分子印迹脱硫技术在油品深度脱硫中的研究进展(英文)

作为一种新型的吸附脱硫技术,分子印迹是制备对模板分子具有专一识别能力的聚合物的技术,具有反应条件温和、工艺简单、投资少、污染小、选择性高、不影响石油辛烷值、可同时得到苯并噻吩类精细化工产品等特点,是一项具有广泛应用前景的经济环保型技术。目前,将识别位点建立在基质表面的表面分子印迹技术可以提高识别位点与印迹分子的结合速率,加强印迹材料吸附分离效率,在油品深度脱硫中具有优越性。近年来,以硅胶、TiO2、K2Ti4O9、炭微球为基质制备出吸附二苯并噻吩和苯并噻吩的表面分子印迹聚合物。综述了分子印迹技术在油品深度脱硫中的最近进展,重点介绍了炭微球表面分子印迹脱硫技术的最新研究。     

单一结合位点分子印迹聚合物的合成及性能

采用分子自组装印迹技术在光引发条件下制备了以(S)-布洛芬为模板分子,α-甲基丙烯酸为功能单体的分子印迹聚合物。通过红外对聚合物的结构进行了表征。透射电镜结果表明,交联剂用量对印迹聚合物的形貌特征具有显著的影响。同时结合Scatchard分析研究了印迹聚合物的吸附性能及选择性识别能力,表明印迹聚合物特异性吸附容量为41μmol/g,印迹指数为2.28,对(S)-布洛芬形成单一结合位点,且表现出明显的吸附选择性。     

分子印迹整体材料在固相萃取中的应用及展望

分子印迹整体柱结合了分子印迹技术高的分子识别选择性能和整体柱制备过程简单、易于修饰改性、重复性好以及传质速度快等优点,是固相萃取和固相微萃取技术的发展趋势和前沿课题之一.主要介绍了分子印迹聚合物整体材料在与高效液相色谱和毛细管液相色谱法联用技术方面的应用,以及在固相微萃取中的应用,展望了分子印迹整体材料在固相萃取方面的发展趋势.     

分子印迹微球的合成吸附性能研究

采用分子印迹技术,分别采用反相乳液聚合方法和反相悬浮聚合法,以阿司匹林为目标印迹分子,分别以丙烯酰胺、β-环糊精(β-CD)为功能单体,合成了阿司匹林分子印迹聚合物微球.2种聚合物微球的红外光谱红移表明丙烯酰胺与Asp之间作用以氢键为主,而β-CD与Asp之间形成氢键和包结并存的两种作用方式.吸附研究表明两种分子印迹微球对Asp保留了印迹效应,且两种分子印迹微球均存在两种不同亲和力的结合位点.但P(βAsp)对Asp的结合性能与P(AAsp)相比更强.     

分子印迹技术在电化学中的应用

分子印迹技术是一种对目标分子进行特异性识别的新技术。分子印迹聚合物具有制备方法简单、稳定性好、识别能力强等特点,这些特点使其在膜分离、固相萃取、传感器、催化等方面有了广泛的应用。总结归纳了分子印迹技术的主要特点、分子印迹电化学传感器的制备方法和类别,并对未来发展趋势进行了展望。     

活性自由基聚合的白藜芦醇分子印迹聚合物的合成及在葡萄皮白藜芦醇分析中的应用

RAFT试剂介入制备白藜芦醇分子印迹聚合物并用于实际样品中白藜芦醇的分离富集。以二苄基三硫代碳酸酯(DBTTC)为RAFT试剂,以白藜芦醇为印迹化合物,以丙烯酰胺作为功能单体,利用可逆加成-断裂链转移自由基聚合法(RAFT)制备了白藜芦醇分子印迹聚合物。利用扫描电镜、红外光谱和色谱法考察了单体与交联剂比例、引发剂用量、溶剂用量、反应时间和反应温度对印迹聚合物形态结构、印迹聚合物的识别能力及分离效率的影响。结果显示,利用RAFT聚合法制备的白藜芦醇分子印迹聚合物对模板分子的结合量Q达到1 283μg/g,并具有特异性识别作用。通过活性自由基聚合法合成的分子印迹聚合物具有更好的形态结构,对目标分子具有较高的吸附效率。     

分子印迹聚合物的热力学与物理表征及模拟研究进展

分子印迹聚合物(MIPs)是一种对目标分子具有特异选择性和识别能力的高分子功能材料。文中从印迹聚合物预聚复合物的形成,聚合过程中印迹网络的构成以及聚合后的吸附性能及吸附位点等几方面综述了分子印迹聚合物的热力学、物理表征和模拟在分子印迹聚合物理论研究中的进展。     

分子印迹聚合物在分离领域的应用

分子印迹技术是近年来集高分子合成、分子设计、分子识别、仿生生物工程等众多学科优势发展起来的一种应用广泛的新型技术.阐述了分子印迹方法的基本原理,介绍了分子印迹聚合物在分离领域的应用.综述了该技术的研究现状,并展望了其发展趋势.     

分子印迹型二氧化钛的制备方法研究进展

分子印迹技术为改善二氧化钛的选择性提供了新思路,将二氧化钛能够受光激发降解有机污染物的能力与分子印迹聚合物的特异识别性能力结合已逐渐成为近年来的研究热点。本文简要综述了分子印迹型二氧化钛的制备方法,主要包括表面分子印迹技术和分子印迹溶胶-凝胶技术。     

表面印迹聚合物的制备及其在药物分离分析中的应用

表面分子印迹技术是在载体表面上发生聚合反应,将分子识别位点建立在载体的外层或者表面。从而使表面分子印迹聚合物具有结合速度快、识别选择性强、结合容量高、提高印迹材料的效率等优点。近年来表面分子印迹技术在药物分离分析中的应用引起人们的关注。简要介绍了表面分子印迹聚合物的原理及4种制备方法(溶胶-凝胶法、接枝共聚法、牺牲载体法、聚合加膜法、活性可控自由基聚合法),并对其在药物分离分析的4个方面(中药提取分离中;药物传感器方面;手性药物拆分中;药物释放中)的应用进行了综述。     

Ordered‐Assembly Conductive Nanowires Array with Tunable Polymeric Structure for Specific Organic Vapor Detection

An artificial organic vapor sensor based on a finite number of 1D nanowires arrays can provide a strategy to allow classification and identification of different analytes with high efficiency, but fabricating a 1D nanowires array is challenging. Here, a coaxial Ag/polymer nanowires array is prepared as an organic vapor sensor with specific recognition, using a strategy combining superwettability‐based nanofabrication and polymeric swelling‐induced resistance change. Such organic vapor sensor containing commercial polymers can successfully classify and identify various organic vapors with good separation efficiency. An Ag/polymer nanowires array with synthetic polyethersulfone polymers is also fabricated, through molecular structure modification of the polymers, to distinguish the similar organic vapors of methanol and ethanol. Theoretical simulation results demonstrate introduction of specific molecular interaction between the designed polymers and organic vapors can improve the specific recognition performance of the sensors.     

分子印迹传感器的研究进展

分子印迹传感器具有灵敏度高、选择性好、价格低廉等优点,因此,受到许多研究者广泛的关注和深入的研究。文章介绍了分子印迹聚合物的主要制备方法,分子印迹聚合物和分子印迹传感器的识别机理,综述了分子印迹技术在光学传感器、电化学传感器方面的应用,并展望了分子印迹传感器未来的研究方向。     

Uniformly sized molecularly imprinted polymer for (S)-nilvadipine. Comparison of chiral recognition ability with HPLC chiral stationary phases based on a protein

Uniformly sized molecularly imprinted polymers (MIPs) for (S)-nilvadipine have been prepared by a multistep swelling and polymerization method using methacrylic acid, 2-(trifluoromethyl)acrylic acid, 2-vinylpyridine, or 4-vinylpyridine (4-VPY) as a functional monomer and ethylene glycol dimethacrylate (EDMA) as a cross-linker. The chiral recognition abilities of the MIPs for nilvadipine and other dihydropyridine calcium antagonists were evaluated using a mixture of sodium phosphate buffer (or water) and acetonitrile or only acetonitrile as the mobile phase. The (S)-nilvadipine-imprinted 4-VPY-co-EDMA polymers gave the highest resolution for nilvadipine among the MIPs prepared. In addition, the enantioseparation of nilvadipine was attained using the (S)-nilvadipine-imprinted EDMA polymers, without use of a functional monomer. 1H NMR and molecular modeling studies suggested a one-to-one hydrogen-bonding-based complex formation of (S)-nilvadipine with 4-VPY in chloroform. These results reveal that the (S)-nilvadipine-imprinted EDMA polymers could recognize the template molecule by its molecular shape, and that in addition to this recognition, hydrophobic and hydrogen-bonding interactions seems to play important roles in the retention and chiral recognition of nilvadipine on the 4-VPY-co-EDMA polymers in hydroorganic mobile phases. By optimizing chromatographic conditions such as column temperature and flow rate, the baseline separation of nilvadipine enantiomers was attained with a short analysis time and with a column efficiency comparable to commercially available chiral stationary phases based on a protein, such as ovomucoid or alpha1-acid glycoprotein.     

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.     

Different approaches to synthesize carnosine selective imprinted polymers

Selective recognition of proteins by synthetic molecularly imprinted polymers is one of the interesting topics in biosciences. Carnosine (β-alanyl-l-histidine) and related histidine containing peptides are distributed in a wide range of tissues in vertebrate organisms. These peptides have been extensively studied because of their important physiological properties besides their metal chelation property. In this study, preparation of carnosine specific imprinted polymers (MIPs) for the recognition of imidazole containing peptides with and without copper ion is reported. Carnosine and copper–carnosine complex were employed as template molecules where 4-vinylpyridine and ethylenglycol dimethacrylate were chosen as monomer and crosslinker, respectively. The selectivity and binding studies of copper–carnosine imprinted polymer showed high selectivity toward both carnosine (template peptide) and the cupric ion. The selectivity of copper–carnosine imprinted polymer was 65% and carnosine imprinted polymer was approximately 40%. These results indicate that specific recognition of carnosine is depending on the basis of metal coordination     

含杯芳烃单体及其聚合方法的研究进展

杯芳烃作为继冠醚和环糊精之后的第三代主体分子具有独特的分子离子识别能力和结构易修饰性.利用聚合物稳定性好、易于加工的特性将杯芳烃键合到聚合物上,有望制备出新型功能高分子材料.共聚法是一种制备含杯芳烃聚合物的重要方法,通过在杯芳烃上沿或下沿接上可聚合基团制备含杯芳烃单体,然后均聚或与其它单体共聚形成聚合物.主要阐述了含杯芳烃单体及其聚合方法的研究进展.     

Aqueous compatible polymers in bionanotechnology

Core-shell molecularly imprinted particles (CS-MIPs) have been synthesised using the technique of emulsion polymerisation with caffeine and theophylline being used in the surface template polymerisation with ethylene glycol dimethacrylate and oleylphenyl hydrogen phosphate. A radiolabelling study with caffeine-8-14C showed that the template was completely located at the particle surface during polymerisation. Caffeine could be specifically bound to a caffeine-imprinted CS-MIP to give a biphasic Scatchard binding curve, whereas the binding profile to a theophylline-imprinted CS-MIP was monophasic. The nanoparticles have the potential to be used in the molecular recognition of small molecules in a complex biological matrix. Water soluble highly-branched imidazole end-chain functionalised polymers of nanodimensions have also been synthesised via reversible addition-fragmentation chain transfer polymerisation. The polymers have lower critical solution temperatures which occur at sub-ambient temperatures and have proven useful in the affinity precipitation of proteins which are particularly temperature sensitive, e.g. the histidine-tagged protein fragment BRCA1. An overview of both of these areas of research is described outlining the diversity of these aqueous compatible polymers in molecular recognition processes at the nanoscale.     

Selective vapor sorption by polymers and cavitands on acoustic wave sensors: is this molecular recognition?

Selectivity patterns for the sorption of organic vapors from the gas phase into cavitand monolayers on acoustic wave sensors are very similar to those seen for sorption of the same vapors by amorphous polymers, demonstrating that the vapor/cavitand selectivity patterns are determined primarily by solubility interactions. The amorphous polymers serve as controls demonstrating that the three-dimensional structure of a cavitand layer is not primarily responsible for the selectivity observed. Binding and selectivity in the examples cited are governed primarily by general dispersion interactions and not by specific oriented interactions that could lead to molecular recognition.     

新型纳米多孔材料——金属有机配位聚合物的包结作用及其应用研究进展

金属有机配位聚合物(MOCPs)具有纳米多孔的特殊结构,且结构具有可设计性,通过MOCPs活性位点与客体分子的包结作用能够选择性地包结多种客体分子,表现出特有的分子识别能力.MOCPs作为一种新型多孔材料在择形及手性催化、吸附分离、气体储存、分子识别与传感、生物模拟、微反应器等研究应用方面具有诱人的潜力.综述了MOCPs的设计、合成及主-客体相互作用方式,并展望了这种聚合物的应用前景.