磁性壳聚糖表面印迹四环素材料的制备及其吸附性能研究

以改性磁性壳聚糖为载体,四环素(TC)为模板分子,采用表面聚合法制备磁性四环素分子印迹材料(MIP)。用FTIR对MIP进行表征。对MIP进行吸附性能研究,结果表明:MIP对TC的最大吸附量为56.60 mg/g;吸附平衡时间为1.5 h,且主要吸附过程由化学吸附控制;M IP对四环素类抗生素(TCs)具有良好的组选择性。同时以该印迹聚合物为固相萃取材料,建立了MISPE-HPLC分析方法,用于猪肉和蜂蜜样品中TCs残留分析,回收率范围84.0%~99.3%,RSD小于4.0%。所制备的M IP对样品中的TCs的分离富集效果良好。     

表面接枝分子印迹聚合物微球的合成及评价

将聚苯乙烯-二乙烯苯微球表面功能基化, 引入引发转移终止剂(initiator-transfer-terminator agent, iniferter), 以活性自由基聚合方式研究了球形树脂表面合成印迹聚合物的方法. 在紫外光引发下, 以左旋麻黄碱为印迹分子, 甲基丙烯酸为功能单体, 在接枝Iniferter后的微球表面进行分子印迹聚合物接枝实验, 并使用不同的反应条件, 探讨了表面接枝印迹层微球制备条件对于识别能力的影响. 平衡吸附的结果表明, 表面接枝聚苯乙烯-二乙烯苯微球对于印迹分子具有亲和能力及选择性, 其识别能力来自于印迹得到的识别位点.     

四氧化三铁纳米粒子表面接枝聚合制备磁性聚合物微球*

四氧化三铁聚合物微球因其结合了纳米四氧化三铁的超顺磁性和有机聚合物的多种特殊性质,如生物相容性、刺激响应性、荧光性,良好的分散性等,而在生物、医学、催化、分离等领域有着重要的应用前景,得到了深入研究。本文按聚合方法分类,综述了利用普通自由基聚合、原子转移自由基聚合（ATRP）、可逆加成断裂链转移聚合（RAFT）、氮氧稳定自由基聚合（NMRP）、活性开环聚合（ROP）等方法在四氧化三铁纳米粒子表面进行接枝聚合制备磁性聚合物微球的研究进展。     

利用接枝微球CPVA-g-PMAA与酮洛芬分子间的氢键相互作用构建结肠定位释药体系

通过表面引发接枝聚合,在交联聚乙烯醇（CPVA）微球表面实施了甲基丙烯酸（MAA）的表面引发接枝聚合,制备了高接枝度的接枝微球CPVA-g-PMAA。利用接枝微球CPVA-g-PMAA与酮洛芬（KPF）主-客体之间的氢键相互作用构建结肠定位释药体系。分析了接枝微球CPVA-g-PMAA对KPF的吸附（载药）性能与吸附机理,深入研究了载药微球在不同pH介质中的释放行为。实验结果表明,在酸性介质中,受主-客体之间强氢键作用的驱动,接枝微球CPVA-g-PMAA对KPF分子表现出强吸附能力,吸附容量接近10mg/g,可实现有效载药。载药微球的释药行为具有强烈的pH依赖性,在pH=1的介质中,释药程度很低;而在pH=7.4的介质中,则发生突释,表现出良好的结肠定位释放行为。     

能够促进细胞黏附的生物活性表面的制备

报道了一种能够促进细胞黏附的生物活性表面的制备方法.首先通过表面引发原子转移自由基聚合方法在硅表面接枝了聚(N-甲基丙烯酰氧基琥珀酰亚胺)(PNMASI)聚合物刷.随着反应时间的增加,接枝层厚度基本呈线性增长,表明聚合反应具有一定的可控性.蛋白质吸附测试表明PNMASI改性后的表面具有高密度固定生物分子的能力.同时,通...     

一种螯合树脂的合成及对金属离子的吸附研究

采用表面引发原子转移自由基聚合(SI-ATRP)技术,以自制的单分散磁性聚合物微球(Fe3O4/PGMA/EDMA)为ATRP大分子引发剂,Cu Br/2,2'-联吡啶(Bpy)为催化剂,将乙烯基四唑聚合在磁性聚合物微球表面,制备了磁性螯合吸附树脂,用元素分析对其进行了表征,并测定了该树脂对几种金属离子的吸附性能,结果发现新型螯合树脂对贵金属离子吸附能力强,具有良好的应用前景,工业推广价值较高。     

光接枝表面修饰法制备牛血红蛋白的分子印迹微球

聚苯乙烯球载体表面经引发转移终止剂修饰后, 采用光接枝表面印迹方法制备了以牛血红蛋白(BHb)为模板分子、丙烯酰胺为功能单体和N,N′-亚甲基双丙烯酰胺为交联剂的分子印迹聚合物微球(MIP). 进一步采用红外光谱(IR)、扫描电子显微镜(SEM)和元素分析对聚合物微球进行了表征, 证实了载体表面成功地接枝了分子印迹层, 并研究了其吸附性能和分子识别选择性能. 结果表明, 采用光接枝表面修饰法制备的分子印迹微球对模板分子有着很好的吸附容量和识别选择性.     

一种温敏型超大孔生物分离介质的制备及表征

采用改性琼脂糖对超大孔聚苯乙烯微球进行亲水化修饰(Agap-PS),通过酰基化反应在微球表面引入溴乙酰基(Agap-PS-Br),然后利用原子转移自由基聚合(ATRP)反应在Agap-PS-Br表面接枝温敏聚合物刷,得到一种温敏型超大孔生物分离介质(Agap-PS-PNIPAM).考察了配体、催化剂、溶剂和温度对N-异丙基丙烯酰胺ATRP反应的影响,在优化条件下PNIPAM的接枝量达到了15.07 mg/m2.采用红外光谱(FTIR)、扫描电镜(SEM)、压汞分析、激光共聚焦和蛋白吸附等手段对温敏型超大孔生物分离介质进行一系列表征,结果表明接枝温敏聚合物刷后Agap-PS-PNIPAM具有良好的温敏性,没有堵塞微球的超大孔,微球对蛋白的非特异性吸附大大降低.由于温敏聚合物刷发生了从亲水到疏水构象的转变,40℃时Agap-PS-PNIPAM对蛋白的吸附量是25℃时的2.69倍.压力流速实验表明Agap-PS-PNIPAM柱具有背压低、渗透性和机械稳定性好的优点,同样地由于PNIPAM链在40℃时收缩,此时Agap-PS-PNIPAM柱的床层渗透系数比25℃时提高了15.7％.     

表面引发聚合新进展及应用

综述了近年来聚合物刷合成与应用方面的新进展.简要介绍了利用表面引发原子转移自由基聚合(SI-ATRP)制备聚合物刷的历程和重要进展.重点论述了通过电化学、光诱导以及牺牲阳极技术、仿生合成等发展了多种表面引发ATRP新方法,基于如何将聚合物从分子尺度过渡到微米尺度的思考,实现了多尺度聚合物刷结构的制备.简要综述了聚合物刷在以下3个方面的应用研究:(1)智能驱动,利用聚合物刷构象变化,实现微悬臂驱动、辅助放大的电驱动以及仿毛毛虫运动.(2)生物润滑,利用聚合物的环境响应行为实现了对摩擦系数的调控,并发展了球刷型润滑材料.(3)表面防污,表面接枝含离子液体官能团的聚合物刷,并与仿生技术相结合,利用化学组成和结构化协同效应,得到一系列高性能低毒海洋防污界面材料.     

在聚合物微球HEMA/NVP表面接枝聚合甲基丙烯酸的研究

采用悬浮聚合法制备了甲基丙烯酸羟乙酯与N-乙烯基吡咯烷酮的交联共聚微球;接着用甲基丙烯酰氯对交联微球进行了表面化学改性,将可聚合双键引入微球表面,制得了改性微球;然后,用"接出"法实施了甲基丙烯酸(MAA)在改性微球表面的接枝聚合,得到了接枝微球.用红外光谱法对几种微球的化学结构进行了表征,使用扫描电镜观察了形貌;考察了对MAA接枝聚合的主要影响因素.结果表明,交联微球在表面改性后,可顺利地实现MAA在微球表面的接枝聚合;在接枝聚合过程中,微球表面所产生的接枝聚合物层会形成动力学位垒,反应12h后接枝度不再变化,且在接枝度-温度与接枝度.引发剂用量曲线上出现最高点;接枝聚合适宜的反应温度为70℃,引发剂用量为单体质量的0.3%.对碱性蛋白的吸附性能的观察表明,在氢键与静电相互作用的协同作用下,接枝微球对溶菌酶具有很强的吸附能力.     

螺旋霉素分子印迹磁性纳米吸附剂的合成及应用

制备了一种以螺旋霉素为模板分子的分子印迹磁性纳米吸附剂。以磁性纳米Fe₃O₄为内核,经丙烯酸表面修饰后再以螺旋霉素为模板分子、甲基丙烯酸为功能单体、乙二醇二甲基丙烯酸酯为交联剂,通过表面自由基聚合反应制备得到。该吸附剂对螺旋霉素、交沙霉素、替米考星和酒石酸泰乐菌素4种大环内酯类抗生素表现出良好的富集效果（富集倍数分别为310、118、758和72）,其选择性明显优于常规C₁₈吸附剂。该吸附剂可重复使用至少6次。结合高效液相色谱-紫外检测器建立了上述4种抗生素的分析方法。方法检出限为0.53~2.75 μg/L,定量限为1.78~9.16 μg/L;在50、100和150 μg/L低中高3个添加水平下,方法回收率在80.78%~123.02%之间,相对标准偏差<15.8%（n=5）。该方法被应用于分析蜂蜜中的上述4种抗生素。     

Preparation of magnetic microspheres with thiol-containing polymer brushes and immobilization of gold nanoparticles in the brush layer

Narrow-disperse magnetic microspheres were prepared by alkaline coprecipitation of Fe²⁺ and Fe³⁺ ions within poly(acrylic acid–divinylbenzene) microspheres that were prepared by distillation–precipitation copolymerization. Magnetic microspheres with polymer brushes that contain epoxy groups were prepared by graft copolymerization of glycidyl methacrylate and glycerol monomethacrylate via atom transfer radical polymerization (ATRP) from the magnetic microsphere surfaces. Subsequently, magnetic microspheres with thiol-containing polymer brushes were prepared by treating the epoxy group-containing magnetic microspheres with sodium hydrosulfide. Gold nanoparticles were immobilized in the brush layer of the thiol-containing magnetic microspheres through Au–S coordination. The catalytic activity of the gold nanoparticle-immobilized magnetic microspheres was investigated using the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride as a model reaction. The catalyst could be reused for over 10 cycles without noticeable loss of catalytic activity.     

Fe3O4纳米粒子修饰多壁碳纳米管的制备及在水和蜂蜜样品中痕量菊酯类农药分析中的应用

通过化学共沉淀法使Fe₃O₄纳米粒子负载于酸化多壁碳纳米管(AMWNTs)表面,得到Fe₃O₄/AMWNTs磁性纳米材料。该材料具有很好的磁响应度和分散性,将其用于富集痕量拟除虫菊酯类农药残留,结果证明该复合材料对菊酯类农药的吸附性能良好。通过对影响萃取性能的几种因素如离子强度、萃取时间和解吸时间依次进行优化,在最优条件下,建立了Fe₃O₄/AMWNTs磁性分散固相萃取-气相色谱测定6种菊酯类农药残留的分析方法。线性范围在0.5~50 μg/L之间,相关系数(R²)大于0.990,检出限为0.07~0.20 μg/L,精密度为3.8%~8.1%。该方法用于河水、鱼塘水和两种市售蜂蜜中菊酯类农药的残留分析,回收率高于78.4%。该方法操作简便、灵敏度高,能够满足环境水样及蜂蜜样品中痕量菊酯农药残留的分析需求。     

一步聚合法制备壳核型、可控阶层结构的羰基铁/聚苯乙烯复合微球

采用改进的悬浮聚合法合成了一系列粒径和结构可调的羰基铁粉/聚苯乙烯磁性高分子微球.利用傅立叶变换红外光谱仪、热重分析仪、X射线衍射仪、扫描电镜等分析了微球的结构、化学成分及形貌.结果表明,通过改变苯乙烯单体和聚乙烯醇(PVA)的加入量,可以制备三类不同形貌和结构的复合微球,即多孔复合微球,无孔复合微球和含"带状"突起的...     

新型磁性分子印迹聚合物的制备及其在氟喹诺酮类抗生素检测中的应用

建立了磁性分子印迹聚合物固相萃取与高效液相色谱联用同时检测环境水中4种氟喹诺酮类抗生素的研究方法。分别利用扫描电子显微镜、透射电子显微镜、X-射线衍射、傅里叶红外光谱、振动样品磁强计对合成的磁性分子印迹聚合物进行表征,对影响吸附实验的参数（包括吸附剂用量、吸附和解析时间、洗脱液种类、样品pH值）进行了考察和优化。在最佳的实验条件下,4种氟喹诺酮类抗生素的方法检出限为4.1~21.3 μg/L,方法定量限为13.7~71.0 μg/L,样品加标回收率为70.6%~103.6%。该方法快速、灵敏,能够满足环境水样中氟喹诺酮类抗生素的残留检测要求。     

Aminosilanized magnetic carbon microspheres for the magnetic solid‐phase extraction of bisphenol A,bisphenol AF,and tetrabromobisphenol A from environmental water samples

Aminosilanized magnetic carbon microspheres as a novel adsorbent were designed and fabricated. The adsorbent was used for the magnetic solid‐phase extraction of bisphenols at trace levels from environmental water samples before liquid chromatography with tandem mass spectrometry analysis. The structure, surface, and magnetic behavior of the as‐prepared aminosilanized magnetic carbon microspheres were characterized by elemental analysis, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, powder X‐ray diffraction, and vibrating sample magnetometry. The effects of the experimental parameters were investigated by the Plackett–Burman design, and then the parameters that were significant to the extraction efficiencies were optimized through a response surface methodology. The aminosilanized magnetic carbon microspheres exhibited high adsorption efficiency and selectivity for bisphenols. Under optimal conditions, low limits of detection (0.011–2.22 ng/L), and a wide linear range (2–3 orders of magnitude), good repeatability (4.7–7.8%, n = 5), and reproducibility (6.0–8.3%, n = 3) were achieved. The results demonstrate that the novel adsorbent possesses great potentials in the determination of trace levels of bisphenols in environmental water samples.     

Raft polymerization of N,N‐dimethylacrylamide from magnetic poly(2‐hydroxyethyl methacrylate) microspheres to suppress nonspecific protein adsorption

Nonspecific interaction is a key parameter affecting the efficiency of proteins, nucleic acids or cell separation. Currently, many approaches to introduce antifouling properties to materials have been developed. Among these, surface modification with polymer brushes plays a prominent role. The aim of this study was to synthesize new magnetic microspheres grafted with poly(N,N‐dimethylacrylamide) (PDMA) that resist nonspecific protein adsorption. Monodisperse macroporous poly(2‐hydroxyethyl methacrylate) (PHEMA) microspheres, 4 μm in size, were synthesized by a multiple swelling polymerization method. To render the microspheres magnetic, iron oxide was precipitated inside the microsphere pores. Functional carboxyl groups, introduced by the hydrolysis of the 2‐(methacryloyl)oxyethyl acetate (HEMA‐Ac) comonomer, were used to react with propargylamine, followed by coupling of a chain transfer agent via an azide‐alkyne click reaction. PDMA was grafted from the PHEMA microspheres using reversible addition‐fragmentation chain transfer polymerization (RAFT), resulting in surfaces with more than 81 wt % PDMA attached. The successful modification of the microspheres was confirmed by XPS. The magnetic microspheres grafted with PDMA showed excellent antifouling properties as tested in bovine serum protein solutions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1036–1043     

Poly(styrene-acrylic acid) magnetic polymer microspheres

Magnetic polymer microspheres have been considered as a kind of new biopolymer materials with great advantages in bioseparation engineering and biomedicine engineering because they have not only polymer functional groups but also magnetic characteristics. Styrene-acrylic acid copolymer (p(S-AA)) magnetic microspheres were synthesized by dispersion polymerization with Fe₃O₄ as core and p(S-AA) as shell. The microspheres were characterized by SEM, size analysis, molecular weight and solid content measurement. All of them indicate that the microspheres are small in size, narrow in distribution, stable in chemistry and rich in functional groups on their surface. __________ Translated from Journal of Beijing Union University (Natural Science) 2008, 21(3): 82–84     

替米考星磁性表面分子印迹聚合物的制备及应用

报道了一种替米考星磁性表面分子印迹聚合物吸附剂。它以Fe₃O₄@SiO₂为磁性基质，替米考星为模板分子，甲基丙烯酸为功能单体，通过硅烷化反应在Fe₃O₄@SiO₂表面键合上3-（甲基丙烯酰氧）丙基三甲氧基硅烷制备得到。该吸附剂对大环内酯类抗生素表现出高选择性和高富集能力（对4种模型大环内酯的富集倍数为212~675倍）。相比传统的非表面分子印迹聚合物，吸附平衡时间可缩短为30 min，可以重复使用至少6次；结合高效液相色谱-紫外检测，将该吸附剂应用于奶粉中4种大环内酯类抗生素的残留检测，所得检出限和定量限分别为0.58~1.36 μg/kg和1.92~4.55 μg/kg，日内（n=5）和日间（n=3）回收率在83.2%~123.0%之间，RSD均小于12.2%。     

Synthesis of cross-linked magnetic composite microspheres containing carboxyl groups

Fe₃O₄ magnetic nano-particles were prepared by a co-precipitation method and were modified using oleic acid. Then, the cross-linked magnetic compsoite microspheres containing a carboxyl group were prepared by using an improved emulsion polymerization with divinylbenzene (DVB) as the cross-linking agent. The composite microspheres comprised the Fe₃O₄ magnetic nano-particles as cores and the copolymer of styrene and acrylic acid as shells. The morphology and structure of the composite microsphere were characterized by FT-IR, transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) and so on. The results show that the composite microspheres were well dispersed in emulsion with uniform sizes and carboxyl groups on their surface. They were cross-linked and stable in 1 mol/L of HCl and DMF. __________ Translated from Journal of Functional Polymers, 2007, 19–20(1): 27–32 [译自: 功能高分子学报]