A new copolymer membrane cured by 2‐hydroxy‐3‐phenoxypropylacrylate, 4‐hydroxybutyl acrylate,and isobutyl methacrylate controlled clonidine linear release in the transdermal drug delivery system

The main objective of this present study was to synthesize a new type of copolymer membrane that presented a linear release property in clonidine transdermal drug delivery system. Three monomers, 2‐hydroxy‐3‐phenoxypropylacrylate, 4‐hydroxybutyl acrylate, and isobutyl methacrylate were treated under strong power UV radiation to prepare a new type of copolymer membrane. The effects of monomers' ratios, membrane thickness, and clonidine concentration on the permeation rates were investigated. It was discovered that the membrane controlled clonidine near zero‐order release. Furthermore, the membrane was characterized by FTIR, DSC, and SEM. Copyright © 2007 John Wiley & Sons, Ltd.     

Gas permeation properties of asymmetric carbon hollow fiber membranes prepared from asymmetric polyimide hollow fiber

Asymmetric carbon hollow fiber membranes were prepared by pyrolysis of an asymmetric polyimide hollow fiber membrane, and their mechanical and permeation properties were investigated. The carbon membrane had higher elastic modulus and lower breaking elongation than the polyimide membrane. Permeation experiments were performed for single gases such as H₂, CO₂, and CH₄, and for mixed gases such as H₂/CH₄ at high feed pressure ranging from 1 to 5 MPa with or without toluene vapor. The permeation properties of the carbon membranes and the polyimide membrane were compared. There was little change in the properties of the carbon membranes with a passage of time. The properties were hardly affected by the feed pressure, whether the feed was accompanied with the toluene vapor or not, because the carbon membranes were not affected by compaction and plasticization.     

Application of cellulose acetate butyrate-based membrane for osmotic drug delivery

The release rate of drugs from an OROS^® is controlled by semipermeable membranes composed typically of cellulose acetate (CA) with various flux enhancers. Cellulose acetate butyrate (CAB) was identified as a viable alternative. The CAB membrane matched the CA membrane in robustness but had superior drying properties, offering particular advantages for thermolabile formulations. Studies were conducted to characterize CAB membrane properties with respect to performance of OROS^® systems. Four different membrane formulations with varying plasticizer type and concentration were investigated. The CAB based membranes exhibited superior drying characteristics and similar functionality to the CA:polyethylene glycol (PEG) membranes used as a control. A linear relationship was observed between the level of flux enhancer and release rate. The stability of the membrane was evaluated based on release profiles after system storage at various conditions. The CAB membranes appeared to have stability comparable to the standard CA membrane. A linear relationship between membrane weight and release rate as well as the time required to release 90% of a drug from the system [T₉₀] for a model formulation was observed. In conclusion, the newly identified alternative membrane composition allows for the use of thinner membranes, thereby reducing cost of goods, coating time and, most importantly, membrane drying time.     

澄清溶液中NaA型分子筛膜的合成及气体渗透性能

The use of zeolite membranes in separation or combined reaction and separation processes is very attractive. Advantages of using such a type of membranes include their ability to discriminate molecules based on the molecular size and their stability[1]. In the past ten years, most efforts were involved in the synthesis and permeation studies of MFI zeolite membrane[2, 3]. Recently, NaA zeolite membrane has attracted much attention because of its high potential in the dehydration of organic liquids[4]. However, few gas permeation results were reported[5]. Furthermore, most of the NaA zeolite membrane was synthesized from gel[4]. In this letter, the synthesis of NaA zeolite membrane from clear solution and its gas permeation properties are reported.     

改性壳聚糖膜用于醇水混合液分离的研究(Ⅱ)─壳聚糖－羧甲基纤维素共混物膜

制备了壳聚糖(CS)─羧甲基纤维素(CMC)共混物膜(I-2),对其成膜反应、溶胀度、交联度及拉伸强度进行了研究,结果表明,壳聚糖与羧甲基纤维素共混物在成膜的同时还发生交联反应;当CS/CMC=1时,交联度最大,此时共混物膜不溶于稀醋酸水溶液。首次将此共混物膜用于乙醇/水混合液的分离,该膜具有优良的醇水分离性能,当CS/CMC=1时,渗透通量和分离因子皆达到最大值[J=0.9kg/(m²·h),a=800,90wt%乙醇,45℃],且该膜的分离因子基本上不随温度变化,醇水透过I-2膜的表现活化能△E为32.6kJ/mol.对CS/CMC2+2+2+2+次序递增,分离因子变化次序则刚好相反。     

Effect of Membrane Preparation Methods on the Release of Theophylline through CA Membranes at In-Vitro Conditions

In this study the effect of the membrane preparation methods on the release of theophylline through cellulose acetate (CA) membranes was studied at in vitro conditions. CA/acetone binary and CA/acetone/water ternary systems were used as casting solutions and poly(ethylene glycol) (PEG) was used as the pore forming, plasticizing agent in the study. Membranes were characterized by FTIR, SEM, and DSC analysis. It was determined that pH, temperature and drug concentration affected the release of theophylline. A decrease in pH, increase in temperature and drug concentration increased the permeated amount of theophylline through the membranes. In addition, receiver solution circulation at a capillary blood rate increased the permeation of theophylline. As a result of the study, it was concluded that the release of theophylline could be controlled for a prolonged period of time and modified CA membranes prepared in the study could be as an advisable membrane material for potential release of theophylline at transdermal conditions.     

Vapor permeation of ethanol-water mixtures using sodium alginate membranes with crosslinking gradient structure

For the vapor permeation of ethanol-water mixtures, two types of dense sodium alginate (SA) membranes have been prepared: a nascent SA membrane and crosslinked SA membranes with glutaraldehyde (GA). In the vapor permeation of the concentrated ethanol-water mixtures through the SA membranes, the effects of feed temperature, cell temperature and crosslinking density in the membrane were investigated on the membrane performance, and a comparison of vapor permeation process was made with pervaporation. SA membranes having different crosslinking gradients have been fabricated by exposing the nascent membrane to different GA content of reaction solutions. The extent of the gradient was controlled by the exposing time. The permeation performance of the membranes will be discussed with the extent of the gradient. An optimal crosslinking gradient was determined in terms of flux and membrane stability. The separation of ethanol-water mixtures through the membrane with the optimal crosslinking gradient was carried out by vapor permeation and the permeation performance will be discussed, and compared with pervaporation.     

Synthesis and properties of functional aliphatic polycarbonates

Two, functional, cyclic carbonate monomers, 5‐methyl‐5‐methoxycarbonyl‐1,3‐dioxan‐2‐one and 5‐methyl‐5‐ethoxy carbonyl‐1,3‐dioxan‐2‐one, were synthesized starting from 2,2‐bis(hydroxymethyl) propionic acid. The ring‐opening polymerization of the cyclic carbonate monomers in bulk with stannous 2‐ethylhexanoate as a catalyst under different conditions was examined. The results showed that the yield and molecular weight of polycarbonates were significantly influenced by the reaction conditions. The polycarbonates obtained were characterized by IR, ¹H NMR, and differential scanning calorimetry. Their molecular weight was measured by gel permeation chromatography. The in vitro biodegradation and controlled drug‐release properties of the polycarbonates were also investigated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 4001–4006, 2003     

Hydrogen Permeation Properties of Perovskite-type BaCe_(0.9)Mn_(0.1)O_(3-δ)Dense Ceramic Membrane

In recent years, mixed-conducting oxides, in which both protonic and electronic charge carriers exist, have received increasing attentions1. Ceramic membranes made of such materials are semipermeable to hydrogen at elevated temperatures. In the early 1980s, Iwahara et al. first reported protonic conduction in SrCeO3-based materials2. Later, BaCeO3 system was extensively studied because of its higher conductivities. However, the electronic conductivity of rare earth doped-BaCeO3 ceramic…     

Prediction of skin permeability of drugs. I. Comparison with artificial membrane

In order to measure the contribution of lipid and pore (aqueous) pathways to the total skin permeation of drugs, and to establish a predictive method for the steady state permeation rate of drugs, the relationship between permeability through excised hairless rat skin and some physicochemical properties of several drugs were compared with those through polydimethylsiloxane (silicone) and poly(2-hydroxyethyl methacrylate) (pHEMA) membranes, as typical solution-diffusion and porous membranes, respectively. A linear relationship was found between the permeability coefficients of drugs for the silicone membrane and their octanol/water partition coefficients. For the pHEMA membrane, the permeability coefficients were almost constant independent of the partition coefficient. On the other hand, the skin permeation properties could be classified into two types: one involves the case of lipophilic drugs, where the permeability coefficient is correlated to the partition coefficient, similar to the silicone membrane; and the other involves hydrophilic drugs, where the permeability coefficients were almost constant, similar to pHEMA membrane. From the above results, the stratum corneum, the main barrier in skin, could be described as a membrane having two parallel permeation pathways: lipid and pore pathways. An equation for predicting the steady state permeation rate of drugs was derived based on this skin permeation model.     

Preparation of chitosan–silica/PCL composite membrane as wound dressing with enhanced cell attachment

In the present study, the asymmetrical polycaprolactone membranes were synthesized using phase inversion method and modified by addition of Pluronic (F‐127) and sodium hydroxide treatment to improve the cell attachment. The chemical structure, physical properties and mechanical behavior of the membranes as well as cell attachment and proliferation on them were characterized and compared to determine the appropriate membrane used in wound dressing fabrication. Then, a composite membrane as wound dressing capable of drug controlled‐release was prepared composed of two merged layers: an asymmetrical poly(ε‐caprolactone) layer coated with a drug‐loaded chitosan – silica matrix. Drug release behavior and biocompatibility of the final system were evaluated. The results showed that the polycaprolactone modified membrane provides appropriate properties to expand fibroblast cell adhesion and proliferation. This in‐vitro study also showed that the controlled‐release composite wound dressing was developed with approximately 70% cumulative release rate, which provided a porous substrate to support skin cells. Copyright © 2017 John Wiley & Sons, Ltd.     

二氧化钛纳米粒子-氧化石墨烯/聚酰亚胺混合基质膜的原位聚合及气体渗透性能

以钛酸四丁酯为前驱体,采用浸渍-沉淀法制备二氧化钛纳米粒子-氧化石墨烯(TiO_2-GO)复合物,再将TiO_2-GO复合物与4,4'-(六氟异亚丙基)邻苯二甲酸酐和4,4'-二氨基二苯醚通过原位聚合构建TiO_2-GO/TiO_2-GO/PI(聚酰亚胺)混合基质膜,用于CO_2的渗透脱除.采用傅里叶变换红外光谱(FTIR)、拉曼光谱(Raman)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、热失重(TG)和Zeta电位等表征了TiO_2-GO复合物和TiO_2-GO/PI混合基质膜的形貌与结构;探讨了TiO_2掺杂量对TiO_2-GO复合物及TiO_2-GO/PI混合基质膜的结构和气体渗透性能的影响.结果表明,TiO_2-GO复合物中TiO_2纳米粒子较均匀地沉积在GO片层上,TiO_2纳米粒子在形成的同时破坏了GO的结构,使其无序度增加.TiO_2的掺杂对TiO_2-GO/PI混合基质膜的形貌与结构影响较小,但提升了TiO_2-GO/PI混合基质膜的CO_2和N2渗透性能.但过量的掺杂使TiO_2粒子在GO片层上团聚,从而导致TiO_2-GO复合物在混合基质膜中的分散性变差,CO_2渗透性及CO_2/N2渗透选择性降低.当TiO_2掺杂质量分数为30%时,TiO_2-GO/PI混合基质膜的CO_2渗透性为360 Barrer[1 Barrer=10~(-10)cm~3(STP)·cm/(cm~2·s·cm Hg)=7.5×10~(-14)cm~3(STP)·cm/(cm~2·s·Pa)],CO_2/N_2的渗透选择性可达31.     

Charged ultrafiltration membranes of polyacrylonitrile covalently binding amphiphilic quaternary ammonium group: effect of aliphatic hydrophobic groups on the filtration properties

Amphiphilic monomers of chloromethylstyrene derivative were synthesized and then copolymerized with acrylonitrile for the preparation of positively charged ultrafiltration membranes. Four types of the polyacrylonitrile charged membranes having quaternary ammonium group with trimethyl, dimethylbutyl, dimethyloctyl and dimethylstearyl groups were prepared by the phase-inversion method. The ultrafiltration properties of the charged membranes were measured by using dextran molecular probes at various NaCl concentrations. Then, the filtration behavior was compared in these charged membranes. For membranes with trimethyl and dimethylbutyl groups on the quaternary ammonium salt, the values of the molecular weight cutoff and the permeation rate of the solute solution increased when the salt concentration increased. However, for membranes having amphiphilic quaternary ammonium groups with octyl and stearyl aliphatic chains, the filtration properties did not change with the salt concentration. We concluded that a compact conformation of the amphiphilic polyionic segments in the membrane causes stable filtration properties.     

清液体系中T型分子筛膜的高重复性合成与渗透汽化性能

以自制微米级分子筛为晶种,在清液体系中成功合成出高性能的T型分子筛膜,考察了硅铝比、水硅比、碱度及合成温度与时间等条件对膜的生长和渗透汽化性能的影响.结果表明,在摩尔组成为1SiO₂:0.015Al₂O₃:0.41(Na₂O+K₂O):30H₂O的清液体系中,于423K晶化6h的条件下可较快地形成一层厚度为5μm的连续致密纯相T型分子筛膜,较大缩短了膜合成时间且提高了膜致密性.在优化条件下所合成的膜具有优良的分离性能和高重复性.348K时,在10wt%水-90wt%异丙醇混合物体系中膜的渗透通量和分离因子分别高达4.20kg/(m²·h)和7800.     

用流动电位法表征纳滤膜的结构及性能

利用测量流动电位的方法考察了纳滤膜的表面电学性能对纳滤膜的截留性能的影响.首先,采用不同功能层材料制备了复合纳滤(NF)膜,考察功能层的交联时间、单体结构等对表面电性能的影响,研究纳滤膜对不同无机盐的选择截留性能与表面电性能的关系.通过流动电位法测定纳滤膜的表面电学参数,如流动电位(ΔE)、zeta电位(ζ)和表面电荷密度(σd).实验表明,这些电学参数的变化与功能层交联时间和纳滤膜截留率的变化一致,在交联时间为45 s时,3种电学参数的绝对值均最大,而纳滤膜对无机盐的截留率也最大.复合纳滤膜zeta电位的绝对值(|ζ|)按照Na2SO4>MgSO4>MgCl2变化,同截留率的变化相同.带侧基单体交联后得到的纳滤膜的表面电性能参数的绝对值小于不带侧基单体的.因此,流动电位法可用于研究复合纳滤膜的截留机理和功能层结构.     

Effect of aqueous and organic solutions on the performance of polyamide thin‐film‐composite nanofiltration membranes

Polyamide/polyacrylonitrile thin‐film‐composite (TFC) nanofiltration (NF) membranes for the separation of oleic acid dissolved in organic solvents (methanol and acetone) were interfacially prepared by the reaction of trimesoyl chloride in an organic phase with an aqueous phase containing piperazine and m‐phenylene diamine. The interfacial reaction was confirmed by an investigation of the attenuated total reflection infrared spectrum. The surface morphology of the polyamide TFC membranes was examined with scanning electron microscopy. The hydrophilic properties of the membrane surfaces were conjectured on the basis of the ζ potential and contact angle. The effects of the monomer concentrations of the monomer blends (aliphatic and aromatic diamines) and drying times on various aspects of membrane performance, such as the solvents (water, alcohols, ketones, and hexane), permeation rates, and organic solute [poly(ethylene glycol) 200 and oleic acid] rejection rates, were investigated. All the membranes showed good solvent resistance. The polar solvent flux for water and methanol was higher than that for a nonpolar solvent (hexane). The membranes gave good rejection rates of oleic acid dissolved in methanol and acetone. The NF membranes were compared with various commercial membranes. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2151–2163, 2002     

Permeability and morphology of poly(cis‐butadiene)/ester‐ether liquid crystal composite membranes

Various amounts of diethylene glycol bis[4‐(4′‐ethoxybenzoyloxy)benzoate] (DEBEB) were added into a poly(cis‐butadiene) (PB) membrane to improve its gas permeation ability. This type of rubber/liquid crystal (LC) composite membranes showed two obvious characteristics that are different from the gas permeation behavior reported in previous literature: (1) The permeabilities to O₂, N₂, and CO₂ were enhanced at room temperature, for example, the permeabilities for the PB/DEBEB (90/10) membrane were higher above six times than those of PB membrane under the same conditions. It is suggested that the interface microvoids probably existed on pontes between polar crystal domains and nonpolar PB matrix. (2) All relationships between the permeability coefficient (P) and temperature (T) were characterized by N‐shape, that is, there were the peaks and valleys on the P‐T curves. Furthermore, morphology studies demonstrated that when DEBEB content in the membranes was above 10 wt %, it was spherically dispersed and embedded in the PB matrix in a crystal domain state. Gas permeation characteristics of the composite membranes were appropriately interpreted as together influence results of DEBEB phase transition behavior and the membrane morphology. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1833–1840, 2000     

Improved Membranes for Hemodialysis

Asymmetric membranes of cellulose acetate and cellulose acetate modified with pendant amino groups have been evaluated for ultrafiltration and dialysis properties. Ultrafiltration rates from 4 to 30 times that of Cuprophan were obtained. During the ultrafiltration test, up to 89% of inulin in the test solution permeated with the ultrafitrate in contrast to the 14% permeation of inulin through a Cuprophan membrane. In spite of the apparently facile permeation of high molecular weight species (e.g., inulin) through the experimental membranes, human albumin was quantitatively reflected. Dialysis tests indicate that cellulose acetate membranes 38 μ or less in thickness should surpass 23-μ-thick (wet) Cuprophan in purely diffusional transport of blood solutes of low molecular weight.

In addition to their promising ultrafiltration and dialysis properties, membranes made from a blend of cellulose acetate and N,N-diethylaminoethylcellulose acetate were found to sorb heparin strongly. The clotting time of rabbit blood in contact with the heparinized membranes was extended, in some cases indefinitely.     

Carbon molecular sieve membrane formed by oxidative carbonization of a copolyimide film coated on a porous support tube

A copolyamic acid was synthesized from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) as the dianhydride and 4,4′-oxydianiline (4,4′-ODA) and 2,4-diaminotoluene (2,4-DAT) as the diamine and was coated on the outer surface of a porous alumina support tube. The film was imidized and then carbonized by varying reaction period, temperature and atmosphere. Permeances of the BPDA-ODA/DAT carbon membrane were much lower than those of BPDA-ODA carbon membranes. However, the performance of the BPDA-ODA/DAT copolyimide-based membrane was greatly improved by treating in air at temperatures up to 500°C for 1 h, followed by carbonizing in nitrogen at temperatures up to 700°C. Permeance to CO₂ for the BPDA-ODA/DAT carbon membrane prepared under optimum conditions was 3 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹, and the separation coefficient of CO₂ to CH₄ was 60 at a permeation temperature of 35°C. These were comparable to the results of carbon membranes prepared from BPDA-ODA polyimide. The micropore structure of the BPDA-ODA/DAT carbon membrane was thus successfully controlled by an optimized combination of oxidation and carbonization after imidization.     

Iontophoretic transdermal drug delivery system using a conducting polymeric membrane

This work investigated the application of a porous polyaniline (PANi) membrane as a conducting polymeric membrane as well as an electrode in an iontophoretic transdermal drug delivery (TDD) system. Model drugs studied were: caffeine (MW: 194.2), lidocaine HCl (MW: 270.8) and doxycycline HCl (MW: 480.1). The PANi membrane was first tested as a simple membrane between the donor and receptor solutions; it provided satisfactory permeation profiles; the observed flux values were well described by a simplified mass transport model. A mouse skin was then mounted beneath the PANi film; such a composite system also presented satisfactory permeation profiles. Iontophoretic TDD experiments were next performed using both Ag|AgCl electrodes and PANi|AgCl electrodes for comparison; a PANi anode replaced the Ag anode in the last set. For doxycycline HCl, the flux and the 24-h accumulation from the PANi|AgCl set were 94.4 ± 81.2 μg/cm² h and 2760 ± 3980 μg/cm², respectively; those from the Ag|AgCl set were zero. For lidocaine HCl, the flux and 10-h accumulation from the PANi|AgCl set were, respectively, 43 ± 15 μg/cm² h and 392 ± 130 μg/cm²; the corresponding values from the Ag|AgCl set were 48 ± 20 μg/cm² h and 348 ± 78 μg/cm². Porous polyaniline membrane appears to be capable of replacing the Ag part of Ag|AgCl electrode system; further such a membrane can exercise additional control over agent transport rate. Aqueous-organic partitioning system through the porous membrane of PANi was tested with this novel technique as well. Because of the rather low porosity of the synthesized PANi film, such a system did not yield a high permeation rate.