PAC与PAC/HPMC水凝胶的结构及溶胀规律研究

制备了PAC与一系列PAC/HPMC水凝胶,并研究了这两类水凝胶的动态流变性。通过扫描电镜观察了其形态、结构,并进行了对比分析;在此基础上,考察了PAC与PAC/HPMC凝胶的溶胀动力学,探讨了PAC与PAC/HPMC水凝胶的溶胀机理。结果表明:冷冻干燥后的纯PAC水凝胶内部具有浅而封闭的孔洞,骨架结构较规则。而PAC/HPMC水凝胶凝胶骨架多褶皱、孔洞互穿。并且HPMC的黏度越大,凝胶的孔洞结构越复杂,孔洞贯穿现象越明显;PAC/HPMC凝胶的平衡溶胀率和溶胀速率均大于纯PAC凝胶;随着HPMC黏度增大,PAC/HPMC凝胶的平衡溶胀率也增大。在所研究的范围内,HPMC的用量对PAC/HPMC凝胶的溶胀速率和平衡溶胀率影响不显著;PAC凝胶的溶胀机理属于水分子的Fickian扩散过程,而PAC/HPMC凝胶的溶胀机理属于非Fickian扩散,HPMC的分子链松弛在其中起着不容忽视的作用。     

过程分析化学的发展与现状

自本世纪五十年代初期国际上有了化学商品和石油化学工业之后就有了过程分析化学(process analytical chmistry简称为PAC)，然而直到最近由于全球性的竞争日渐激烈，产品的品种不断增多和质量要求不断提高，以及对环境保护的严格控制才使PAC得以承认和发展。     

磁场耦合电化学合成聚合氯化铝的性能

以金属铝板为阳极,金属铁板为阴极,0.1 mol/L的AlCl3水溶液作电解液,应用与重力方向平行的外加磁场耦合直流电解法合成聚合氯化铝(PAC).在磁通密度0.4 T,相邻电极间距15 mm,电解槽电压2.4V,电流密度300 A/m2下,成功制备出盐基度Ba=2.4,总铝含量(AlT)为0.6 mol/L,有效絮凝成分Al13占AlT83.2%的PAC产品,其电压效率85.2%,电能效率81.5%,比电极面积为140.1 m2/m3.恒流法测试表明,磁场对电极极化有抑制作用,并可增大电极表面膜溶解速率,且随磁通密度增加而增强.     

凝胶色谱法分离聚合氯化铝中Al13形态的特性研究

采用缓慢滴碱法制备聚合氯化铝(PAC)溶液, 并采用Bio-Gel P-100型凝胶层析法将溶液中铝形态进行了分离. 采用常规的化学方法(Al-Ferron逐时络合比色法)和Al²⁷Al-NMR法对分离过程中收集的各级分进行了测定. 在分离过程中通过改变洗脱速度, 洗脱液离子强度和pH值等实验条件来研究影响分离的各因素. 实验结果表明, 在层析分离过程中除被分离物的分子尺寸之外, 分子电荷对分离也会产生相应的影响. 降低洗脱流速、提高洗脱液离子强度, 以及调节合适的pH值都能提高分离效率. 通过对实验条件的优化, 可以分离得到大量高纯Al₁₃形态(即 AlAl_b含量为100%的产品), 可占被分离PAC产品总量50%以上.     

高浓度高Al13含量聚合氯化铝溶液的制备

通过快速加碱在82 ℃下合成0.2 mol·L^-1、Al_b为60%～70%的低浓度高Al_b聚合氯化铝(L-PAC)，在热侧温度为50～95 ℃，冷侧温度约9～12 ℃的条件下进行膜蒸馏浓缩，制备出总铝浓度在2 mol·L^-1以上，Al_b含量大于90%，Al₁₃含量约为70%的高浓度高Al_b含量的聚合氯化铝溶液。对膜蒸馏浓缩过程中热侧温度、PAC的碱化度和初始pH值等因素对最终聚合氯化铝溶液产品中聚铝形态分布、总铝浓度的影响进行了初步研究，发现在热侧温度低于70 ℃、碱化度为2.47、初始pH值为5.0 ± 0.2的条件下，可以得到高浓度、高Al_b含量的聚合氯化铝溶液，纳米Al₁₃形态在较高的浓度下可以存在；低温贮存条件下，高浓度PAC中Al_b相当稳定。     

过程分析化学的新进展

综述了国外过程分析化学（PAC）的最新进展,内容包括过程量测、传感器、化学计量学等,并展望了PAC的发展趋势。引用文献62篇。     

铝系混凝剂的混凝动力学研究: 循环剪切力和硫酸根的影响

采用透光率脉动检测技术(PDA)对Al₁₃形态、聚合氯化铝(PAC)和AlCl₃在混凝过程中絮体的形成以及受到剪切力影响后恢复能力的强弱作了对比性研究. 并对三种混凝剂在混凝过程中硫酸根的影响作了一定的研究. 实验结果表明, Al₁₃形态是混凝过程中起电中和作用的主要形态, 在絮体形成过程中可以大大增加颗粒间的有效碰撞率, 因此较其他形态有较强的絮体凝聚恢复力. 在硫酸根离子存在的条件下, 尽管会导致三种混凝剂正电荷的损失, 但Al₁₃形态仍能够保持较强的絮凝稳定性和稳定的除浊效率. 通过以上实验可以进一步证明, 在硫酸根离子存在的情况下, 体系的zeta电位值不是表征体系脱稳的唯一手段.     

植酸镁基修饰电极的制备及其对双酚A的检测

采用水热法制备了植酸基材料（PAC）和植酸镁基复合材料（PA-Mg）,并用扫描电镜（SEM）, X射线衍射（XRD）, X射线光电子能谱（XPS）对PAC和PA-Mg进行了表征。分别采用循环伏安法（CV）和交流阻抗法（EIS）探究了2种材料的电化学性能,采用微分脉冲伏安法（DPV）探究了2种材料对双酚A(BPA)的响应。结果表明,相比PAC, PA-Mg表现出更优异的电化学性能,分别以PA-Mg和PAC为修饰材料,以玻碳电极（GCE）为基底电极构建PA-Mg/GCE和PAC/GCE。PA-Mg/GCE对BPA的响应电流值是PAC/GCE的2.2倍。PA-Mg/GCE在最佳检测条件下对BPA的线性响应范围为0.8～50μmol/L,检出限为0.1μmol/L,相关系数为0.996。将PA-Mg/GCE用于模拟废水中BPA浓度的测定,加标回收率在92.5%～101.5%之间。     

Triton X—100存在下3,5—二溴—PAC与镍显色反应的研究

2-[(3,5-二溴-2-吡啶)偶氮]-4-甲酚(简称3,5-二溴-PAC)与镍的显色反应已有报道.但在Triton X-100存在下的反应条件未见报道.本文系统研究了在Triton X-100存在下,3,5-二溴-PAC与镍显色反应的条件及应用.发现在Triton X-100增溶作用下,试剂与Ni~(2 )的络合物的最大吸收峰红移较明显.其表观摩尔吸光系数达10~5数量级.在试验条件下,大多数金属离子不干扰测定.应用于银钨材料中微量镍的测定,结果满意.     

聚硅硫酸铝在中原油田注水处理中的应用

用硅酸钠和硫酸铝制备了聚硅硫酸铝 (PASS)混凝剂 ,应用于中原油田废水的混凝处理 .考察了硅铝配比、熟化时间、水样pH值和温度等因素对混凝性能的影响 ,并与聚合硫酸铁 (PFS)、聚合氯化铝 (PAC)进行比较 .结果表明PASS在降低悬浮物 (SS)和总铁量、增大絮凝体的直径、加快沉降速度等方面均优于PFS和PAC ,在常温下的混凝性能尤其显著 .     

硫酸根型阴离子交换树脂法改善PAC絮凝性能的研究

体系以聚合氯化铝溶液为原料，以硫酸型强碱性阴离子交换树脂为载体，进行离子交换反应。结果表明，在保持氧化铝含量基本不变的情况下，能有效地提高聚合铝的碱化度。同时生成含ＳＯ４＾２－的聚合氯化铝，实验证明它的絮凝效果优于了聚合氯化铝。     

硫酸根型阴离子交换树脂法改善PAC絮凝性能的研究

体系以聚合氯化铝溶液为原料、以硫酸型强碱性阴离子交换树脂为载体， 进行离子交换反应．结果表明，在保持氧化铝含量基本不变的情况下，能有效 地提高聚合铝的碱化度。同时生成含ＳＯ_４~（２－）的聚合氯化铝（简称ＰＡＣＳ），实验证明它的絮凝效果优于聚合氯化铝（简称ＰＡＣ）．     

氢化物发生原子荧光法测定聚氯化铝中的砷含量

建立了氢化物发生原子荧光法测定聚氯化铝中砷含量的检测方法。将聚氯化铝样品用硫酸溶解,蒸至近干,用氢化物发生原子荧光法测定其中的砷含量。在最佳测定条件下,砷的质量浓度在0~10.0μg/L范围内与荧光强度呈良好的线性关系,相关系数r=0.999 3,砷的检出限为0.03μg/g,样品加标回收率为82.5%~90.0%,测定结果的相对标准偏差为1.5%~1.9%。该法具有快速、准确、灵敏度高等优点。     

Backflush HPLC for the isolation of polycyclic aromatic compounds — A comparative study

Summary Semipreparative HPLC utilizing a polar bonded phase was applied to the isolation of polycyclic aromatic compounds (PAC) from complex samples using a backflush technique. Aminopropyl- and cyanopropyl-modified silica was tested. Aminopropyl-modified silica was found to be superior in achieving rapid, selective and non discriminating isolation of PAC. This was compared with the most commonly used isolation methods, dimethylsulfoxide (DMSO), dimethylformamide (DMF) and nitromethane liquid-liquid extractions, and silica and SephadexLH-20 open column chromatography. Strong discrimination of alkylated PAC and polycyclic aromatic nitrogen heterocyclics (PANH) was found for the liquid-liquid extractions and the LH-20 column chromatography. These comparisions were made using both standard compounds and a sample of used crankcase oil, indicating the necessity of using a real sample for evaluation of extraction methods. Recoveries of 42 PACs are reported.     

Probing the Coordination Environment of the Human Copper Chaperone HAH1: Characterization of HgII‐Bridged Homodimeric Species in Solution

Although metal ion homeostasis in cells is often mediated through metallochaperones, there are opportunities for toxic metals to be sequestered through the existing transport apparatus. Proper trafficking of Cu^I in human cells is partially achieved through complexation by HAH1, the human metallochaperone responsible for copper delivery to the Wilson and Menkes ATPase located in the trans‐Golgi apparatus. In addition to binding copper, HAH1 strongly complexes Hg^II, with the X‐ray structure of this complex previously described. It is important to clarify the solution behavior of these systems and, therefore, the binding of Hg^II to HAH1 was probed over the pH range 7.5 to 9.4 using ¹⁹⁹Hg NMR, ^199mHg PAC and UV–visible spectroscopies. The metal‐dependent protein association over this pH range was examined using analytical gel‐filtration. It can be concluded that at pH 7.5, Hg^II is bound to a monomeric HAH1 as a two coordinate, linear complex (HgS₂), like the Hg^II–Atx1 X‐ray structure (PDB ID: 1CC8). At pH 9.4, Hg^II promotes HAH1 association, leading to formation of HgS₃ and HgS₄ complexes, which are in exchange on the μs–ns time scale. Thus, structures that may represent central intermediates in the process of metal ion transfer, as well as their exchange kinetics have been characterized.     

Enhancing electrochemical preparation of polyaluminum chloride by a magnetic field

A novel effective method for preparing polyaluminum chloride (PAC) with high content of Al₁₃ polymer through conventional electrolysis coupled with rare earth Nd-Fe-B magnetic field was introduced. The content of Al₁₃ polymer in PAC synthesized by this method was highly influenced by the electrobath voltage (E), the magnetic flux density (B), the current density (i) and the distance between the two adjacent electrodes (d_adj). A total aluminum concentration (Al_T) in the PAC solution of 0.8 mol l⁻¹ was obtained when the E, B and i was 2.2 V, 0.4 T and 3.2 A dm⁻², respectively. The optimum d_adj and circulating flow (Q_f) were 20 mm and 23.7 l h⁻¹. With accelerated mass transfer rate by external magnetic field and high Q_f, this process had the advantages of forming more Al(OH)₄⁻ as the precursor of Al₁₃ polymer and inhibiting the concentration polarization more obviously than conventional electrolysis process. Under the optimum conditions, the amount of Al₁₃ polymer in PAC accounted for 82.3% of the Al_T (Al_T = 0.8 M, basicity = 2.2), which was higher than that of PAC prepared by other methods.     

Characterzation and separation of Al13 species using gel-filtration chromatography

A polyaluminum chloride (PAC) sample was prepared using a slow alkaline titration method. The Bio-Gel P-100 gel column chromatographic technique was used to separate and characterize the various forms of aluminum present in the prepared PAC solution. The effluents from a gel column were monitored using online chemical method: Al-Ferron timed complexation spectrophotometry and by 27Al nuclear magnetic resonance (NMR) spectroscopy. Effects of different experimental conditions such as eluent flow rate, ionic strength and pH on separation of Al13 were investigated. Experimental results indicated that molecule size exclusion was not the only parameter affecting the column chromatographic separation efficiency of Al13 but molecule charge as well. Reducing the eluent flow rate, increasing the ionic strength and suitable pH resulted in increase in the separation efficiency. Experimental results clearly indicated that by varying the experimental conditions, it is possible to produce pure Al13 species using a gel column chromatographic technique.     

Preparation of magnetic separable CoFe2O4/PAC composite and the adsorption of bisphenol A from aqueous solution

CoFe₂O₄/PAC composite adsorbent has been prepared via an immersing-calcination process, using ethylene diamine tetraacetic acid (EDTA) and citric acid (CIT) ligands containing sol as the CoFe₂O₄ precursor. The microstructure characterization and magnetic property of as-prepared sample were performed by means of XRD and VSM measurements. The adsorption kinetics, isotherms and thermodynamic process toward Bisphenol A molecules (BPA, which is considered as one of the typical endocrine disrupting chemicals) occurred on as-prepared magnetic adsorbent which were investigated by the pseudo-second order kinetic/intraparticle models, the Langmuir/Freundlich adsorption isothermal models and basic chemical thermodynamics principles, respectively.