温度感应复合型控制释放膜系统的性能研究

采用等离子诱导填孔接枝聚合法将聚N-异丙基丙烯酰胺(PNIPAM)开关接枝到聚偏氟乙烯膜(PVDF)膜孔上,同自由基聚合法制备的PNIPAM交联水凝胶结合,成功地组成了一种温度感应复合型控制释放膜系统。在该膜系统中,PNIPAM接枝PVDF膜作为控制释放开关,PNIPAM交联水凝胶作为药物载体。通过改变交联水凝胶和开关膜的微观结构,研究了该复合膜系统的温度感应控制释放特性。结果表明,该复合膜系统具有良好的温度感应特性,优于单独的开关膜控制释放系统或是单独的交联水凝胶控制释放系统。研究结果将为温度感应型控制释放系统或给药系统的设计与开发提供理论基础。     

乙醇浓度及温度响应型智能高分子的制备及其性能

采用自由基聚合法将亲水单体N,N-二甲基丙烯酰胺(DMAA)和疏水单体甲基丙烯酸丁酯(BMA)分别与N-异丙基丙烯酰胺共聚,从而制备聚(N-异丙基丙烯酰胺-co-N,N-二甲基丙烯酰胺)高分子(PND)和聚(N-异丙基丙烯酰胺-co-甲基丙烯酸丁酯)高分子(PNB)。考察了共聚高分子在水溶液中的相转变温度以及在相转变温度以下对乙醇溶液浓度的响应特性。实验证明亲水单体DMAA和疏水单体BMA能够很好地调节PN共聚高分子的相转变温度和乙醇响应浓度。     

pH或/和温度双重响应嵌段接枝膜的开关特性

利用原子转移自由基聚合法(ATRP)成功地制备了聚甲基丙烯酸-嵌段-聚N-异丙基丙烯酰胺(PMN)和聚N-异丙基丙烯酰胺-嵌段-聚甲基丙烯酸(PNM)接枝开关膜。通过通量实验系统考察了两类开关膜分别或同时对pH和温度的响应性。结果表明:用ATRP法接枝嵌段共聚物开关中第一段接枝物的接枝率总是高于第二段接枝物的接枝率;该嵌段接枝开关膜对pH和温度同时响应的开关系数要大于其对单一pH或温度响应的开关系数;嵌段接枝开关中第一段接枝物对膜孔的开或关起主导作用,而第二段接枝物的影响相对较小。实验结果还表明,PMAA的pH响应开关系数比PNIPAM的温度响应开关系数显著。研究结果为设计和制备双重或多重嵌段接枝开关膜提供了有价值的参考。     

快速响应的温敏性PNIPAAm／粘土复合水凝胶的合成及性能研究

以碳酸钠为制孔剂合成了快速响应的温敏性PNIPAAm／粘土复合水凝胶(NNC水凝胶),DSC分析表明,其体积相转变温度在33℃左右,与传统的PNIPAAm水凝胶没有很大的偏差。动力学研究表明,该水凝胶在温敏膨胀或收缩时,具有快速的响应速率,在5 min内的失水率达90％以上,这与扫描电镜观察到水凝胶具有大而连贯的孔洞结构相一致。     

接枝量对等离子体接枝聚异丙基丙烯酰胺开关的多孔膜的温度感应透过性的影响

The effect of graft yield on both the thermo-responsive hydraulic permeability and the thermo-respousive diffusional permeability through porous membranes with plasma-grafted poly(N-isopropylacrylamide) (PNIPAM)gates was investigated. Both thermo-respousive flat membranes and core-shell microcapsule membranes with a wide range of graft yield of PNIPAM were prepared using a plasma-graft pore-filling polymerization method. The grafted PNIPAM was formed homogeneously throughout the entire thickness of both the fiat polyethylene membranes andthe microcapsule polyamide membranes. Both the hydraulic permeability and the diffusional permeability were heavily dependent on the PNIPAM graft yield. With increasing the graft yield, the hydraulic permeability (water flux) decreases rapidly at 25℃ because of the decrease of the pore size; however, the water flux at 40℃ increases firstly to a peak because of the increase of hydrophobicity of the pore surface, and then decreases and finally tends to zero because of the pore size becoming smaller and smaller. For the diffusional permeability, the temperature shows different effects on the diffusional permeability coefficients of solutes across the membranes. When the graft yield was low, the diffusional coefficient of solute across the membrane was higher at temperature above the lower critical solution temperature (LCST) than that below the LCST; however, when the graft yield was high, the diffusional coefficient was lower at temperature above the LCST than that below the LCST. It is very important to choose or design a proper graft yield of PNIPAM for obtaining a desired thermo-respousive “on/off“ hydraulic or ditfusional permeability.     

快速响应聚(N-异丙基丙烯酰胺)水凝胶的制备及性能

以N-异丙基丙烯酰胺为单体、N,N′-亚甲基双丙烯酰胺为交联剂、过硫酸铵为引发剂、N,N,N,′N′-四甲基乙二胺为加速剂,在不同浓度的羧甲基纤维素的水溶液中,在低温下聚合/交联制备了一系列快速响应的温度敏感性聚(N-异丙基丙烯酰胺)水凝胶。用SEM观察了其表面形态,测定了不同温度下达到平衡时水凝胶的溶胀比,研究了水凝胶的去溶胀动力学。结果表明,与传统水凝胶相比,该水凝胶的溶胀性能有所提高,并且对温度的变化具有较快的响应速率。以质量分数为0.75%的羧甲基纤维素水溶液中制备的水凝胶为例,该水凝胶在20℃时的溶胀比为21.4,而传统水凝胶在相同温度时的溶胀比仅为12.9;该水凝胶在1 m in内失去60%的水,在4 m in内失去约80%的水,而传统水凝胶在15 m in内仅失去66%左右的水。     

聚(N-异丙基丙烯酰胺-共聚-烯丙基硫脲)智能微凝胶的制备及其Hg2+响应性能的研究

以N-异丙基丙烯酰胺(NIPAM)和烯丙基硫脲(ATU)为共聚单体,N,N’-亚甲基双丙烯酰胺(MBA)为交联剂,2,2′-偶氮二(2-甲基丙基咪)二盐酸盐(V50)为引发剂,通过沉淀聚合法制备了一种可用于Hg²⁺检测与去除的聚(N-异丙基丙烯酰胺-共聚-烯丙基硫脲)(PNA)智能微凝胶。利用傅里叶变换红外光谱仪(FT-IR)、X射线光电子能谱仪(XPS)和扫描电镜(SEM)对微凝胶进行了化学成分和形貌表征。利用动态光散射纳米粒度分析仪(DLS)对微凝胶的粒径分布及温度响应性进行了研究。探究了干扰离子、pH和温度对微凝胶Hg²⁺响应性能的影响。利用原子吸收光谱仪(AAS)探究了PNA微凝胶对Hg²⁺的吸附去除效果。结果显示,PNA微凝胶具有良好的温敏性以及对Hg²⁺的特异响应性,响应Hg²⁺后引起的收缩比(RD)随着ATU单体比例的增加而减小,并确定了最佳检测温度为30℃。随着Hg²⁺浓度的增加,RD值逐渐减小,根据Hg²⁺浓度与RD...     

pH值对N-异丙基丙烯酰胺与甲基丙烯酸共聚形成微凝胶的影响

在pH值为4．0和7．0的水介质中分别采用乳液聚合法使N-异丙基丙烯酰胺（NIPAM）和甲基丙烯酸（MAA）共聚,合成了具有温度／pH双重刺激响应性的P（NIPAM—CO—MAA）共聚微凝胶。傅立叶红外变换光谱、元素分析和电位滴定分析结果表明,在pH为4．0条件下合成的微凝胶中MAA单元含量偏高,微凝胶的粒径随着MAA用量的增加而增大,而pH为7．0时合成的微凝胶的粒径随着单体MAA用量的增加而减小。通过动态激光光散射测试P（NIPAM—CO—MAA）微凝胶的动力学直径随介质温度或pH值的变化关系发现,pH为4．0条件下合成的微凝胶具有更明显的pH刺激响应性,其温度刺激响应性受介质pH值的影响较大,表明MAA单元有可能更均匀地分布于微凝胶聚合物网络中。     

新型温敏性中空纤维膜的制备与表征

采用自由基聚合方法对中空纤维膜（hollow fiber membranes,HFMs）进行了N-异丙基丙烯酰胺（NIPAAm）的接枝聚合,制备了一系列PNIPAAm-g-HFMs,同时考察了成纤维细胞在PNIPAAm-g-HFMs表面的培养与降温脱附情况。傅里叶红外光谱和元素分析结果表明PNIPAAm成功地在中空纤维膜上接枝聚合。动态接触角分析结果显示,当温度降至LCST以下,PNIPAAm-g-HFMs表面接触角明显降低;蛋白黏附测定结果进一步证实了当温度发生改变时,PNIPAAm-g-HFMs表面呈现亲疏水性质变化,即具有温敏性。37℃时,成纤维细胞在HFMs-0.005,HFMs-0.01和HFMs-0.05表面均能正常黏附、铺展与增殖;而HFMs-0.2不适宜细胞的黏附与生长。降温孵育后,黏附于PNIPAAm-g-HFMs表面的细胞发生明显的形态变化并从其表面发生脱附,细胞脱附率高达90%以上。以上实验结果表明,PNIPAAm-g-HFMs具有良好的温敏性,可实现细胞的降温脱附,可与生物反应器相结合用于贴壁型细胞的大规模扩增与降温收获。     

基于纤维素模板的聚合物空心微球作为药物载体的性能研究及分析

以羟丙基纤维素为模板材料,分别采用不同的聚合方法制备了2种不同形态和结构的聚合物空心微球--聚N-异丙基丙烯酰胺-co-聚丙烯酸(PNIPAm-co-PAA)微凝胶和聚N-异丙基丙烯酰胺-聚丙烯酸(PNIPAm-PAA)水凝胶微囊。以盐酸阿霉素(Dox)作为模型药物,考察了聚合物空心微球作为药物载体的载药能力和体外释放性能。研究表明,PNIPAm-co-PAA微凝胶、PNIPAm-PAA水凝胶微囊和Dox分子能够通过正负电荷的相互吸引实现有效结合;载药微球具有良好的缓释性能,并对Dox的释放表现出明显的pH值敏感性和温度敏感性。体外细胞毒性实验表明,载药PNIPAm-co-PAA微凝胶、PNIPAm-PAA水凝胶微囊具有很高的抗肿瘤活性,细胞相对存活率均可达20%左右。PNIPAm-co-PAA微凝胶、PNIPAm-PAA水凝胶微囊在作为水溶性药物或蛋白类药物载体方面,具有潜在的应用价值,同时有望应用于木材胶黏剂防腐等。     

Effect of Graft Yield on the Thermo-Responsive Permeability Through Porous Membranes with Plasma-Grafted Poly(N-isopropylacrylamide)Gates

The effect of graft yield on both the thermo-responsive hydraulic permeability and the thermo-responsive diffusional permeability through porous membranes with plasma-grafted poly(AT-isopropylacrylamide) (PNIPAM) gates was investigated. Both thermo-responsive flat membranes and core-shell microcapsule membranes with a wide range of graft yield of PNIPAM were prepared using a plasma-graft pore-filling polymerization method. The grafted PNIPAM was formed homogeneously throughout the entire thickness of both the flat polyethylene membranes and the microcapsule polyamide membranes. Both the hydraulic permeability and the diffusional permeability were heavily dependent on the PNIPAM graft yield. With increasing the graft yield, the hydraulic permeability (water flux) decreases rapidly at 25℃ because of the decrease of the pore size; however, the water flux at 40℃ increases firstly to a peak because of the increase of hydrophobicity of the pore surface, and then decreases and finally tends to zero because o     

非对称陶瓷膜管渗透性能的CFD模拟研究

陶瓷膜因其化学稳定性好、机械强度大等优点得到广泛应用。计算流体力学(CFD)的快速发展使得计算模拟成为研究和优化陶瓷膜管结构性能的有效手段。为了优化非对称结构陶瓷膜管的结构和操作参数,对其渗透性能进行了CFD计算模拟。针对非对称结构陶瓷膜管的膜层和过渡层的厚度在10 μm级的特点,采用Navier-Stokes方程和Darcy定律来分别描述膜管内和膜多孔介质内的纯水流动,利用多孔介质模型描述膜管的主体支撑层,用多孔跳跃边界简化膜管的膜层和过渡层,利用Konzey-Carmen方程对膜元件各层的渗透率进行估算。计算结果与实验值吻合较好,为优化陶瓷膜管的通道结构提供了便捷的工具。     

The effect of particle rotation on the motion and rejection of capsular particles in slit pores

The results from a two‐dimensional computational model describing the motion of capsule‐shaped particles in a slit pore under small Re conditions are reported. Average particle velocities and particle rejection coefficients were determined for capsules with aspect ratios of 2 and 4. Two different approaches were used to characterize particle rotation and hydrodynamic particle‐pore wall interactions. In one approach, all sterically allowed particle orientation angles had equal probability, i.e., infinite rotational diffusion was assumed. In the second approach, particles were allowed to freely rotate in the pore; particle orientations were dictated by hydrodynamic forces acting on the particle surface and rotational particle diffusion was neglected. Minimal lateral migration across the pore was observed for the freely rotating particles. Although particle alignment was observed for the freely rotating particles, rejections predicted from the two approaches were found to be in close agreement. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2828–2836, 2018     

CFD simulation on membrane distillation of NaCl solution

A computational fluid dynamics (CFD) simulation that coupled an established heat and mass transfer model was carried out for the air-gap membrane distillation (AGMD) of NaCl solution to predict mass and heat behaviors of the process. The effects of temperature and flowrate on fluxes were first simulated and compared with available experimental data to verify the approach. The profiles of temperature, temperature polarization factor, and mass flux adjacent to the tubular carbon membrane surface were then examined under different feed Reynolds number in the computational domain. Results show that the temperature polarization phenomena can be reduced, and mass flux can be enhanced with increase in the feed Reynolds number.     

流体流动型态对膜通量影响的实验和计算流体力学研究

This paper reports a study on the role of fluid flow pattern and dynamic pressure on the permeate flux through a micro filtration membrane in laboratory scale. For this purpose, a dead-end membrane cell equipped with a marine type impeller was used. The impeller was set to rotate in the clockwise and counter clockwise directions with the same angular velocities in order to illustrate the effect of rotation direction on permeate flux. Consequently, permeate fluxes were measured at various impeller rotational speeds. The computational fluid dynamics (CFD) pre-dicted dynamic pressure was related to the fluxes obtained in the experiments. Using the CFD modeling, it is proven that the change in dynamic pressure upon the membrane surface has direct effect on the permeate flux.     

A computational fluid dynamics study of supercritical antisolvent precipitation: Mixing effects on particle size

Supercritical fluids have been extensively used for particle production of many natural and pharmaceutical substances providing useful alternatives for pharmaceutical and nutraceutical particulate system formulation. Among the different methods, the gas or supercritical antisolvent (GAS or SAS) process and its variants, have received a considerable interest due to the wide range of materials that can be micronized. Controlling particle formation in order to nucleate small particles is a key issue in GAS and SAS processes and this is directly related to mixing at all scales. In this work, we focus on numerical simulation of the process, emphasizing mixing modeling. Different mixing devices characterized by different nozzles are analyzed, to get an insight into mixing dynamics and its influence on the final particle size distribution. Results show that mixing is determinant in obtaining small particles, and that mixing at the microscale is a significant parameter to account for in the proper design of precipitators. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

The effect of axial impeller geometry on the link between power and flow numbers

Stirred vessels are used to facilitate mixing processes across a wide range of industries. Their performance can often be predicted with certain characteristics of the agitator, like the dimensionless power and flow numbers. Since there exists a large number of agitator designs and geometries, it is desirable to be able to predict these characteristics using models rather than rely on previous experimental data. In this study, we use an angular momentum balance combined with computational fluid dynamics to correlate the power, flow, and mixer geometry across a wide range of down-pumping pitched blade turbine geometries. The models developed from the results allow us to predict the power from the flow (or vice versa) for the geometries investigated. We tested two methods for the measurement of the flow rate and found that the choice of measurement method can affect the relationship between the power, flow, and impeller geometry.     

Preparation of polyelectrolyte complex membranes based on sodium cellulose sulfate and poly(dimethyldiallylammonium chloride) and its permeability properties

In this study, polyelectrolyte complex (PELC) membranes prepared by the simultaneous interfacial reaction between aqueous solutions of sodium cellulose sulfate (NaCS) as polyanion and poly(dimethyldiallylammonium chloride) (PDMDAAC) as polycation were proposed. The preparation conditions were optimized. The influence of two important factors, molecular weight (MW) of PDMDAAC and reaction time on the membrane formation procedure and permeability was investigated. Membranes with the preparation conditions as NaCS 3.5% (w/v), PDMDAAC (MW = 200–350 kDa) 7.0% (w/v), the reaction time 30 min, hold a favorable performance, and steady state in water flux experiment. To testify the feasibility of the membrane used in salt separation, membrane performances and selectivity of the inorganic salts as well as their relations to the preparation conditions, the operation parameters, the species of inorganic salts, etc., were investigated in the pressure‐driven experiments. The results showed that this single‐layer PELC membrane afforded higher rejections of divalent ions (SO) to that of monovalent ions (Cl⁻), which indicated the potential application of this membrane system in the salt rejection process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fine tuning the hydrophobicity of counter‐anions to tailor pore size in porous all‐poly(ionic liquid) membranes

Charged porous polymer membranes (CPMs) emerging as a multifunctional platform for diverse applications in chemistry, materials science and biomedicine have been attracting widespread attention. Fabrication of CPMs in a controllable manner is of particular significance for optimizing their function and maximizing practical values. Herein, we report the fabrication of CPMs exclusively from poly(ionic liquid)s (PILs), and their pore size and wettability were precisely tailored by rational choice of counter‐anions. Specifically, a stepwise subtle increase in hydrophobicity of the counter‐anions by extending the length of fluorinated alkyl substituents, i.e. from bis(trifluoromethane sulfonyl)imide to bis(pentafluoroethane sulfonyl)imide and bis(heptafluoropropane sulfonyl)imide, decreased the average pore size gradually from 1546 to 157 and 77 nm, respectively. Meanwhile, the corresponding water contact angles increased from 90° to 102° and 120°. The sensitive control over the porous architectures and surface wettability of CPMs by systematic variation of anion hydrophobicity provides solid proof of the impact of PIL anions on CPM structure. © 2019 Society of Chemical Industry