Atomic absorption spectrometric determination of copper,zinc, and lead in geological materials

An atomic absorption spectrometric method is described for the determination of copper, zinc, and lead in geological materials. The sample is digested with HF—HCl—H₂O₂; the final solution for analysis is in 10 % (v/v) HCl. Copper and zinc are determined directly by aspirating the solution into an air—acetylene flame. A separate aliquot of the solution is used for determination of lead; lead is extracted into TOPO-MIBK from the acidic solution in the presence of iodide and ascorbic acid. For a 0.50-g sample, the limits of determination are 10–2000 p.p.m. for Cu and Zn, and 5–5000 p.p.m. for Pb. As much as 40 % Fe or Ca. and 10 % Al, Mg, or Mn in the sample do not interfere. The proposed method can be applied to the determination of copper, zinc, and lead in a wide range of geological materials including iron- and manganese-rich, calcareous and carbonate samples.     

Simplification of the robinson-biggs spectrophotometric treatment of overlapping prototropic equilibria by use of isosbestic points

The appearance and disappearance of isosbestic points between acid—base conjugate pairs of a diprotic acid with changing pH can be used to simplify the resolution of individual overlapping equilibria. Absorbance vs. pH data at an isosbestic wave-length can be treated in the same way as those from a monoprotic acid by using the Henderson—Hasselbalch equation. Application of the method is illustrated for hydroxy N-heterocycles having overlapping equilibria. Good precision and reasonable agreement with literature values was obtained for acidity constants determined by the method.     

Determination of phosphite,hypophosphite, tellurium and mercury

A new catalytic oxidation procedure, involving the use of a cerium(IV) sulfate reagent in perchloric acid with a mixed silver(I)—manganese(II) perchlorate catalyst, has been developed for the determination of phosphite, hypophosphite, and tellurium. By this method 15—100 mg of phosphite, 5—35 mg of hypophosphite, and 10—105 mg of tellurium may be determined with standard deviations of ±0.17, ±0.32, and ±0.21% respectively. A direct titration procedure for mercury(I) is described using a ceric perchlorate solution as titrant with the mixed catalyst system. Samples from 65–510 mg may be analyzed with a standard deviation of ±0.36%.     

A comparative study in the prediction of thermal conductivity enhancement of nanofluids using ANN-MLP,ANN-RBF,ANFIS, and GMDH methods

In this work, four types of data mining methods, namely adaptive neuro-fuzzy inference system, artificial neural network—multilayer perceptron algorithm (ANN-MLP), artificial neural network—radial basis function algorithm (ANN-RBF), and group method of data handling (GMDH) have been used to predict the enhancement of the relative thermal conductivity of a wide range of nanofluids with different base fluids and nanoparticles. The total number of experimental data used in this work is 483 from 18 different nanofluids. The input parameters are thermal conductivity of base fluid and nanoparticles, volume fraction percent, the average size of nanoparticles, and temperature. Although the results showed that all four models are in relatively good agreement with experimental data, the ANFIS method is the best. The average absolute relative deviations (AARD%) between the experimental data and those of obtained using ANFIS, ANN-MLP, ANN-RBF, and GMDH methods were calculated as 2.7, 2.8, 4.2, and 4.3, respectively, for the test sets and as 1.1, 2.4, 3.9, and 4.5, respectively, for the training sets. Comparison between the predictions of the proposed ANN-MLP, ANN-RBF, ANFIS, and GMDH models and those predicted by traditional models, namely Maxwell and Bruggeman models showed that much better agreements can be obtained using the four models especially ANFIS model. Accordingly, the ANFIS method can able us to predict the relative thermal conductivity of new nanofluids in different conditions with good accuracy.

     

部分还原氧化石墨烯的制备、 表征及对人宫颈癌HeLa细胞的体外杀伤作用

以氧化石墨烯(GO)为原料, 利用温和方法制备了3种不同还原程度的部分还原氧化石墨烯pRGO₁, pRGO₂和pRGO₃(pRGO_1—3)； 利用傅里叶变换红外光谱(FTIR)、 拉曼光谱(Raman)、 X 射线光电子能谱(XPS)、 紫外-可见光谱(UV-Vis)、 透射电子显微镜(TEM)和 EDS能谱对其结构和形貌进行了表征. 细胞实验结果表明, 无激光照射下pRGO_1—3本身的细胞毒性较低; 近红外(NIR)激光照射下pRGO_1—3通过光热和光毒性双重作用杀伤肿瘤细胞. 实验结果显示了pRGO 在肿瘤光热疗法和光动力疗法领域的应用潜力.     

A new procedure for the wet chemical analysis of the lead—noble metals button

Thiobarbituric acid can be used as a group precipitant for the recovery of Pt, Pd, Rh and Au from the lead perchlorate—perchloric acid solution, obtained after the lead—noble metals button has been parted with perchloric acid. By integration of this procedure with the recovery of Ir, Ru and Os from the parting residue, a scheme is evolved which makes possible the determination of all the platinum metals and gold from a single button. The results of analyses of various platiniferous materials by the proposed lead—wet method and the classical lead-cupellation method are compared.     

Liquid—liquid equilibrium data: Their retrieval,correlation and prediction Part II: Correlation

The correlation of liquid—liquid equilibrium data using models for the liquid phase activity coefficients — for example NRTL and UNIQUAC — is reviewed. Different numerical procedures used in the computation of liquid—liquid equilibrium compositions on the basis of these models are evaluated. Methods for obtaining parameters from liquid—liquid equilibrium data are described, and a method leading to improved representation of tie lines using relatively few parameters is recommended. The NRTL and UNIQUAC equations are compared with respect to their ability of representing binary and ternary liquid—liquid equilibrium data. The UNIQUAC equation appears to be more convenient to use and to correlate the data slightly better than does NRTL with the same number of parameters.     

Energy characteristics of poly(olefin ketone) surfaces at different interfaces

The energy characteristics of surfaces of new polymers belonging to the class of poly(olefin ketone)s at the interfaces with air and polar (water) and nonpolar (octane) liquids were determined by the ?ontact angle method. The objects of the study were binary copolymer (propyl-ene—carbon monoxide, PCO) and ternary copolymers (propylene—carbon monoxide—ethyl-ene—carbon monoxide, PECO; but-1-ene—carbon monoxide—ethylene—carbon monoxide, BECO). It was shown that the ternary copolymers can be recommended for further medicobio-logical tests as a base for the development of hemocompatible materials. The equilibrium values of the interfacial energy of poly(olefin ketone)s at the interfaces with water and octane make it possible to predict their adhesion properties for designing composite materials.     

高灵敏度分光光度法测定茶叶中锌的含量

研究了在聚乙烯醇(PVA)存在下,Zn2+ - SCN—- RhB高灵敏度显色反应体系,采用分光光度法测定茶叶中微量锌的新方法.结果表明,络合物的最大吸收峰在605 nm处,摩尔吸光系数为1.59×106 L·mol—1·cm—1,Zn2+的质量浓度在0.0~0.04 μg/mL范围内服从比尔定律.该法用于测定茶叶中锌...     

Solvent effects on the vibrational structure of the ultraviolet spectra of cyanoaromatics. The influence of electron—donor—acceptor (EDA) interactions—II. Studies in binary solvent mixtures

The concept of preferential solvation has been used to detect and quantify specific interactions, particularly electron—donor—acceptor (EDA) interactions for the solutes 1-cyanonaphthalene and 1,2-dicyanobenzene which can act as π electron acceptors. These acceptors have been studied in binary solvent mixtures, in which one of the solvents can act as an electron donor while the other is an “inert” cosolvent.Thus we analysed the preferential solvation of the aromatic compounds in the following mixtures: cyclohexane—diethylether, cyclohexane—diethylamine, diethylamine—diethylether, cyclohexane-diisopropylamine, cyclohexane—diisopropylether and diisopropylamine—diisopropylether.The evaluation of the degree of preferential solvation was performed by an analysis of the intensity enhancements of the vibronic absorption spectral bands of the acceptors in the binary mixtures. This method seems to be a useful approach to observing preferential solvation, is proposed as a method to detect EDA interaction, for systems where no new bands are observed such as in complexes between cyanoaromatics and aliphatic amines.     

氯化钕异丙醇配合物的电子结构与络合活化的研究

本文用INDO方法计算了氯化钕异丙醇配合物的电子结构。计算结果指出, 配位后, 与Nd-Cl键对应的分子轨道能量升高, Nd-Cl键级降低, Nd的正电荷降低, Cl的负电荷增多。从而表明。由于配位发生轨道重迭, 使得异丙醇氧的孤对电子移向钕离子的空价轨道。钕离子上的电子云密度增高加强了对Nd—Cl键的价电子的推斥作用, 使Nd-Cl间的价电子密度减小, 导致Nd-Cl键的削弱, 降低了键的能量, 有效地活化了Nd-Cl键,有利于生成活性物种的烷基化反应的进行。同时表明, 对Nd-Cl的络合催化有某种选择性。     

The formation of MoS<Subscript>2</Subscript> secondary phase at the Cu—Zn—Sn—S/Mo interface during the sulfurization process of Cu—Zn—Sn precursor films

We report on the influence of the sulfurization conditions on the MoS₂ secondary phase formation in Cu—Zn—Sn—S thin films synthesized by thermal evaporation method of metals and intermetallics that can be used for the formation of absorbing layers of solar cells. The dependence between photoconductivity and the intensity of the base line of MoS₂ was found in Raman spectra, which is described by a curve with characteristic maximum. It was found that the secondary phase formation on the Cu—Zn—Sn—S/Mo boundary and photoconductivity of sulfurized films are strongly dependent on the applied temperature conditions. Specifically, films without MoS₂ phase have a low photoconductivity, whereas a high photoconductivity was observed for the films with significant content of secondary phase.     

Characterization of Hydrogen-Bonded Supramolecular Assemblies by MALDI-TOF Mass Spectrometry after Ag+ Labeling

The high affinity of Ag ⁺ ions for aromatic π donors and cyano groups is exploited in a novel MALDI-TOF mass spectrometric method for the identification of hydrogen-bonded assemblies. The interaction with the Ag⁺ ions—which, for example, can be complexed by two phenyl groups in a sandwich-type manner (see drawing on the right)—provides positively charged assemblies in a nondestructive way.     

Cathodic stripping voltammetry of selenocystine,cystine, and cysteine in dilute aqueous acid

Selenocystine, cystine, and cysteine can be determined by cathodic stripping voltammetry (c.s.v.) in 0.1 M HClO₄ or 0.1 M H₂SO₄. The amino acids are accumulated at potentials more positive than —0.35 V, —0.20 V, and —0.10 V vs. s.c.e., respectively, and the stripping peak potentials are —0.45 V, —0.38 V and —0.15 V, respectively. Limiting coverage of the mercury electrode surface is observed for cysteine and selenocystine, but not for cystine. The detection limit for selenocystine is 5 × 10^-10 M in the presence of 100-fold amounts of cystine and cysteine. The detection limits for cystine and cysteine are 1 × 10^-5 M and 1 × 10^-9 M, respectively.     

The analysis of volatile liquid mixtures by thermal conductivity measurements on their vapors

The composition of solutions of volatile liquids can be determined by volatilization into a stream of inert gas and measurement of the thermal conductivity of the resulting gas mixture. The method is directly applicable to binary liquid mixtures which do not show maxima or minima in the conductivity-composition curve and, with modification, it may be applied to the analysis of other mixtures.The observed and calculated thermal conductivities for the acetone— water— nitrogen system showed good agreement that was typical of a number of systems     

Vapour—liquid equilibrium of the systems 1-propanol—2,2,4-trimethylpentane and 2-propanol-n-hexane

The vapour—liquid equilibrium data were measured for the binary systems 2-propanol—n-hexane at 328.21 K and 1-propanol—2,2,4-trimethylpentane at 328.37 K and 348.52 K by using the recirculation still proposed by Berro et al. (1975). The excess volumes for these systems were measured with an Anton Paar densimeter. The reduction of VLE data and analysis of experimental errors were performed. The NRTL temperature-dependence parameters were estimated. The measured VLE data and the activity coefficients were compared with the values predicted by the chemical-reticular group-contribution method (CRG) (Neau and Péneloux, 1979). For both systems satisfactory agreement was found. This proves that the CRG model can be used to predict the vapour—liquid equilibria of alcohol—alkane systems containing branched components.     

固态萃取搅拌棒技术/气相色谱联用分析废水中的痕量爆炸物

制备了以聚醚砜酮(PPESK)为萃取相的新型固态萃取搅拌棒, 建立了一种固态萃取搅拌棒/热解吸器直接热解吸/气相色谱联用分析水样品中痕量爆炸物的新方法. 将萃取搅拌棒放入水样品中完成萃取后, 再直接放入热解吸器中于250 ℃热解吸, 将萃取到搅拌棒上的分析物一次性全部导入气相色谱柱中. 对于硝基苯类爆炸物, PPESK固态萃取搅拌棒的萃取容量比萃取纤维针提高1个数量级以上; 其萃取效率比PDMS固态萃取搅拌棒高2个数量级. 对所测定的7种爆炸物的最低检出限为0.008~0.022 μg/L, 方法的重复性误差(RSD)为6.9%~16%, 在线性浓度范围0.06~10.0 μg/L(除TNT)内, 线性相关系数r为0.9962~0.9998. 在优化的条件下对硝基苯类炸药生产过程中产生的废水进行了分析, 结果表明, 方法的回收率分别为88%~100%(低浓度样品)和61%~88%(高浓度样品), 该方法的重复性误差(RSD)小于11%.     

Solvent self-diffusion,polymer NMR relaxation,and free volume in polymer solutions

The self-diffusion coefficient of chloroform in poly(isopropyl acrylate)—chloroform solutions has been studied as a function of concentration and temperature by using the pulsed-field-gradient spin-echo NMR method. It is found that the self-diffusion coefficient of the solvent can be adequately fitted by using a simple free-volume approach with either a concentration or temperature superposition. It was noted that the free-volume parameters derived from the self-diffusion data are the same as those derived from deuterium NMR transverse relaxation-time measurements of the polymer in the same system. The equality of these two sets of experiments suggests a fundamental relationship between the two different processes. The simplest explanation is that the free volume necessary for the local segmental motion of the polymer and the translation of the solvent are similar.     

Stoichiography for investigation of the functional materials composition,structure, and properties

Principles of the stoichiography and differential dissolution method (DD) providing deep insight into the composition of mixtures containing unknown chemical compounds are considered. Compounds can be identified using their primary feature — the stoichiometry of elemental composition; reference samples of the compounds are not needed. The DD method makes it possible to analyze mixtures of crystalline and/or amorphous phases with constant and/or variable composition in the form of dispersed powders, ceramics, crystals, thin films and nanosize objects. Various aspects of the stoichiography and DD method application to investigation of composition, structure and properties of the functional materials are discussed.     

Au(II)化合物[Au(CH2)2PH2]2X2 (X＝F, Cl, Br, I)的量子化学理论研究

采用从头计算HF, MP2方法和密度泛函理论, 对Au(II)系列化合物[Au(CH₂)₂PH₂]₂X₂ (X＝F, Cl, Br, I)的几何结构、电子结构和振动频率进行了研究. 研究表明Au的5d和6s电子参与Au—Au以及Au—X之间的成键. Au—Au, Au—X键强烈的电子相关作用使HF方法不适于该体系的研究, BP86和B3LYP两种泛函给出较大的Au—Au和Au—X键长, 而MP2方法和局域的密度泛函方法则给出了合理的结构参数. 局域密度泛函方法计算得到的Au—Au键和 Au—X键振动频率也与实验数据符合较好. 还运用含时密度泛函理论计算了[Au(CH₂)₂PH₂]₂X₂的电子激发能, 对分子在紫外-可见光谱范围内的电子跃迁进行了分析, 考察了卤素配体对激发能的影响, 并结合分子轨道能级的变化对此给予了解释.