pH对接枝磺化碱木质素聚合物吸附特征的影响

采用动态光散射技术、透射电镜等表征了接枝磺化碱木质素聚合物(SBAL)在不同pH条件下的溶液行为,结果表明随着pH的增加,SBAL分子中的亲水官能团磺酸基、羧基和酚羟基逐步解离,分子链由卷曲变得伸展.利用频率-耗散联用型石英晶体微天平和静电逐层自组装技术,借助紫外光谱、原子力显微镜等表征了不同pH条件下SBAL在固/液界面上的吸附特征,结果发现随着pH由3增加到12,SBAL在金片和石英玻片上的吸附量先减小后增大,pH=9时吸附量最小.随着pH的增加,SBAL的吸附特征由刚性变得柔软,吸附构型呈现由致密到松散再到致密的变化趋势,吸附构象在酸性、中性和碱性条件下依次为mushroom结构、pancake结构和高分子刷,在中性和酸性条件下SBAL与聚二烯丙基二甲基氯化铵之间的作用力以阳离子-π相互作用为主,吸附强度较弱,而在强碱条件下以静电作用为主,吸附强度较大.     

不同相对分子质量对接枝磺化木质素水煤浆分散剂吸附分散性能的影响

采用接枝磺化缩聚法制备了不同相对分子质量碱木质素系水煤浆分散剂(GCL3J系列),研究相对分子质量对水煤浆吸附分散性能的影响。流变学研究结果表明,具有三维空间网络结构的GCL3J分散降黏性能均优于具有线性结构的萘系分散剂。等温吸附和Zeta电位测试结果表明,GCL3J在煤粒表面的吸附特征属于Langmuir型单分子层吸附,随着相对分子质量的增加,其在煤粒上的吸附量逐渐减少,吸附作用力逐渐增强,并逐渐以疏水作用吸附为主。中等相对分子质量的GCL3J-3(M_w为31 500 Da,特性黏度为8.06 mL/g)在煤粒表面吸附后,具有适宜的吸附量和吸附强度,且负电性最高,对水煤浆具有最优的分散降黏作用。     

木质素磺酸钠在氧化铁表面的吸附驱动力

研究吸附介质的pH值、 尿素及盐类对木质素磺酸钠(SL)在氧化铁表面吸附性能的影响规律, 结果表明, 络合能力较强的柠檬酸钠使SL的吸附量几乎减少至零, 较弱络合能力的亚硫酸钠使SL的吸附量具有一定程度的降低, 而无络合能力的硫酸钠增大了SL的吸附量. 说明SL的羧基与氧化铁之间的络合吸附驱动力对吸附起主导作用, 磺酸基对其在氧化铁上吸附的影响很弱. 采用氯化锂屏蔽部分羧基后SL在氧化铁上的吸附量也有所降低, 进一步证明了羧基与氧化铁表面的络合作用是其吸附的主要驱动力.     

聚合物分散剂对氟虫脲水悬浮剂分散稳定性的影响

通过测定药物颗粒界面Zeta电位和平均粒径, 研究了聚合物分散剂苯乙烯磺酸聚合物钠盐(GY-D08)用量、pH和盐离子对氟虫脲水悬浮剂分散稳定性的影响, 研究结果表明, 分散剂GY-D08的加入量与水悬浮剂分散效果密切相关, 制备质量分数为5%氟虫脲水悬浮剂的GY-D08最佳用量为2%, GY-D08用量过多或过少都会使分散效果下降; pH影响分散剂GY-D08在水中的电离能力, 当pH=9时, GY-D08分子完全电离, 能为颗粒提供较大的静电位阻, 水悬浮剂分散稳定性最好; Mg²⁺或Ca²⁺压缩颗粒界面的双电层, 降低Zeta电位, 使颗粒因带电量减少而聚结, 导致水悬浮剂分散稳定性变差, 且Mg²⁺或Ca²⁺浓度愈大, 其分散稳定性愈差; 当离子浓度相同时, Ca²⁺压缩双电层的能力比Mg²⁺强, 添加Ca²⁺后的水悬浮剂的分散稳定性更差.     

辣根过氧化物酶改性木质素磺酸钠的结构特征及吸附分散性能

在室温及水溶液体系中,采用辣根过氧化物酶(HRP)对亚硫酸法制浆造纸废液的副产物木质素磺酸钠(木钠)进行改性,通过凝胶渗透色谱、电位滴定、红外光谱和核磁共振波谱等表征了HRP改性木钠的结构.结果表明,HRP可以有效聚合木钠大分子,调节HRP的用量,得到不同分子量的木钠产品,当HRP浓度为6 g/L时,可使木钠分子量增大155%.HRP可氧化木钠分子上的酚羟基变成苯氧自由基,该自由基可直接交联,也可转移到酚羟基的邻位或对位再发生聚合作用,其聚合方式主要为β-O-4'及β-β'连接.HRP改性还可使木钠磺化度增加27%.采用静电逐层自组装技术研究了HRP改性对木钠吸附特征的影响,结果表明,经HRP改性后,木钠在平板上的吸附量增大;对TiO2浆体的分散稳定性能也得到改善,这主要是因为分子量增大,空间位阻作用增强;磺化度增大,静电排斥作用增强,从而使TiO2颗粒更好地分散在水中.     

漆酶活化碱木质素的磺甲基化反应活性研究

采用漆酶对碱木质素进行活化预处理,并对活化碱木质素进行磺甲基化改性,揭示了漆酶活化对碱木质素磺甲基化反应活性影响的作用机理.采用顶空气相色谱、红外光谱、凝胶渗透色谱、核磁共振等研究了漆酶活化碱木质素的结构特征,结果表明,漆酶对碱木质素既有聚合作用又有解聚作用,分子量变化不大,多分散性增加;漆酶活化使得碱木质素发生脱甲基作用,酚羟基含量增大,紫丁香基含量减低;另外,漆酶可氧化酚羟基变成苯氧自由基使碱木质素聚合.采用分子模拟对漆酶活化碱木质素的电子云密度进行了计算,结果表明脱甲基作用增大了木质素苯环上的电子云密度,有利于磺甲基化反应的进行.采用电位滴定测试磺甲基化产物的磺化度来表征其反应活性的大小,结果表明漆酶活化磺甲基化碱木质素的磺化度提高了35%,且对二氧化钛悬浮体系的分散性能得到明显提高.     

磺甲基化木质素的辣根过氧化物酶催化聚合研究

以碱木质素为原料,采用磺甲基化反应,得到磺甲基化木质素(SAL),并进一步采用辣根过氧化物酶(HRP)催化以提高其分子量,制备了高分子量高磺化度磺甲基化木质素(HPSAL).采用凝胶渗透色谱、红外光谱、核磁共振氢谱、紫外光谱和顶空气相色谱等研究了改性前后SAL的结构特征.结果表明,经HRP催化后,与SAL相比,HPSAL的重均分子量和磺化度显著增加,分别提高20倍和30%以上,羧基含量升高,而甲氧基和酚羟基含量降低.HRP使SAL形成酚氧自由基,活化其酚羟基的邻、对和侧链Cβ位,增加磺化反应活性,而磺化度的提高又有利于增加HRP催化SAL的聚合反应活性,其聚合方式主要为β-O-4'、β-β'、β-1'和β-5'联结.分子模拟结果表明,甲氧基含量的降低和磺酸基含量的增加能显著提高以β-O-4'连接键为主的聚合反应活性.     

木质素磺酸盐在烯酰吗啉颗粒表面的吸附特性

考察了常用分散剂木质素磺酸钠(Sodium Lignosulfonate, SLS)在烯酰吗啉(Dimethomorph, DMM)上的吸附性能, 并测试了吸附SLS后DMM颗粒表面Zeta电位和接触角的变化, 从理论上探讨了分散剂的吸附对农药颗粒表面物化性能的影响, 指导农药分散剂的开发. 结果显示, 浓度为0~10 g/L时, SLS在DMM表面呈现双层吸附; 低浓度(0~1.0 g/L)时, 吸附等温线符合Langmuir方程. SLS在DMM表面上的吸附属于自发、 放热吸附过程, 吸附力主要包括疏水作用、 范德华力和氢键作用力. SLS在DMM表面吸附后提高了其Zeta电位, 且SLS磺化度越高其提高作用越明显. 随着SLS溶液浓度增大, DMM在SLS溶液中的接触角先减小后增大, 到70º~80º后趋于稳定.     

一种球形木质素吸附剂对L-天门冬氨酸的吸附行为研究

以硫酸盐木质素为原料,利用反相悬浮技术制备出球形木质素吸附剂.通过静态吸附试验,研究了球形木质素吸附剂对L-天门冬氨酸的吸附动力学和热力学特性,探讨了pH对吸附过程的影响.结果表明,当溶液pH值为3.0时,SLA的平衡吸附容量为518.0mg/g,球形木质素吸附剂对L-天门冬氨酸的吸附速率同时受液膜扩散和颗粒内扩散过程控制.吸附符合Langmuir和Freundlich等温吸附方程.且焓△H-16.81kJ/mol,表明该吸附反应是以吸热的化学吸附过程为主,活化能Ea=3.3406kJ/mol,说明球形木质素吸附剂的吸附过程是以颗粒内扩散为主.     

磺化碱木质素和磺化碱木质素聚氧乙烯醚的溶液行为研究

分别制备了不同磺酸基含量的磺化碱木质素(SAL)、不同交联度和分子量的磺化碱木质素聚氧乙烯醚(SAL-PEG),采用动态光散射(DLS)法分别研究磺酸基含量和PEG非离子长链对SAL和SAL-PEG溶液行为的影响规律.结果表明,不同磺酸基含量(1.28~2.09 mmol/g)的SAL在1.0 g/L的水溶液中存在聚集行为,磺酸基含量的增加使SAL的分子舒展程度增加,聚集程度越弱;Na Cl的加入使SAL的分子舒展程度减小,聚集体发生解聚.不同PEG含量的SAL-PEG在1.0 g/L的水溶液中主要以单分子状态存在,聚集行为较弱,分子的流体动力学半径与其分子量和交联度成正比;Na Cl的加入使SAL-PEG的PEG非离子长链却被严重压缩,分子流体动力学半径显著减小,减小程度与其分子量和交联度成正比,但SAL-PEG的聚集程度仍然较弱.     

刷状结构的阳离子性接枝微粒QPDMAEMA/SiO_2对牛血清白蛋白的吸附特性

以微米级硅胶微粒为基质,通过接枝聚合和大分子反应,制备了具有刷状结构的阳离子性接枝微粒,深入研究了其对牛血清白蛋白(BSA)的强吸附能力、吸附机理和吸附热力学.首先使含叔胺基团的单体甲基丙烯酸二甲基氨基乙酯(DMAEMA)在硅胶微粒表面发生接枝聚合,制得接枝微粒PDMAEMA/SiO2,然后以氯乙胺为试剂,使接枝大分子PDMAEMA链中的叔胺基团发生季铵化反应,获得了具有刷状结构的阳离子聚电解质的功能接枝微粒QPDMAEMA/SiO2.测定了微粒QPDMAEMA/SiO2的zeta电位,实施了对BSA的等温吸附实验,考察了介质pH值、离子强度及温度对吸附作用的影响,研究了吸附热力学.研究结果表明,功能接枝微粒QPDMAEMA/SiO2比接枝微粒PDMAEMA/SiO2具有更高的zeta电位,在静电相互作用驱动下,微粒QPDMAEMA/SiO2对BSA具有很强的吸附能力.吸附容量随介质pH值的增大呈现先增大后减小的变化趋势,当pH值等于BSA的等电点(pI=4.7)时,具有最高的吸附容量(高达112 mg?g-1).以等电点为界,离子强度对吸附容量会产生完全相反的影响作用:当介质pH值小于BSA的等电点时,电解质浓度增大,吸附容量增高;当介质pH值等于BSA的等电点时,吸附容量几乎不随电解质的浓度发生变化.吸附过程熵值减小而且放出热量,是一个焓驱动的吸附过程.     

Alumina interaction with AMPS-MPEG random copolymers I. Adsorption and electrokinetic behavior

Adsorption of brush copolymers, bearing sulfonate groups and polyethylene glycol segments, on to alumina particles in suspension in water has been investigated. Study of the adsorption isotherms revealed that the copolymers displayed a strong affinity for the surface of the alumina regardless of the fraction of ionic groups on the polymer. For poly(ethylene glycol) content greater than 50%, the adsorption isotherms revealed an initial adsorption plateau followed by a second one. The shape of the adsorption isotherms was interpreted in terms of the polymer configuration at the solid-to-liquid interface. The effects of the pH and the ionic force on adsorption were studied and connected to the effects of interaction between chain segments at the surface of the alumina particles. Changes in the electrokinetic properties of the alumina particles after addition of the copolymers were investigated by following the zeta potential of particles as a function of pH. In the presence of the copolymer continuous shift of the isoelectric point IEP to a more acidic values was observed. Beyond a certain concentration the zeta potential remained negative regardless of the pH.     

刷状结构的阳离子性接枝微粒QPDMAEMA/SiO2对牛血清白蛋白的吸附特性

以微米级硅胶微粒为基质, 通过接枝聚合和大分子反应, 制备了具有刷状结构的阳离子性接枝微粒, 深入研究了其对牛血清白蛋白(BSA)的强吸附能力、吸附机理和吸附热力学. 首先使含叔胺基团的单体甲基丙烯酸二甲基氨基乙酯(DMAEMA)在硅胶微粒表面发生接枝聚合, 制得接枝微粒PDMAEMA/SiO₂, 然后以氯乙胺为试剂, 使接枝大分子PDMAEMA链中的叔胺基团发生季铵化反应, 获得了具有刷状结构的阳离子聚电解质的功能接枝微粒QPDMAEMA/SiO₂. 测定了微粒QPDMAEMA/SiO₂的zeta 电位, 实施了对BSA的等温吸附实验, 考察了介质pH值、离子强度及温度对吸附作用的影响, 研究了吸附热力学. 研究结果表明, 功能接枝微粒QPDMAEMA/SiO₂ 比接枝微粒PDMAEMA/SiO₂ 具有更高的zeta 电位, 在静电相互作用驱动下, 微粒QPDMAEMA/SiO₂对BSA具有很强的吸附能力. 吸附容量随介质pH值的增大呈现先增大后减小的变化趋势,当pH值等于BSA的等电点(pI=4.7)时, 具有最高的吸附容量(高达112 mg·g^-1). 以等电点为界, 离子强度对吸附容量会产生完全相反的影响作用: 当介质pH值小于BSA的等电点时, 电解质浓度增大, 吸附容量增高; 当介质pH值等于BSA的等电点时, 吸附容量几乎不随电解质的浓度发生变化. 吸附过程熵值减小而且放出热量,是一个焓驱动的吸附过程.     

Change of zeta potential of biocompatible colloidal oxide particles upon adsorption of bovine serum albumin and lysozyme

The amounts of negatively charged bovine serum albumin and positively charged lysozyme adsorbed on alumina, silica, titania, and zirconia particles (diameters 73 to 271 nm) in aqueous suspensions are measured. The adsorbed proteins change the zeta potentials and the isoelectric points (IEP) of the oxide particles. The added to adsorbed protein ratios at pH 7.5 are compared with the protein treated particle zeta potentials. It is found that the amounts of adsorbed proteins on the alumina, silica, and titania (but not on the zirconia) particle surfaces are highly correlated with the zeta potential. For the slightly less hydrophilic zirconia particles high amounts of protein adsorption are observed even under repulsive electrostatic conditions. One reason could be that the hydrophobic effect plays a more important role for zirconia than electrostatic interaction.     

Stability of dispersions of colloidal alumina particles in aqueous suspensions

The colloidal stability of suspensions of alumina particles has been investigated by measuring particle size distribution, sedimentation, viscosity, and zeta potential. Alumina particles were found to be optimally dispersed at pH around 3 to 7.8 without dispersant and at pH 8.5 and beyond with dispersant. The above results corroborate zeta potential and viscosity measurement data well. The surface charge of alumina powder changed significantly with anionic polyelectrolyte (ammonium polycarboxylate, APC) and the iep shifted toward more acidic range under different dispersant conditions. It was found that the essential role played by pH and dispersant (APC) on the charge generation and shift in the isoelectric point of alumina manifests two features: (i) the stability decreases on approaching the isoelectric point from either side of pH, and (ii) the maximum instability was found at pH 9.1 for alumina only and at pH 6.8 for alumina/APC, which is close to the isoelectric points for both the system, respectively. Using the model based on the electrical double-layer theory of surfactant adsorption through shift in isoelectric points, the authors could estimate the specific free energy of interaction (7.501 kcal/mol) between particles and dispersant. The interaction energy, zeta potential, sedimentation, and viscosity results, were used to explain the colloidal stability of the suspension.     

Electrosteric Stabilization of Al(2)O(3), ZrO(2), and 3Y-ZrO(2) Suspensions: Effect of Dissociation and Type of Polyelectrolyte

The mechanisms of eight anionic polyelectrolytes stabilizing colloidal sized alpha-Al(2)O(3), pure ZrO(2), and Y(2)O(3)-doped ZrO(2) particles in aqueous solution are discussed. The polyelectrolytes studied were the Na(+) and NH(4)(+) salts of polyacrylic acid and polymethacrylic acid having different molecular weights. The particle-dispersant interactions were studied by measuring adsorption isotherms, particle size, thickness of adsorbed layer, and zeta potentials by elektrokinetic sonic analysis at different powder volume fractions (straight phi=0.01-0.3), pH, and electrolyte (KCl) content. The dissociation of the polyelectrolytes was studied by potentiometric titrations. The dissociation constant of the polymethacrylates was found to be 0.6 pH unit higher than that for the polyacrylates. High-affinity adsorption isotherms were observed over the pH range when the polyelectrolytes were fully ionized. The results show good correlation between adsorption isotherms and zeta potential data in systems of dispersed, dilute alumina particles. When particles and polymers were of equal charge (the same sign of charge) the polymer shell was thicker. At higher volume fractions (straight phi=0.3), and when alumina particles/added ammonium polyelectrolyte were of equal charge, a maximum in the absolute value of zeta potential resulted. Due to adsorption all the anionic polyelectrolytes studied provided electrosteric stabilization of the alpha-Al(2)O(3), and Y(2)O(3)-doped ZrO(2) suspensions by enhancing the zeta potential to 40 mV or over and by shifting the isoelectric point to lower pH, the low-molecular-weight polyelectrolytes decreasing the isoelectric point more than the polyelectrolytes having higher molecular weight. The polyelectrolytes studied failed to stabilize pure monoclinic ZrO(2) particles. Due to the shortness of the chain of polyelectrolytes studied, no bridging was observed between oppositely charged polyelectrolyte/alumina particles. Copyright 2000 Academic Press.     

Spectroscopic investigation of the adsorption mechanisms of polyacrylamide polymers onto iron oxide particles

The mechanisms of high-molecular-weight polyacrylamide nonionic homopolymer and 25 mol% anionic acrylate-substituted copolymer adsorption onto iron oxide particles were investigated via DRIFT and UV-vis spectroscopies at three pH values (6, 8.5, and 11). While electrostatic interactions play an important role in charged polymer adsorption, this information is not spectroscopically available. At pH values above and below pH 8.5 (the isoelectric point for the anionic polymer), bidentate chelation and hydrogen bonding were the main adsorption mechanisms. At the isoelectric point, monodentate chelation was observed to be the main mode of adsorption, along with hydrogen bonding. For the nonionic polymer, in all cases, hydrogen bonding through the carbonyl group was the main mode of adsorption. The adsorption of both polymers conformed well to the Freundlich model, suggesting that the adsorbed polymer amount increases with increasing polymer concentration up to 7500 g/t solid, rather than approaching monolayer coverage. Spectroscopic evidence was found to suggest that hydrolysis of nonionic polyacrylamide occurs at high pH.     

水葫芦木质素的提取及其苯胺吸附性能

采用碱提法从生态入侵植物水葫芦中提取木质素,利用傅立叶红外光谱(FT-IR)和扫描电镜(SEM)等手段对所获得的木质素进行表征,研究了水葫芦木质素对水中苯胺的吸附性能,考察了溶液p H值、吸附时间、初始浓度等因素对水葫芦木质素吸附苯胺的影响。当Na OH溶液浓度0.1 mol/L,提取时间4 h,温度100℃,料液比1∶20时,水葫芦木质素的收率最大为6.81%。红外图谱显示,在1 456~1 656 cm-1处存在木质素的芳香环骨架振动吸收峰;扫描电镜显示,木质素呈大量细小的颗粒,木质素颗粒表面存在许多微小的孔状结构,有利于吸附作用的发生。在室温下,溶液p H 6.0,苯胺初始浓度为150 mg/L,吸附剂用量为5 mg,吸附时间120 min时,水葫芦木质素对苯胺的最大吸附容量为12.2 mg/g。苯胺吸附实验数据拟合符合准二级动力学模型以及Langmuir吸附等温模型。水葫芦木质素对苯胺的吸附以单分子层化学吸附为主,属于优惠吸附。相同吸附条件下,水葫芦木质素对湖泊水样中苯胺的吸附与实验模拟水样的吸附效果相近。水葫芦木质素可作为富集分离材料用于分析样品制备以及水中污染物的吸附。     

聚乙烯亚胺表面改性硅藻土及其对苯酚吸附特性的研究

使用紫外吸收光度法研究了硅藻土对聚乙烯亚胺(PEI)的等温吸附;采用浸渍法,用PEI对硅藻土进行了表面改性;使用4-氨基安替比林光度法研究了经PEI表面改性的硅藻土对苯酚的捕集行为.研究结果表明,凭借强烈的静电相互作用,表面带负电荷的硅藻土粉体对阳离子性大分子PEI具有很强的吸附能力,等温吸附满足Freundlich吸附方程;经PEI表面改性后,硅藻土粉体表面的电性发生了根本性改变,且等电点由pH=2.0移至pH=10.5;在中性溶液中,改性粉体通过氢键作用与静电相互作用的协同,对水溶液中的苯酚会产生很强的捕集作用,饱和吸附量可达92 mg/g;在酸性溶液中改性粉体通过氢键相互作用,对水溶液中的苯酚产生一定的吸附作用,但由于PEI分子链高度的质子化,氮原子对苯酚的氢键相互作用很弱,吸附量很低.