Development and characterization of on-chip biopolymer membranes

In lab-on-a-chip applications, filtration is currently performed prior to sample loading or through pre-cast membranes adhered to the substrate. These membranes cannot be patterned to micrometer resolution, and their adhesion may be incompatible with the fabrication process or may introduce contaminants. We have developed an on-chip separation process using a biocompatible polymer that can be patterned and has controllable molecular rejection properties. We spun cast cellulose acetate (CA) membranes directly onto silicon wafers. Characterization of the molecular flux across the membrane showed that molecular weight and charge are major factors contributing to the membranes' rejection characteristics. Altering casting conditions such as polymer concentration in the casting solution and the quenching-bath composition and/or temperature allowed control of the molecular weight cut-off (MWCO). Three MWCOs; 300, 350, and 700 Da have been achieved for non-linear molecules. Molecular shape is also very important as much higher molecular weight single-stranded DNA was electrophoresed across the membranes while heme with a similar negative charge density was rejected. This was due to DNA's small molecular cross section. This is an important result because heme inhibits polymerase chain reactions (PCR) reducing the detection and characterization of DNA from blood samples.     

A graphene oxide facilitated a highly porous and effective antibacterial regenerated cellulose membrane containing stabilized silver nanoparticles

Regenerated nanocomposite cellulose membranes embedded with silver nanoparticles (AgNP) and AgNP-graphene oxide (AgGO) were prepared in this study. The as-synthesized AgNP and AgGO were added respectively to a cellulose solution that was prepared by dissolving cellulose in a precooled NaOH/urea (NU) solvent. The solution mixtures were further regenerated into nanocomposite membranes through coagulation in an acidic solution. UV-Vis and TEM results revealed the improved stability of the AgGO compared to that of the AgNP in NU solutions. As revealed by FESEM, the AgGO nanocomposite membrane possessed a more porous structure than a membrane containing AgNP. Antibacterial tests demonstrated that the cellulose membrane of AgGO inhibited the growth of both Staphylococcus aureus and Escherichia coli more effectively than the AgNP nanocomposite membrane, with a lower concentration of AgGO. This work provides a proven and effective method to prepare novel functional cellulose membranes with antibacterial properties, thus broadening the applications of cellulose.     

Removal of aromatic compounds in the aqueous solution via micellar enhanced ultrafiltration: Part 1. Behavior of nonionic surfactants

The effects of nonionic surfactants having different hydrophilicity and membranes having different hydrophobicity and molecular weight cut-off on the performance of micellar-enhanced ultrafiltration (MEUF) process were examined. A homologous series of polyethyleneglycol (PEG) alkylether having different numbers of methylene groups and ethylene oxide groups was used for nonionic surfactants. Polysulfone membranes and cellulose acetate membranes having different molecular cut-off were used for hydrophobic membranes and hydrophilic membranes, respectively. The concentration of surfactant added to pure water was fixed at the value of 100 times of critical micelle concentration (CMC). The flux through polysulfone membranes decreased remarkably due to adsorption mainly caused by hydrophobic interactions between surfactant and membrane material. The decline of solution flux for cellulose acetate membranes was not as serious as that for polysulfone membranes because of hydrophilic properties of cellulose acetate membranes. The surfactant rejections for the cellulose acetate membranes increased with decreasing membrane pore size and with increasing the hydrophobicity of surfactant. On the other hand the surfactant rejections for polysulfone membranes showed totally different rejection trends with those for cellulose acetate membranes. The surfactant rejections for the polysulfone membranes depend on the strength of hydrophobic interactions between surfactant and membrane material and molecular weight of surfactants.     

CELLULOSE ACETATE AND EPOXY RESIN BLEND ULTRAFILTRATION MEMBRANES: REPARATION,CHARACTERIZATION, AND APPLICATION

ABSTRACT

Membranes based on cellulose acetate used in ultrafiltration applications lack good, chemical, mechanical and thermal resistance. In order to prepare membranes with improved properties, modification of cellulose acetate with epoxy resin through solution blending was attempted. In the present work, the membrane casting solutions with different polymer blend compositions of cellulose acetate and diglycidyl ether of bisphenol-A (DGEBA) were prepared at 30±2°C. The maximum percent compatibility of the two polymers, cellulose acetate and diglycidyl ether of bisphenol-A, was estimated to be 60/40%. Ultrafiltration blend membranes based on various blend compositions were prepared, characterized in terms of compaction, pure water flux, water content, membrane hydraulic resistance and molecular weight cut-off. The application of these membranes, in rejection of proteins of various molecular weights, are discussed.     

三醋酸纤维素膜辐射可控接枝甲基丙烯酸缩水甘油酯及其性能

三醋酸纤维素(CTA)是一种高强度的天然高分子衍生物,对其进行表面接枝改性将扩展其在物质分离、吸附、检测等领域的广泛应用,但是化学接枝改性CTA比较困难。 本文结合辐射引发接枝和可逆加成-断裂链转移(RAFT)聚合方法,成功地在CTA膜表面可控接枝了聚甲基丙烯酸缩水甘油酯(PGMA)。 研究了吸收剂量、单体GMA质量分数和RAFT试剂含量等因素对接枝率的影响,采用傅里叶变换红外光谱仪(FT-IR)、扫描电子显微镜(SEM)和接触角技术手段对CTA膜接枝前后的结构、形貌和表面性质进行了表征。 实验结果表明,为了得到较高的接枝率,同时又保持较好的形貌,合适的条件为:吸收剂量为10~12 kGy,GMA质量分数为30%,RAFT试剂与GMA的物质的量比为1：400;在不同条件下得到的最高接枝率为41%,接枝聚合物相对分子质量分布最低为1.33。 此外,接枝PGMA后的CTA膜疏水性增加。 该工作提供了可控接枝CTA的简便方法,与传统辐射接枝相比,RAFT辅助辐射接枝反应更加可控,得到的PGMA接枝链更加均匀,有利于根据实际应用来控制接枝率和进行后续的功能修饰。     

Effect of aging on UF membranes by a streaming potential (SP) method

In this paper we have determined, by a streaming potential (SP) method, the isoelectric point (IEP) of a new cellulose membrane, the regenerated cellulose material. This membrane is more hydrophilic than the classical cellulose acetate material and less sensitive to protein adsorption, with an IEP of 3.4.Furthermore, we have validated an SP method as a new method to control aging of porous membranes. We validate the SP technique on a surface of 30 cm² for a membrane with a molecular weight cut-off of 10 kDa.In this new field of research where nondestructive techniques are not many, we have shown, for the first time, the efficiency of coupling permeability and SP measurements to control aging of mesoporous polymer membranes.     

Theoretical study of the transport processes occurring during the evaporation step in asymmetric membrane casting

A mathematical model is developed for the evaporation step in asymmetric membrane casting which allows for the convective transport induced by local film shrinkage because of both solvent loss and the excess volume of mixing effect. Realistic boundary conditions account for the gas phase mass transfer characteristics. Predictions for the cellulose acetate/acetone system are presented for the instantaneous concentration profiles, film thickness, and time required for the interface to skin. The results are presented in the form of dimensionless correlations which allow predicting the behavior during evaporative casting for generalized operating conditions. The predictions are compared with limited data for cellulose acetate/acetone. The model suggests that once the polymer/solvent system has been selected, the most influential process parameter is the gas phase mass transfer coefficient and that inadequate control of this parameter may account for the variability in membranes cast in similar devices operated under ostensibly the same conditions.     

Formation and Characterization of Cellulose Membranes from N‐Methylmorpholine‐N‐oxide Solution

Regenerated cellulose membranes have been traditionally manufactured using the viscose or the copper‐ammonia process. Today, membranes made by this process are still used in many fields such as dialysis. However, there are some serious environmental problems inherent in the existing processing routes. The new N‐methylmorpholine‐N‐oxide (NMMO) process can overcome these disadvantages and provides membranes with improved mechanical properties. In the present work, cellulose membranes were successfully prepared from NMMO solution under various conditions. It was found that the cellulose concentration is a decisive factor in controlling the membrane permeation properties. For a given coagulation system, higher cellulose concentration leads to membranes with greater rejection of bovine serum albumin (BSA) and lower pure water flux. It was also found that both the degree of polymerization (DP) and the type of cellulose pulp have great effect on the morphology and permeation properties of the membrane support layer. With increasing NMMO concentration and temperature of the coagulation bath, the pure water flux increases while the rejection of BSA decreases; a result of the larger mean pore size formed during coagulation.     

亲水膜的表面改性及在膜蒸馏中的应用

膜的微孔性和疏水性是水溶液膜蒸馏的两个基本条件,迄今人们均采用疏水性高分子材料制成疏水微孔膜用于膜蒸馏研究。本文采用辐照接枝聚合和等离子体表面聚合的方法,将亲水的醋酸纤维素微孔膜和硝酸纤维素微孔膜表面疏水化改性,成功地用于膜蒸馏研究,大大扩展了疏水微孔膜的材料来源。实验结果表明,亲水膜表面改性得到的疏水膜,其膜蒸馏性能不低于疏水材料制成的膜,尤其是等离子体聚合法可以实现多种特殊单体在多孔的材料表面聚合,成为制备高性能疏水微孔膜的有效手段,为膜蒸馏的深入发展和实用化创造了有利条件。     

Microfiltration performance of regenerated cellulose membrane prepared at low temperature for wastewater treatment

A series of regenerated cellulose membranes with pore diameters ranging from 21 to 52 nm have been prepared by dissolving cellulose in 5 wt% LiOH/12 wt% urea aqueous solution re-cooled to −12 °C. The influences of cellulose concentration on the structure, pore size, and the mechanical properties of the membrane were studied by using Wide angle X-ray diffraction, scanning electron micrography and tensile testing. Their pore size, water permeability, equilibrium-swelling ratio and fouling behaviors of the cellulose membranes were characterized. The water-soluble synthetic and natural polymers as organic matter were used to evaluate the microfiltration performance of the regenerated cellulose membrane for wastewater treatment in aqueous system. The results revealed that the organic matter with molecular weight more than 20 kDa effected significantly on the membrane pore density, and reducing factor a _2, whereas that having molecular weight less than 20 kDa exhibited a little influence on the membrane pore size reducing factor a ₁. Furthermore, a simple model to illustrate of microfiltration process of the RC membrane for wastewater treatment was proposed.     

Molecular (osmotic and electro-osmotic) backwash of cellulose acetate hyperfiltration membranes

A technique using osmosis and/or electro-osmosis was developed to clean and possibly decompact contaminated modified (asymmetric)cellulose acetate membranes. p]The rejuvenation technique developed is called “molecular backwash”. When contaminated with ferric hydroxide, the membranes (cured at 92°C) exhibited considerable flux decrease. After molecular backwashing, the hyperfiltration flux increased again. In some cases, molecular backwash also partially restored the salt rejection loss which had occurred during contamination. Flux loss recovered by molecular backwashing varied from 30% to over 100% (i.e. the flux of the compacted membrane was greater than before contamination, but not greater than the flux of a clean uncompacted membrane).     

Synthesis, characterization and thermal studies on cellulose acetate membranes with additive

Cellulose acetate (CA) membranes are used in ultrafiltration applications, although they show low chemical, mechanical and thermal resistance. In order to prepare membranes with improved properties, modification of cellulose acetate with polyethelene glycol (PEG 600) has been attempted. In this study, CA has been mixed with PEG 600 as an additive in a polar solvent. The effects of CA composition and additive concentration given by a mixture design of experiments on membrane compaction, pure water flux, water content and membrane hydraulic resistance have been studied and discussed. The efficiency of protein separation by the developed CA membranes have been quantified using model proteins such as pepsin, egg albumin (EA) and bovine serum albumin (BSA). The thermal stability of the developed membranes prepared with PEG 600 additive has also been investigated using thermogravimetric analysis and differential scanning calorimetry.     

Structure and properties of novel fibers spun from cellulose in NaOH/thiourea aqueous solution

Cellulose was dissolved rapidly in a NaOH/thiourea aqueous solution (9.5:4.5 in wt.-%) to prepare a transparent cellulose solution, which was employed, for the first time, to spin a new class of regenerated cellulose fibers by wet spinning. The structure and mechanical properties of the resulting cellulose fibers were characterized, and compared with those of commercially available viscose rayon, cuprammonium rayon and Lyocell fibers. The results from wide angle X-ray diffraction and CP/MAS 13C NMR indicated that the novel cellulose fibers have a structure typical for a family II cellulose and possessed relatively high degrees of crystallinity. Scanning electron microscopy (SEM) and optical microscopy images revealed that the cross-section of the fibers is circular, similar to natural silk. The new fibers have higher molecular weights and better mechanical properties than those of viscose rayon. This low-cost technology is simple, different from the polluting viscose process. The dissolution and regeneration of the cellulose in the NaOH/thiourea aqueous solutions were a physical process and a sol-gel transition rather than a chemical reaction, leading to the smoothness and luster of the fibers. This work provides a potential application in the field of functional fiber manufacturing.     

Preparation of polyelectrolyte multilayer membranes by dynamic layer-by-layer process for pervaporation separation of alcohol/water mixtures

In the past decades, the layer-by-layer (LBL) adsorption of oppositely charged polyelectrolytes has proven to be a promising method for the preparation of polyelectrolyte multilayer membranes. However, to obtain a good separation capability, LBL adsorption involved relatively long periods because 50–60 bilayers were normally required. The aim of this study was to develop such a new method that would allow simplification of the LBL procedure. LBL adsorption was proposed to proceed under a dynamic condition to prepare polyelectrolyte multilayer membranes. The polyacrylic acid (PAA) and polyethyleneimine (PEI) were alternatively deposited on polyethersulfone (PES) ultrafiltration support membrane under a pressure of 0.1 MPa. The polyelectrolyte multilayer membranes prepared by dynamic LBL process were compared with those prepared by the static LBL process for the pervaporation separation of water–ethanol mixture. The results suggested that a relatively high separation factor could be obtained with only four composite bilayers by using dynamic LBL process. The preparative conditions including bilayer number, filtration time of the first PAA layer, reaction time, ratio between polayanion and polycation concentrations, PAA molecular weight and salt addition were investigated. The pervaporation conditions such as feed temperature and water concentration in the feed were also evaluated. Under the temperature of 40 °C, the separation factor and the permeate flux of the polyelectrolyte multilayer membranes were about 1207 and 140 g/(m² h), respectively.     

Various approaches to modify biomaterial surfaces for improving hemocompatibility

In this paper, the mechanism of thrombus formation on the surface of polymeric materials and the various approaches of modifying biomaterial surfaces to improve their hemocompatibility are reviewed. Moreover, the blood compatibility of the cellulose membrane grafted with O-butyrylchitosan (OBCS) by using a radiation grafting technique was studied. Surface analysis of grafted cellulose membrane was verified by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and electron spectroscopy for chemical analysis (ESCA), which confirmed that OBCS was successfully grafted onto the cellulose membrane surfaces. Blood compatibility of the grafted cellulose membranes was evaluated by platelet rich plasma (PRP) contacting experiments and protein adsorption experiments using blank cellulose membranes as the control. The blood compatibility of OBCS grafted cellulose membranes is better than that of blank cellulose membranes. These results suggest that the photocrosslinkable chitosan developed here has the potential of serving in blood-contacting applications in medical use.     

Fabrication of highly ordered porous membranes of cellulose triacetate on ice substrates using breath figure method

Highly ordered porous membranes of cellulose triacetate (CTA) were prepared successfully on ice substrates using breath figure method. The pore size and structure of the membrane were modulated by changing CTA concentrations and substrate materials. As the CTA concentration in the casting solution increased, the pore size in the formed membrane decreased. The regularity of the membrane cast on the ice substrate was much better than that of the membrane cast on glass substrate, because the low temperature of ice substrate slowed down the evaporation rate of organic solvent, which offered enough time for condensed water droplets to self‐organize into an ordered array dispersed in the polymer solution before their coagulation. The ordered porous CTA membrane was not only used for microfiltration, but also used for fabrication of functional microstructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 552–558     

细菌纤维素膜的制备与性能

以细菌纤维素为原料,氯化锂(LiCl)/二甲基乙酰胺(DMAc)为溶剂,通过相转化法制备了细菌纤维素膜.用单纤维强力仪对膜的拉伸强度和伸长率进行测试,分析了细菌纤维素浓度、凝固浴温度、凝固浴浓度、凝固时间及塑化条件对膜力学性能的影响.结果表明:在一定范围内,随着制膜液中细菌纤维素浓度的增加、凝固浴温度的降低和凝固浴浓度的增大,膜的拉伸强度和伸长率均提高;随着甘油浓度的增大和塑化时间的延长,膜的拉伸强度逐渐减小,伸长率逐渐增大.     

Water in polymer membranes. Part III : Water sorption and pore volume in cellulose acetate films

Changes in waveguide properties of several cellulose acetate membranes and one polyimide membrane were measured as a function of their exposure to varying levels of relative humidity. The volume fraction of water in the films and the occupied pore volumes were determined from refractive index and thickness changes. The dependence of the refractive index on water absorption is related to a competition between two processes: one of filling pores with no film expansion and one of “free expansion” where the film expands to completely accommodate the added water volume. The term “pore” is taken to mean a volume with molecular and not macroscopic dimensions. The hydration properties of these dense cellulose acetate membranes were affected by degree of acetylation, casting temperatures and annealing treatments. Annealing CA398 membranes at 180°C decreased film water concentration by reducing the amount of free expansion. Annealed CA398 membranes that were tested in a reverse osmosis cell were found to have high salt rejection compared to unannealed films. The hydration characteristics of a polyimide membrane are compared to cellulose acetate membranes.     

CO2／CH4分离膜及沸石填料影响渗透过程的研究

报导了甲基硅橡胶和纤维素（ＣＡ、ＣＴＡ、ＥＣ）膜对ＣＯ２、ＣＨ４的选择透气性能，并讨论了沸石作为填料所引起的分子筛作用的气体渗透过程。甲基硅橡胶的气体渗透系数最高，而选择性最低，且不受填料沸石的影响。纤维素膜的气体选择性较大，渗透系数可以通过沸石的加人而明显增加。特别是沸石１３Ｘ．沸石３Ａ、４Ａ、５Ａ在ＥＣ膜中对气体分子筛作用，改变了气体原有的渗透过程，提高了选择性。使用Ａｒｒｈｅｎｉｕｓ公式计算出ＥＣ－沸石３Ａ膜的气体渗透活化能。     

The Role of the Prod1 Membrane Anchor in Newt Limb Regeneration

Prod1 is a protein that regulates limb regeneration in salamanders by determining the direction of limb growth. Prod1 is attached to the membrane by a glycosylphosphatidylinositol (GPI) anchor, but the role of membrane anchoring in the limb regeneration process is poorly understood. In this study, we investigated the functional role of the anchoring of Prod1 to the membrane by using its synthetic mimics in combination with solid‐state NMR spectroscopy and fluorescent microscopy techniques. Anchoring did not affect the three‐dimensional structure of Prod1 but did induce aggregation by aligning the molecules and drastically reducing the molecular motion on the two‐dimensional membrane surface. Interestingly, aggregated Prod1 interacted with Prod1 molecules tethered on the surface of opposing membranes, inducing membrane adhesion. Our results strongly suggest that anchoring of the salamander‐specific protein Prod1 assists cell adhesion in the limb regeneration process.