线状铜电极在磷酸溶液中电流混沌振荡的同步行为

研究了恒电位下两个铜线电极在磷酸溶液中的电流混沌振荡行为,通过恒定不同的电位数值,改变单个电极的电流振荡混沌行为,研究了不同混沌间的相互作用.调整线电极间的距离,研究了电极间距对电流振荡行为的影响.实验中两电极的振荡间呈现了复杂的耦合作用,耦合后的频率与耦合前电极原有的频率不同.两电极的混沌电流振荡中呈现出同步、准周期同步和反相同步等现象.电极距离一定时,振荡波形差别很大的两电极的电流容易呈现反相同步和准周期同步,波形差别不大时容易产生同步.强的耦合导致电极间电流振荡的同步,电极距离的加大,电极间电流振荡难以产生同步.对耦合作用机制也进行了探讨.     

超声波-微波法制备NiW/Al2O3加氢脱硫催化剂

 采用一次浸渍技术制备了NiW/Al2O3加氢脱硫(HDS)催化剂,在制备过程中采用超声波处理浸渍液,采用微波进行样品干燥. 以噻吩为模型化合物,在微反装置上评价了该催化剂的加氢脱硫活性. 使用X射线光电子能谱和透射电镜等表征手段研究了催化剂的表面状态和物化性. 结果表明,使用超声波及微波技术制备的NiW/Al2O3催化剂具有较高的加氢脱硫活性,催化剂的活性组分较易硫化,可生成更多的硫化物种参与反应. 催化剂中硫化态钨的表面原子浓度较高,从而使硫化态钨物种保持较高的表面分散度,有利于增加活性中心的数目. 该催化剂的活性中心结构具有较多配位不饱和的边缘位和棱边位,因而具有较高的加氢脱硫活性.     

锌试剂与壳聚糖的结合反应机理的研究

为从分子水平认识多糖分子与小分子之间相互作用的机理,应用光谱法研究了壳聚糖(CTS)与锌试剂(ZCN)的相互作用机理;测得ZCN-CTS复合物吸收光谱出现新的吸收峰所需的临界ZCN/CTS摩尔比为2.67×103, CTS对ZCN的最大结合数为6.93×103,实验值与理论值相吻合,证明了多糖与生物探针相互作用理论模型的可靠性;探讨了ZCN与CTS相互作用产生变色反应的机理,认为其是在ZCN与CTS大分子间发生静电相互作用的基础上,主要由ZCN与CTS大分子间的疏水相互作用所引起.     

煤中矿物质及其燃烧后的变化分析

以淮北煤田6煤层煤为样品，采用中子活化法、化学方法、X射线衍射及扫描电镜等方法对煤及其灰样品中的矿物质、微量元素进行了分析，在此基础上，研究了样品中主要矿物的种类及其形成时的影响因素，分析了它们在燃烧前后的主要变化。通过分析可知，样品中主要含有高岭石、石英、方解石和黄铁矿以及多种微量元素；在燃烧过程中，微量元素的含量以及矿物的种类发生了变化，并形成高温稳定的矿物种类。     

Synthesis,analytical characterization and bioactivity of Ag and Cu nanoparticles embedded in poly-vinyl-methyl-ketone films

The electrosynthesis of copper and silver core-shell nanoparticles (NPs) by the sacrificial anode technique, employing tetraoctylammonium (TOA) salts as base electrolyte for the first time, is described. These surfactants were selected because they combine high NP stabilizing power with useful disinfecting properties. The resulting colloids were mixed with a solution of an inert dispersing polymer and used to prepare nanostructured composite thin films. The morphologies and chemical compositions of the nanomaterials were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The TEM reveals that the average core diameter of the metal NPs ranges between 1.7 and 6.3 nm, as a function of the nature of the metal and of the electrosynthesis conditions, and does not change significantly upon inclusion in the polymer matrix. An appreciable concentration of the metal is detected on the nanoparticle surface by XPS. High-resolution XP spectra indicate that both copper and silver are present at zero oxidation state in all of the materials (colloids and composite films). This demonstrates the high efficiency of the surfactant at controlling the morphology and the chemical composition of the nanodispersed metal in both the as-synthesized colloid and in the polymeric dispersion. The nanocoatings are shown to exert a marked inhibitory effect on the growth of eukaryote and prokaryote target microrganisms, and experimental evidence of a synergic disinfecting effect due to the surfactant and the nanodispersed metal is provided. On the basis of these stability and bioactivity results, it is clear that Cu-NPs and Ag-NPs are suitable for application in disinfecting or antifouling paint and coating formulations.Electronic Supplementary Material Supplementary material is available for this article at Dedicated to the memory of Wilhelm Fresenius     

Contributions to the Chemistry of the Binary Compounds of the Transition Elements

Phase and structural relationships of the sulfur, selenium, and tellurium compounds of the 4d and 5d transition elements of groups IV to VII of the periodic system are discussed. Homologous elements behave very similarly with respect to the chalcogens, and this is particularly the case for niobium and tantalum, and for molybdenum and tungsten. However, zirconium, niobium, and molybdenum have a greater tendency towards formation of chalcogen-poor phases than their homologues hafnium, tantalum, and tungsten. Subchalcogenides are known only for zirconium and niobium. The number of phases and the tendency towards formation of solid solutions are considerably smaller among the tellurides than among the sulfides and selenides. The crystal structures of the telluride phases also differ from those of the sulfide and selenide phases of analogous composition. In addition, a review of the phase and structural relationships of the arsenic and antimony compounds of the 4d and 5d transition elements of groups V to VII is given.     

Determination of neutral and cationic herbicides in water by micellar electrokinetic capillary chromatography

The separation and determination of two s-triazines and two quats in water samples by MEKC was described. The influence of pH, type and concentration of buffer, concentration and type of surfactant, organic modifier and the added salt on the separation of the two neutral and the two cationic herbicides was studied. Simazine and atrazine (neutral compounds at the working pH) were little influenced by the chemical variables, while the cationic paraquat and diquat were more influenced. In the optimisation on the separation voltage, the total concentration of salt in the run buffer and the repeatability of the separation were taken into consideration. The composition of dissolution, in which the analytes were dissolved, was also studied.A solid-phase extraction method to retain and to elute the four analytes in a single step was also developed. Recoveries between 80 and 95% and R.S.D. between 6 and 10% was obtained in the analysis of a well-water sample spiked with 2 and 5 ppb of triazines and quats, respectively. Detection limits were between 0.6 and 1.9 ppb.     

LOW DENSITY POLYETHYLENE/CLAY NANOCOMPOSITES MODIFIED BY ETHYLENE COPOLYMERS： EFFECTS OF FUNCTIONALIZED SEGMENTS ON MORPHOLOGY

Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene （LDPE）, ethylene copolymer and organoclay. X-ray diffraction （XRD） and transmission electron microscopy （TEM） were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.     

载体对包埋酶微环境的影响分析

包埋法固定化酶过程中,酶固定化载体的选择和设计是酶固定化过程的关键因素,适宜的载体微环境对酶活性和稳定性的影响尤为重要。论文首先分析并提出了影响固定化酶所处载体微环境的主要因素,包括载体的亲疏水性、结构形态和反应活性。载体的亲疏水性决定固定化酶微环境中的水分含量。载体的结构形态对酶形成的笼效应,以及载体的反应活性,包括共价键合、静电和氢键等的结合能力,影响酶构象的稳定性和运动性。另外,底物／产物的扩散速率和酶的可及性也同样受到载体的孔结构、孔分布以及载体反应活性的影响。本文介绍了常用的酶包埋载体,包括sol-gel二氧化硅、高分子水凝胶以及高分子－二氧化硅杂化凝胶固定化酶过程,结合上述影响酶微环境的因素,分析比较了三类载体固定化酶的包埋率、活性和稳定性,综述了为改善固定化酶微环境所进行改进研究的进展。     

Ga、Zn改性方法对HZSM-5催化剂丙烯芳构化性能的影响

以浸渍法和水热合成法对ZSM-5分子筛进行Ga、Zn改性,制得不同酸性的分子筛催化剂。采用XRD、SEM、NH3-TPD和XPS等表征手段,研究考察了Ga、Zn和不同引入方法对催化剂的孔结构、骨架结构特性和表面酸性的影响,并以丙烯芳构化为模型反应,考察了Ga、Zn改性对ZSM-5催化剂烯烃芳构化催化性能的影响。研究结果表明,Ga、Zn改性对催化剂形貌影响较小,但能明显改变催化剂的表面酸性和烯烃芳构化性能。Zn改性能降低催化剂的酸性,而Ga改性与其引入的方式有关,浸渍法引入催化剂的中强酸位略有下降,而水热合成法引入则显著增加了催化剂的总酸量。Ga、Zn改性均提高了芳构化反应的活性和芳烃选择性,并抑制催化剂表面积炭。     

Polymorphism and Conformational Equilibrium of Nitro-Acetophenone in Solid State and under Matrix Conditions

Conformational and polymorphic states in the nitro-derivative of o-hydroxy acetophenone have been studied by experimental and theoretical methods. The potential energy curves for the rotation of the nitro group and isomerization of the hydroxyl group have been calculated by density functional theory (DFT) to estimate the barriers of the conformational changes. Two polymorphic forms of the studied compound were obtained by the slow and fast evaporation of polar and non-polar solutions, respectively. Both of the polymorphs were investigated by Infrared-Red (IR) and Raman spectroscopy, Incoherent Inelastic Neutron Scattering (IINS), X-ray diffraction, nuclear quadrupole resonance spectroscopy (NQR), differential scanning calorimetry (DSC) and density functional theory (DFT) methods. In one of the polymorphs, the existence of a phase transition was shown. The position of the nitro group and its impact on the crystal cell of the studied compound were analyzed. The conformational equilibrium determined by the reorientation of the hydroxyl group was observed under argon matrix isolation. An analysis of vibrational spectra was achieved for the interpretation of conformational equilibrium. The infrared spectra were measured in a wide temperature range to reveal the spectral bands that were the most sensitive to the phase transition and conformational equilibrium. The results showed the interrelations between intramolecular processes and macroscopic phenomena in the studied compound.     

Identification of the Flavone in the Flower Bud of Panax Quinquefolium and Its Content Determination in the Different Parts

ＰａｎａｘｑｕｉｎｑｕｅｆｏｌｉｕｍＬ .ｂｅｌｏｎｇｓｔｏｔｈｅＰａｎａｘｇｅｎｕｓｏｆｔｈｅＡｒａｌｉａｃｅａｅ .ＩｔｏｒｉｇｉｎａｔｅｓｉｎＡｍｅｒｉｃａａｎｄＣａｎａｄａ .Ｉｔｓｒｏｏｔｓ ,ａｆａｍｏｕｓａｎｄｅｘｐｅｎｓｉｖｅｔｒａｄｉｔｉｏｎａｌＣｈｉｎｅｓｅｍｅｄｉｃｉｎａｌｍａｔｅｒｉ ａｌ,ｈａｖｅｂｅｅｎｓｔｕｄｉｅｄｃｏｎｔｉｎｕａｌｌｙｓｉｎｃｅｉｔｓｓｕｃｃｅｓｓｆｕｌｃｕｌｔｉｖａｔｉｏｎｉｎＣｈｉｎａｉｎｔｈｅ 1 970’ｓ .Ｉｎｒｅ ｃｅｎｔｙｅａｒｓｔｈｅｄｅｖｅｌｏｐ…     

失之东隅收之桑榆——从“实验失败”中引导本科生的实验探究和创新能力

Failed experiments occur frequently in laboratory. How the laboratory teacher actively and effectively deal with the failed experiments and guide students plays an important role in the cultivation of undergraduates' creativity. If he loses on the swings, he may win on the roundabouts. We show how teacher guide and enlighten the undergraduate students to get the inspiration and learn from the failed experiments by two examples of Chemistry Laboratory of undergraduates. Let the students find problems with curiosity, analyze problems, and solve the problem in the "experiment-failure-improvement-experiment" process based on relevant knowledge and rules. The teaching and learning efficiency of laboratory class is significantly improved. Undergraduates not only have a profound discussion and analysis of experimental results, but also receive effective training in scientific research literacy and quality.     

Conducting polymer/alumina composites as viable adsorbents for the removal of fluoride ions from aqueous solution

The polyaniline/alumina (PANi-AlO) and polypyrrole/alumina (PPy-AlO) composites were prepared and characterized by FT-IR, SEM and X-ray diffraction studies and were employed as adsorbents for the removal of fluoride ions from aqueous solution by the batch sorption method. The amount of fluoride ions adsorbed per unit mass of the adsorbents was observed to be higher than that by the individual constituents. The maximal amount of adsorption is 6.6 mg/g for PANi-AlO and for PPy-AlO it is 8 mg/g. The Langmuir and Freundlich isotherms were used to describe adsorption equilibrium. The kinetics of the adsorption process was investigated using Natarajan-Khalaf equation and intraparticle diffusion model. FT-IR and XRD pattern of the adsorbent, before and after the adsorption is recorded to get better insight into the mechanism of the adsorption process. The results of equilibrium and spectral investigations revealed that the mechanism of fluoride ion removal by these composites involve both the formation of aluminium-fluoro complexes on the alumina surface and doping/dopant-exchange of fluoride ions in the polymer.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Preventing biofilm development on DGT devices using metals and antibiotics

The DGT technique has potential as a tool for monitoring reactive phosphorus in freshwater aquaculture effluents. Because those waters have high concentrations of suspended matter and nutrients, biofilms may form on the surface of the DGT devices. Those biofilms may hinder the movement of reactive phosphorus and hence interfere with the DGT measurements. We tested two antibiotics, glutaraldehyde and chloramphenicol, two metal-iodides, copper and silver and also two alternative filter types, nucleopore membrane and silver-based filters, to evaluate their respective potential to prevent the formation of algae. The treatment with silver iodide seems to affect the properties of the diffusive gel and changes the flux measurements of the DGT device. The DGT response observed using the copper iodide and chloramphenicol treatments was not significantly different from the control. Glutaraldehyde changed the macroproperties of the diffusive gel and interfered with the phosphorus detection using spectrophotometric determinations. The effect of the anti-biofilm treatments on the DGT measurements was independent of pH and ionic strength of the water. For the field deployment in fish farms, copper and silver were the best anti-biofilm agents. Copper prevented algal colonisation for 14-days post-deployment and the response was unaffected by the anti-biofilm agent throughout this period. Silver was even better and prevented biofilm formation up to a 21-days post-deployment. Conversely, chloramphenicol did not prevent algal colonisation for the 14- and 21-days deployments. However, for deployments longer than 14 days, it was difficult to obtain consistently good results for all of anti-biofilm agents tested, due to the high concentration of suspended matter in the freshwater effluents of the fish farms tested. This approach suggests a metal pre-treatment of the membrane filters is useful to prevent biofilm formation for DGT deployments aimed at P measurements. DGT deployments for metal measurements would likely require a different approach.     

Molecular mechanism of the protective effect of monomer polyvinylpyrrolidone on antioxidants – experimental and computational studies

We previously developed a lutein–polyvinylpyrrolidone (PVP) complex with improved aqueous saturation solubility and stability, though the conjugation mechanism is still unclear. In this paper, experiments with astaxanthin–PVP complex and curcumin–PVP complex were carried out, which indicated that PVP could improve the solubility and stability of astaxanthin and curcumin. We aimed to construct a computational model capable of understanding the protective effect in complexes formed between PVP and antioxidants, through which the binding mode of PVP and antioxidants was investigated with molecular modelling in order to obtain the interactions, binding energy, binding site and surface area between PVP and antioxidants. Solubility enhancement was attributed to the H-bonds between PVP and antioxidants, and the saturation solubility was curcumin > lutein > astaxanthin. Binding energy, binding site and surface area were beneficial for the stability of complex, and the stability enhancement was lutein > astaxanthin > curcumin. The experimental results were in agreement with the computational results. Furthermore, we established a method for the exploration of a similar system with other polymer complexes. Additionally, the proposed PVP model could predict the interactions between PVP and various ligands, such as antioxidants and drugs.     

宝日希勒褐煤在合成气与复合溶剂系统下的液化性能研究

在合成气（CO+H₂）与复合溶剂（水+有机溶剂）液化系统下研究了气氛、温度、催化剂类型对宝日希勒褐煤转化率、油气水产率和CO转化率等液化特征的影响,从而探讨其液化性能。结果表明,在高含水复合溶剂系统中,合成气气氛、反应温度430-450℃适宜宝日希勒褐煤液化转化,转化率可达到81.15%,油气水产率达到71.53%。该液化系统下,含铁、碱和硫复合型催化剂能有效地提高液化转化率和油气水产率,在430℃催化液化下褐煤转化率达92.27%,油气水产率达79.39%。该催化剂有效促进了煤中大分子的裂解和系统中水煤气变换反应进程,沥青质减少,油含量增多。液化油中多环芳烃衍生物在催化液化过程中向单环芳烃衍生物和烷烯烃转化,分子量降低,提高了油品质量。     

ZnO和TiO2粒子的光催化活性及其失活与再生

 利用XRD，TEM，BET和UV－Vis等测试技术对商品的ZnO及TiO2和纳米ZnO及TiO2粒子进行了表征．无论是商品的还是纳米的，在光催化氧化降解气相n－C7H16和SO2及液相苯酚的反应中，TiO2均表现出比ZnO高的光催化活性，并从光腐蚀性和表面电荷两方面分析了其原因．在光催化氧化降解n－C7H16的反应中，ZnO粒子易失活，而TiO2粒子不易失活．但是，在光催化氧化降解SO2的反应中，ZnO和TiO2粒子均易失活．SPS和XPS测试结果表明，光催化剂表面的导电类型由反应前的n型变成了失活后的p型．这主要是由于反应产物发生吸附所致．失活后的光催化剂可以通过浸洗和干燥再生．     

Thermodynamics of dissolving and solvation processes for benzoic acid and the toluic acids in aqueous solution

Experimental data are presented for the solubility in water of benzoic and toluic acids from 5° to 65°C. From the solubility the molality of the monomeric form of the acid is calculated using literature data for both ionization and dimerization of the acid. These data for the monomer combined with data from the literature for vaporization of the solid and ionization in both the gas phase and the aqueous phase yield entropy and enthalpy changes for the solvation of molecular and anionic forms of the acid. A similar procedure is also applied to literature data for the solubility of benzene in water. It is shown that the hydration entropies of the monomeric forms are a linear function of their partial molar volumes. It is concluded that hydration of the undissociated o-toluic acid may be crucial to the increased acidity of that acid compared to benzoic acid.