银—铜—铁—镍体系测定条件的实验设计优化和卡尔曼滤波法的同时测定

利用二次通过旋转组合设计的方法建立了吸光度与显色剂，增敏剂用量以及ｐＨ值之间的数学模型，进而得到使吸光度量最大的显色剂用量，增敏剂用量及ｐＨ值，在此优化的基础上，用卡尔曼滤波分析分光光度法对银，铜，铁，镍的合成样品的合谱进行了解析处理，得到较为满意的结果。     

银—铜—铁—镍体系测定条件的旋转设计优化和目标转换因子分析？…

利用二次通用旋转组合设计的方法，建立了吸光度与显色剂、增敏剂用量以及ｐＨ值之间的数学模型，进而得到使吸光度最大的显色剂用量、增敏剂用量及ｐＨ值。在此优化的基础上，用目标转换因子分析分光光度法对银、铜、铁、镍的合成样品的合谱进行了解析处理，得到较为满意的结果。     

二次旋转设计和反向人工神经网络在铅、镉、汞、镍同时测定中的应用

利用二次通用旋转组合设计法建立了吸光度与显色剂，增敏剂用量及pH 值之间的数学模型，进而得出使吸光度最大的显色剂用量，增敏剂用量及PH值，在优化的基础上，用B－P人工地Pb,Cd,Hg,Ni同时测定的数据进行解析，并与经典最小二乘法进行了对比，结果较准确。     

导数分光光度法直接测定贵金属中的金

TMK是推荐为测定金的显色剂,具有较高的灵敏度,但选择性尚不能令人满意。本实验用TMK为测金的显色剂,非离子表面活性剂Triton X-100为增溶、增敏剂,在水溶液中研究用导数分光光度法消除其它贵金属宽带背景吸收的干扰条件。所制定的方法,不需分离可直接测定电解铜阳极泥及合金中的微量金。选择性很好,而且精密度和准确度均得到满意的结果。     

非离子型微乳液对结晶紫-硅钼杂多酸光度分析的增敏作用

研究了非离子O W型微乳液OP n C5H11OH n C7H16 H2O对结晶紫 硅钼杂多酸显色体系的增敏作用。与相应的胶束体系比较,微乳液体系的测定灵敏度提高了30%。对钢样、水样、发样的测定结果令人满意。通过测定显色剂在微乳液及胶束体系中的分配系数、胶束位和结合常数探讨了非离子型微乳液对结晶紫 硅钼杂多酸显色体系的增敏作用机理。     

有机试剂的分子结构与胶束增敏的关系: TAMB2-(2-噻唑偶氮)-5-二甲氨基苯甲酸和BTAMB2-(2-苯骈噻唑偶氮)-5-二甲氨基苯甲酸的比较研究

本文以TAMB和BTAMB为探针试剂, 考查了有表面活性剂胶束存在时有机试剂的亲水-疏水程度对金属-有机试剂配合物增敏效应的影响, 研究了两体系的光度性质, 显色剂及镍-显色剂配合物在各不同胶束中的分配情况, 并用析相、核磁共振、萃取及动力学试验等手段比较了两个试剂及配合物的特点和差异。结果表明, 试剂的“两亲"结构对配合物能否被增敏至关重要, 而试剂憎水性或亲水性过强, 均不利于配合物被增敏, 仅当具有“两亲"结构时, 配合物同时感受胶束“刚性不对称微环境"中两端不同作用力,配合物才会有较大增敏现象出现。     

有机试剂的分子结构与胶束增敏的关系: TAMB2-(2-噻唑偶氮)-5-二甲氨基苯甲酸和BTAMB2-(2-苯骈噻唑偶氮)-5-二甲氨基苯甲酸的比较研究

本文以TAMB和BTAMB为探针试剂, 考查了有表面活性剂胶束存在时有机试剂的亲水-疏水程度对金属-有机试剂配合物增敏效应的影响, 研究了两体系的光度性质, 显色剂及镍-显色剂配合物在各不同胶束中的分配情况, 并用析相、核磁共振、萃取及动力学试验等手段比较了两个试剂及配合物的特点和差异。结果表明, 试剂的“两亲"结构对配合物能否被增敏至关重要, 而试剂憎水性或亲水性过强, 均不利于配合物被增敏, 仅当具有“两亲"结构时, 配合物同时感受胶束“刚性不对称微环境"中两端不同作用力,配合物才会有较大增敏现象出现。     

碳增强效应与内标选择-电感耦合等离子体质谱法测定高温合金中痕量碲

采用电感耦合等离子体质谱法直接测定镍基高温合金中痕量碲,不需要对基体进行萃取等复杂的分离手段,通过对碳增敏剂与内标选择等因素进行优化,同时降低了多原子离子的干扰。依照质量数和ICP指数的角度选择铑为内标,校正了测定过程中信号的漂移,乙醇作为增敏剂,确定了在线的内标和增敏剂的加入模式,提高了痕量碲的检测灵敏度,测定下限达到(0.4μg/g)。对高温合金的标准物质(GBW01619-01620)进行了测定,其结果的相对标准偏差(RSD,n=3)<10%,测定值与认定值吻合良好。     

人工神经网络光度法同时测定土壤中铅-镉-镍

研究了以4－（2－吡啶偶氮）－间苯二酚（PAR）为显色剂、十二烷基硫酸钠（SDS）为增敏剂、乙酸－乙酸钠为缓冲液，在水相中对铅、镉、镍进行同时测定。利用二次回归正交组合设计，对体系因子进行了优化。以苏州吴县水稻田土壤为研究对象，利用反向人工神经网络对其中铅、镉、镍的全量、有效态、活化态分别进行了同时测定，预测结果与AAS法所测结果基本一致。     

碳增强效应与内标选择-电感耦合等离子体质谱法测定高温合金中痕量碲

采用电感耦合等离子体质谱法直接测定镍基高温合金中痕量碲,不需要对基体进行萃取等复杂的分离手段,通过对碳增敏剂与内标选择等因素进行优化,同时降低了多原子离子的干扰。依照质量数和ICP指数的角度选择铑为内标,校正了测定过程中信号的漂移,乙醇作为增敏剂,确定了在线的内标和增敏剂的加入模式。方法提高了痕量碲的检测灵敏度,测定下限达到0.00004% (0.4 ppm)。为了验证该方法的有效性,对高温合金的标准物质(GBW01619-01620)进行了分析,测定值与认定值吻合良好,其中结果精密度试验RSD(n=3)<10%。     

Computer-Assisted Modeling, Prediction, and Multifactor Optimization of Hydrophobic Compounds in Liquid Chromatography

The traditional overlapping resolution mapping (ORM) scheme was modified for application in HPLC with the flow rate of the mobile phase as a new factor. The mobile phase composition and a flow rate were taken as parameters to influence effective resolution and elution time. Chromatograms were obtained for the separation of the 16 compounds for ten trial conditions. Computer-assisted mathematical simulation was used to obtain optimum conditions for resolution and separation time of the compounds. The validity of the model developed was confirmed by experiments.     

Application of central composite designs for optimisation of the chromatographic separation of monomethylarsonate and dimethylarsinate and of selenomethionine and selenite by ion-pair chromatography coupled with plasma mass spectrometric detection

Central composite designs (CCDs) were used in the study of the ion-pair chromatographic separation of arsenic and selenium species in tap water: monomethylarsonate, dimethylarsinate, selenomethionine and selenite. The ternary eluent consisted of tetrabutylammonium phosphate (TBA), sodium hydrogenphosphate (Na2HPO4) and 1% acetonitrile. CCD allowed the investigation of the influence of the eluent parameters, which varied from 0.5 to 4.2 mmol l-1 Na2HPO4, 0.5 to 4.2 mmol l-1 TBA and pH 4.9 to 8.2, on the capacity factors (k') of arsenic and selenium compounds. Furthermore, another mathematical model that permitted the variation of the chromatographic selectivity of species, computed from their retention data to be followed, was investigated. This showed the ability to locate the optimum conditions within the experimental design, so that arsenic and selenium species could be simultaneously quantified with good efficiency and resolution. A comparison between the predicted and the experimental response values was made in order to assess the prediction quality of the model. Response surfaces and isoresponse curves obtained from the mathematical models allowed the determination of the optimum chromatographic conditions and the robustness of the method. The predicted optimum zone allowing satisfactory determination of both arsenic and selenium compounds was pH 5.5-6.5, 2.5 mmol l-1 Na2HPO4 and 3.0-4.0 mmol l-1 TBA.     

A systematic approach for optimisation of supercritical-fluid extraction of polycyclic aromatic hydrocarbons from earthworms

A systematic approach using a mathematical model as an alternative to time-consuming empirical optimisation of a supercritical-fluid extraction (SFE) procedure is presented. The model was applied to the extraction of 15 polycyclic aromatic hydrocarbons (PAH). The selected fat-containing matrix is the earthworm used in ecotoxicological absorption studies. Settings for optimal recovery were established for the important parameters (temperature, pressure, amount of trapping sorbent, flow, and dynamic extraction time) using a D-optimal experimental design (including quadratic terms and interactions). The recoveries were modelled using a two sigmoid-model with parameters for each of the individual PAH. The main objective was to optimise the conditions for 15 PAH congeners by maximisation of the lowest recovery. The results show that for some parameters, e.g. the amount of sorbent material, optimal conditions are identical for all PAH. For other parameters, e.g. extraction time, the optimum is PAH dependent. The advantage of this optimisation procedure is that, within three days of analysis (73 experiments), optimised extraction conditions for the extraction of the set of 15 PAH were found but also optimum conditions for specific subsets can be extracted from the collected data for specific subsets.     

The effect of preparation parameters on performance of polyvinyl alcohol thin‐film composite membrane: Experimental study,modeling, and optimization

To systematically investigate the influence of preparation conditions on pure water permeability (PWP) and solute removal performance of polyvinyl alcohol (PVA) thin‐film composite (TFC) membrane, fractional factorial design was applied. The considered conditions were related to 3 steps of the TFC preparation, including support membrane preparation, PVA coating, and cross‐linking. The results showed that among the selected factors, polysulfone concentration (polymer of the support membrane), heat curing time (related to cross‐linking condition), and their interaction have the most significant effects on the both permeability and salt rejection. The effects of significant factors interaction on permeability and solute rejection of PVA TFC membrane were discussed. Finally, optimum preparation conditions were calculated by numerical optimization to achieve maximum permeability and solute removal, simultaneously. The prepared membrane at optimum conditions showed PWP of 1.74 L/m²hbar and 96.19% Na₂SO₄ rejection. It was realized that the prediction of mathematical models at optimum conditions was reliable with absolute average relative error 7.43% and 1.18% for PWP and rejection, respectively.     

Studies on the process variables of the condensation reaction of cardanol and formaldehyde by response surface methodology

Different types of cardanol-based novolac-type phenolic resins are produced under a wide range of operating conditions for the application in the resin producing industries. Different operating conditions employed for the production of such resins result in different extent of conversion. In order to understand the system behavior, mathematical relationship between the process variables and the extent of conversion was established by employing the ‘Response surface methodology’. Geometrical representation of the mathematical models in three-dimensional surface plots served as a good aid in understanding the behaviour of reaction under different operating conditions. The maximum extent of conversion of the condensation reaction of cardanol and formaldehyde was found to be 93.0 percent at optimum sets of condition of reaction temperature, time, catalyst concentration and pH of the reaction mixture. All the predicted values for optimum process conditions were in good agreement with experimental data.     

β-Carotene removal from soybean oil with smectite clay using central composite design

In this study removal of β-carotene from soybean oil by adsorption on acid activated smectite clay from Serbia was investigated and a factorial 2³ experimental design was applied. The effects of relevant factors, such as temperature, solid-to-liquid ratio and time, on removal of β-carotene were investigated. In order to check these factors and their effect on the removal of β-carotene, we have established a model of this technique following a methodological strategy using experiments design. The mathematical model is established using a central composite design. The model describes the changes of the measured responses of β-carotene removal efficiency according to the temperature, solid-to-liquid ratio and time. The graphical representation of this model in the space of the variables enabled us to define the optimum conditions of these parameters. The optimum conditions to obtain the maximum removal of β-carotene from soybean oil were a temperature of 80°C, a solid-to-liquid ratio of 1: 25 and a time of 1255 s. Under these optimal conditions, the experimental values agreed with the predicted values, using analysis of variance, indicating a high goodness of fit of the model used and the success of response surface methodology for optimizing adsorption β-carotene of acid activated smectite clay from soybean oil. The article is published in the original.     

微波预处理提取蛇足石杉中总生物碱的工艺优化

蛇足石杉为厥类植物,属石松类石杉科(Huperziacease)石杉属(Huperzia),又名千层塔、蛇足草.从蛇足石杉中提取分离得到的石杉碱甲(Hup A),是一种强效的可逆性胆碱酯酶抑制剂,在临床上主要用于治疗重症肌无力、改善老年性记忆功能减退 [1-2].     

正戊烷异构化催化剂的研究

20世纪80年代以来,由于环保的要求,C5/C6烷烃异构化工艺在国外得到迅速发展,并已成为生产高辛烷值汽油组分的重要工艺[1,2]。我国目前尚无轻烃异构化装置,但国内许多部门进行了C5/C6异构化催化剂的研究[3～5]。为了尽快发展我国轻烃异构化工艺,研究轻烃异构化催化剂具有重要的意义。以铂为活性组分的烷烃异构化催化剂具有活性高、选择性好、反应条件温和等优点。本文选用铂为金属活性组分、丝光沸石为载体制备了Pt/HM异构化催化剂。研究残钠、金属Pt、助催化剂锆含量,制备方法及反应条件对正戊烷异构化反应性能的影响。1　实　验1 1…