Influence of the seed polymer on the chromatographic properties of size monodisperse polymeric separation media prepared by a multi-step swelling and polymerization method

Monodisperse polymer particle-based separation media were prepared by a multi-step swelling and polymerization method with two pairs of monomers and two porogenic solvents. Their chromatographic properties were compared to those of beads prepared by a corresponding suspension polymerization method without the use of seed polymer to ascertain the influence of the seed polymer on their porous structures. A large change in porous structure was observed when the swollen particle consisting of monomers and porogenic solvents contained at least one good solvent for the polystyrene seed polymer, allowing it to remain in the polymerizing medium. In contrast, when the polystyrene seed particle was excluded from the swollen oil droplets, due to its poor solubility in the monomers and the porogenic solvents, there was no difference in the chromatographic properties such as pore volume, pore size, pore size distribution, or retention selectivity between the multi-step swelling and polymerization method and the suspension polymerization method. Since the only difference between the multi-step swelling and polymerization method and the suspension method is the use of the seed polymer, it appears that a very small amount (< 1% v/v) of seed polymers in the enlarged swollen droplets plays an important role as a porogen and affects the porous structure as well as the chromatographic properties of the monodisperse polymer particle-based separation media. © 1993 John Wiley & Sons, Inc.     

Influence of diluent composition on the porous structure of methacrylate copolymers

The porous structure of copolymers obtained by suspension polymerization has been investigated. Three different copolymers were synthesized—styrene‐divinylbenzene, ethylene glycol dimethacrylate‐divinylbenzene, and 1,4‐phenylene dimethacrylate‐divinylbenzene. All the copolymers were porous. As a pore‐forming diluent, the mixture of toluene (good solvent) and n‐dodecane (nonsolvent) was used. The influence of the composition of two‐component diluent on the porous structure of the copolymers has been examined. Surface areas, pore volumes, pore size distributions, skeletal and apparent densities, and swellability coefficients were determined for the copolymers obtained in the presence of 0, 15, 50, 85, and 100% (v/v) toluene in the mixture with n‐dodecane. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3079–3085, 2002     

Characterization of internal surface reversed-phase silica supports for liquid chromatography

Internal surface reversed-phase (ISRP) supports synthesized from commercially available porous silica particles with a variety of nominal pore diameters and specific surface areas are characterized with regard to physical and chromatographic properties. Bonded phase coverage, pore size, capacity and efficiency measurements are made upon the various ISRP supports in order to evaluate the effect that the physical properties of silica have upon the chromatographic performance of ISRP packings. In addition, various models that describe the pore structure of silica supports are discussed.     

Properties of Calcium Phosphate Scaffolds Produced by Freeze-Casting

The pore structure of three-dimensional scaffolds applied in tissue engineering may influence the mechanical properties and cellular activity. As the optimal pore size is dependent on the specifics of the biomaterial or tissue engineering application, the ability to alter the pore size over a wide range is necessary for several scaffolds in order to meets the requirements of the applications. The aim of this study is to develop methodologies to produce calcium phosphate scaffolds with acceptable pore size and defined pore-channel interconnectivity. The pore size of calcium phosphate scaffolds is established during the freeze-drying fabrication process. In this process, material suspension is simply frozen and then dried by freeze-drier, which able to produce material with unique porous architectures, where the porosity is almost a direct replica of the frozen solvent crystals. There are two different method of freeze-casting carried out in order to study the effect of freezing temperature by which in the first method; sample being soaked with liquid nitrogen (-196 °C) for about 10 minutes before been place inside a freezer (-40 °C). In the second method, the sample was directly placed inside a freezer for casting at temperature of -40 ̊C. The results show that the pore size of the scaffolds decreased as the freezing temperature was reduced. Taken together, these results demonstrate that the methodologies applied in this study can be used to produce a range of calcium phosphate scaffolds exhibiting better compressive strength, approximately 665-875 KPa for 54-64.3% of porosity with mean pore size from 102-113 μm. The methods developed in this study provide a basis for the investigation on the effects of different freezing temperature in freeze-casting process on the porosity, morphology, and compressive properties of the calcium phosphate scaffolds.     

Fabrication of Porous Polyimide Membrane with Through-Hole via Multiple Solvent Displacement Method

Porous polyimide (PI) membranes are widely used in separation processes because of their excellent thermal and mechanical properties. However, the applications of porous PI membranes are limited in the nanofiltration range. In this study, porous PI membranes with through-holes have been successfully fabricated by the novel multiple solvent displacement method. This new method requires only a porous polyamic acid (PAA) membrane, which was prepared by immersing PAA film in N-methylpyrrolidoneebk; (NMP) prior to immersing it in a mixed solvent consisting of NMP and a poor solvent, followed by immersion only in poor solvent. The pore size, morphology, porosity, and air permeability demonstrated that the fabricated PI membranes had a uniformly porous structure with through-holes over their surface. This new method enabled control of pore size (3–11 μm) by selecting a suitable poor solvent. This multiple solvent displacement method is highly versatile and promising for the fabrication of porous PI membranes.     

A statistical model for the heterogeneous structure of porous catalyst pellets

The complex structures of the void space of porous media are often characterised by parameters such as pore network connectivity and lattice size. This paper presents a comparison of the estimates of these parameters obtained from two previous methods based on nitrogen sorption and mercury porosimetry, and also from a new, completely independent approach based on pulsed-gradient spin-echo nuclear magnetic resonance (PGSE NMR). It was found that the new PGSE NMR technique obtains estimates of connectivity and lattice size in agreement with nitrogen sorption but different to mercury porosimetry. This difference was attributed to the various physical processes involved actually probing different aspects of the pore space geometry. It was further suggested that the representation of the pore structure derived from either nitrogen sorption or PGSE NMR is really a mapping of the real pore space onto an equivalent abstract, random pore bond network. However, it has been shown that this mapping does capture some of the characteristic properties of the pore space that control transport over mesoscopic ( < 10 microm) length scales. For materials which additionally possessed macroscopic (> 10 microm) structural heterogeneity, it was found that the model could also be adapted to predict the macroscopic transport properties of the porous medium.     

致孔剂对HP（MA—VAc—MMA）载体孔结构的影响

以二乙烯苯和双丙烯酸多缩乙二醇酯为交联剂、聚醋酸乙烯酯（ＰＶＡｃ）或它与醋酸丁酯（ＢＡＣ）的混合物为致孔剂、ＢＰＯ为引发剂，用悬浮聚合随后水解的方法制得了部分水解聚（丙烯酸甲酯－醋酸乙烯酯－甲基丙烯酸甲酯）［ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）］多孔载体，研究了ＰＶＡｃ及（ＰＶＡｃ＋ＢＡＣ）用量、分子量及混合比对ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）孔结构的影响。结果表明，当ＰＶＡｃ的Ｍ＞２．５×１０５，ＰＶＡｃ／ＢＡＣ为２．３，用量为１０～２０％时，可制得孔隙率较高，孔径分布较窄，孔表面积较大的多孔载体。这种载体适用于微生物固定化。     

Deposition of silver nanoparticles into porous system of sol–gel silica monoliths and properties of silver/porous silica composites

Porous monolithic gels based on silica with pore size from 16 nm to 3–5 μm have been synthesized using sol–gel technology. Parameters of porous structure are determined by the components molar ratio in the reaction mixture. The reduction processes of silver ions by formamide in the synthesized porous gel were studied. It has been shown that at the initial stage of the reaction, silver particles with size up to 10 nm are formed in the absence of any stabilizers. The composites Ag/SiO₂ were synthesized by means of the threefold impregnation of porous monoliths using the solution of silver nitrate in the mixture of methanol and formamide. Their catalytic activity in the CO oxidation was studied. It was discovered that after activation in oxygen and hydrogen the samples display a low temperature activity, which depends on the number of Si–O-nonbridging oxygen groups on the surface of silica porous monoliths.     

Silk Fibroin/Wool Keratin Composite Scaffold with Hierarchical Fibrous and Porous Structure

The present study describes a silk microfiber reinforced meniscus scaffold (SMRMS) with hierarchical fibrous and porous structure made from silk fibroin (SF) and wool keratin (WK) using electrospinning and freeze-drying technology. This study focuses on the morphology, secondary structure, mechanical properties, and water absorption properties of the scaffold. The cytotoxicity and biocompatibility of SMRMS are assessed in vivo and in vitro. The scaffold shows hierarchical fibrous and porous structure, hierarchical pore size distribution (ranges from 50 to 650 µm), robust mechanical properties (compression strength can reach at 2.8 MPa), and stable biodegradability. A positive growth condition revealed by in vitro cytotoxicity testing indicates that the scaffold is not hazardous to cells. In vivo assessments of biocompatibility reveal that only a mild inflammatory reaction is present in implanted rat tissue. Meniscal scaffold made of SF/WK composite shows a potential application prospect in the meniscal repair engineering field with its development.     

Unsteady-State Flow of Flexible Polymers in Porous Media

In this paper we report an investigation of the unsteady-state flow of polymer solutions through granular porous media. The experiments were performed using high-molecular-weight nonionic and anionic polyacrylamides dissolved in water containing NaCl and model porous media obtained by packing silicon carbide (SiC) grains having a narrow grain size distribution. Before injection in porous media, the polymer solutions were carefully filtered according to a method that was proved to be efficient in removing any possibly remaining microgels. The SiC grain surface was passively oxidized by a controlled thermal treatment in order to obtain a surface partially covered by a thin silica layer having adsorption properties similar to those of quartzitic sand. By packing SiC grains of different sizes, porous media having identical adsorption properties and well-known pore throats sizes can be obtained with a good reproducibility. Parameters investigated include pore size, velocity gradient, polymer concentration, and adsorption energy. A striking unsteady-state flow behavior (pressure build-up at constant flow rate) is observed when three conditions are fulfilled: (a) the velocity gradient is larger than that known to be able to induce a coil-stretch transition, (b) the polymer adsorbs on the pore surfaces, and (c) the length of stretched macromolecules is larger than the effective pore throat diameter. When one of these conditions is not satisfied the flow remains steady. These observations are interpreted by a mechanism involving the adsorption and bridging across pore restrictions of elongated chains. We propose to refer to this peculiar mode of polymer adsorption as bridging adsorption. Copyright 2001 Academic Press.     

交联聚苯乙烯型多孔吸附剂的中孔性质研究

采用77K温度下的氮气吸附方法,测定了经悬浮聚合制备的不同交联度的交联聚苯乙烯多孔吸附剂的吸附/脱附等温线.根据BET吸附模型计算了比表面,由吸附量计算了总的孔体积,由孔体积和比表面计算出平均孔径,并依据脱附等温线采用BJH方法计算孔径分布.结果表明,交联度对交联聚苯乙烯多孔吸附剂的孔结构均具有显著影响.随着交联聚苯乙烯多孔吸附剂的交联度升高,其孔径变小,比表面增大,而且低交联度吸附剂的中孔接近圆柱形,高交联吸附剂的中孔形状接近“墨水瓶”形.显然,交联度对孔性质的影响与孔结构在交联聚苯乙烯多孔吸附剂制备和后处理过程中的稳定性密切相关.交联度低时,初期形成的小孔不能保持稳定,在后续聚合及后处理过程中合并为大孔,结果造成低交联吸附剂大孔径、低比表面的现象.通过对孔径分布的研究,揭示了不同吸附剂在中孔范围内的孔特征,并对其形成机制进行了分析.     

Microstructure and mechanical properties of bacterial cellulose/chitosan porous scaffold

A family of polysaccharide based scaffold materials, bacterial cellulose/chitosan (BC/CTS) porous scaffolds with various weight ratios (from 20/80 to 60/40 w/w%) were prepared by freezing (−30 and −80 °C) and lyophilization of a mixture of microfibrillated BC suspension and chitosan solution. The microfibrillated BC (MFC) was subjected to 2,2,6,6-tetramethylpyperidine-1-oxyl radical (TEMPO)-mediated oxidation to introduce surface carboxyl groups before mixing. The integration of MFC within chitosan matrix was performed by 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC)-mediated cross-linking. The covalent amide bond formation was determined by ATR-FTIR. Because of this covalent coupling, the scaffolds retain their original shapes during autoclave sterilization. The composite scaffolds are three-dimensional open pore microstructure with pore size ranging from 120 to 280 μm. The freezing temperature and mean pore size take less effect on scaffold mechanical properties. The compressive modulus and strength increased with increase in MFC content. The results show that the scaffolds of higher MFC content contribute to overall better mechanical properties.     

Effects of organic solvents on ultrafiltration polyamide membranes for the preparation of oil-in-water emulsions

Hydrophilic ultrafiltration membranes made of polyamide with molecular weight cutoff 10 and 50 kDa have been studied for the preparation of oil-in-water emulsions by a cross-flow membrane emulsification technique. Isooctane and phosphate buffer were used as disperse and continuous phase, respectively. The permeation of apolar isooctane through the polar hydrophilic membrane was achieved by pretreatment of membranes with a gradient of miscible solvents of decreasing polarity to remove water from the pores and replace it with isooctane. Four different procedures were investigated, based on the solvent mixture percentage and contact time with membranes. After pretreatment, the performance of the membranes in terms of pure isooctane permeate flux and emulsion preparation was evaluated. The influence of organic solvents on polyamide (PA) membranes has been studied by SEM analysis, which showed a clear change in the structure and morphology of the thin selective layers. The effects proved stronger for PA 10 kDa than for 50 kDa. In fact, similar pretreatment procedures caused larger pore size and pore size distribution for PA 10 kDa than for 50 kDa. The properties of emulsions in terms of droplet size distribution reflected the membrane pore sizes obtained after pretreatment. The correlation between pore size and droplet size, for the physicochemical and fluid dynamic conditions used, has been evaluated.     

Evaluation of silica from different vendors as the solid support of anion‐exchange chiral stationary phases by means of preferential sorption and liquid chromatography

Chromatographic performance of a chiral stationary phase is significantly influenced by the employed solid support. Properties of the most commonly used support, silica particles, such as size and size distribution, and pore size are of utmost importance for both superficially porous particles and fully porous particles. In this work, we have focused on evaluation of fully porous particles from three different vendors as solid supports for a brush‐type chiral stationary phase based on 9‐O‐tert‐butylcarbamoyl quinidine. We have prepared corresponding stationary phases under identical experimental conditions and determined the parameters of the modified silica by physisorption measurements and scanning electron microscopy. Enantiorecognition properties of the chiral stationary phases have been studied using preferential sorption experiments. The same material was slurry‐packed into chromatographic columns and the chromatographic properties have been evaluated in liquid chromatography. We show that preferential sorption can provide valuable information about the influence of the pore size and total pore volume on the interaction of analytes of different size with the chirally‐modified silica surface. The data can be used to understand differences observed in chromatographic evaluation of the chiral stationary phases. The combination of preferential sorption and liquid chromatography separation can provide detailed information on new chiral stationary phases.     

Simulation of electrical-conduction and filtration processes in porous media

Results of simulation of electrical-conduction and filtration processes in porous media have been reported. For better visualization and simplification of the analysis of the results obtained, simple model distributions of pore sizes with the patterns of a triangle, rectangle, semiellipse, etc., have been used. The porous medium has been simulated in terms of a capillary lattice model, which represents a three dimensional cubic lattice of capillaries the sizes and number of which are selected according to a preset pore size distribution. The data obtained reflect the general regularities of the influence of the pore structure on the transfer processes, show the interrelation between the parameters characterizing these processes, and illustrate the potential of the capillary-lattice model for describing the properties of porous media.     

Control of heterogeneous structure of porous polymer microspheres prepared from polymerization system and preformed polymer system

The studies on control of heterogeneous structure of porous polymer microspheres prepared for suspension polymerization system and preformed polymer system in author’s research group were reviewed. Firstly, the phase-separation behavior in O/W suspension polymerization system for preparation of porous poly(divinylbenzene) microspheres was quantitatively studied by combining transmittance and gelation point measurement, from which the morphology can be manipulated. The same method can be employed to study the pore size control in W/O hydrophilic polymerization system. Because the simple porous microsphere could not satisfy new applications, we developed new methods to prepare gigaporous microsphere, which possessed much larger pores than those obtained by general diluents, for chromatographic separation media, as well as hollow-porous microsphere for construction of cell-like microreactor. Furthermore, in order to overcome the difficulty of heterogeneous structure control for preformed polymer system, we developed special methods to obtain porous, hollow-porous, and hollow chitosan microspheres. Finally, some application results by utilizing special morphologies were introduced.     

The influence of mercury contact angle, surface tension, and retraction mechanism on the interpretation of mercury porosimetry data

The use of a semi-empirical alternative to the standard Washburn equation for the interpretation of raw mercury porosimetry data has been advocated. The alternative expression takes account of variations in both mercury contact angle and surface tension with pore size, for both advancing and retreating mercury meniscii. The semi-empirical equation presented was ultimately derived from electron microscopy data, obtained for controlled pore glasses by previous workers. It has been found that this equation is also suitable for the interpretation of raw data for sol-gel silica spheres. Interpretation of mercury porosimetry data using the alternative to the standard Washburn equation was found to give rise to pore sizes similar to those obtained from corresponding SAXS data. The interpretation of porosimetry data, for both whole and finely powdered silica spheres, using the alternative expression has demonstrated that the hysteresis and mercury entrapment observed for whole samples does not occur for fragmented samples. Therefore, for these materials, the structural hysteresis and overall level of mercury entrapment is caused by the macroscopic (> approximately 30 microm), and not the microscopic (< approximately 30 microm), properties of the porous medium. This finding suggested that mercury porosimetry may be used to obtain a statistical characterization of sample macroscopic structure similar to that obtained using MRI. In addition, from a comparison of the pore size distribution from porosimetry with that obtained using complementary nitrogen sorption data, it was found that, even in the absence of hysteresis and mercury entrapment, pore shielding effects were still present. This observation suggested that the mercury extrusion process does not occur by a piston-type retraction mechanism and, therefore, the usual method for the application of percolation concepts to mercury retraction is flawed.     

Electrochemistry-enabled fabrication of orthogonal nanotopography and surface chemistry gradients for high-throughput screening

Gradient surfaces are emerging tools for investigating mammalian cell-surface interactions in high throughput. We demonstrate the electrochemical fabrication of an orthogonal gradient platform combining a porous silicon (pSi) pore size gradient with an orthogonal gradient of peptide ligand density. pSi gradients were fabricated via the anodic etching of a silicon wafer with pore sizes ranging from hundreds to tens of nanometers. A chemical gradient of ethyl-6-bromohexanoate was generated orthogonally to the pSi gradient via electrochemical attachment. Subsequent hydrolysis and activation of the chemical gradient allowed for the generation of a cyclic RGD gradient. Whilst mesenchymal stem cells (MSC) were shown to respond to both the topographical and chemical cues arising from the orthogonal gradient, the MSC's responded more strongly to changes in RGD density than to changes in pore size during short-term culture.