基于手性功能单体的L-色氨酸分子印迹复合膜的研制及性能研究

以L-色氨酸为印迹分子,S-2-巯基丙酸为手性功能单体,分别制备了25个L-色氨酸分子印迹复合膜(MICM_1~25)及相应的非印迹复合膜(NICM_1~25)。采用扫描电镜(SEM)表征最优印迹复合膜(MICM₅)及相应的非印迹复合膜(NICM₅)的外观形态,通过等温吸附模型对印迹复合膜的吸附性能进行评价,并结合高效液相色谱法(HPLC法)分析MICM₅对外消旋体DL-色氨酸的手性拆分能力。结果表明:以聚四氟乙烯膜为支撑膜,印迹分子、功能单体和交联剂的摩尔比为1∶8∶90,甲醇∶水(1∶1,体积比)为致孔剂可制备出较优的分子印迹复合膜,其对外消旋体DL-色氨酸有较好的手性拆分能力,拆分因子达到2.41。相对于常用功能单体制备的L-色氨酸分子印迹复合膜,采用S-2-巯基丙酸为手性功能单体制备的L-色氨酸分子印迹复合膜具有更高的亲和性和更好的手性拆分能力。     

双连续相微乳液聚合制备L-色氨酸分子印迹膜

以L-色氨酸(L-Trp)为模板分子,丙烯酸(AA)为功能单体,同时作为双连续相微乳液的乳化剂,采用光引发无皂双连续相微乳液聚合制备L-色氨酸分子印迹膜。考察了丙烯酸、L-色氨酸、骨架单体比例对印迹膜分离性能的影响,结果表明印迹膜对L-Trp具有良好的选择吸附性和优先渗透性,相比于结构类似物L-酪氨酸其分离因子可达1.97,具有良好的应用前景。     

L-色氨酸分子印迹膜的制备及其性能研究

以L-色氨酸(L-Trp)为模板,壳聚糖(CTS)为功能单体,硅烷偶联剂KH-560为前躯体,采用共混、相转化法制备壳聚糖/硅烷偶联剂KH-560手性分子印迹杂化膜。考察了热处理温度、L-Trp与CTS质量比以及硅烷偶联剂KH-560与CTS质量之比对印迹膜分离性能的影响,结果表明热处理温度在100℃、L-Trp与CTS质量比为1.02×10-2、硅烷偶联剂KH-560与CTS质量之比为53.4时,对L-Try的吸附容量约为9.8μmol/g,分离因子达到7.25。     

苯丙氨酸衍生物分子印迹聚合物的制备及手性识别机理

以L-特丁氧羰基苯丙氨酸(Boc-L-Phe)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(EDMA)为交联剂,合成了一种新型的分子印迹聚合物(MIP),将其作为色谱固定相,对其对映异构体进行手性拆分。分别采用红外光谱和核磁共振氢谱系统研究了印迹聚合物的结合位点和识别机理。结果表明,该聚合物通过协同氢键作用形成1∶3型配合物,专一地结合Boc-L-Phe分子。MAA分子羧基上的C=O是氢键的质子接受体;Boc-L-Phe分子上的氨基以及羧基上的氢氧键是质子的给予体,是与MAA形成氢键作用的选择性识别位点。     

L-苹果酸分子印迹聚合物微球的制备及性能评价

以L-苹果酸为模板分子,丙烯酰胺(AA)、乙二醇二甲基丙烯酸酯(EGDMA)分别为功能单体和交联剂,采用沉淀聚合法制备了分子印迹聚合物微球,研究了聚合体系组成对模板聚合物吸附特性的影响。实验表明,以1∶4∶20的物质的量比加入模板分子、AA和EGDMA时,制备的模板聚合物吸附容量高,印迹效果好。通过Scat-chard分析研究了聚合物的选择结合性能,结果表明分子印迹聚合物微球在识别L-苹果酸的过程中存在2类结合位点,而空白印迹聚合物微球只存在1类结合位点。印迹聚合物微球对L-苹果酸和D-苹果酸的手性分离因子α达2.05。     

水相中色氨酸分子印迹聚合物微球的合成、表征及其识别性能研究

分别以色氨酸、α-甲基丙烯酸或丙烯酸胺、三羟甲基丙烷丙烯酸酯、甲苯作为模板分子、功能单体、交联剂和致孔剂,在较佳工艺条件下水体系中合成了色氨酸分子印迹聚合物微球;其形貌、粒径分布以及模板分子与功能单体之间的相互作用分别通过SEM、激光粒度分析仪及紫外分光光度法进行表征.其吸附能力分别通过静态吸附法测定其分离因子(α)和相对分离因子(β)来确定.实验结果表明,该法合成的色氨酸分子印迹聚合物对底物具有较高的吸附选择性和较大的吸附容量.     

辐射法制备布洛芬金属分子印迹聚合膜

以消炎镇痛药(S)-布洛芬与Cu2+配合物为模板分子,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,聚砜膜为多孔支撑层,利用辐射引发聚合制备了Cu2+配位分子印迹复合膜。通过紫外光谱研究发现,(S)-布洛芬、Cu2+和甲基丙烯酸形成了配位比为1∶2∶2的3元配合物。通过扫描电镜及渗透实验发现聚砜基膜固含量为17%时,修饰后印迹膜形态及性能最好。同时,通过选择渗透实验发现,印迹膜对其手性对称物(R)-布洛芬及结构类似物酮洛芬渗透选择性较差。     

分子印迹聚合物膜的制备及其应用

分子印迹膜兼具分子印迹与膜技术的优点,近年来已成为分子印迹技术领域研究的热点之一.首先对分子印迹技术及分子印迹膜进行了简介,继而重点对分子印迹膜的主要制备方法,包括原位聚合法、相转化法、表面修饰法和电化学聚合法等进行了评述,对现有分子印迹膜的分离性能进行了总结和分析.最后对分子印迹膜在手性物质拆分、固相萃取、农药残留检测及仿生传感等领域的应用及其研究方向进行了介绍和展望.     

优化阿魏酸印迹微球的制备条件及其分子识别性能

以阿魏酸(FA)为模板分子、乙二醇二甲基丙烯酸酯(EDMA)为交联剂、丙烯酰胺(AM)为功能单体、偶氮二异丁腈(AIBN)为引发剂,制备的分子印迹聚合物微球对阿魏酸具有高选择性.通过优化制备条件获得阿魏酸分子印迹聚合物微球(MIPs),并对其结构、形貌及热稳定性进行表征.结果表明,模板分子为功能单体,交联剂的最佳比例为...     

醋酸纤维-奎宁分子印迹复合膜的制备及分离性能研究

采用多孔醋酸纤维膜为支撑体,制备了奎宁分子印迹复合膜,并对膜的选择结合性及分离性能进行了研究.研究结果表明,奎宁分子印迹复合膜对模板分子奎宁具有较好的选择结合性,奎宁在膜上结合量达到20.6μmol/g,奎宁/辛可宁的分离因子则为5.6;膜透过实验表明辛可宁透过奎宁分子印迹复合膜速率远大于奎宁的透过速率,该透过机理符合膜渗透的"溶解一扩散"模型.     

Protein recognition via surface molecularly imprinted polymer nanowires

In this paper, we present a technique for the preparation of polymer nanowires with the protein molecule imprinted and binding sites at surface. These surface imprinting nanowires exhibit highly selective recognition for a variety of template proteins, including albumin, hemoglobin, and cytochrome c. This recognition may be through a multistep adsorption, with the specificity conferred by hydrogen bonding and shape selectivity. Due to the protein imprinted sites are located at, or close to, the surface; these imprinted nanowires have a good site accessibility toward the target protein molecules. Furthermore, the large surface area of the nanowires results in large protein molecule binding capacity of the imprinted nanowires.     

Data on the structure and recognition properties of the template-selective binding sites in semi-IPN-based molecularly imprinted polymer membranes

Data on the structure and recognition properties of the template-selective binding sites in molecularly imprinted polymer membranes are presented. Porous molecularly imprinted polymer membranes based on semi-interpenetrating polymer networks (semi-IPN) were synthesized using the method of molecular imprinting in a combination with the method of computational modeling. Methacrylic acid, itaconic acid, and acrylamide were identified as optimal functional monomers for a model template — atrazine. Optimal ratios between atrazine and functional monomers as well as their binding energies were determined using the method of computational modeling and compared with the experimental data on the adsorbtion capability of porous molecularly imprinted polymer membranes. The factors influencing quality of the template-binding sites in MIP membranes (binding energy template-functional monomer and the number of functional groups taking part in the recognition of the template molecule) were revealed. The computational atrazine-selective membranes were capable of highly-selective and effective adsorbtion of atrazine from its 10^− 9–10^− 4 M aqueous solutions, and were characterized by high stability during prolonged storage. The apparent structure of the synthetic mimics of biological receptors to triazine herbicides was compared with the structure of their natural counterparts.     

Imprinting of nucleotide and monosaccharide recognition sites in acrylamidephenylboronic acid-acrylamide copolymer membranes associated with electronic transducers

Molecular recognition sites for the nucleotides adenosine 5'-monophosphate (1), guanosine 5'-monophosphate (2), cytosine 5'-monophosphate (3), and uridine 5'-monophosphate (4) are imprinted in an acrylamide-acrylamidephenylboronic acid copolymer (5) membrane. The imprinted membranes are assembled on piezoelectric Au quartz crystals or Au electrodes via electropolymerization or on the gate surface of an ISFET device by radical polymerization. The imprinted membranes reveal selectivity toward the imprinted nucleotide, and the association of the respective nucleotides with the recognition sites is transduced by the following: (i) microgravimetric, quartz crystal microbalance (QCM) measurements; (ii) Faradaic impedance analyses, and (iii) potentiometric responses of the ISFET devices. While the microgravimetric QCM measurements reflect the swelling of the polymers upon the association of the nucleotides with the recognition sites, the ISFET response is due to the charging of the polymer membrane as a result of the formation of the nucleotide-boronate complex. The selective detection of the nucleotides may lead to new DNA/RNA sequencing methods. Also, specific recognition sites for beta-D(+)-glucose (6), D(+)-galactose (7), and beta-D(-)-fructose (8) were imprinted in an acrylamide-acrylamidephenylboronic acid copolymer (5) membrane associated with an ISFET device. Selective sensing of the respective monosaccharides is accomplished in the presence of the imprinted membrane-functionalized ISFET devices.     

17β-雌二醇乙酸纤维分子印迹复合膜的制备及性能研究

以多孔乙酸纤维膜为载体,17β-雌二醇为模板,采用紫外光引发制备了17β-雌二醇乙酸纤维分子印迹复合膜。试验对膜的选择吸附性和分离透过性进行了探讨。实验结果表明,所合成的乙酸纤维分子印迹复合膜对模板分子17β-雌二醇具有较好的选择吸附性,吸附量达10.2μmol/g;17β-雌二醇/17α-炔雌醇的分离因子为4.7。膜透过实验表明,该分子印迹复合膜能将17β-雌二醇与17α-炔雌醇分离开,表明17α-炔雌醇作为结构类似物在复合膜上的结合牢固性不如模板分子。     

掺杂无机纳米粒子的阿魏酸分子印迹复合膜的制备

分子印迹膜是一种兼具分子印迹技术与膜分离技术双重优点的新兴技术,但由于有机膜的力学强度较小,在分离过程中容易使印迹孔穴的空间变形和互补官能团位置的失稳,使得其分离效率大大降低。文中使用紫外光引发原位聚合的方法,以聚偏氟乙烯(PVDF)作为支撑膜,将无机纳米材料和铸膜液共混制备了含有无机纳米材料的阿魏酸分子印迹复合膜。利用红外光谱和扫描电镜测试了膜的结构和表面形貌,发现纳米粒子是以纯物理方式共混的,且都分散在孔的周围,有利于维持膜的孔穴结构。通过平板超滤装置对改性膜的分离性能、水通量和承压能力进行了研究,结果表明,添加质量分数0.5%18 nm TiO_2的改性膜性能最好,承压能力在0.4 MPa以上,分离因子在3.4左右,水通量为6696 L/(m~2·h)。     

Exploiting β-cyclodextrin as functional monomer in molecular imprinting for achieving recognition in aqueous media

A series of molecularly imprinted polymers (MIPs) for 4,4′-(1,4-phenylenediisopropylidene)bisphenol (BPP) were prepared by using β-cyclodextrin (β-CD) as functional monomer, toluene 2,4-diisocyanate (TDI) or 4,4′-Diphenylmethane diisocyanate (DDI) as the cross-linker. The results of binding experiments showed that the MIPs can bind the template selectively in aqueous media. The binding specificity mechanism of the polymers was investigated in detail. The template molecule is too large and cannot be included in the cavity of one β-CD molecule. The mutual orientation of β-CD molecules in the imprinted polymers is regulated by molecular imprinting, so that they can cooperatively bind the template molecule. It is suggested that the major contribution to the recognition ability of the imprinted polymer was the stereo-shape effect inherent in the MIPs. The study indicated that hydrophobic effects play an important role in the recognition process.     

分子识别材料D-萘普生印迹聚合物的制备与结构性能

以D-萘普生为目标分子,采用差示紫外吸收光谱法研究了萘普生分子与功能单体间的作用力性质,确证了萘普生与丙烯酰胺通过氢键和离子键方式自组装形成超分子复合物。按不同的溶剂(致孔剂)用量合成了一组分子印迹聚合物材料,利用红外光谱对产物结构进行了分析,表明合成的产品具有所需的特征结构。首次使用透射电镜表征了分子印迹聚合物的微观形貌特征,阐明了溶剂的致孔作用机理,并结合吸附动力学研究了该材料的网孔结构对吸附速率的影响。根据选择性吸附实验的结果计算了所合成材料的特异吸附容量和印迹指数,其中,印迹指数最高达3.756。     

Thermal bonding of polymeric capillary electrophoresis microdevices in water

A new method for thermally bonding poly(methyl methacrylate) (PMMA) substrates to form microfluidic systems has been demonstrated. A PMMA substrate is first imprinted with a Si template using applied pressure and elevated temperature to form microchannel structures. This embossing method has been used to successfully pattern over 65 PMMA pieces using a single Si template. Thermal bonding for channel enclosure is accomplished by clamping together an imprinted and a blank substrate and placing the assembly in boiling water for 1 h. The functionality of these water-bonded microfluidic substrates was demonstrated by performing high-resolution electrophoretic separations of fluorescently labeled amino acids. Testing of bond strength in four microdevices showed an average failure pressure of 130 kPa, which was comparable to the bond strength for devices sealed in air. Subsequent profilometry of separated substrates revealed that the dimensions of the channels were well preserved during the bonding process. This new methodology for generation of microfluidic constructs should facilitate the permanent incorporation of hydrated, molecular size-selective membranes in microdevices, thus circumventing problems associated with membrane swelling in microfluidic systems upon exposure to water.     

茶碱-铜(Ⅱ)离子配位分子印迹膜的制备及表征

以茶碱为模板分子,铜离子为配体、4-乙烯吡啶(4-VP)为功能单体、乙二醇二甲基丙烯酸酯(EDMA)为交联剂,在聚偏氟乙烯(PVDF)基膜上采用表面涂覆热聚合的方法制备了金属配位分子印迹膜,通过平衡结合实验研究了印迹膜对茶碱的结合性能和结合选择性。结果表明,铜离子的配位作用能提高印迹膜的结合性,在茶碱浓度为0.2 mmol/L时结合量从1.61μmol/g提高到了2.69μmol/g。在铜离子配位的作用下印迹膜对茶碱的结合能力高于同样化学组成的非印迹膜。相比于可可碱印迹膜对茶碱有较好的选择性,在浓度为0.05 mmol/L时选择性达到了2.39。