离子强度和溶质浓度对蛋白质在Q Sepharose FF中吸附动力学的影响

采用孔扩散模型, 模拟不同盐浓度和不同蛋白质初始浓度条件下,吸附牛血清白蛋白(BSA)的动态吸附曲线并获得孔扩散系数;考察了离子强度和溶质浓度对蛋白质在阴离子交换剂Q Sepharose FF中吸附动力学的影响.结果表明,蛋白质的孔扩散系数随初始浓度的增大而下降;在氯化钠浓度小于0.10 mol•L^-1的范围内,蛋白质的孔扩散系数随着盐浓度的增加而增大,但当盐浓度增大到0.15 mol•L^-1时又有所降低,表明存在着一个最佳的离子强度,使蛋白质的孔扩散系数最大.     

盐种类和浓度对蛋白质疏水性吸附过程有效孔扩散系数的影响

研究了牛血清白蛋白在配基密度不同的两种疏水性吸附剂Phenyl Sepharose FF low sub和Phenyl Sepharose FF high sub上的吸附平衡和孔内传质动力学,重点考察了盐种类和浓度的影响.结果表明,Na2SO4溶液中盐浓度的增加导致蛋白质吸附容量的增大和解离常数的降低比(NH4)2SO4溶液更显著.利用孔扩散模型得到的有效扩散系数随盐浓度及配基密度的增大而提高,表明表面扩散作用对孔内传质的贡献随吸附容量提高而增大.     

琼脂糖-DEAE离子交换介质的配基密度和孔径对BSA吸附的影响

离子交换色谱是蛋白质分离纯化的有效方法之一,配基密度和介质孔径是影响蛋白质吸附的关键因素。采用3种不同琼脂糖浓度的凝胶为基质,具有不同的平均孔径,分别偶联上阴离子交换配基DEAE,通过调控反应条件,包括反应温度、反应时间、碱浓度和DEAE浓度,得到了不同配基密度和介质孔径的系列DEAE离子交换介质。考察了牛血清白蛋白（BSA）的静态和动态吸附性能,发现随配基密度增加或介质孔径减小,BSA饱和吸附容量有所增大;对于吸附动力学,介质孔径显著影响有效扩散系数。结果表明,配基密度和介质孔径共同决定了蛋白质的吸附性能,介质孔径主导蛋白质的孔内扩散,而配基密度则影响配基-蛋白质间的相互作用。     

吸附密度对蛋白质在离子交换吸附剂中孔扩散系数的影响

通过间歇吸附动力学实验,采用孔扩散模型研究了牛血清白蛋白和γ-球蛋白在阴离子交换剂中的扩散行为,考察了蛋白质初浓度和平均吸附密度对孔扩散系数的影响.结果表明,随蛋白质初浓度和平均吸附密度增大,孔扩散系数均呈指数下降,且蛋白质分子尺寸越大下降趋势越明显.     

蛋白质水力学半径的测定及用于蛋白质变性过程的实时监控

采用纳米粒度分析仪Zetasizer Nano测定了牛血清白蛋白（BSA）的水力学半径,考察了pH、离子强度、表面活性剂等的影响,并用于BSA热变性和脲变性过程的实时跟踪。随pH增大,BSA水力学半径呈“U”形变化趋势;酸性条件下,分子膨胀,随着盐浓度升高,BSA分子先小幅减小后显著增大;中性pH范围,离子强度对蛋白质分子尺寸影响很小,蛋白质性质相对稳定。离子型表面活性剂在蛋白质表面吸附,从而影响BSA水力学半径。通过水力学半径的测量实时跟踪蛋白质变性过程的分子变化,发现增加热变性中离子强度可加快变性速率,SDS加入增大了BSA变性温度Tm。脲在促使BSA分子扩张的同时,对链伸展有抑制作用;在DTT存在下,BSA的水力学半径随着时间变化逐渐增大。结果表明,简便的水力学半径测量可以用于蛋白质大小的表征,并可实时跟踪蛋白变性过程的分子尺度变化。     

盐响应型蛋白质吸附阳离子交换膜

通过简单可控的“一锅法”将聚甲基丙烯酸-3-磺酸丙酯钾盐（PSPM）接枝到化学稳定性良好的富含叔胺基的聚醚砜酮（PTA）膜表面,制备得到盐响应型阳离子交换膜（PTA-GS）。以中性时带正电的溶菌酶（Lys）和带负电的牛血清白蛋白（BSA）作为模型蛋白质,系统研究了PTA-GS膜对蛋白质的静态吸附性能、吸附动力学以及盐响应的吸附性能,并采用等温吸附模型、吸附动力学模型对实验结果进行拟合。结果表明,PTA-GS膜对Lys的吸附更符合Redlich-Peterson、Langmuir等温吸附模型和拟二级动力学方程。在25℃,中性缓冲溶液中PTA-GS膜对Lys和BSA的平衡吸附量具有显著差异,它们的饱和吸附量分别为(174.2±22.8)mg/g和(8.1±2.5)mg/g。PTA-GS膜对Lys的吸附量随盐浓度的升高而降低,其在含1mol/L氯化钠的缓冲溶液中再生后蛋白质脱附率可达79.3%。研究结果可为简单制备吸附性能优异的盐响应型离子交换膜提供新思路,并为阳离子交换膜上蛋白质的吸附行为研究提供指导。     

蛋白质在云母上吸附/解吸附的原子力显微镜研究

文章以牛血清白蛋白(BSA)和溶菌酶为例利用原子力显微镜(AFM)研究了蛋白质在云母表面的吸附与解吸附行为。首次利用十二烷基苯磺酸钠(SDBS)与蛋白质分子之间的相互作用实现了蛋白质从云母上的解吸附。采用轻敲模式,获得清晰的AFM图像表明:蛋白质的吸附量随蛋白质浓度及吸附时间的增加而增大;蛋白质的解吸附程度随SDBS浓度及解吸附时间的增加而增大。     

混合模式吸附中辛酸钠和牛血清白蛋白间相互作用

混合模式吸附是一种抗体分离新方法,适量添加辛酸钠,可以减弱血清白蛋白等杂质吸附,提高抗体结合的选择性。本文以MEP HyperCel介质和牛血清白蛋白（BSA）为模型,结合静态吸附平衡和等温滴定量热（ITC）法,考察了辛酸钠浓度、pH、盐和温度等影响,探讨了辛酸钠的作用机制。随辛酸钠浓度增大,BSA和牛血免疫球蛋白的饱和吸附量均呈现先降低后升高的趋势,不过辛酸钠对BSA影响更显著,ITC分析表明辛酸钠与BSA之间存在较强的相互作用,且以疏水作用为主导。添加辛酸钠后,BSA吸附量随pH或温度升高而降低,不同盐具有不同效果,ITC分析表明pH、盐和温度均不同程度影响辛酸钠-BSA相互作用,从而影响MEP HyperCel吸附BSA。结果表明,等温滴定量热分析与宏观吸附现象相一致,可量化分析小分子-蛋白间相互作用,为研究蛋白吸附过程中小分子添加物的作用机制提供了新思路。     

无纺布改性膜的制备及其抗污染性能研究

利用原子转移自由基聚合（ATRP）方法引发乙烯基吡咯烷酮（NVP）在聚丙烯无纺布膜表面接枝聚合。聚合物在膜上的接枝度随着接枝时间的增加而增加。傅里叶红外光谱分析表明了NVP在膜表面的成功接枝聚合;扫面电子显微镜观察表明接枝反应使膜的表面粗糙度增加,孔径降低;改性膜表面的亲水性增加,水动态接触角由基膜的113°降至改性后52.1°。静态蛋白质（BSA）吸附试验用来评价改性膜的抗蛋白质污染能力,结果显示改性膜表面BSA的吸附量降低了82.5%。通过纯水和活性污泥上清液过滤试验来分析改性膜的渗透和抗污染性能,结果表明和无纺布基膜相比,改性膜的抗污染能力大大提高,通量衰减率由基膜的91.93%降低到74.60%。     

双级孔材料内组分有效扩散系数的理论计算

双级孔材料中扩散与吸附现象广泛存在于化工过程中,准确预测其传递性质对指导过程设计具有重要意义。从最小尺度的孔隙开始采用体积平均方法推导出一个扩散型方程,并且得到该孔隙尺度下有效扩散系数的表达式。然后以此扩散方程为基础逐级扩大孔隙尺度,直至获得最大尺度孔隙中对应的扩散型方程及其对应的有效扩散系数的理论表达式。基于此,推导出一个扩散型方程描述双级孔材料内的组分扩散与吸附过程。孔隙结构、扩散速率、吸附强度的影响由有效扩散系数衡量。将上述理论模型与孔尺度模拟方法结合,对多孔圆柱阵列内的扩散吸附过程进行预测,预测结果与文献报道的直接数值模拟的结果吻合。结果表明:体积平均理论以及推导得到的封闭方程可用于预测双级孔材料内组分的有效扩散系数,为理解孔隙结构对有效扩散系数的影响以及调控相关过程性能提供了新的方法。     

Kinetic analysis of phenol adsorption from aqueous systems

The kinetic adsorption of mixtures of phenolic compounds onto a polymeric adsorbent from aqueous solutions was studied. Experimental data for single‐component solutions were obtained and fitted to a parallel diffusion model. Effective diffusion coefficients were related to liquid‐phase diffusion and surface diffusion. The effect of solute concentration and salinity on these parameters was also analysed. Van Laar's equation is proposed to evaluate the influence of concentration on diffusion. The adsorption kinetics for phenol and pcresol mixtures at different initial concentration ratios were determined and correctly adjusted to the mentioned kinetic model. Results confirm that adsorption from multicomponent aqueous solutions is a surface diffusion‐controlled process.     

蛋白质离子交换的空间质量作用模型分析

引　言离子交换层析具有分离容量大、选择性高和介质种类多、价格适中等特点 ,是蛋白质类生物大分子分离纯化的主要手段[1] .离子交换或吸附平衡研究是离子交换层析过程设计和优化分析的基础 ,也是分离实践中评价和选择离子交换介质的重要步骤 .目前已提出多种模型用于描述离子交换平衡 ,其中应用最多的是基于Ｌａｎｇｍｕｉｒ理论的经验模型[2 ] .但是 ,Ｌａｎｇｍｕｉｒ模型不能直接反映溶液离子强度对平衡的影响 ,不利于在盐浓度梯度洗脱的离子交换层析过程中的应用 .近年来 ,基于离子交换反应和蛋白质空间屏蔽作用的空间质量作用模型受…     

Protein adsorption dynamics in cation-exchange chromatography quantitatively studied by confocal laser scanning microscopy

A self-contained research system based on the technique of confocal laser scanning microscopy (CLSM) was put up to quantitatively analyze the dynamics of protein adsorption to porous cation exchanger by mathematical modeling. Bovine serum albumin adsorption to the cation exchanger SP Sepharose FF was performed by batch adsorption and micro-flow cell in which protein concentration in single absorbent was visualized by CLSM. The effects of ionic strength and the protein concentration in liquid phase (50 mmol/L acetate buffer, pH 5.0) on the adsorption dynamics were examined. The intraparticle concentration profile data experimentally obtained from CLSM were quantitatively analyzed by three diffusive mass transfer models (i.e., pore diffusion, surface diffusion and Maxwell-Stefan models (MSM)) in virtue of the attenuation equation for the CLSM visualization developed earlier. The nuance between the model simulations and experimental results of the developing protein distribution in a single adsorbent particle could thus be found out. Without salt addition to the buffer, the adsorption isotherm was strongly favorable, and the pore diffusion model (PorDM) and MSM gave similarly good simulations of the experiments, whereas the surface diffusion model was unreasonable in the model presumption. Moreover, it was observed that the experimentally obtained adsorption front was relative flatter as compared with the calculated results from the PorDM, which implied the possible existence of surface diffusion. With increasing salt concentration, the simulations became to deviate from the experiments. Especially, when the salt concentration approached 50 mmol/L, all the three mass transfer models could hardly give good simulation of the experiment. This was considered due to the difference in adsorption behavior between the fluorescence labeled and unlabeled proteins therein.     

Adsorption characteristics of methylene blue on poplar leaf in batch mode: Equilibrium,kinetics and thermodynamics

Adsorption characteristics of methylene blue (MB) from aqueous solution on natural poplar leaf were investigated. Batch experiments were carried out to study the effects of initial pH, contact time, adsorbent dosage, and initial MB concentration, salt concentration (Ca²⁺ and Na⁺) as well as temperature on MB adsorption. The optimum condition for adsorption was found at pH 6–9 and adsorbent dosage of 2 g L⁻¹. The equilibration time was 240 min. The salt concentration had a negative effect on MB removal. The equilibrium data were analyzed with Langmuir, Freundlich and Koble-Corrigan isotherm models using nonlinear regression method. The adsorption process was more effectively described by Langmuir isotherm based on the values of the correlation coefficient R² and chi-square statistic x². The maximum monolayer adsorption capacity of poplar leaf from the Langmuir model was 135.35 mg g⁻¹ at 293 K. The pseudo second order equation provided a better fit to experimental data in the kinetic studies. Intraparticle diffusion was involved in adsorption process, but it was not the only rate-controlling step. Thermodynamic quantities such as ΔG, ΔH and ΔS were calculated, indicating that the adsorption process was spontaneous and endothermic. Dye-adsorbent interactions were examined by FTIR and SEM analysis. The FTIR results suggested that there were hydroxyl and carboxyl groups on the surface of poplar leaf, which would make MB adsorption possible. The SEM images showed effective adsorption of MB molecules on the adsorbent surface.     

聚合物强化超滤过程处理含Hg~(2+)废水

研究聚丙烯酸钠(PAASS)与Hg2+络合反应动力学,当PAASS大量过剩及pH值恒为5时,络合反应达到平衡时间为25 m in,反应行为可用拟一级速率方程描述。测定PAASS对Hg2+络合能力,pH=5时每mg PAASS络合容量为1.0 mg。考察pH值、盐浓度和竞争络合剂对Hg2+截留系数的影响,可得:pH=5及负载比LR=1时适宜截留Hg2+;当C l-和SO42-浓度增大时,Hg2+截留系数逐渐降低;酒石酸钠和三乙醇胺不干扰PAASS与Hg2+的络合。进一步研究超滤浓缩行为,结果表明:当pH=5,PAASS及Hg2+初始质量浓度均为100 mg/L时,原料液浓缩15倍,膜通量仅衰减15.0%,浓缩液及渗透液汞质量浓度分别为1499.6,0.03 mg/L。     

Analysis of steric mass-action model for protein adsorption equilibrium onto porous anion-exchange adsorbent

The ion-exchange equilibrium of bovine serum albumin (BSA) to an anion exchanger, DEAE Spherodex M, has been studied by batch adsorption experiments at pH values ranging from 5.26 to 7.6 and ionic strengths from 10 to 117.1 mmol/l. Using the unadjustable adsorption equilibrium parameters obtained from batch experiments, the applicability of the steric mass-action (SMA) model was analyzed for describing protein ion-exchange equilibrium in different buffer systems. The parametric sensitivity analysis was performed by perturbing each of the model parameters, while holding the rest constant. The simulation results showed that, at high salt concentrations or low pHs close to the isoelectric point of the protein, the precision of the model prediction decreased. Parametric sensitivity analysis showed that the characteristic charge and protein steric factor had the largest effects on ion-exchange equilibrium, while the effect of equilibrium constant was about 70%-95% smaller than those of characteristic charge and steric factor under all conditions investigated. The SMA model with the relationship between the adjusted characteristic charge and the salt concentration can well predict the protein adsorption isotherms in a wide pH range from 5.84 to 7.6. It is considered that the SMA model could be further improved by taking into account the effect of salt concentration on the intermolecular interactions of proteins.     

Competitive removal of malachite green and Rhodamine-B using Amberlite-XAD-4 impregnated with Aliquat 336: experimental and modelling studies

ABSTRACT

Use of solvent impregnated resin in the separation has emerged as a new area of interest. It is a hybrid process with the characteristics of adsorption, ion-exchange and extraction. Here, Aliquat 336 impregnated Amberlite XAD-4 resin was used to remove Rhodamine-B and malachite green individually and from their mixtures in the aqueous solution. The performance of prepared resin was studied in batch mode to analyze the effect of adsorbent dosage, pH, concentration of dye solution, salt concentration, time, and temperature. Characterization (using FE-SEM, EDS, FTIR, and point of zero charge), regeneration, and cost analysis of the adsorbent were also done.     

Effects of divalent salt on adsorption kinetics of a hydrophobically modified polyelectrolyte at the neutral surface-aqueous solution interface

Adsorption of a hydrophobically modified polyelectrolyte on hydrophobized silica surfaces in aqueous divalent salt solutions was studied using an ellipsometric technique. The results indicate three distinct stages in adsorption: a relatively short induction period, a surface accumulation region, and a plateau (quasi equilibrium) region. The induction period remains unchanged with increasing divalent salt concentration. The surface accumulation rate decreases while the equilibrium (quasi) adsorbed amount increases with increasing divalent ionic strength. Divalent salt (CaCl₂) produces much higher adsorbed amounts compared to a monovalent salt (NaCl). The analysis of kinetic data (surface accumulation rate) with a transport-limited regime model suggests the reduction of diffusion coefficient (i.e. the increase of size of the adsorbent) with increasing divalent salt concentration. At low concentrations of divalent salt (namely 0.01 M CaCl₂), it is possible that the substantially screened individual chains are predominantly adsorbed on the surface. On the contrary, at moderate and high concentrations of divalent salt (namely 0.075 M onwards), polyelectrolyte aggregates or micelles are predominantly adsorbed on the surface.     

PBMA/GMA-SiO2吸附剂的制备及其高效去除铅离子

以甲基丙烯酸丁酯(BMA)和甲基丙烯酸缩水甘油酯(GMA)功能化的纳米SiO2为单体,通过可逆加成-断裂链转移自由基聚合(RAFT)法制备了PBMA/GMA-SiO2有机/无机复合吸附材料,并将其用于吸附含Pb2+的水溶液。考察了吸附时间、温度、pH以及Pb2+初始质量浓度对吸附效果的影响,并对其吸附动力学和热力学特性进行了探讨。结果表明,PBMA/GMA-SiO2对Pb2+具有良好的吸附性能,其对Pb2+的饱和吸附量为423.84mg/g,吸附最佳pH=5~6,平衡时间为1 h,去除率随Pb2+初始质量浓度的减小而增加。优化实验条件下,50 mg吸附剂在298 K时,对pH=6的50 mL 0.02 g/L含Pb2+溶液的去除率高达100%。热力学和动力学过程模拟结果表明,吸附的动力学过程比较符合准二级动力学速率方程,Langmuir等温方程比Freundlich等温方程更适合于描述此吸附行为。颗粒内扩散过程是吸附速率的控制步骤,但不是唯一的速率控制步骤。吸附剂经过5次脱附、吸附后,依然具有较强吸附Pb2+的能力。     

Adsorptive removal of uranium from water by sulfonated phenol–formaldehyde resin

Adsorption characteristics of a sulfonated phenol‐formaldehyde resin (SPR) have been studied for U removal from aqueous solution by means of batch method. Adsorption experiments have been carried out as a function of contact time, solution/adsorbent ratio, particle size and pH. Adsorption isotherm has been evaluated by changing adsorbent dosage in the range of 0.04–80 g/L at an initial uranyl nitrate concentration of 0.05 mol/L. The enormous adsorption capacity of 0.29 mol/g estimated from the plateau region of the S shaped isotherm is well comparable the Langmuir capacity of 0.31 mol/g. Equilibrium data are also adequately well described by the Freundlich and the Dubinin‐Radushkevich (D‐R) isotherm equations. The parameters of the isotherms and pH dependency of distribution coefficients (K_D) indicate that polymeric uranyl chains form on bidentate surface complex as a result of solute–solute interactions on the adsorbent surface. Both desorption and elution studies show that uranyl chains are irreversibly bounded on the SPR. Kinetic curves having a fast initial part followed by a slower process well fit both McKay model based on two‐resistance diffusion and Nernst‐Plank model with single diffusion coefficient. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009