Am(III) adsorption on oxides of aluminium and silicon: effects of humic substances,pH, and ionic strength

The adsorption of Am(III) (total concentration 10(-9) mol/l) on alumina, silica, and hematite was studied by a batch technique. The effects of pH, ionic strength, and humic substances on the adsorption of Am(III) on alumina and silica were investigated, and the adsorption isotherms of Am(III) on alumina and silica at different pH values were determined. It was found that compared with the adsorption of Am(III) on alumina, the adsorbability of silica on the basis of mass is less, the relative adsorption rate on silica is slower, the sensitivity of adsorption on silica to ionic strength is less, the dependence of adsorption on silica on pH is gentler, and consequently that the adsorption characteristics of Am(III) on alumina and silica are distinctly different. The negative effect of fulvic acid on the adsorption on silica and the positive effect of humic acid on the adsorption on alumina were found. In contrast to the Am(III) adsorption on alumina and silica, a tremendously high adsorbability of Am(III) on hematite was found. The sequence of adsorbabilities of Am(III) on the basis of mass is Fe2O3 > Al2O3 > SiO2.     

环取代基对金属化聚苯胺衍生物膜修饰电极性能的影响

通过比较聚2，5－二甲氧基苯胺（PDMAn）、聚邻甲基苯胺（POT）和聚间氯苯胺（PmClAn）膜修饰电极的氧化还原电位、沉积在这3种聚合物上的铂微粒的表面形态与晶面取向以及异丙醇在分散Pt微粒的聚苯胺膜修饰电极上的氧化行为，从电子效应和立体效应探讨了聚合物电化学性质与环取代基的关系以及不同聚合基质对Pt沉积机理和有催化性能的影响,结果表明，在硫酸溶液中PDMAn膜修饰电极的氧化还原电位最负、POT次之、PmClAn最正，Pt在PDMAn和POT膜上的电沉积机理与在PmClAn膜上的不同，聚合物膜上沉积的Pt微粒呈现（200)晶面择优取向，其中POT膜上择优取向度最大，PDMAn次之，Pm-ClAn最小，异丙醇在金属化聚合物膜电极上的氧化电位取决于聚苯胺的本质，在POT膜修饰电极上异丙醇的电氧化主要发生在POT的活性电位区，而在PDMAn与PmClAn膜上的电氧化则主要发生在Pt上的氧化电位区，说明聚合物膜不仅作为Pt微粒的分散介质，而且本身有产生催化作用。     

Determination of complex reaction mechanisms. Analysis of chemical, biological and genetic networks

We present several methods of determining, not guessing, complex chemical reaction mechanisms and their functions. One method is based on the theory of correlation functions of measured time series of concentrations of chemical species; another is on measurements of temporal responses of concentrations to various perturbations of arbitrary magnitude; a third deals with the analysis of oscillatory systems; a fourth is on the use of genetic algorithms to determine functions of chemical reaction networks. All methods are applicable to chemical, biochemical, and biological reaction systems and to genetic networks and systems biology. The methods depend on the design of appropriate experiments on the whole system and corresponding theories for interpretation that lead to information on the causal chemical connectivity of species, on reaction pathways, on reaction mechanisms, on control centers in the system, and on functions of the system. The first three methods require no assumption of a model or hypothesis, nor extensive calculations, unlike the interpretation of measurements made on a gene network at only one time.     

Recent progress in experiments for sessile droplet wetting on structured surfaces

Wetting of a sessile droplet on structured or patterned surface can be found in a broad range of applications. The researchers have been promoted to keep working on the topic. The review is on the basis of the recent experimental advances on the sessile droplet wetting on the hydrophobic, hydrophilic, or combined hydrophobic and hydrophilic surfaces under isothermal conditions, and on heating or cooling substrates having nonisothermal conditions. More attention has been paid on the wetting configuration between the sessile droplet and the structured substrate; the research gap has been discussed on identifying the three-phase line shape. Further, the three-dimensional measurement for the sessile droplets on the patterned surfaces with focusing more on the contact line of sessile droplets might reveal new physical insights. This review targets at building a holistic overview on the sessile droplet wetting behaviors on the structured substrate in the past 2 years.     

核酸的有机化学研究在分子生物学发展中的作用

本文主要综述有机化学在建立核酸的顺序测定法和自动顺序仪,在破译遗传密码,在建立核酸片段的化学合成方法,固相合成法及DNA合成仪的设计,在合成许多有生物活力的核酸分子,在发展并完善遗传工程以及新近发现酶RNA(Ribozyme)等方面的卓越贡献。最后简要地展望有机化学将对生物学发展作出进一步贡献的几个方面。     

Thermische und spektroskopische Untersuchungen zur Wassersorption an Alkalihalogeniden

Investigations on the extension of the diffuse reflectance spectroscopy by means of the dilution method of KORTÜM show the decisive influence of water sorption on the dilution substances, particularly on their absolute reflectance. Water sorption is investigated on alkali halides (NaCl and LiF) as dilution substances by gravimetric, thermal desorption and reflectance methods. Sorption gravimetry gives data on the quantities of adsorbed substances and the time function of adsorption processes, thermal desorption on chemical binding of adsorbed molecules and reflectance spektroscopy on the molar absorptivity of adsorbed water molecules.     

Dewetting of liquids on ceramic surfaces at high temperatures.

The influence of surface structure and chemistry on high-temperature dewetting of silicate liquids on ceramic surfaces has been investigated. Model systems based on well-defined crystallography and known chemistry have been used to illustrate the effect of surface roughness and chemistry on the dewetting process. Reconstructed ceramic surfaces provide ideal substrates to study effects of surface roughness. It has been shown that the morphology of dewet droplets depend on the length scale and the crystallography of the facets on the surface. Complex pattern formation due to solute redistribution during dewetting is illustrated in the case of SiO2 dewetting on (001) rutile substrates. The role of kinetics on the dewetting process has also been clarified.     

吸附相反应技术用于不同载体表面纳米TiO2的制备

研究了不同载体对吸附相反应技术制备TiO2粒子的影响, 设计了两种不同表面形貌载体的温度实验(A型SiO2: 粒径20 nm, 比表面积640 m2·g-1; B型SiO2: 粒径12 nm, 比表面积200 m2·g-1), 并用电子能谱仪测定了两种载体表面TiO2含量随温度的变化. 结果表明, 两种载体表面Ti含量都随着温度的升高而减少, 且在一定温度范围内存在着突变, 但A载体突变的温度范围是40-60 ℃, 而B载体为30-50 ℃. TEM表征结果则显示, B表面TiO2粒子要比A表面的均匀. XRD得到的晶粒粒径曲线表明, A 载体表面TiO2晶粒粒径随着温度升高而减小并存在着突变, B载体表面粒子粒径则基本不变. 根据硅胶表面的吸附特性, 提出SiO2吸附的共性导致载体表面Ti含量变化曲线存在着共同点, 而载体内外表面的不同形貌则引起其表面吸附层的形貌以及温度敏感性不同, 最终导致两种载体表面Ti含量、晶粒粒径以及形貌上的差别.     

含铈Cu-Fe-O催化剂的氧化还原性研究

用TPR等方法研究了Cu-Fe-Ce-O/γ-Al₂O₃(Ⅰ)催化剂的氧化还原性能。结果表明,在(Ⅰ)中铜的存在有利于Fe₂O₃的还原,铈作为助催化剂能增强Cu-Fe-O/γ-Al₂O₃(Ⅱ)的氧化还原性能,配合CO、NO和CO+NO气对试样进行预处理后发现,铜吸附CO的能力比铁强,铁吸附NO的能力比铜强,铈的存在可增强(Ⅱ)在NO+CO反应气氛中对CO的吸附能力,并对NO在催化剂表面吸附形成硝酸盐物种产生影响。     

Growth and characterization of pyrene crystals on carbon nanofibers

Pyrene crystals were grown on carbon nanofibers (CNFs) by dispersing pyrene polycrystals and CNFs in water during ultrasonic irradiation, and they were characterized by scanning electron microscopy, X-ray diffractometry (XRD) and spectroscopy. The XRD measurements indicated that the orientation and size of the pyrene crystals on the CNF aggregates were different from that of the added pyrene polycrystals. Based on the spectroscopic properties of the pyrene crystals on the CNFs, the pyrene crystals on the CNF aggregates and on the individual CNFs were determined to be polycrystals and single crystals, respectively. These results indicate that pyrene crystals are produced on the CNFs by recrystallization of the added pyrene polycrystals and their crystal states depend on the aggregation state of the CNFs.     

不同取代基的噻碳菁和吲哚碳菁染料对其在溴化银微晶上吸附能力及形成J-聚集体尺寸分布的影响

本文研究了5-位不同取代基的噻碳菁和吲哚碳菁染料对其在立方型颗粒和T-颗粒溴化银微晶上吸附能力的影响,并采用ACFEM(Analytical Color Fluore scence Electron Microscopy)研究了上述结构染料对其吸附在溴化银微晶所形成的J-聚集体尺寸分布的影响。实验结果表明,对吲哚碳菁染料来说,立方体溴化银微晶表面的吸附能力较T-颗粒溴化银微晶表面的吸附能力强;但对噻碳菁染料来说则相反,它们在T-颗粒溴化银微晶表面的吸附能力较立方体溴化银微晶表面的吸附能力强。另外,对5-位不同取代基的噻碳菁染料而言,无论是在立方型颗粒或T-颗粒溴化银微晶上的吸附能力来说,含取代基(无论4-取代基是吸电子型还是推电子型)的噻碳菁染料较未取代的噻碳菁染料强;而5-位取代基是吸电子型的噻碳菁染料更有利于其吸附在T-颗粒溴化银微晶表面。此外,本文还进一步证明了溴化银微晶表面上染料J-聚集体的生长过程是符合奥斯瓦尔特成熟过程的。吲哚碳菁染料在T-颗粒溴化银微晶上形成的J-聚集体的平均尺寸明显大于在立方体溴化银微晶上形成的J-聚集体的平均尺寸。吸附在立方体溴化银微晶上的5-不同取代基的噻碳菁染料对其形成J-聚集体尺寸分布的影响的研究结果表明,含取代基(-CH₃,-Ph,-Cl)的噻碳菁染料形成的J-聚集体的尺寸分布几乎相同,但与未取代的噻碳菁染料形成的J-聚集体的尺寸分布明显不同;5-位含取代基的噻碳菁染料形成的J-聚集体平均尺寸大于未取代的噻碳菁染料的。     

Influence of Mg^2＋ on Initial Stages of CaCO3 Scale Formed on Metal Surface

Magnesium ions, which exist in formation water and injection water under downhole conditions in the oil and gas production industry, are a key determinant in the CaCO3 scale formation. Many studies have focused their attention on the effect of magnesium on the kinetics, the morphology and the content of Mg in the Ca-CO3 scale. Little attention has been paid to the effect of Mg^2 on the initial stages of CaCO3 formation on a metal surface. In this study, an electrochemical technique was used to study the influence of Mg^2 on the ini-tial stages of CaCO3 scale formed on a metal surface. With this electrochemical technique, the reduction of the dissolved oxygen in an analysis solution is considered on the surface of a rotating disk electrode (RDE) un-der potentiostatic control. The rate of oxygen reduction on the surface of the RDE enables the extent of sur-face coverage of scale to be assessed. With this electrochemical technique, a new insight into the effect of Mg^2 on CaCO3 scale formed on a metal surface is given.     

Activity of an enzyme immobilized on polyelectrolyte multilayers

The immobilization of α-chymotrypsin on the surface of boron silicate glass microspheres is conducted via the technique of multilayer adsorption of polyelectrolytes. It is shown that the enzyme is adsorbed on both positively and negatively charged surfaces and its activity is partially preserved relative to that in solution. The activity of the enzyme depends on the number of polyectrolyte layers preliminarily adsorbed on glass microspheres and on the charge of the surface. The activity of α-chymotrypsin adsorbed on the negatively charged surface is four times higher than the activity of this enzyme adsorbed on a positively charged surface.     

三种甲氧基黄烷酮在纤维素衍生物手性柱上的对映体分离及手性识别机理研究

在四种自制的涂敷型纤维素衍生物手性柱，即纤维素三苯甲酸酚（CTB）、纤 维素三（4-甲基苯甲酸酯）（C素三苯基氨基甲酸酯（CTPC）和纤维素三（3，5- 二甲基苯基氨基甲酸酯）（cDMPC）上对4'-甲氧基黄烷酮，56-甲氧基黄烷酮进行 了对映体分离，研究了溶质的结构及流动相的组成对手性分离的影响，并对手性识 别的机理进行了讨，认为π-π作用很可能是上述三种甲氧基黄烷酮在四种纤维素 衍生物手性固定相上保留与手性识别的主要因素，CDMPC，氢键作用也对手性识别 有非常重要的作用.     

阻光染料对氯化银乳剂光谱增感的影响

增感染料在卤化银微晶上吸附并形成J-聚集体是染料光谱增感和超增感的关键步骤.本文利用紫外-可见吸收光谱研究了增感染料和阻光染料在氯化银微晶上的吸附,并考察了阻光染料对增感染料J-聚集体的形成及乳剂感光性能的影响.结果表明:不同阻光染料在氯化银微晶表面的吸附程度不同,对增感染料J-聚集体形成的影响也有差异.其中,吸附较小的不影响增感染料J-聚集体的形成,而吸附较大的阻碍增感染料J-聚集形成,特别是阻光染料在增感染料之前加入乳剂中时.在氯化银微晶上吸附很小的阻光染料基本不影响增感染料对乳剂的光谱增感,而吸附较强的阻光染料不仅吸收入射光,还抑制或破坏增感染料的光谱增感.因此,在氯化银微晶表面没有吸附的阻光染料才是优良的阻光染料.     

Pt/HL和Pt/KL沸石在异丙醇分解反应中的不同催化行为

Ｐｔ／ＫＬ沸石在异丙醇分解反应中具有很高的脱氢活性,而Ｐｔ／ＨＬ沸石具有明显的缺电子性,在此反应中难以显示出脱氢活性,通过加氢作用,可使沸石的酸位免受积炭覆盖,从而可增强Ｐｔ／ＨＬ沸石的酸性催化作用。     

Electrooxidation of methanol on upd-Ru and upd-Sn modified Pt electrodes

The electrochemical oxidation of methanol has been investigated on underpotentially deposited-ruthenium-modified platinum electrode (upd-Ru/Pt) and on underpotentially deposited-tin-modified platinum electrode (upd-Sn/Pt). The submonolayers of upd-Ru and upd-Sn on a Pt electrode increased the rate of methanol electrooxidation several times as large as that on a pure Pt electrode. The best performance for methanol electrooxidation was obtained on a ternary platinum based catalyst modified by upd-Ru and upd-Sn simultaneously. The influence of the submonolayers of upd-Ru adatoms and upd-Sn adatoms on the oxidation of methanol in acid has been investigated. The effect of Ru on methanol electrooxidation lies on the distribution of Ru adatoms on a Pt surface. It has been shown that as long as the amount of upd-Ru deposits were controlled in a proper range, upd-Ru deposits would enhance the methanol oxidation obtained on a Pt electrode at whichever deposition potential the upd-Ru deposits were obtained. The effects of tin are sensible to the potential range. The enhancement effect of upd-Sn adatoms for the oxidation of methanol will disappear as the electrode potential is beyond a certain value. It is speculated that there exists a synergetic effect on the Pt electrode as adatoms Ru and Sn participate simultaneously in the methanol oxidation.     

Influence of coadsorbates on the NO dissociation on a rhodium(311) surface.

Density functional theory (DFT) studies were performed to investigate the influence of coadsorbates on the nitrogen oxide dissociation on the vicinal rhodium(311) surface. This study amplifies prior studies on the dissociation of oxygen and nitrogen oxide on the (111) facet of rhodium. The influence of coadsorbates on the kinetic parameters and thermochemistry of the NO dissociation on Rh311 was studied. In addition, the activation energy and thermochemistry of this reaction were determined as a function of oxygen preoccupation/initial coverage. Steric and electronic effects and their influence on the dissociation reaction were examined. The results are discussed in the face of an NOx dissociation catalyst system proposed by Nakatsuji.     

一些含硫、含氮化合物在卤化银成像过程中的作用

采用在曝光前后用不同浓度的化合物溶液分别处理硫增感立方乳剂样品方法,观察它们在感光特性上的差别,从而判断这些化合物在卤化银成像过程的不同阶段各自所起的作用.本工作中所选用的化合物有-1-苯基-5-巯基四氮唑(PMT),6-硝基苯并咪唑-(硝酸盐-),5-硝基苯并咪唑,5-硝基吲唑,4-羟基-6-甲基-1,3,3a,7-四氮茚-(TAI)和硫代乙酰胺.结果表明:PMT在一定的浓度范围内对潜影的形成有促进作用,但对显影有抑制作用;6-硝基苯并咪唑和-5-硝基苯并咪唑的情况相似,对潜影的形成无显著影响,而对显影的抑制作用明显;5-硝基吲唑不仅对潜影的形成有明显阻滞作用,而且对显影也有抑制作用;TAI则对潜影的形成有明显的促进作用,对显影的影响较小;硫代乙酰胺在弱酸性介质中对潜影的形成有显著阻滞作用,对显影也有一定的抑制作用,但对灰雾的增长十分显著.