pH值和离子强度对空间质量作用模型参数的影响

以牛血清白蛋白（BSA）为模型蛋白质研究了pH值和离子强度对空间质量作用模型参数的影响。通过静态吸附实验确定了不同pH值和离子强度条件下BSA在阴离子交换剂DEAE-Spherodex M上的吸附平衡,利用色谱实验及非线性最小二乘法确定模型参数。研究发现,只有在pH值远大于BSA等电点时,蛋白质的特征电荷数和空间因子才为常数;离子交换平衡常数不仅是pH值的函数,也受到液相离子强度的影响。     

空间质量作用模型预测小分子离子交换平衡

The steric mass-action (SMA) model has been widely reported in the literature for ion-exchange and metal-affinity interaction adsorption equilibrium of biomacromolecules. In this paper, the usefulness of SMA model is analyzed for describing micromolecule ion-exchange equilibrium onto cation exchangers, CM Sephadex C-25 and Streamline SP. Batch adsorption experiments with ephedrine hydrochloride as a model adsorbate are carried out to determine the model parameters, that is, steric factor, characteristic charge and equilibrium constant. The result shows that the SMA model parameters of micromolecule cannot be obtained using the nonlinear least-square fitting method as protein‘s due to the remarkable difference between the molecular mass and dimension of micromolecule and protein. It is considered that the small size of the adsorbates dealt with in this study justifies the neglect of steric hindrances arising from adsorbate bulkiness. Thus, the three-parameter SMA model is reduced to two-parameter one (i.e., steric factor is equal to zero) for describing micromolecule ion-exchange equilibrium. It is found that the equilibrium constant for CM Sephadex C-25 increases with increasing ionic strength, while the equilibrium constant for Streamline SP shows an opposite trend. This is probably due to the remarkable difference between the physicalpro perties of the two adsorbents. Then, the relationship between the equilibrium constant and ionic strength is described by an expression. The computer simulations show that, the theoretical model with the correlation is promising in the prediction of micromolecule adsorption decrease with increasing ionic strength in a wide range of salt concentration.     

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…     

VMT/P(AMPS-co-AA)复合高吸水树脂的性能测试

研究了溶液pH、盐浓度对辉光放电电解等离子体引发合成的蛭石/聚(2-丙烯酰胺-2-甲基丙磺酸-co-丙烯酸) (VMT/P(AMPS-co-AA)) 复合高吸水树脂的溶胀行为的影响,考察了染料pH、吸附时间、染料浓度等因素对复合高吸水树脂吸附量的影响,同时对树脂的吸附-解吸性能进行了研究。结果表明, VMT/P(AMPS-co-AA)具有高吸水性、pH敏感性、盐敏感性以及高吸附性。该树脂在蒸馏水中的最大溶胀率达到822.4 g/g,对阳离子染料亚甲基蓝(MB)、结晶紫(CV)和孔雀石绿(MG)的吸附量分别可达2027.8, 2171.8和883.2 mg/g。在pH=6.5和25℃下,其对染料的吸附行为符合动力学准二级模型,该树脂还具有一定的吸附-解吸性能和重复利用性能。     

蛋白质离子交换平衡的实验研究

本实验研究了离子交换色谱法和直接实验法建立蛋白质离子交换平衡等温线和确定平衡参数的问题。结果表明,在低浓度溶液中,用离子交换色谱法估算的平衡常数K与直接实验法确定的参数有很好一致性,而且色谱法还具有快速又经济的特点。     

蛋白质在离子交换吸附剂颗粒中的扩散系数

采用以化学势梯度作为扩散推动力的Maxwell-Stephan扩散方程（MS方程）,结合平行扩散模型,对阴离子吸附剂Q-SepharoseFF吸附牛血清白蛋白（BSA）的动态试验数据进行了模拟,拟舍得到了BSA的表面扩散和孔扩散系数。研究表明表面扩散系数随pH降低、盐浓度增加而增大;孔扩散系数随pH增加、盐浓度降低而增加,随蛋白质初始浓度增加而减小。在表面扩散不容忽视且为非线性吸附的条件下采用Fick定律时得到的表面扩散系数是蛋白质浓度的函数,且大于根据MS方程得到的表面扩散系数。     

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.     

Study of equilibrium,kinetic and thermodynamic parameters about methylene blue adsorption onto natural zeolite

Adsorption equilibrium and kinetic of methylene blue (MB) onto natural zeolite was studied in a batch system. Variables of the system include contact time, pH, salt concentration, temperature, and initial MB concentration. The increase in temperature resulted in a higher MB loading per unit weight of the zeolite. Langmuir, Freundlich, Redlich–Peterson, Koble–Corrigan and Temkin isotherm models were applied to experimental equilibrium data of MB adsorption depending on temperature. The effect of contact time at different temperatures and initial concentration were fitted to pseudo-second-order kinetic model. Linear regressive method and nonlinear regressive method were used to obtain the relative parameters. The error analysis was conducted to find whether linear method or nonlinear method was better to predict the experimental results and which model was better to fit the experimental data. Both methods were suitable to obtain the parameters. The Redlich–Peterson equation was best to fit the equilibrium data. The pseudo-second-order kinetic model can be used to describe the adsorption behavior. The nonlinear method may be better with the absolute error as limited condition. The adsorption process was spontaneous and endothermic.     

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.     

基于氨基酸的新型树枝状色谱置换剂的合成及性能

高效置换剂的设计与合成一直是置换色谱发展的重要方向。采用固相合成方法合成了新型树枝状聚电解质置换剂Phe-D和Leu-D，并与置换剂BAEE进行了对比研究。研究结果显示，置换剂的动态亲和性随着lgΔ值增大而降低。在lgΔ<0.845时，BAEE具有最高的动态亲和力;而随着lgΔ进一步升高，Phe-D展现出最强的动态亲和力，这种趋势一直维持至lgΔ值达到3.08。蛋白质的静态置换实验表明，新型置换剂对蛋白质具有更高的置换百分率。这种高置换率主要源于置换剂中伯胺基团数量的增加;同时，Phe-D分子中苯基的引入使模型蛋白的置换百分率提高了70%，展示了苯基对蛋白质置换的促进作用。     

基于吸附-扩散机理研究钒离子透膜传质过程（Ⅱ）——钒离子透膜传质实验研究

吸附-扩散模型基于离子交换膜固定电荷理论,涉及离子选择性系数和透膜扩散通量,通过三种离子交换膜内VO2＋吸附平衡和透膜扩散实验,由吸附-扩散模型计算钒离子透膜扩散系数,揭示钒离子透膜传质过程。膜面FT-IR红外谱揭示基膜内不饱和键及RSO3-交换能力是影响膜稳定性和VO2＋膜内吸附量主要因素,膜面光滑、平整能有效地降低VO2＋吸附,抑制膜内水吸附和VO2＋透膜扩散。该模型能较真实揭示钒离子透膜传质过程,可快速有效的筛选电池隔膜,并指导高性能钒电池隔膜制备。     

离子交换树脂吸附TP5的热力学和动力学研究

针对凝胶型阳离子交换树脂对TP5的吸附行为,研究了间歇反应中TP5水溶液的吸附热力学与动力学特性。热力学研究表明,TP5在所用树脂上的吸附平衡数据符合Langmu ir吸附等温方程。在283.15~303.15 K之间,TP5的质量浓度在10 g/L时,离子交换树脂对TP5的吸附过程可分两个阶段,第一阶段受液膜扩散控制,第二阶段主要吸附过程受颗粒扩散的控制。利用TP5在不同条件下的动态吸附性能实验,考察了pH值、温度、溶液初始浓度、搅拌转速等因素的影响。采用两相阻力模型描述了TP5在离子交换介质中的动态吸附性能,通过计算得到了TP5在吸附剂颗粒中的颗粒扩散系数,有助于进一步研究小肽在吸附过程中的传质现象。     

Simulation and validation of ethanol removal from water in an adsorption packed bed: Isotherm and mass transfer parameter determination in batch studies

Preferential adsorption of ethanol from ethanol/water mixtures in batch equilibrium and kinetic experiments were carried out on a commercially available activated carbon adsorbent Filtrasorb 600 (F‐600). A model based on finite difference method was developed and employed to determine the mass transfer parameters and equilibrium behaviour for the adsorption of ethanol from simple batch systems. The estimates of the adsorption isotherm along with the mass transfer parameters were used to simulate the transient performance that could be expected in a packed bed under various operating conditions (feed flow rate, feed concentration, and particle size). The applicability of the simulation results were found to be a good match with experimental packed bed experiments over the entire range of operating conditions tested.     

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.     

The effect of protein binding on ibuprofen adsorption to activated carbons

The potential of a range of polymer-based activated carbons to remove a non-steroidal anti-inflammatory drug ibuprofen from protein containing and protein-free solutions was studied. The adsorption capacity of five activated carbons produced from phenol-formaldehyde resin precursors (MAST Carbon Ltd) was compared to a cellulose coated activated carbon Norit RBX used in a commercial Adsorba^®300C haemoperfusion column (Gambro).Ibuprofen adsorption was studied in batch experiments over 24 h at pH=7.6 and 25 °C and adsorption equilibrium data were correlated with the Langmuir and Freundlich equations.Results showed that uncoated mesoporous MAST carbons can remove ibuprofen from model solutions both in the presence and absence of serum albumin. Ibuprofen is a highly protein-bound drug and the presence of serum albumin significantly affects the adsorption of ibuprofen by cellulose-coated microporous carbon used in Adsorba^®300C column.     

神府煤对大豆分离蛋白质的吸附特性研究

采用静态吸附法探讨了神府煤粉(SFC)对大豆分离蛋白质(SPI)的吸附特性。研究了SPI溶液初始质量浓度(3.0—12.0 kg/m3)、温度(20、30、40、50℃)、pH值(4.0—9.0)等条件对吸附量的影响。结果表明,吸附平衡时间为12 h,适宜的pH值为6.0。SFC对SPI吸附过程为非自发的放热过程,吸附过程符合二级动力学模型。红外光谱分析表明,蛋白质分子主要通过C O和NH与煤大分子结构中的OH和C O对应形成2个活性位点的氢键作用,吸附于煤表面。     

ION EXCHANGE OF SEVERAL RADIONUCLIDES ON THE HYDROUS CRYSTALLINE SILICOTITANATE,UOP IONSIV IE-911

ABSTRACT

The crystalline silicotitanate, UOP IONSIV IE-911, is a proven material for removing radionuclides from a wide variety of waste streams. It is superior for removing several radionuclides from the highly alkaline solutions typical of DOE wastes. Our laboratory previously developed an equilibrium model applicable to complex solutions for IE-910 (the powder form of the granular IE-911), and more recently, we have developed several single component ion-exchange kinetic models for predicting column breakthrough curves and batch reactor concentration histories. In this paper, we model ion-exchange column performance using effective diffusivities determined from batch kinetic experiments. This technique is preferable because the batch experiments are easier, faster, and cheaper to perform than column experiments. We also extend these ideas to multicomponent systems. Finally, we evaluate the ability of our equilibrium model to predict data for IE-911.     

Removal Of methylene blue dye from simulated wastewater by alginic acid fiber as adsorbent: Equilibrium,kinetic, and thermodynamic studies

Alginic acid fiber was used as a novel adsorbent to remove methylene blue from aqueous solution, and adsorption mechanisms were investigated. System variables, including contact time, pH, temperature, and initial concentration were examined to investigate the effect on adsorption in batch experiments. The results showed that equilibrium reached in less than 20 min and pH significantly influenced the equilibrium value. Langmuir, Freundlich, and Temkin isotherm models were employed to analyse the isotherm behaviours. It was found the isotherm behaviours conform to Freundlich and Temkin models well, indicating a chemisorption process. Pseudo‐first‐order, pseudo‐second‐order, and intraparticle diffusion models were employed to investigate kinetic behaviours. The kinetic behaviour is best described by pseudo‐second‐order model. Thermodynamic parameters indicate that the process is spontaneous and exothermic.     

生物炭对重金属(Zn)的吸附特性及动力学

在300～700℃下制备了水葫芦炭和玉米秸秆炭,研究了生物质种类、热解温度、溶液初始pH和Zn(Ⅱ)初始浓度对两种生物炭吸附溶液中Zn(Ⅱ)的影响,并结合吸附过程曲线拟合获得了吸附动力学模型。结果表明：随着热解温度的升高,生物炭理化特性发生显著变化,生物炭的挥发分、氧含量、氢含量以及O/C和H/C显著降低,而固定碳、灰分和热值显著升高,生物炭的比表面积、总孔容、微孔容、pH以及KCl等盐类物质均得到了显著增加。随着溶液初始pH增加,生物炭对Zn(Ⅱ)的吸附能力呈现先快速增加然后逐步趋于稳定或稍有下降的趋势,不同生物炭的最大平衡吸附量出现在pH=4~6之间。Zn(Ⅱ)初始浓度<30mg/L时,生物炭对Zn(Ⅱ)平衡吸附量随溶液Zn(Ⅱ)初始浓度的增加呈线性快速增长,而当Zn(Ⅱ)初始浓度>30mg/L,其平衡吸附量增长趋势变缓。在相同Zn(Ⅱ)初始浓度下,随着热解温度的提高,生物炭对溶液中Zn(Ⅱ)平衡吸附量逐渐提高,且在同一热解温度下制备的水葫芦炭对Zn(Ⅱ)的平衡吸附量显著高于玉米秸秆炭。两种生物炭对溶液Zn(Ⅱ)的吸附符合Lagergren准二级动力学模型,其吸附过程均受化学吸附控制,水葫芦炭和玉米秸秆炭对Zn(Ⅱ)吸附机制主要包括含氧官能团的络合作用和无机盐离子的沉淀作用。     

油页岩灰渣合成Na-A沸石用于去除水溶液中Cu2+（英文）

Na-A zeolite was synthesized using oil shale ash （OSA）, which is a solid by-product of oil shale proc- essing. The samples were characterized by various techniques, such as scanning electron microscopy, X-ray diffrac- tion and Brunaner Emmet Teller method. The batch isothermal equilibrium adsorption experiments were performed to evaluate the ability of Na-A zeolite for removal of Cu （II） from aqueous solutions. The effects of operating pa- rameters, such as concentration of copper solutions, adsorbent dosages, pH value of solutions and temperature, on the adsorption efficiency were investigated. The equilibrium adsorption data were fitted with Langmuir and Freundlich models. The maximum adsorption capacity of Na-A zeolite obtained from the Langmuir adsorption iso- therm is 156.7 mg.g-t of Cu （lI）. The increase of pH level in the adsorption process suggests that the uptake of heavy metals on the zeolite follows an ion exchange mechanism. The batch kinetic data fit the pseudo-second order equation well. The thermodynamic parameters, such as changes in Gibbs free energy （AG）, enthalpy （AH） and en- tropy （AS）, are used to predict the nature of the adsorption process. The negative AG values at different tempera- tures confirm that the adsorption processes are spontaneous.