The influence of solvent choice,acid activation and surfactant addition on the hydrolytic kinetic resolution (HKR) of terminal epoxides

The recently developed hydrolytic kinetic resolution (HKR) of epoxides catalysed by the Co-Jacobsen catalyst, is one of the most useful methods to obtain enantiomerically pure epoxides and/or diols. Several parameters can significantly influence the homogeneous reaction. Several factors including the used solvent, the activation of the catalyst and the use of surfactants, are investigated.     

Solvent‐Resistant Nanofiltration for Product Purification and Catalyst Recovery in Click Chemistry Reactions

The quickly developing field of “click” chemistry would undoubtedly benefit from the availability of an easy and efficient technology for product purification to reduce the potential health risks associated with the presence of copper in the final product. Therefore, solvent‐resistant nanofiltration (SRNF) membranes have been developed to selectively separate “clicked” polymers from the copper catalyst and solvent. By using these solvent‐stable cross‐linked polyimide membranes in diafiltration, up to 98 % of the initially present copper could be removed through the membrane together with the DMF solvent, the polymer product being almost completely retained. This paper also presents the first SRNF application in which the catalyst permeates through the membrane and the reaction product is retained.     

低共熔溶剂中原位合成ZIF-8膜及其气体分离性能

在α-氧化铝载体上,采用原位合成法,在尿素/氯化胆碱低共熔溶剂中合成了ZIF-8膜。采用X射线衍射(XRD)和扫描电子显微镜(SEM)对合成的ZIF-8膜进行了表征。考察了反应溶液浓度、降温速率对ZIF-8膜合成的影响。通过优化合成条件合成了表面平整致密,厚度为8 μm的ZIF-8膜。采用Wicke-Kallenbach技术对优化条件下合成的ZIF-8膜进行了单组分气体渗透和双组分混合气体分离性能表征。在室温(293 K)下,ZIF-8膜对H2/CO2、H2/O2、H2/N2、H2/CH4双组分气体的分离系数分别为7.4、5.2、9.1、13.8,均大于相应的努森扩散分离系数,说明合成的ZIF-8膜具有分子筛分性能。     

Membrane potential across reverse osmosis membranes under pressure gradient

Membrane potential measurement has been widely used for the characterization of ionic membranes such as ion-exchange membranes without solvent permeability. However, there have been few studies on membrane potentials across pressure-driven processes such as reverse osmosis (RO) membranes with solvent permeability. In the present study, the membrane potential across RO membranes in NaCl and MgCl2 under the pressure gradient, DeltaP=0-0.3 MPa, was measured. The experimental results were analyzed by the theoretical model based on the Donnan equilibrium and the extended Nernst-Planck flux equation considering the pressure effect. The theoretical values agreed well with the experimental ones. This indicates that membrane potential is useful for characterizing the effective charge density of the active layer of RO membranes under pressure gradient.     

The effect of production method on the properties of high impact polystyrene and polyaniline membranes

In this study, different membranes were prepared using conventional polymer (high impact polystyrene) and polyaniline to evaluate their use in electrodialysis. Two different preparation modes were tested: chemical mixture with subsequent solvent evaporation; and mechanical mixture with subsequent pressing under heating. The purpose was to understand the effect of production methods on membrane microstructure and ionic transport. Membranes were characterized by swelling study, Fourier transformed infrared spectroscopic, scanning electron microscopy, thermogravimetric analysis and dynamic mechanical analysis. Ionic transport through the membranes was evaluated using a three-compartment cell. The results of the produced membranes were compared with those of the commercial Nafion 450 membrane.     

Promotion of PEM self-humidifying effect by nanometer-sized sulfated zirconia-supported Pt catalyst hybrid with sulfonated poly(ether ether ketone)

A self-humidifying membrane based on low-cost sulfonated poly (ether ether ketone) (SPEEK) hybrid with sulfated zirconia (SO4(2-)/ZrO2, SZ)-supported platinum catalyst (Pt-SZ catalyst) was investigated for fuel cell applications. The SZ particle, a solid-state superacid with hygroscopic and high proton conductivity properties, was employed as the catalyst support. The SPEEK/Pt-SZ self-humidifying membrane was characterized by TEM and SEM coupled with EDX. FT-IR was conducted to verify the effect of SPEEK/Pt-SZ membrane on catalytic combination of crossover hydrogen and oxygen. To display the advantages of Pt-SZ catalyst as the additive, the IEC, water uptake, proton conductivity, single-cell performance, and areal resistance measurements were compared between the plain SPEEK membrane, SPEEK/Pt-SiO2 membrane, and the SPEEK/Pt-SZ membrane. The SPEEK/Pt-SZ membrane exhibited the highest IEC value, proton conductivity, single-cell performance, and the lowest areal resistance relative to the plain SPEEK and SPEEK/Pt-SiO2 membranes. The SPEEK/Pt-SZ self-humidifying membrane exhibited peak power density of 1.0 W/cm2 under dry operation condition compared with 0.89 W/cm2 and 0.58 W/cm2 of SPEEK/Pt-SiO2 and plain SPEEK membranes, respectively. The incorporation of the catalytic, hygroscopic and proton conductive Pt-SZ catalyst in the SPEEK/Pt-SZ self-humidifying membrane facilitated water balance and proton conduction, and accordingly improved its single cell performance under dry operation. In addition, the enhanced OCV and the decreased areal ohmic resistance confirmed the promotion effect of Pt-SZ catalyst in the self-humidifying membrane on suppressing reactant crossover and the membrane self-humidification.     

Palladium-catalyzed addition of disulfides and diselenides to alkynes under solvent free conditions

An efficient methodology was developed for performing palladium-catalyzed E-E (E = S, Se) bond addition to alkynes under solvent free conditions. Compared to reaction in solvent significant enhancement of reaction rate, improved efficiency and remarkable catalyst stability were observed under solvent free conditions. The addition reactions were carried out with high stereoselectivity and yields in a short reaction time.     

Eval membranes for blood dialysis

Both dry- and wet-process were employed for preparing membrane of ethylene-vinylalcohol copolymer (EVAL) for blood dialysis. Asymmetric and symmetric, dense or porous membranes were prepared by the dry-process. The relationship between the structure of membranes and the experimental variables is explained by using a solubility curve model. This model predicts the membrane structure successfully under various conditions, including the change of temperature of the environment, the solvent system and the temperature of polymer solution. For wet-processes, the casting solutions were coagulated in a precipitation bath (water). Three different structures were obtained: finger type, sponge type and particle-bonded type. The cloud point experiment and the polymer segment motion help to understand and control the membrane structure. Some properties of the EVAL membrane for blood dialysis are shown. It is comparable with or better than the commercialized one. This study may prove useful in determing the controlling parameters for the preparation of membranes from other polymers.     

The effect of aprotic solvent on the selectivity of ion-exchange membranes

The effect of N,N-dimethylacetamide on the selectivity of heterogeneous (MK-40, MA-40, and MA-41) and homogeneous (MF-4SK) ion-exchange membranes is studied for the first time. Concentration dependences of electrical conductivity and diffusion permeability of the membranes were measured experimentally over wide lithium chloride concentrations; on their basis, electrodiffusion coefficients of the co- and counterions were calculated. The interrelation between the electrodiffusion coefficients and the specific moisture capacity of the heterogeneous and homogeneous membranes (which affect their selectivity) is revealed. The calculated electrodiffusion coefficients were used in the calculations of the electromigration transport numbers of counterions in the initial membranes and those processed in mixed solvent. It is shown that the heterogeneous membrane selectivity either increased under the action of the aprotic solvent to polymer material (MA-40, MA-41) or remained practically unchanged (MK-40); the selectivity of homogeneous perfluorinated membranes (e.g., MF-4SK) decreased, thus approaching that of the studied heterogeneous anion-exchange membranes.     

Sorption and diffusion of methanol and water in PVDF‐g‐PSSA and Nafion® 117 polymer electrolyte membranes

Sorption and diffusion properties of poly(vinylidene fluoride)‐graft‐poly(styrene sulfonic acid) (PVDF‐g‐PSSA) and Nafion® 117 polymer electrolyte membranes were studied in water/methanol mixtures. The two types of membranes were found to have different sorption properties. The Nafion 117 membrane was found to have a maximum in‐solvent uptake around 0.4 to 0.6 mole fraction of methanol, while the PVDF‐g‐PSSA membranes took up less solvent with increasing methanol concentration. The proton NMR spectra were recorded for membranes immersed in deuterated water/methanol mixtures. The spectra showed that the hydroxyl protons inside the membrane exhibit resonance lines different from the resonance lines of hydroxyl protons in the external solvent. The spectral features of the lines of these internal hydroxyl groups in the membranes were different in the Nafion membrane compared with the PVDF‐g‐PSSA membranes. Diffusion measurements with the pulsed field gradient NMR (PFG‐NMR) method showed that the diffusion coefficient of the internal hydroxyl groups in the solvent immersed Nafion membrane mirrors the changes in the diffusion coefficients of hydroxyl and methyl protons in the external solvent. For the PVDF‐g‐PSSA membranes, a decrease in the diffusion coefficient of the internal hydroxyl protons was seen with increasing methanol concentration. These results indicate that the morphology and chemical structure of the membranes have an effect on their solvent sorption and diffusion characteristics. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3277–3284, 2000     

催化膜和催化膜反应器:整合的高效和环保催化过程

 The design of new heterogeneous photooxygenation systems able to employ visible light, oxygen, mild temperatures, and solvent with a low environmental impact has been investigated. In particular, the heterogenization of decatungstate (W10O4-32), a polyoxometalate with photocatalytic activity in oxidation reactions, has been carried out in polymeric membranes of polyvinylidenefluoride. The polymeric catalytic membranes prepared by phase inversion technique have been successfully applied in the aerobic mineralization of phenol in water, which was used as an example of organic pollutant. In order to evaluate the effect of the polymeric environment on the overall catalyst behavior, we have also heterogenized the decatungstate (opportunely functionalized) in perfluorinated membrane made of Hyflon. The photocatalytic composite membranes are characterized by different and tuneable properties depending on the nature of the polymeric micro-environment, in which the catalyst is confined. Moreover, the selective separation function of the membrane results in enhanced performance in comparison with homogeneous reactions.     

Catalytic Membranes and Membrane Reactors： An Integrated Approach to Catalytic Process with a High Efficiency and a Low Environmental Impact

The design of new heterogeneous photooxygenation systems able to employ visible light,oxygen,mild temperatures,and solvent with a low environmental impact has been investigated. In particular,the heterogenization of decatungstate (W10O4-32),a polyoxometalate with photocatalytic activity in oxidation reactions,has been carried out in polymeric membranes of polyvinylidenefluoride. The polymeric catalytic membranes prepared by phase inversion technique have been successfully applied in the aerobic mineralization of phenol in water,which was used as an example of organic pollutant. In order to evaluate the effect of the polymeric environment on the overall catalyst behavior,we have also heterogenized the decatungstate (opportunely functionalized) in perfluorinated membrane made of Hyflon. The photocatalytic composite membranes are characterized by different and tuneable properties depending on the nature of the polymeric micro-environment,in which the catalyst is confined. Moreover,the selective separation function of the membrane results in enhanced performance in comparison with homogeneous reactions.     

壳聚糖／褐藻酸钠聚离子复合膜的渗透汽化分离性能研究

以红外光谱和扫描电镜表征壳聚糖／褐藻酸钠聚离子复合膜的结构与表面形态。研究了该膜组成、料液浓度、温度等对乙醇－水溶液的渗透汽化分离性能的影响。实验结果表明，壳聚糖／褐藻酸钠聚离子复合膜不仅对乙醇－水溶液，而且对许多水溶性有机溶剂与水的溶液都具有很高的渗透汽化脱水的选择分离性能。     

从醛无溶剂制备1,1-二乙酸酯的催化剂Cu3/2PMo12O40/SiO2

芳香醛和脂肪醛在温和条件下经乙酸酐和Cu3/2PMo12O40/SiO2催化可转变成 1,1-二乙酸酯. 发现Cu3/2PMo12O40/SiO2是在无溶剂存在下制备 1,1-二乙酸酯的有效催化剂. 使用同一催化剂和乙腈作溶剂可使生成的 1,1-二乙酸酯发生逆反应脱保护生成醛. 这种新的方法具有反应时间短和收率高的优点,而且催化剂重复使用几次不丧失活性.     

On the unusual solvent retention and the effect on the gas transport in perfluorinated Hyflon AD membranes

Dense membranes of Hyflon AD 60X were prepared by the solvent evaporation method and by melt pressing. The diffusion coefficient, solubility and permeability of the membranes were measured for six permanent gases using time lag and steady state permeation measurements. The thermal properties were determined by Differential Scanning Calorimetry (DSC) and the solvent content was measured gravimetrically and was estimated by the Fox equation. It was found that unusually strong solvent retention in the solution-cast membrane leads to considerable plasticization of the polymer, to possible foam formation upon drying and, most important, to significant changes in the permeation properties. The residual solvent increases the diffusion coefficient and permeability of the larger gas species up to almost one order of magnitude, and it reduces the permselectivity. For most gas species the solubility is about two times higher in the solvent-free melt-pressed film than in the solution-cast film. The relation between the residual solvent and the membrane properties is discussed.     

有机溶剂对PEM燃料电池CCM结构和性能的影响

采用直接喷涂法将催化剂涂覆在质子交换膜上形成CCM(catalyst coated membrane),CCM与碳纸扩散层组成膜电极用于质子交换膜燃料电池.制备CCM的混合液由质量分数20%的Pt/C催化剂、质量分数5%的Nafion溶液、有机溶剂和水组成.不同的有机溶剂(乙醇、异丙醇和叔丁醇)、有机溶剂的含量、溶剂的...     

Functionalized Membranes for Photocatalytic Hydrogen Production

Functionalized vesicles for photocatalytic hydrogen production in water have been prepared by co‐embedding of amphiphilic photosensitizers and a hydrogen‐evolving catalyst in phospholipid membranes. The self‐assembly allows a simple two‐dimensional arrangement of the multicomponent system with close spatial proximity, which gave turnover numbers up to 165 for the incorporated amphiphilic cobaloxime water reduction catalyst 3 b under optimized conditions in purely aqueous solution. Superior photocatalytic activity in fluid membranes indicates that mobility and dynamic reorganization of catalytic subunits in the membrane promote the visible‐light‐driven hydrogen production. The functionalized membranes represent nanostructured assemblies for hydrogen production in aqueous solution mimicking natural photosynthesis.     

应用于膜蒸馏过程的F26微孔膜的初步研究

以N-甲基吡咯酮作为溶剂 ,丙酮为溶胀剂 ,聚乙二醇 4 0 0为添加剂利用相转换法制备出偏氟乙烯 六氟丙烯共聚物 (F2 6 )的疏水微孔膜并且应用在膜蒸馏过程中 .研究了丙酮以及N 甲基吡咯酮 丙酮体系对膜参数以及结构的影响 .通过SEM观察了膜的微观结构 ,发现用N 甲基吡咯酮 丙酮体系制得的微孔膜兼具指状孔和海绵状孔结构 .无添加剂条件下制得的F2 6膜其对蒸馏水的接触角比相同条件下制备的PVDF膜大 .在用相转换法制备的F2 6和PVDF的疏水膜中 ,选择具有适当孔径结构的微孔膜用于膜蒸馏实验 ,F2 6膜的膜蒸馏系数比PVDF膜来得大 ,相同操作条件下的膜蒸馏通量也比PVDF膜高 .     

FTIR-ATR-spectroscopic analysis of Bis-Crown ether based PVC-membranes

Summary To get more information on the phase boundary and bulk membrane processes, the short and long time behaviour of potassium selective solvent polymeric membranes was studied. In parallel with the measurement of the dynamic response of model membranes, in situ spectroscopic measurements applying the Attenuated Total Reflection (ATR) technique in the infrared region, were carried out in solutions containing anions of different lipophilicity (Cl^– and SCN^–). Thin membranes (thinner than the penetration depth of IR beam) coated on the germanium reflection element by the dipping technique show no time dependence of the SCN bands in contact with KSCN solution of different concentrations, while the diffusion process of species can be monitored in thick membranes as it was shown in a time resolved study. The extremely short response times of ionophore based solvent polymeric membranes (determined under appropriate experimental conditions in this work) imply that the fundamental potential determining step of the overall response of this type of electrodes is a phase boundary process. Thus the slow inner membrane diffusion process followed by IR spectroscopy on the molecular level may affect only the long-term membrane behaviour.

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FTIR-ATR-spektroskopische Analyse von Bis-Kronenether-PVC-MembranenIII. Spektroskopische und elektrochemische in situ-Methoden zur Untersuchung von OberflÄchen- und Bulk-Membran-Prozessen

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Part II: see [4]

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Dedicated to Prof. Dr. W. Fresenius on the occasion of his 75th birthday     

Diastereoselective synthesis of propargylamines catalyzed by Cu-MCM-41

In this work, a rapid, efficient and protecting group free diastereoselective synthesis of propargylamines through a multicomponent coupling reaction between (S)-prolinol, phenylacetylene and commercially available aldehydes catalyzed by Cu-MCM-41 in heterogeneous phase is reported. The reactions were carried out under solvent free conditions with good yields and moderate reaction times. In all the cases, catalyst was recovered and reused up to five cycles. Recyclability of the catalyst, low catalyst loading, solvent and protecting group free conditions, and the use of inexpensive catalyst are the key features that provide green aspects to this synthetic protocol.