targeting drug carrier.     

磁微球负载氯化血红素仿酶催化剂制备及催化降解DMP

采用超声辅助反向共沉淀法制得磁纳米Fe3O4颗粒,然后以磁纳米Fe3O4颗粒为种子采用种子乳液聚合法制得羟基功能化的磁纳米复合物微球,再以三聚氯氰为桥联剂键合氯化血红素制得磁微球负载氯化血红素仿酶催化剂.利用傅里叶变换红外光谱仪（FT-IR）、配置积分球的紫外-可见（UV-Vis）分光光度计、透射电子显微镜（TEM）、热重分析仪（TGA）和振动样品磁强计（VSM）对催化剂进行了表征.结果表明,催化剂粒径大小为10～12 nm,粒度均一,分散性好,在300 K下具有一定顺磁性,饱和磁化强度为21.61 emu/g,磁性物质含量为52.50%.催化剂在紫外光照和H2O2存在下对水中邻苯二甲酸二甲酯（DMP）有较高的氧化降解活性,且重复使用效果较好.     

Studies on anticancerious and photocatalytic activity of carboxymethyl cellulose-cl-poly(lactic acid-co-itaconic acid)/ZnO-Ag nanocomposite

In this paper, the microwave-assisted synthesis of carboxymethyl cellulose-cl-poly(lactic acid–co-itaconic acid)/ZnO-Ag nanocomposite [CMC-cl-p(LA-co-IA)/ZnO-Ag] has been discussed. Lactic acid (LA) and itaconic acid (IA) monomers were grafted onto carboxymethyl cellulose (CMC) using potassium persulphate and N, N^'-methylene-bis-acrylamide (MBA) as initiator and crosslinker, respectively at optimized conditions of temperature and pressure. The nanocomposite was characterized using different techniques such as Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and energy dispersive X-ray (EDX). XRD, TEM and FTIR spectral analysis confirmed the formation of the nanocomposite. The release of amoxicillin drug-using nanocomposite as a function of pH and time has been investigated. The maximum drug release of 94.64% was pragmatic at pH 2.2 after 6 h. The degradation of congo red using nanocomposite followed the pseudo-first-order reaction model with the regression coefficient (R²) values of 0.99312. The nanocomposite was also explored for anticancer behavior against yeast cells.     

羧甲基纤维素钠/聚(N-异丙基丙烯酰胺)纳米复合水凝胶的制备及结构性能表征

以无机粘土为交联剂制备了具有温度、pH双重敏感特性的羧甲基纤维素钠/聚(N-异丙基丙烯酰胺)/粘土半互穿网络纳米复合水凝胶(CMC/PNIPA/Clay semi-IPN),并通过红外和透射电镜对其结构和形态进行了表征。在酸性(pH=1.2)和20℃条件下,分别研究了温度和不同pH缓冲液对该凝胶溶胀度的影响,测定了复合水凝胶的力学性能。结果表明:水凝胶中的粘土被剥离成单片层,且均匀分散在凝胶网络中,起交联剂的作用,而CMC以线性大分子的形态存在;CMC/PNIPA/Clay具有良好的温度、pH双重敏感特性;凝胶的断裂伸长率>1 000%。     

Synthesis,structural and optical properties of tin oxide nanoparticles and its CMC/PEG–PVA nanocomposite films

Polyethylene glycol–polyvinyl alcohol (PEG–PVA) blend is a multifunctional material and controlling its properties is important for various medical and industrial uses. In this paper, we report the influence of carboxymethyl cellulose (CMC) and doping with tin oxide (SnO₂) nanoparticles (NPs) on the structural and optical properties of PEG–PVA. The prepared samples were investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and UV–Vis-NIR spectroscopies. SnO₂ NPs of rutile structure, average crystallite size of ～30.2 nm and optical band gap (E_g) of 3.68 eV were prepared by a simple sol–gel process. CMC addition enhances the crystallinity of PEG–PVA that then gradually reduced by increasing SnO₂ doping ratio. The optical transmittance of PEG–PVA increased from 77 to 90% after mixing with CMC and then decreased to 64% with increasing SnO₂ content to 1.5%. Also, the E_g of PEG–PVA increased from 5.20 to 5.28 eV and then decreased to 4.88 eV due to CMC addition and SnO₂ incorporation, respectively. The refractive index, the dispersion parameters and the optical conductivity of PEG–PVA, CMC/PEG–PVA and of its nanocomposite films are discussed. The correlation between the structural modifications and the resultant optical properties are reported.     

A novel sodium carboxymethylcellulose/poly(N‐isopropylacrylamide)/Clay semi‐IPN nanocomposite hydrogel with improved response rate and mechanical properties

A novel semi‐IPN nanocomposite hydrogel (CMC/PNIPA/Clay hydrogel) based on linear sodium carboxymethylcellulose (CMC) and poly(N‐isopropylacrylamide) (PNIPA) crosslinked by inorganic clay was prepared. The structure and morphology of these hydrogels were investigated and their swelling and deswelling kinetics were studied in detail. TEM images showed that the clay was substantially exfoliated to form nano‐dimension platelets dispersed homogeneously in the hydrogels and acted as a multifunctional crosslinker. The CMC/PNIPA/Clay hydrogels swell faster than the corresponding PNIPA/Clay hydrogels at pH 7.4, whereas they swell slower than the PNIPA/Clay hydrogels at pH 1.2. The CMC/PNIPA/Clay nanocomposite hydrogels showed much higher deswelling rates, which was ascribed to more passway formed in these hydrogels for water to diffuse in and out. The deswelling process of the hydrogels could be approximately described by the first‐order kinetic equation and the deswelling rate decreased with increasing clay content. The mechanical properties of the CMC/PNIPA/Clay nanocomposite hydrogels were analyzed based on the theory of rubber elasticity. It was found that with increasing clay content, the effective crosslink chain density, v_e, increased whereas the molecular weight of the chains between crosslinks M_c decreased. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1546–1555, 2008     

Synthesis of polymer-stabilized magnetic nanoparticles and fabrication of nanocomposite fibers thereof using electrospinning

Polymer-stabilized magnetic nanoparticles were obtained using two biocompatible polyelectrolytes: N-carboxyethylchitosan (CECh) and poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS). The size of the particles (mean diameter 10 or 30 nm, respectively) and the stability of the dispersions could be effectively controlled depending on the polyelectrolyte nature. The presence of polyelectrolyte shell was proved by transmission electron microscopy (TEM) studies and confirmed by thermogravimetric analyses. Depending on the polyelectrolyte nature the magnetic nanoparticles existed in different magnetic states - superparamagnetic or intermediate state between superparamagnetic and ferrimagnetic one, as evidenced by the measurements of the magnetization and Mössbauer analyses. Fabrication of nanocomposite magnetic fibers with mean diameter in the range 100-500 nm was achieved using electrospinning of the system CECh/ferrofluid/non-ionogenic polymer.     

Double emulsion droplets as microreactors for synthesis of magnetic macroporous polymer beads

An easy method is presented to fabricate monodisperse magnetic macroporous polymer beads（MMPBs）. Waterin-oil high internal phase emulsion（HIPE） is prepared by emulsifying aqueous iron ions solution in an oil phase containing monomers. The HIPE is introduced into a simple microfluidic device to fabricate monodisperse（water-in-oil）-in-water double emulsion droplets. The droplets serve as microreactors to synthesize Fe3O4 nanoparticles and are on-line polymerized to form MMPBs. The prepared MMPBs display uniform size, interconnected porous structure, superparamagnetic behavior and uniform distribution of Fe3O4 in polymer matrix. The MMPBs are characterized by scanning electron microscopy（SEM）, Fourier transform infrared spectroscopy（FTIR）, X-ray diffraction（XRD）, transmission electron microscopy（TEM）, vibrating sample magnetometry（VSM）. We believe that this method is a universal technique in preparing macroporous nanocomposite beads.     

Immobilization of Au nanoparticles on poly(glycidyl methacrylate)-functionalized magnetic nanoparticles for enhanced catalytic application in the reduction of nitroarenes and Suzuki reaction

We report a novel strategy for the synthesis of magnetic nanocomposite for highly efficient catalysis. Poly(glycidyl methacrylate) (PGMA) chains were grafted to the surface of magnetic nanoparticles (MNPs) through surface-initiated reversible addition-fragmentation chain transfer polymerization. Then, the oxirane rings in the PGMA chains were opened with 2,6-diamino pyridine (DAP) molecules as ligands to prepare the solid support. Finally, this magnetic nanocomposite was used for the immobilization of gold nanoparticles. Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, transmission electron microscopy, scanning electron microscopy, gel permeation chromatography, vibrating sample magnetometry, and atomic absorption spectroscopy were used for characterization of the catalyst. The loading of gold nanoparticles on the solid support was 0.52 mmol/g. The catalytic activity of the prepared catalyst (MNP@PGMA@DAP@Au) was evaluated for the reduction of nitro compounds and C–C coupling reaction in water. The catalyst can be easily recovered and reused seven times without significant loss of catalytic activity.     

A novel dual thermo- and pH-responsive silver nanocomposite hydrogel as a drug delivery system

The purpose of this study was to develop a novel dual thermo- and pH-responsive silver nanocomposite hydrogel (SNH) for drug release applications. This smart SNH was prepared in a facile one-pot method by in situ reduction of silver ions in salep solution and then grafting of poly(vinylpyrrolidone-co-acrylic acid) onto it. The SNH was characterized by transmission electron microscopy (TEM), scanning electron microscopy with energy-dispersive X-ray analysis (SEM–EDAX), thermo-gravimetric analysis (TGA), Fourier transform infrared (FT-IR), UV–Vis spectroscopy, and cyclic voltammetry. The dependence of swelling properties of the prepared SNH on the reaction variables (such as monomer, Ag NO₃, and cross-linker concentrations), temperature, pH, and salt was investigated. The potential of obtained SNH was examined for the deferasirox release from prepared hydrogel under different temperatures and pHs. The evaluation of release mechanism and determination of diffusion coefficients were also studied. In addition, SNH showed good antibacterial potentials. The results of this study provide valuable information regarding the development of dual stimuli-sensitive SNH for biomedical applications.     

Stable aqueous dispersion of magnetic iron oxide core–shell nanoparticles prepared by biocompatible maleate polymers

A new method is applied to prepare stable aqueous dispersion of magnetic iron oxide nanoparticles (MNPs) by biocompatible maleate polymers. Fe₃O₄ magnetic core–shell nanoparticles are obtained via forming an inclusion complex between carboxylic acid groups of maleated biocompatible polymers shell and Fe₃O₄ MNPs core surface. Maleate polymers are synthesized via esterification of poly(ethylene glycol), poly(vinyl alcohol) and starch with maleic anhydride (MA). The Fe₃O₄ magnetic core–shell nanoparticles are characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy and vibrating sample magnetometer. The obtained magnetic core–shell nanoparticles exhibit superparamagnetic property and reveal long‐term aqueous stability. This work represents a valid methodology to produce highly stable aqueous dispersion of Fe₃O₄ MNPs ferrofluids which can be expected to have great potential as contrast agent for magnetic resonance imaging. Furthermore, the shell composition of biocompatible maleate polymers with double bond of MA as crosslinker agent allows the polymerization with other monomers to design preferred drug delivery systems. Copyright © 2014 John Wiley & Sons, Ltd.     

First successful design of semi-IPN hydrogel-silver nanocomposites: a facile approach for antibacterial application

Semi-IPN hydrogels in which poly(vinyl pyrrolidone) (PVP) chains were physically dispersed throughout poly(acrylamide) (PAM) gel networks were synthesized. These semi-IPN hydrogel networks can act as excellent nanoreactors for producing and stabilizing metal nanoparticles. The current methodology allows us to entrap metal nanoparticles throughout hydrogel networks via PVP chains. An optimized semi-IPN hydrogel formulation was found to produce silver nanoparticles, ca. 3-5 nm. The synthesized semi-IPN hydrogel-silver nanocomposites were fully characterized by using UV-vis, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The developed semi-IPN hydrogel-silver nanocomposite (SHSNC) was evaluated for preliminary antibacterial applications.     

Magnetic solid-phase extraction of organophosphorus pesticides from apple juice and environmental water samples using magnetic graphene oxide coated with poly(2-aminoterephthalic acid-co-aniline) nanocomposite as a sorbent

An effective magnetic solid-phase extraction method was proposed using magnetic graphene oxide coated with poly(2-aminoterephthalic acid-co-aniline) as a sorbent for preconcentration and extraction of organophosphorus pesticides from environmental water and apple juice samples, and determined using the gas chromatography-mass spectrometry analysis. To approve the successful synthesis of the magnetic nanocomposite, the prepared sorbent was characterized by field emission scanning electron microscopy, X-ray diffraction, vibrating sample magnetometer, and Fourier transforms infrared techniques. The main parameters affecting the extraction efficiency were considered and studied to afford an optimized procedure. Systematic method validation verified its suitable recoveries (89.4–107.3%), and precision (relative standard deviations < 6.8%). The method showed a wide linear dynamic range (0.04–700 ng/mL) with low limits of detection (0.01–0.06 ng/mL) and quantification (0.04–0.21 ng/mL). This method presented good potential and great sensitivity for the pesticides determination.     

Photoluminescent Fe3O4/carbon nanocomposite with magnetic property

Fe(3)O(4)/carbon nanocomposite has been prepared by a facile chemical method, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, fourier transform infrared spectroscopy and scanning electron microscopy. The fluorescent and magnetic properties of the sample were investigated by fluorescence spectroscopy and vibrating-sample magnetometer, respectively. The results indicate that the Fe(3)O(4)/carbon nanocomposite exhibit good photoluminescent (emission ranging from 425 to 550 nm) and strong magnetic (saturation magnetization of 44.2 emu/g) properties.     

Carboxymethylcellulose (CMC)–hydroxyethylcellulose (HEC) based hydrogels: synthesis and characterization

A novel carboxymethylcellulose (CMC)–hydroxyethylcellulose (HEC)-based hydrogel with sensitivity to environmental changes, pH and salts was synthesized by using fumaric acid and malic acid at various concentrations. Water uptake capacity of hydrogels was investigated in distilled water, various salt and pH solutions. From pH-dependent studies, it was found that greater water uptake values were observed at greater pH values (7.4), and reversible pH responsiveness of CMC–HEC based hydrogels was obtained. Decreasing the water uptake capacity with increasing of the charge of the metal cation (Al³⁺ < Ca²⁺ < Na⁺) demonstrated metal ion responsiveness of CMC–HEC-based hydrogels. From tensile tests of the hydrogels, a greater crosslinker concentration led to greater tensile strength values. Thermogravimetric analysis and scanning electron microscopy images were used to determine the thermal stability and to observe morphological properties of the samples, respectively.