种子溶胀悬浮聚合法制备分子印迹聚合物微球

 以酪氨酸为印迹分子 ,甲基丙烯酸为功能单体 ,三羟甲基丙烷三甲基丙烯酸酯 (TRIM )为交联剂 ,采用种子溶胀悬浮聚合法在水溶液中制备了一系列分子印迹聚合物微球 (MIPMs)。利用扫描电镜 (SEM)对此微球的粒径大小、粒径分布、表面孔与孔径分布等进行了分析研究 ,探讨了影响其形貌的主要因素 ,并将所得微球用作固定相研究了其分子选择吸附性能。研究表明 ,种子溶胀悬浮聚合法能够制得单分散性较好的、表面带有微孔的分子印迹聚合物微球 ,且该微球呈现出较好的特异吸附性能。     

Two‐Dimensional Membranes: New Paradigms for High‐Performance Separation Membranes

Two‐dimensional (2D) materials with atomic thicknesses have aroused great interest as promising building blocks for the preparation of ultrathin 2D membranes. These 2D membranes can exhibit unprecedentedly high separation permeance owing to their ultrasmall membrane thicknesses and superior selectivity because of their size‐selective nanopores and/or nanochannels. Until now, a large number of 2D membranes with good performance have been reported, highlighting the potential of these novel membranes for efficient liquid and gas separations. Summarized in this review are the latest advances in 2D membranes, with a special focus on industrially attractive separation processes, fabrication methods of laminar membranes, choices of membrane materials, designs of membrane structures, and unique membrane transport properties. Opportunities and challenges of 2D membranes for commercial applications are also briefly discussed.     

Template synthesized molecularly imprinted polymer nanotube membranes for chemical separations

In this report, we describe the synthesis of a molecularly imprinted polymer (MIP) nanotube membrane, using a porous anodic alumina oxide (AAO) membrane by surface-initiated atom transfer radical polymerization (ATRP). The use of a MIP nanotube membrane in chemical separations gives the advantage of high affinity and selectivity. Furthermore, because the molecular imprinting technique can be applied to different kinds of target molecules, ranging from small organic molecules to peptides and proteins, such MIP nanotube membranes will considerably broaden the application of nanotube membranes in chemical separations and sensors. This report also shows that the ATRP route is an efficient procedure for the preparation of molecularly imprinted polymers. Furthermore, the ATRP route works well in its formation of MIP nanotubes within a porous AAO membrane. The controllable nature of ATRP allows the growth of a MIP nanotube with uniform pores and adjustable thickness. Thus, using the same route, it is possible to tailor the synthesis of MIP nanotube membranes with either thicker MIP nanotubes for capacity improvement or thinner nanotubes for efficiency improvement.     

Self‐Assembled Isoporous Block Copolymer Membranes with Tuned Pore Sizes

The combination of nonsolvent‐induced phase separation and the self‐assembly of block copolymers can lead to asymmetric membranes with a thin highly ordered isoporous skin layer. The effective pore size of such membranes is usually larger than 15 nm. We reduced the pore size of these membranes by electroless gold deposition. We demonstrate that the pore sizes can be controlled precisely between 3 and 20 nm leading to a tunable sharp size discrimination in filtration processes. Besides fractionation of nanoparticles and biomaterials, controlled drug delivery is an attractive potential application.     

Molecularly Mixed Composite Membranes for Advanced Separation Processes

Porous organic cages (POCs) are individual soluble, porous molecules. When fabricated into mixed‐matrix membranes (MMMs), the soluble POC molecules have the potential to exhibit intimate molecular‐level mixing with the polymer matrix. POCs have only recently been incorporated into mixed matrix membrane materials, but this process has not yet resulted in significant improvements of membrane performance. Now, vertex‐functionalized amorphous scrambled porous organic cages (ASPOCs) have been utilized as membrane performance enhancers and the amorphous ASPOC mixtures are observed to distribute throughout the matrix without any indication of particle formation or agglomeration, creating unique, molecularly mixed composite membranes. Overall, the molecularly mixed composite membrane provide significant increases in both membrane permeability and selectivity, offering new avenues for creation of membranes with unique properties in industrially relevant separations.     

Solvent-extraction and Langmuir-adsorption-based transport in chemically functionalized nanopore membranes

We have investigated the transport properties of nanopore alumina membranes that were rendered hydrophobic by functionalization with octadecyltrimethoxysilane (ODS). The pores in these ODS-modified membranes are so hydrophobic that they are not wetted by water. Nevertheless, nonionic molecules can be transported from an aqueous feed solution on one side of the membrane, through the dry nanopores, and into an aqueous receiver solution on the other side. The transport mechanism involves Langmuir-type adsorption of the permeating molecule onto the ODS layers lining the pore walls, followed by solid-state diffusion along these ODS layers; we have measured the diffusion coefficients associated with this transport process. We have also investigated the transport properties of membranes prepared by filling the ODS-modified pores with the water-immiscible (hydrophobic) liquid mineral oil. In this case the transport mechanism involves solvent extraction of the permeating molecule into the mineral oil subphase confined with the pores, followed by solution-based diffusion through this liquid subphase. Because of this different transport mechanism, the supported-liquid membranes show substantially better transport selectivity than the ODS-modified membranes that contain no liquid subphase.     

Correlating anomalous diffusion with lipid bilayer membrane structure using single molecule tracking and atomic force microscopy

Anomalous diffusion has been observed abundantly in the plasma membrane of biological cells, but the underlying mechanisms are still unclear. In general, it has not been possible to directly image the obstacles to diffusion in membranes, which are thought to be skeleton bound proteins, protein aggregates, and lipid domains, so the dynamics of diffusing particles is used to deduce the obstacle characteristics. We present a supported lipid bilayer system in which we characterized the anomalous diffusion of lipid molecules using single molecule tracking, while at the same time imaging the obstacles to diffusion with atomic force microscopy. To explain our experimental results, we performed lattice Monte Carlo simulations of tracer diffusion in the presence of the experimentally determined obstacle configurations. We correlate the observed anomalous diffusion with obstacle area fraction, fractal dimension, and correlation length. To accurately measure an anomalous diffusion exponent, we derived an expression to account for the time-averaging inherent to all single molecule tracking experiments. We show that the length of the single molecule trajectories is critical to the determination of the anomalous diffusion exponent. We further discuss our results in the context of confinement models and the generating stochastic process.     

Polyacrylonitrile enzyme ultrafiltration and polyamide enzyme microfiltration membranes prepared by diffusion and convection

Glucose oxidase (GOD) and catalase (CAT) were covalently immobilized onto three types of polyacrylonitrile (PAN 1, PAN 2, and PAN 3) ultrafiltration (UF) membranes with different pore sizes and one type of polyamide (PA) microfiltration (MF) membrane by the bifunctional reagent, glutaraldehyde. The initial membranes were pre-modified to generate active amide groups in the PAN membranes and active amino groups in the PA membranes. The PAN 3 membrane contained the highest amount of active groups, and the membrane PA the lowest. The modified membranes were enzyme-loaded by diffusion and convection (UF). The effect of membrane pore size and immobilization methods on enzymatic activity and bound protein were studied. The most effective immobilized system was prepared by diffusion using a PAN 3 membrane as a carrier (bound protein: 0.055 mg/cm(2), relative activity: 87.6%). This membrane had the highest pore size of all the PAN membranes. Despite the highest pore size of PA membrane, the enzyme PA membranes prepared by diffusion showed the lowest amount of bound protein (0.03 mg/cm(2)) and the lowest relative activity (35.38%). This correlates with the lowest amount of active groups found in these membranes. The relative activity was higher for all the enzyme systems loaded by diffusion. The systems prepared by convection of the enzyme solution contained higher amounts of enzymes (0.035-0.13 mg/cm(2) protein), which led to internal substrate diffusion resistance and a decrease in the GOD relative activity (21.55-68.5%) in these systems. The kinetic parameters (V(max) and K(m)) and the glucose conversion of the immobilized systems prepared by diffusion were also studied. [diagram in text].     

The use of moment theory to interpret diffusion and sieving measurements in terms of the pore size distribution in heteroporous membranes

Moment theory has been applied to model porous membranes to show that one can place reasonable bounds on the cumulative pore size distribution, the hindered diffusivity or the reflection coefficient of large solutes in a heteroporous membrane by measuring the diffusive permeability to a small solute, the hydraulic permeability and one or two additional transport characteristics. These additional measurements involve either the flux of a small solute at Pe1, the hindered diffusivity of a large solute or the reflection coefficient of a large solute at Peå1. Membrane heteroporosity is incroporated in the predicted bounds without requiring one to make any a priori assumptions about the nature of the pore size distribution. In this paper, the results from calculations performed with different model membranes containing log-normal pore size distributions are reported. A comparison of the results obtained with three different membranes shows that one can distinguish between membranes with the same average pore size but different pore size distributions by measuring either the hindered diffusion coefficient or the reflection coefficient of two different sized solutes. A comparison of the bounds on D and the bounds on σ predicted from different types of transport measurements shows that, under certain conditions, one can place tighter bounds on one transport characteristic by measuring a different one.     

Electrochemical sensing with electrodes modified with molecularly imprinted polymer films

This article summarises our work on the development of voltammetric sensors based on molecularly imprinted polymers. Several recognition elements and integration strategies were used:1.membranes electropolymerised at the electrode surface; 2.casting of polymeric membranes by drop-coating a solution of pre-formed polymer (polyphosphazene) and template in a low-boiling-point solvent on to the electrode surface; 3.preparation of composite membranes containing conductive material (graphite or carbon black), acrylic-type molecularly imprinted polymers (small particle size), and PVC as binder; and 4.in-situ polymerisation of a thin layer of acrylic imprinted polymer deposited on the electrode surface by spin coating.All the options evaluated offer the possibility of controlling electrode characteristics such as hydrophobic/hydrophilic character, permeability, or film thickness, which are essential for obtaining good sensor performance.     

分子印迹溶胶-凝胶材料的制备及应用

分子印迹技术是制备对特定分子具有选择性识别的聚合物的技术。分子印迹技术与溶胶-凝胶过程相结合,可设计多孔无机主体,增强分子识别能力,并具有极好的热稳定性和水解稳定性。改变溶胶-凝胶过程的条件,可制备具有最佳孔隙率和表面积,并用于分离复杂的混合物、选择性吸附富集模板分子(或目标分子)、催化、微合成器应用的分子印迹溶胶-凝胶材料。综述了溶胶．凝胶技术和分子印迹技术的特点,分子印迹溶胶-凝胶技术和分子印迹溶胶．凝胶材料的概念、基本原理、制备方法及应用。     

Grafting of molecularly imprinted polymer to porous polyethylene filtration membranes by plasma polymerization

An application of plasma-induced grafting of polyethylene membranes with a thin layer of molecularly imprinted polymer (MIP) was presented. High-density polyethylene (HDPE) membranes, “Vyon,” were used as a substrate for plasma grafting modification. The herbicide atrazine, one of the most popular targets of the molecular imprinting, was chosen as a template. The parameters of the plasma treatment were optimized in order to achieve a good balance between polymerization and ablation processes. Modified HDPE membranes were characterized, and the presence of the grafted polymeric layer was confirmed based on the observed weight gain, pore size measurements, and infrared spectrometry. Since there was no significant change in the porosity of the modified membranes, it was assumed that only a thin layer of the polymer was introduced on the surface. The experiments on the re-binding of the template atrazine to the membranes modified with MIP and blank polymers were performed. HDPE membranes which were grafted with polymer using continuous plasma polymerization demonstrated the best result which was expressed in an imprinted factor equal to 3, suggesting that molecular imprinting was successfully achieved.

Factors influencing the transport of short-chain alcohols through mesoporous gamma-alumina membranes

The pressure-driven transport of water, ethanol, and 1-propanol through supported gamma-alumina membranes with different pore diameters is reported. Water and alcohols had similar permeabilities when they were transported through gamma-alumina membranes with average pore diameters of 4.4 and 6.0 nm, and the permeability coefficient was found to be proportional to the square of pore size, in accordance with a viscous flow mechanism. For transport through membranes with an average diameter of 3.2 nm, the behavior of water was in accordance with the viscous flow mechanism, but the permeability of the membrane for ethanol and 1-propanol was much smaller than expected and could not be explained in terms of viscous flow. Although the low permeability of the membrane with 3.2 nm pores for ethanol and 1-propanol was partly due to the presence of small amounts of water in the alcohols, the permeability coefficients were still substantially smaller when water was absent. This intrinsic difference between water and alcohol may be due to differences in molecular size, chemisorption of alcohols on the oxide pore wall, which would lead to a reduction of the effective pore size, and/or a certain degree of translational ordering of the alcohol molecules inside the membrane pores, which leads to an effectively higher viscosity and, therefore, to a higher transport resistance.     

Transport of Carbamazepine,Ciprofloxacin and Sulfamethoxazole in Activated Carbon: Solubility and Relationships between Structure and Diffusional Parameters

The transport of carbamazepine, ciprofloxacin and sulfamethoxazole in the different pores of activated carbon in an aqueous solution is a dynamic process that is entirely dependent on the intrinsic parameters of these molecules and of the adsorbent. The macroscopic processes that take place are analyzed by interfacial diffusion and reaction models. Modeling of the experimental kinetic curves obtained following batch treatment of each solute at 2 µg/L in tap water showed (i) that the transport and sorption rates were controlled by external diffusion and intraparticle diffusion and (ii) that the effective diffusion coefficient for each solute, with the surface and pore diffusion coefficients, were linked by a linear relationship. A statistical analysis of the experimental data established correlations between the diffusional parameters and some geometrical parameters of these three molecules. Given the major discontinuities observed in the adsorption kinetics, the modeling of the experimental data required the use of traditional kinetic models, as well as a new kinetic model composed of the pseudo first or second order model and a sigmoidal expression. The predictions of this model were excellent. The solubility of each molecule below 60 °C was formulated by an empirical expression.     

渗透物在致密聚合物膜中扩散的分形介质模型

利用自由体积理论讨论了渗透物分子在致密聚合物膜内的扩散机理, 提出了“扩散通道”的概念, 建立了渗透物在致密聚合物膜中扩散的分形介质模型, 考虑了自由体积分布对扩散过程的影响. 根据建立的模型, 渗透物在膜内的扩散是由在“扩散通道”上的一系列跳跃构成的. 根据致密膜内扩散通道的关联长度ξ(p)与膜厚L的关系, 可以把扩散分为正常扩散、 过渡扩散和分形扩散三部分, 给出了扩散相图, 提出并解释了分形渡越现象.     

Molecular Separation Barriers and Their Application to Catalytic Reactor Design

The use of semipermeable membranes for multicomponent separations based on molecular size has long been recognized. In certain applications, however, it is often desirable not to effect a separation of chemical constituents, but to sustain a separation which already exists. As an example, the efficient and economical design of a. chemical reactor using an enzyme as a catalyst depends on the accessibility of the reactant to the catalyst as well as on the degree to which a physical separation between the enzyme and the reactor product stream is maintained. A particularly simple and attractive means of achieving this is through the use of semipermeable asymmetric hollow fiber membranes. For example, by sequestering an enzyme solution within the annular macroporous support regions of an asymmetric hollow fiber, a physical separation between enzyme and a reactant solution flowing through the fiber lumen is achieved. In this way, small reactant molecules are free to diffuse across the ultrathin membrane skin into the opencell support structure where reaction will occur. Product molecules will diffuse back into the lumen, and a compact chemical reactor results. The operating behavior of this type of catalytic reactor will be described and its application to the hydrolysis of o-nitro-phenyl-B-d-galactopyranoside and of lactose is discussed.     

Separation of gas mixtures using a range of zeolite membranes: a molecular-dynamics study

Gas separation efficiencies of three zeolite membranes (Faujasite, MFI, and Chabazite) have been examined using the method of molecular dynamics. Our investigation has allowed us to study the effects of pore size and structure, state conditions, and compositions on the permeation of two binary gas mixtures, O(2)N(2) and CO(2)N(2). We have found that for the mixture components with similar sizes and adsorption characteristics, such as O(2)N(2), small-pore zeolites are not suited for separations, and this result is explicable at the molecular level. For mixture components with differing adsorption behavior, such as CO(2)N(2), separation is mainly governed by adsorption and small-pore zeolites separate such gases quite efficiently. When selective adsorption takes place, we have found that, for species with low adsorption, the permeation rate is low, even if the diffusion rate is quite high. Our results further indicate that loading (adsorption) dominates the separation of gas mixtures in small-pore zeolites, such as MFI and Chabazite. For larger-pore zeolites such as Faujasite, diffusion rates do have some effect on gas mixture separation, although adsorption continues to be important. Finally, our simulations using existing intermolecular potential models have replicated all known experimental results for these systems. This shows that molecular simulations could serve as a useful screening tool to determine the suitability of a membrane for potential separation applications.     

Design of a new,twelve-channel electrophoretic apparatus based on the Gradiflow technology

The Gradiflow technology, originally designed to carry out binary, size-based and charge sign-based electrophoretic protein separations, has been extended to simultaneously obtain multiple protein fractions from a single electrophoretic separation. The separation unit of the new apparatus houses the anode and cathode compartments and up to twelve shallow separation compartments through which the background electrolyte solution that contains the separated protein fractions is recirculated. The separation compartments are formed from grids as thin as 1.2 mm and polyacrylamide membranes as thin as 0.15 mm, all with corresponding multiple inlet and outlet ports. The average pore size of the polyacrylamide membranes can be varied to permit passage of proteins in the 5000-800 000 molecular mass range. The electric field, orthogonal to the flow paths of the recirculated background electrolyte, selectively moves the sample components across the polyacrylamide separation membranes. Selective protein transport can be achieved by exploiting differences in either the relative size of the proteins or the charge sign of the proteins. The advantages of the new apparatus stem from the synergistic combination of the short electrophoretic transfer distances, high electric field strength, large effective surface areas of the separation membranes, and the great flexibility with which apparati containing one to twelve separation compartments can be created.     

Evaluation of the porous structures of new polymer packing materials by inverse size-exclusion chromatography

A highly cross-linked porous polymer resin based on styrene-divinylbenzene matrix with pores created by the use of micellar imprinting technique was used as chromatographic packing material. Its performance as a column packing material in inverse size-exclusion chromatography was compared with a non-imprinted resin of the same polymer matrix. The porous structures (the pore size and the porosity) of the resins in the dry and wet states and their relationships with the elution volume of probe solutes (alkanes and polystyrene standards) were established. Characteristic properties of the resins such as specific pore volume, specific surface area and porosity are compared with results obtained by other methods of characterization such as mercury intrusion porosimetry, solvent regain and nitrogen sorption. The results show that the new porous resin can be used in the separation of small molecules. The separation is based on the size of the molecules, and the larger pores (meso- and macropores) in the porous resin can provide a much easier access to the smaller pores (micropores) which are useful in the chromatographic separations.