纳滤膜分离技术分离纯化多肽和氨基酸

综述了近十年来纳滤膜技术在氨基酸和多肽分离与纯化方面的研究进展。多肽和氨基酸的纳滤分离过程受溶液物化性质、氨基酸和多肽分子尺寸、所带电荷以及膜孔径、膜带电状态等多种因素的影响,建立该过程的分离机理模型、组合并优化分离条件是当前研究的热点。     

解读纳滤:一种具有纳米尺度效应的分子分离操作

纳滤膜是20世纪80年代末期发展起来的一种广泛用于液体分离的新型分离膜。早期研究中,先后提出的基于筛分效应的细孔模型,基于静电效应的电荷模型,以及同时考虑上述两种效应的静电位阻模型和道南位阻模型等为人们更好地理解纳滤膜分离机理和指导纳滤膜过程应用发挥了十分重要的作用。然而由于这些具有“疏松型反渗透膜”特点的纳滤膜没有相应的膜性能预测评价软件,使得针对具体应用过程的纳滤膜的大规模标准化应用受到了一定的制约。为此,结合上述模型,根据一些特定实验拟合确定混合盐体系同号离子间的竞争作用和异号离子间的调节作用,提出了一个适于混合盐体系的纳滤膜分离性能评价模型,促进了纳滤膜技术在水处理过程的大规模推广。最近,根据纳滤膜对离子选择性分离性能及其伴随的动电性质的细致而深入的实验研究,发现仅考虑筛分效应和静电效应并不能完全合理地解释纳滤膜的分离性能,且在动电性质的解析上也存在一定缺陷,进而对纳滤膜纳米级孔径引起的特殊效应和溶液体系中复杂相互作用引起的荷电性质变化有了更为深刻的认识和理解,提出并定量分析了离子透过纳滤膜时存在的介电排斥效应。     

纳滤膜新型材料研究

纳滤是一种介于超滤与反渗透之间的重要膜分离过程,具有工作压力低、无相转变及分离效率高等独特优势。膜污染及渗透性/选择性之间的平衡是纳滤膜在使用和研发过程中面临的亟待解决的两个主要问题。膜材料是膜与膜分离技术的核心,开发新型的纳滤膜材料是解决上述问题的重要手段。本文从新型纳滤膜材料的设计与选择的角度出发,总结归纳了近年来新型材料在纳滤膜的制备与应用研究现状,包括新型有机纳滤膜材料、新型无机纳滤膜材料和新型有机-无机杂化纳滤膜材料三个方面,拓展了对纳滤膜材料的认知,探讨了新型纳滤膜材料的共性及其存在的主要问题,并对未来高性能纳滤膜材料的研制方向进行了展望。     

耐溶剂纳滤膜*

纳膜分离过程是一种选择性高、操作简单、能耗低的分离技术,已在各工业领域和科学研究中得到广泛的应用。纳滤过程的诸多优点,使其在石油化工、医药、食品等领域的非水溶液体系中具有极大的潜在应用价值,而传统的纳滤膜难以拓宽到非水溶液体系中使用,为此进一步研究和发展耐溶剂纳滤膜,对于拓宽纳滤过程的应用极其重要。目前,耐溶剂纳滤膜已成为膜分离科学领域的研究热点,在现有报道的文献基础上,本文综述了有关在非水溶液体系中使用的耐溶剂纳滤膜制备的研究进展,并对将来的发展方向提出了建议。     

荷正电聚乙烯亚胺纳滤膜的制备与应用

纳滤是介于超滤与反渗透之间的膜分离技术,具有操作压力低,无相变,分离效率高及运行成本低等优点,广泛地应用于饮用水制备、污水处理、化工、制药和食品等领域.近年来,随着分离体系复杂程度的增加及对膜分离性能要求的提高,荷正电纳滤膜越来越受到研究者的关注.聚乙烯亚胺(PEI)是一类重要的多胺类荷正电纳滤膜材料,具有优异的亲水性、高荷电密度及反应活性.开发具有高分离性、高稳定性、耐酸碱性、耐溶剂性、抗菌性和耐污染性的荷正电PEI纳滤膜(P-PEI-NFM)日益成为研究的热点.本文对近年来P-PEI-NFM的制备方法进行归纳,总结了P-PEI-NFM在水软化、重金属脱除、碱性染料的分离及浓缩、抗生素分离和耐溶剂纳滤的应用.探讨了P-PEI-NFM存在的主要问题,并对未来的研究方向进行了展望.     

盐湖提锂纳滤膜研究进展

锂是我国发展新能源等产业的关键资源,进口依赖度大。盐湖提锂是应对锂短缺问题的重要途径,然而盐湖中高浓度的伴生镁离子给高效提锂带来挑战。纳滤膜可通过孔径筛分和电荷排斥效应的协同,有效分离镁锂离子,在盐湖提锂中扮演着重要的角色。本文从纳滤膜结构(孔径、电荷、厚度)调控出发,介绍了新单体设计、表面改性、共混掺杂、底膜改性等膜结构调控策略,阐述了膜结构与镁锂分离性能的构效关系,总结了不同制膜方法在镁锂分离过程中的优劣,展望了新型镁锂分离纳滤膜的研究方向。     

聚电解质层层自组装纳滤膜*

层层自组装技术能够方便地对膜的微观结构和组成进行调控,已在制备复合型纳滤膜方面取得了迅速的发展。本文综述了近年来用于聚电解质层层自组装纳滤膜的制备方法,种类以及影响因素。介绍了静态层层交替沉积、压力驱动自组装和电场强化自组装等三种制备方法;归纳了均聚型、共聚型和有机/无机杂化型等三类用于层层自组装纳滤膜的聚电解质的特点;讨论了聚电解质的荷电性、电荷密度和电离程度等因素对其自组装膜分离性能的影响。总结了聚电解质自组装纳滤膜在水处理和有机溶剂中物质的分离等方面的应用。同时,对提高聚电解质自组装纳滤膜的组装效率,分离性能和发展方向提出了设想和建议。     

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.     

纳滤膜的研究进展

纳滤膜是一种新型分离膜,其截流分子量介于反渗透膜和超滤膜之间,且对无机盐有一定的截流率。国内外纳滤膜制备方法有L-S相转化法、复合法、荷电化法和无机改性等。纳滤膜研究中存在着膜通量小、膜制作成本较高及抗污染性差等问题,因此选择和制备纳滤膜的材料,优化纳滤技术水处理工艺设计,提高纳滤性能,降低制膜成本,减轻膜污染等已成为当今科学研究的重要课题。     

纳滤膜对电解质溶液分离特性的理论研究(II): 混合电解质溶液

假定纳滤膜具有狭缝状孔, 使用纯水透过系数、膜孔径及膜表面电势来表征纳滤膜的分离特征, 用流体力学半径和无限稀释扩散系数表征了离子特性. 采用扩展Nernst-Planck方程、Donnan平衡模型和Poisson-Boltzmann理论描述了混合电解质溶液中离子在膜孔内的传递现象, 计算了三种商用纳滤膜(ESNA1-LF, ESNA1和LES90)对同阴离子、同阳离子和含四种离子的混合电解质体系中离子的截留率, 并与实验数据进行了比较. 计算结果表明, 电解质溶液中离子在纳滤膜孔内传递的主要机理是离子的扩散和电迁移, 纳滤膜对混合电解质溶液中离子的分离效果主要由空间位阻和静电效应决定. 该模型在低浓度时对含一价离子的混合电解质溶液通过纳滤膜的截留率计算结果比较准确, 但对高浓度或含高价离子的混合电解质溶液则偏差较大.     

高分子纳滤膜的制备技术

纳滤膜是介入于反渗透膜和超滤膜之间的一种压力驱动的新型分离膜,已成为近年来研究的热点,由于其载留分子量范围相对较窄（200－1000）且孔径处于纳米级（10^-9m),因此膜材质的选择及制备技术成为制备出高性能纳滤膜的关键。本文介绍了高分子纳滤膜的几种主要的制备工艺,并概述了近年来国内外在高分子纳滤膜材质、制备方法以及所制膜性能及应用方面的研究进展。     

Prediction of physical properties of nanofiltration membranes using experiment and theoretical models

Two commercial nanofiltration (NF) membranes, viz., Desal-HL and NF 700 MWCO were investigated experimentally using neutral and charged solutes, viz., glucose, sodium chloride and magnesium chloride. Effect of pH was studied for sodium chloride rejection and isoelectric point of the membrane was deduced. Experimental results were analyzed using Donnan steric pore and dielectric exclusion models. Dielectric exclusion arises due to the difference in dielectric constant between the bulk and the nano-pore. Born dielectric effect was used as dielectric exclusion phenomena in the present investigation. Stokes–Einstein, Born effective and Pauling radii were used for theoretical simulation, which accurately predicted different charge densities. Empirical correlations were proposed between charge density, concentration and pH for each radius. Charge density decreased drastically when dielectric exclusion term was included in the theoretical model, which showed the real physical characteristics of the membranes employed. Charge density and radius of pore was found to be an important surface parameter in predicting the separation effects in NF membranes.     

Aqueous two-phase systems for protein separation: a perspective

Aqueous two-phase systems (ATPS) that are formed by mixing a polymer (usually polyethylene glycol, PEG) and a salt (e.g. phosphate, sulphate or citrate) or two polymers and water can be effectively used for the separation and purification of proteins. The partitioning between both phases is dependent on the surface properties of the proteins and on the properties of the two phase system. The mechanism of partitioning is complex and not very easy to predict but, as this review paper shows, some very clear trends can be established. Hydrophobicity is the main determinant in the partitioning of proteins and can be measured in many different ways. The two methods that are more attractive, depending on the ATPS used (PEG/salt, PEG/polymer), are those that consider the 3-D structure and the hydrophobicity of AA on the surface and the one based on precipitation with ammonium sulphate (parameter 1/m*). The effect of charge has a relatively small effect on the partitioning of proteins in PEG/salt systems but is more important in PEG/dextran systems. Protein concentration has an important effect on the partitioning of proteins in ATPS. This depends on the higher levels of solubility of the protein in each of the phases and hence the partitioning observed at low protein concentrations can be very different to that observed at high concentrations. In virtually all cases the partition coefficient is constant at low protein concentration (true partitioning) and changes to a different constant value at a high overall protein concentration. Furthermore, true partitioning behavior, which is independent of the protein concentration, only occurs at relatively low protein concentration. As the concentration of a protein exceeds relatively low values, precipitation at the interface and in suspension can be observed. This protein precipitate is in equilibrium with the protein solubilized in each of the phases. Regarding the effect of protein molecular weight, no clear trend of the effect on partitioning has been found, apart from PEG/dextran systems where proteins with higher molecular weights partitioned more readily to the bottom phase. Bioaffinity has been shown in many cases to have an important effect on the partitioning of proteins. The practical application of ATPS has been demonstrated in many cases including a number of industrial applications with excellent levels of purity and yield. This separation and purification has also been successfully used for the separation of virus and virus-like particles.     

Modeling and simulation of nanoparticle separation through a solid-state nanopore

Recent experimental studies show that electrokinetic phenomena such as electroosmosis and electrophoresis can be used to separate nanoparticles on the basis of their size and charge using nanopore‐based devices. However, the efficient separation through a nanopore depends on a number of factors such as externally applied voltage, size and charge density of particle, size and charge density of membrane pore, and the concentration of bulk electrolyte. To design an efficient nanopore‐based separation platform, a continuum‐based mathematical model is used for fluid. The model is based on Poisson–Nernst–Planck equations along with Navier–Stokes equations for fluid flow and on the Langevin equation for particle translocation. Our numerical study reveals that membrane pore surface charge density is a vital parameter in the separation through a nanopore. In this study, we have simulated high‐density lipoprotein (HDL) and low‐density lipoprotein (LDL) as the sample nanoparticles to demonstrate the capability of such a platform. Numerical results suggest that efficient separation of HDL from LDL in a 0.2 M KCL solution (resembling blood buffer) through a 150 nm pore is possible if the pore surface charge density is ～ ?4.0 mC/m². Moreover, we observe that pore length and diameter are relatively less important in the nanoparticle separation process considered here.     

Modeling the separation performance of nanofiltration membranes for the mixed salts solution

A new model is proposed to evaluate the separation performance of nanofiltration (NF) membranes for the mixed salts solution. In the model, the observed transmission of an ion through a NF membrane is applied to express the separation performance of the membrane for the ion in the mixed salts solution, which has a relationship with the total concentration, the equivalent fraction and the species of each ion in the mixed salts solution. The verification of the model was carried out in the permeation experiments of some mixed salts solutions ((1) Na⁺, Cl⁻ and F⁻; (2) Na⁺, K⁺ and Cl⁻; (3) Na⁺, F⁻, Cl⁻ and NO₃⁻; (4) Na⁺, Cl⁻, NO₃⁻ and SO₄²⁻) through three commercial NF membranes (ESNA 1-LF, ESNA 1 and LES 90). According to the permeation experiments of three NF membranes for some binary salts solutions, the competition coefficients of ions were obtained. The model evaluation results agreed quite well with the experimental data. Finally, the model was applied to evaluate the observed transmission of each ion in the mixed salts solution (Na⁺, F⁻, Cl⁻, NO₃⁻ and SO₄²⁻) through three NF membranes. The agreement between the model evaluation results and the experimental data indicated that the model is suitable for evaluating the separation performance of three NF membranes for the mixed salts solution.     

低聚壳聚糖制备液纳滤纯化的可行性研究

通过对筛选的3种纳滤膜结构及对低聚壳聚糖、氨基葡萄糖和NaAc溶液的截留性能和纯化过程研究发现,3种纳滤膜的膜面粗糙度大小依次为:DL>DK>NTR-7450,均能对低聚壳聚糖100%截留,但只能部分截留氨基葡萄糖和NaAc,其截留率大小为:DK>DL>NTR-7450。从低聚壳聚糖的纯化工艺要求和抗污染能力方面考虑,NTR-7450纳滤膜更具有工业应用价值。此外,纳滤膜对溶质的分离效果主要由空间位阻和静电效应决定,综合作用结果导致了低聚壳聚糖体系中的各种主要阳离子在纳滤过程中存在竞争透过,截留次序依次为:高分子低聚壳聚糖>氨基葡萄糖>Na+>H+。在Donnan效应和电离平衡的影响下,体系中Ac-在纳滤过程中也被脱出。纳滤纯化低聚壳聚糖制备液在技术上可行。     

基于贻贝仿生化学的分离功能材料

贻贝仿生的表面化学是近年来材料学、化学、生物医学等领域的交叉研究热点。多巴胺可以作为贻贝足丝蛋白(Mfp)超强黏附特性的模型分子,通过复杂的氧化-自聚和组装,形成多种功能的聚多巴胺(PDA)纳米涂层和纳米粒子,在分离膜、吸附材料、生物医用材料、生物黏结剂等领域有着广阔的应用前景。本研究小组近年来持续开展了基于贻贝仿生化学的分离功能材料制备与结构调控的研究工作,率先将多巴胺表面沉积方法应用于多孔分离膜表面的构建与功能化,提出了多巴胺的自聚-沉积过程模型,进而验证了PDA沉积层的纳滤分离特性,建立了一条简单方便的膜表面功能化与纳滤膜制备新途径。本文主要对基于贻贝仿生化学的分离功能材料,特别是分离膜的研究进展进行综述,并对将来的发展趋势进行展望。     

Characterization and separation of semiconductor quantum dots and their conjugates by capillary electrophoresis

Semiconductor quantum dots (QDs) are very important luminescent nanomaterials with a wide range of potential applications. Currently, QDs as labeling probes are broadly used in bioassays, including immunoassay, DNA hybridization, and bioimaging, due to their excellent physical and chemical properties, such as broad excitation spectra, narrow and size‐dependent emission profiles, long fluorescence life time, and good photostability. The characterization of QDs and their conjugates is crucial for their wide bioapplications. CE has become a powerful tool for the separation and characterization of QDs and their conjugates. In this review, some CE separation models of QDs are first introduced, mainly including CZE, CGE, MEKC, and ITP. And then, some key applications, such as the measurements of size, surface charge, and concentration of QDs and the characterization of QDs conjugates (e.g. QD–protein, QD–DNA, QD–small molecule), are also described. Finally, future perspectives are discussed.