左氧氟沙星印迹聚合物微球及其特异吸附研究

以甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用沉淀聚合法制备了左氧氟沙星印迹聚合物(MIP)微球,用SEM和IR分别对微球形貌和结构进行表征,用静态吸附法和Scatchard分析考察了聚合物微球对模板及其结构类似物的吸附行为和选择性识别能力.结果表明,MIP对模板分子的吸附平衡速度快,40min即可达到吸附...     

DNA adsorption via Co(II) immobilized cryogels

The separation and purification of important biomolecule deoxyribonucleic acid (DNA) molecules are extremely important. The adsorption technique among these methods is highly preferred as the adsorbent cryogels are pretty much used due to large pores and the associated flow channels. In this study, the adsorption of DNA via Co(II) immobilized poly(2-hydroxyethyl methacrylate-glycidyl methacrylate) [poly(HEMA-GMA)] cryogels was performed under varying conditions of pH, interaction time, initial DNA concentration, temperature, and ionic strength. For the characterization of cryogels; swelling test, Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), surface area (BET), elemental and ICP-OES analysis were performed. L-lysine amino acid was chosen as Co(II)-chelating agent and the adsorption capacity of cryogels was determined as 33.81 mg DNA/g cryogel. Adsorption of pea DNA was studied under the optimum adsorption conditions and DNA adsorption capacity of cryogels was found as 10.14 mg DNA/g cryogel. The adsorption process was examined via Langmuir and Freundlich isotherm models and the Langmuir adsorption model was determined to be more appropriate for the DNA adsorption onto cryogels.     

New acrylamide‐based monomer containing metal chelating units: Homopolymer grafted magnetite nanoparticles via ATRP for the magnetic removal of Co(II) ions

In this research, we synthesized and characterized a new acrylamide‐based monomer containing pyridine and 1,3,4‐oxadiazole moieties, N‐(4‐(5‐(pyridin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl)phenyl)acrylamide (POPA). Poly(POPA)‐grafted magnetite nanoparticles were then obtained via surface‐initiated atom transfer radical polymerization. The grafted nanoparticles were characterized by Fourier transform infrared analysis, scanning electron microscopy, wide angle X‐ray diffraction, and vibrating sample magnetometry. The amount of the grafted polymer was 126 mg/g, as calculated from thermo gravimetric analysis experiment. The capability of poly(POPA)‐g‐magnetite nanoparticles (MNPs) to remove Co(II) cations, under optimal time period, pH and adsorbent mass, was shown by atomic absorption. The adsorption kinetics obeyed the pseudo–second‐order kinetic equation, and the adsorption isotherm was best described by the Freundlich model with a maximum adsorption capacity of 59.90 mg/g. In addition, the poly(POPA)‐g‐MNPs were regenerated by simply washing with an aqueous 0.1M HCl solution, and no considerable decrease was observed in the extraction efficiency following the test of up to 7 cycles. These findings suggest that poly(POPA)‐g‐MNPs are stable and reusable adsorbent, and they could be potentially applied to water treatments for an efficient removal of Co(II) cations.     

Biofouling-resistance expanded poly(tetrafluoroethylene) membrane with a hydrogel-like layer of surface-immobilized poly(ethylene glycol) methacrylate for human plasma protein repulsions

In general, it is a challenge to control the highly polar material grafting from the chemically inert Teflon-based membrane surface. This work describes the surface modification and characterization of expanded poly(tetrafluoroethylene) (ePTFE) membranes grafted with poly(ethylene glycol) methacrylate (PEGMA) macromonomer via surface-activated plasma treatment and thermally induced graft copolymerization. The chemical composition and microstructure of the surface-modified ePTFE membranes were characterized by Fourier transform infrared spectroscopy (FT-IR), contact angle, and bio-atomic force microscopy (bio-AFM) measurements. Biofouling property of the modified membranes was evaluated by the measurements of the plasma protein (γ-globulin, fibrinogen, or albumin) adsorption determined using an enzyme-linked immunosorbent assay (ELISA). In general, the hydrophilicity of the surface of ePTFE membranes increases with increasing the grafting degree of the copolymerized PEGMA. The highly hydrated PEGMA chain on the resulting ePTFE membranes was found to form a surface hydrogel-like layer with regulated coverage in aqueous state, which can be controlled by the content of PEGMA macromonomer in the reaction solution. The relative protein adsorption was effectively reduced with increasing capacity of the hydration for the PEGMA chain grafted on the ePTFE membrane surface. From both results of protein adsorption and platelet adhesion test in vitro, it is concluded that the PEGMA-grafted hydrophilic ePTFE membranes could provide good biofouling resistance to substantially reduce plasma protein and blood platelet fouling on the membrane surface in human body temperature.     

Poly(amino acid)-based thermoresponsive molecularly imprinted magnetic nanoparticles for specific recognition and release of lysozyme

In this study, poly(amino acid)-based thermoresponsive molecularly imprinted magnetic nanoparticles for recognition and release of lysozyme was prepared via surface imprinting method. For constructing the molecularly imprinted polymer (MIP) layer, amino acid-based thermoresponsive monomer (N-methacryloyl-l-alanine methyl ester, MA-L-Ala-OMe) was mainly selected for the functional monomer along with N,N′-methylenebis(acrylamide) as the crosslinker. The resultant magnetic MIP nanoparticles were characterized in detail. Meanwhile, the dynamic light scattering studies and swelling ratios measurements were carried out for demonstrating the thermoresponsive property of the imprinted nanoparticles. The prepared magnetic MIP nanoparticles showed good adsorption capacity and selective recognition properties to lysozyme. Moreover, the fast adsorption process could reach equilibrium within 15 min. Importantly, the capture and release of lysozyme could be easily realized simply by altering the temperature of aqueous solution. Furthermore, the prepared imprinted nanoparticles were applied to separate lysozyme from the real egg white samples. The results proved that the thermoresponsive MIPs based on MA-L-Ala-OMe have great potential for selectively enriching target proteins in real samples.     

Synthesis of molecularly imprinted polymer nanoparticles for the fast and highly selective adsorption of sunset yellow

Novel molecularly imprinted polymer nanoparticles were synthesized by precipitation polymerization with sunset yellow as the template and [2‐(methacryloyloxy)ethyl] trimethylammonium chloride as the functional monomer. The molecularly imprinted polymer nanoparticles were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and their specific surface area and thermal stability were measured. The molecularly imprinted polymer nanoparticles had a high adsorption capacity in wide pH range (pH 1–8) for sunset yellow. The adsorption equilibrium only needed 5 min, and the quantitative desorption was very fast (1 min) by using 10.0 mol/L HCl as the eluant. The maximum adsorption capacity of the molecularly imprinted polymer nanoparticles for sunset yellow was 144.6 mg/g. The adsorption isotherm and kinetic were well consistent with Langmuir adsorption model and pseudo‐second‐order kinetic model, respectively. The relative selectivity coefficients of the molecularly imprinted polymer nanoparticles for tartrazine and carmine were 9.766 and 12.64, respectively. The prepared molecularly imprinted polymer nanoparticles were repeatedly used and regenerated ten times without significant absorption capacity decrease.     

Preparation of novel bovine hemoglobin surface-imprinted polystyrene nanoparticles with magnetic susceptibility

In this research, a surface imprinting strategy has been adopted in protein imprinting. Bovine hemoglobin surface-imprinted polystyrene (PS) nanoparticles with magnetic susceptibility have been synthesized through multistage core-shell polymerization system using 3-aminophenylboronic acid (APBA) as functional and cross-linking monomers. Superparamagnetic molecularly imprinted polystyrene nanospheres with poly(APBA) thin films have been synthesized and used for the first time for protein molecular imprinting in an aqueous solution. The magnetic susceptibility is imparted through the successful encapsulation of Fe₃O₄ nanoparticles. The morphology, adsorption, and recognition properties of superparamagnetic molecularly imprinted polymers (MIPs) have been investigated using transmission electron microscopy, X-ray diffraction, thermogravimetric analysis, and vibrating sample magnetometer. Rebinding experimental results show that poly(APBA) MIPs-coated superparamagnetic PS nanoparticles have high adsorption capacity for template protein bovine hemoglobin and comparatively low nonspecific adsorption. The imprinted superparamagnetic nanoparticles could easily reach the adsorption equilibrium and achieve magnetic separation in an external magnetic field, thus avoiding some problems of the bulk polymer.     

Fabrication and characterization of CMC‐based magnetic superabsorbent hydrogel nanocomposites for crystal violet removal

In this research work, novel magnetic superabsorbent hydrogel nanocomposites (MSHNs) based on carboxymethyl cellulose were prepared via a facile “one‐pot” two step approach. Magnetic iron oxide nanoparticles were in situ synthesized and incorporated into carboxymethyl cellulose/poly(acrylic acid) polymer hydrogel. The morphology and chemical composition of MSHNs as well as the presence of magnetic iron oxide nanoparticles were evaluated by using Fourier transform infrared, scanning electron microscopy, transmission electron microscopy, X‐Ray diffraction, ultraviolet–visible spectroscopy, thermogravimetric analysis, and vibrating sample magnetometer. The effect of different reaction parameters on the swelling capacity of MSHNs was investigated. Furthermore, batch adsorption experiments of crystal violet dye onto MSHNs were studied by varying solution pH, initial dye concentration, and temperature. Evaluation of thermodynamic parameters of crystal violet adsorption confirmed that the adsorption was spontaneous and endothermic process in nature. The equilibrium study revealed that the dye adsorption behavior of MHSNs followed the Redlich‐Peterson isotherm model. Finally, the dye adsorption experiment data was well fitted by the pseudo‐second‐order kinetic model with the regression coefficient (R²) of 0.9979. Our results suggest that the MHSNs with facile preparation method, high swelling capacity, and high dye adsorption capacity may be used as promising adsorbents for fast removal of various dyes from aqueous solutions. Copyright © 2016 John Wiley & Sons, Ltd.     

Highly efficient removal of Cr(VI) from wastewater via adsorption with novel magnetic Fe3O4@C@MgAl-layered double-hydroxide

Novel magnetic Fe₃O₄@C@MgAl-layered double-hydroxide (LDH) nanoparticles have been successfully prepared by the chemical self-assembly methods. The properties of surface functional groups, crystal structure, magnetism and surface morphology of magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermal gravity-differential thermal gravity (TG-DTG), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The adsorption studies of the novel adsorbent in removing heavy metals Cr (VI) from waste water showed that the maximum absorption amount of Cr(VI) was 152.0 mg/g at 40℃ and pH 6.0. The excellent adsorption capacity of the Fe₃O₄@C@MgAl-LDH nano-absorbents plus their easy separation, environmentally friendly composition and reusability makes them more suitable adsorbents for the removal of metal ions from waste water.     

多壁碳纳米管表面熊果酸印迹聚合物的制备及固相萃取

以聚乙烯醇修饰的多壁碳纳米管(MWCNTs)为基材,熊果酸(UA)为模板分子,甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,采用表面印迹技术在碳纳米管表面合成对熊果酸具有良好选择性的分子印迹聚合物( MWCNTs-MIPs).讨论了不同摩尔比例的功能单体与模板分子合成印迹聚合物的效果,得出...     

Synthesis and characterization of multifunctional Fe3O4/poly(fluorescein O-methacrylate) core/shell nanoparticles

Multifunctional fluorescent and superparamagnetic Fe(3)O(4)/poly(fluorescein O-methacrylate) [Fe(3)O(4)/poly(FMA)] nanoparticles with core/shell structure were synthesized via surface-initiated polymerization. First, polymerizable double bonds were introduced onto the surface of Fe(3)O(4) nanoparticles via ligand exchange and a condensation reaction. A fluorescent monomer, FMA, was then polymerized to the double bonds at the surface via free-radical polymerization, leading to form a fluorescent polymer shell around the superparamagnetic Fe(3)O(4) core. The resultant Fe(3)O(4)/poly(FMA) nanoparticles were characterized by Fourier transform infrared, nuclear magnetic resonance, and X-ray diffraction spectroscopy to confirm the reactions. Transmission electron microscopy images showed that the Fe(3)O(4)/poly(FMA) nanoparticles have a spherical and monodisperse core/shell morphology. Photoluminescence spectroscopy and superconducting quantum interference device magnetometer analyses confirmed that the Fe(3)O(4)/poly(FMA) nanoparticles exhibited fluorescent and superparamagnetic properties, respectively. In addition, we demonstrated the potential bioimaging application of the Fe(3)O(4)/poly(FMA) nanoparticles by visualizing the cellular uptake of the nanoparticles into A549 lung cancer cells.     

Two-step polymerization approach for synthesis of macroporous surface ion-imprinted cryogels

Today, the surface imprinted polymers emerge in various fields as synthetic adsorbents gaining attention in a variety of application areas. In this study, Cu(II) ion surface imprinted poly(2-hydroxyethyl methacrylate-glycidyl methacrylate), poly(HEMA-GMA), cryogels were synthesized via modified two-step polymerization which is different from given in literature and the adsorption of Cu(II) ion from aqueous solution was investigated batch wise. In this respect, the method applied in this study is new in the literature despite heavy metal removal studies reported. The polyethyleneimine (PEI) molecule was used in polymeric structure as a ligand. The poly(HEMA-GMA) cryogels prepared was characterized via Fourier transform infrared spectroscopy (FTIR), inductively coupled plasma optical emission spectrometry (ICP-OES), elemental analysis, scanning electron microscopy (SEM) and the micro-computed tomography (μCT).     

Novel antifouling oligo(ethylene glycol) methacrylate particles via surfactant-free emulsion polymerization

The use of particle formulations with antifouling surface properties attracts increasing interest in several biotechnological applications. Majority of these studies utilize a poly(ethylene glycol) coating to render the corresponding surface nonrecognizable to biological macromolecules. Herein, we report a simple way to prepare novel antifouling colloids composed of oligo(ethylene glycol) backbones via surfactant-free emulsion polymerization. Monodisperse cross-linked poly(ethylene glycol) ethyl ether methacrylate particles were characterized by dynamic light scattering and transmission electron microscopy. The effects of monomer, cross-linker and initiator on particle characteristics were investigated. More importantly, a prominent blockage of bovine serum albumin adsorption was obtained for the poly(ethylene glycol)-based sub-micron (~200 nm) particles when compared with similar-sized poly(methyl methacrylate) counterparts.     

有机-无机杂化聚离子液体材料制备及其对染料吸附性能的评价

以烯丙基三乙氧基硅烷与1-乙烯基-3-辛基咪唑溴盐离子液体为单体通过自由基聚合及溶胶-凝胶制备了有机-无机杂化聚离子液体材料。通过红外光谱和扫描电镜对所制备的杂化聚离子液体材料进行了表征,并考察了其对柠檬黄、日落黄、苋菜红以及诱惑红等常见染料的吸附性能。研究结果表明:所制备的聚离子液体材料对日落黄和诱惑红具有优异的吸附性能,其吸附容量分别为29.20和86.17 mg/g;当吸附时间为5 min时,该材料对诱惑红和日落黄的吸附分别达到平衡时吸附量的87.5%和72.8%,显示了较快的吸附速率。     

Phase behavior of poly(sulfobetaine methacrylate)-grafted silica nanoparticles and their stability in protein solutions

Biocompatible and zwitterionic poly(sulfobetaine methacrylate) (PSBMA) was grafted onto the surface of initiator-modified silica nanoparticles via surface-initiated atom transfer radical polymerization. The resultant samples were characterized via nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy, and thermogravimetric analysis. Their molecular weights and molecular weight distributions were determined via gel permeation chromatography after the removal of silica by etching. Moreover, the phase behavior of these polyzwitterionic-grafted silica nanoparticles in aqueous solutions and stability in protein/PBS solutions were systematically investigated. Dynamic light scattering and UV-visible spectroscopy results indicate that the silica-g-PSBMA nanoparticles exhibit an upper critical solution temperature (UCST) in aqueous solutions, which can be controlled by varying the PSBMA molecular weight, ionic strength, silica-g-PSBMA nanoparticle concentration, and solvent polarity. The UCSTs shift toward high temperatures with increasing PSBMA molecular weight and silica-g-PSBMA nanoparticle concentration. However, increasing the ionic strength and solvent polarity leads to a lowering of the UCSTs. The silica-g-PSBMA nanoparticles are stable for at least 72 h in both negative and positive protein/PBS solutions at 37 °C. The current study is crucial for the translation of polyzwitterionic solution behavior to surfaces to exploit their diverse properties in the development of new, smart, and responsive coatings.     

Synthesis of magnetic nanoparticle‐based molecularly imprinted polymer as a selective sorbent for efficient extraction of ezetimibe from biological samples

In the present study, a novel and efficient adsorbent constructed of molecularly imprinted polymer on the surface of modified magnetic nanoparticles with oleic acid (MNPs) was applied for the selective extraction of ezetimibe. The magnetic molecularly imprinted polymer (MMIP) was polymerized at the surface of modified MNPs using methacrylic acid as functional monomer, ezetimibe as template and ethylene glycol dimethacrylate as cross‐linker. The resulting MMIP showed high adsorption capacity, good selectivity and fast kinetic binding for the template molecule. It was characterized by Fourier transform infrared analysis, scanning electron microscopy and transmission electron microscopy methods. The maximum adsorption capacity of MMIP was obtained as 137.1 mg g^?1 and it took about 20 min to achieve the equilibrium state. The adsorption model of the adsorbent was fitted with the Freundlich and Langmuir isotherm equations. The assay exhibited a linear range of 0.003–20.000 mg L^?1 for ezetimibe with a correlation coefficient of 0.995. The relative standard deviations for the recoveries were <5.2. The method was also examined for the analysis of ezetimibe in the biological samples.     

Improving hydrophilicity and protein resistance of poly(vinylidene fluoride) membranes by blending with amphiphilic hyperbranched-star polymer

To endow hydrophobic poly(vinylidene fluoride) (PVDF) membranes with reliable hydrophilicity and protein resistance, an amphiphilic hyperbranched-star polymer (HPE-g-MPEG) with about 12 hydrophilic arms in each molecule was synthesized by grafting methoxy poly(ethylene glycol) (MPEG) to the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent and blended with PVDF to fabricate porous membranes via phase inversion process. The chemical composition changes of the membrane surface were confirmed by X-ray photoelectron spectroscopy (XPS), and the membrane morphologies were measured by scanning electron microscopy (SEM). Water contact angle, static protein adsorption, and filtration experiments were used to evaluate the hydrophilicity and anti-fouling properties of the membranes. It was found that MPEG segments of HPE-g-MPEG enriched at the membrane surface substantially, while the water contact angle decreased as low as 49 degrees for the membrane with a HPE-g-MPEG/PVDF ratio of 3/10. More importantly, the water contact angle of the blend membrane changed little after being leached continuously in water at 60 degrees C for 30 days, indicating a quite stable presence of HPE-g-MPEG in the blend membranes. Furthermore, the blend membranes showed lower static protein adsorption, higher water and protein solution fluxes, and better water flux recovery after cleaning than the pure PVDF membrane.     

Dye attached poly(hydroxyethyl methacrylate) cryogel for albumin depletion from human serum

Cibacron Blue F3GA was immobilized on poly(hydroxyethyl methacrylate) cryogel and it was used for selective and efficient depletion of albumin from human serum. The poly(hydroxyethyl methacrylate) was selected as the basic component because of its inertness, mechanical strength, chemical and biological stability, and biocompatibility. Cibacron Blue F3GA was covalently attached to the poly(hydroxyethyl methacrylate) cryogel to produce poly(hydroxyethyl methacrylate)-Cibacron Blue F3GA cryogel affinity column. The poly(hydroxyethyl methacrylate)-Cibacron Blue F3GA cryogel was characterized with respect to gelation yield, swelling degree, total volume of macropores, Fourier Transform Infrared spectroscopy, and scanning electron microscopy. It was found that the maximum amount of adsorption (343 mg/g of dry cryogel) obtained from experimental results is very close to the calculated Langmuir adsorption capacity (345 mg/g of dry cryogel). The maximum adsorption capacity for poly(hydroxyethyl methacrylate)-Cibacron Blue F3GA cryogel column was obtained as 950 mg/g of dry cryogel for nondiluted serum. The adsorption capacity decreased with increasing dilution ratios while the depletion ratio of albumin remained as 77% in serum sample. Finally, the poly(hydroxyethyl methacrylate)-Cibacron Blue F3GA cryogel was optimized for using in the fast protein liquid chromatography system for rapid removal of the high abundant proteins from the human serum.     

Selective Removal of Amikacin From Simulated Polluted Water Using Molecularly Imprinting Polymer (MIP)

In the present study, the antibiotic drug Amikacin has been used as template molecule to prepare poly(methacrylic acid) based molecularly imprinting polymer using acetonitrile (Acn) as a porogenic solvent. The polymer has been characterized by FTIR, SEM analysis. The poly(MAAc) MIP has been used for effective and selective removal of Amikacin (Amk) in batch mode process. The equilibrium uptake data was fitted to various isotherm models namely, Langmuir, Freundlich, Temkin and Dubinin-Redushkevich (RD). Based on the regression values obtained, the order of fitness was DR>Freundlich>Temkin>Langmuir. The maximum adsorption capacity (Q_o), as determined using Langmuir plot was 60.60 mg/g at 30°C. The presence of the drugs Streptomycin and Gentamycin in the solution did not affect the adsorption capacity of MIP. Finally, the adsorption capacity was found to be independent of the temperature of the adsorption system.     

聚甲基丙烯酸甲酯-牛血清白蛋白核壳纳米粒子在金表面的吸附过程及在传感器中的应用

利用铜离子引发体系, 制备出核层为聚甲基丙烯酸甲酯(PMMA)壳层为牛血清白蛋白(BSA)的PMMA-BSA核壳纳米粒子. 通过透射电子显微镜(TEM)表征, 直接观察到PMMA-BSA纳米粒子的核壳结构.结合X射线光电子能谱(XPS)测试, 分析PMMA-BSA纳米粒子的表面成分, 证明PMMA-BSA纳米粒子的壳层是BSA. 利用带耗散的石英晶体微天平(QCM-D)研究了PMMA-BSA纳米粒子在金片表面的吸附行为. 频率的迅速下降, 耗散因子的快速上升, 说明PMMA-BSA粒子快速地吸附到金片表面. 利用磷酸盐缓冲液反复冲洗时, 频率和耗散没有变化, 表明PMMA-BSA 纳米粒子在金片上吸附较牢固. 以金电极为基底电极, 吸附PMMA-BSA纳米粒子后, 利用戊二醛修饰粒子壳层, 再通过氨基与醛基的反应来固定葡萄糖氧化酶, 制备出电流型葡萄糖传感器. 电化学测试表明该传感器对葡萄糖具有良好的电流响应, 在0.3 V的工作电位下, 响应电流与葡萄糖浓度在0.20-5.85 mmol·L^-1范围内呈现出较好的线性关系, 相关系数为0.989. 传感器的灵敏度高达28.6 μA·L·mmol^-1·cm^-2, 响应时间仅为11 s. 传感器还具有良好的稳定性, 在25℃下储存30 d, 响应电流仅下降了16%.