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.     

Anionic Graft Copolymers. III. Hydrogenation of Polydienes Grafted with Vinylaromatics

A new method is described to prepare graft copolymers of polystyrene and polyvinylcyclohexane on polyethylene and poly (ethylene, butene-1). Hydrogenation of the butadiene moieties of graft copolymers of polystyrene on poly-1, 4-butadiene and high vinyl polybutadiene forms graft copolymers of polystyrene on polyethylene and on poly (ethylene, butene-1). Graft copolymers of polyvinylcyclohexane on polyethylene and on poly (ethylene, butene-1) are prepared by completely hydrogenating graft copolymers of polystyrene on poly-1, 4-butadiene and on high vinyl polybutadiene. The physical properties of these polymer systems depend on composition and graft level, resulting in either tough polymers or elastomers.     

Resonance Raman spectra of polyacetylene on zeolite and alumina surfaces

Raman spectra are reported for polyacetylene on exchanged zeolites and on alumina. The polymerization of acetylene on zeolites is found to depend on the zeolitic cation size and on surface coverage. Mean chain lengths of about fifteen CC bonds are formed on alumina.     

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。     

化学发光酶免疫分析研究进展

叙述了化学发光免疫分析的分类及特点,从发光底物、增强剂、过氧化物酶、过氧化物及其他方面,对鲁米诺类化合物化学发光酶免疫分析的进展进行了综述,引用文献34篇。     

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.     

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.     

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。     

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.     

Layer-selective epitaxial self-assembly of porphyrins on ultrathin insulators

Copper-Octaethyl Porphyrin self-assembly has been studied on NaCl islands, 1–3 monolayers thick, grown on metal substrates. Extended ordered molecular monolayers are observed for the first time on ultrathin insulator films. The assembly occurs in hierarchical fashion, starting on the metal substrate, then followed by assembly on the first and second NaCl layers, clearly demonstrating a decrease in adsorption energy for increasing insulator layer thickness. The underlying mechanisms are discussed on the basis of molecule–substrate interactions. Voltage-dependent STM images reveal differences of the electronic structure for molecules adsorbed on metal and NaCl/metal areas.     

ToF‐SIMS and principal component analysis: Effect of film thickness on crystal surfaces of polymers

The effect of film thickness on the structural conformation of the surfaces of the amorphous state, edge‐on lamellae and flat‐on lamellae of a semiflexible polymer, poly(bisphenol‐A‐etheroctane), was investigated by time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) with the aid of principal component analysis (PCA). PCA results empirically indicate that a structurally regular polymer surface was obtained with the formation of the flat‐on lamellae from the amorphous state at a low degree of supercooling. A higher concentration of end group and cilium ion fragments, which are indicative of free chain ends, was observed on the edge‐on lamellar surfaces than on the amorphous and the flat‐on lamellar surfaces. This finding was attributed to the fact that the lateral surface of the edge‐on lamellae contains many growth fronts, leaving behind a large number of uncrystallized chain remnants on the surfaces. Structural disorder was facilitated on both edge‐on and flat‐on lamellar surfaces as the film thickness decreased. Hence, this PCA study offers new insights into the nonequilibrium nature of polymer crystals and the mechanism of polymer crystallization in thin and ultrathin films. Copyright © 2010 John Wiley & Sons, Ltd.     

Ionic reaction of halogens with terminal alkenes: the effect of electron-withdrawing fluorine substituents on the bonding of halonium ions

Ionic reactions of terminal alkenes with chlorine (Cl(2)), bromine (Br(2)), and iodine monochloride (ICl) are sensitive to the alkyl substituents, and the positions and number of vinyl fluorine atoms. These perturbations influence the symmetry of the halonium ion intermediates, which can be determined by the distribution of the Markovnikov to anti-Markovnikov products. A vinyl fluorine on the number-2 carbon favors an unsymmetrical intermediate with greater charge on the number-2 carbon unless the alkyl group is electron withdrawing. A vinyl fluorine on the terminal number-1 carbon favors positive charge development on that carbon unless a resonance stabilizing group is on the number-2 carbon. The symmetry of halonium ions with vinyl fluorines on both carbons-1 and -2 depends primarily on the characteristics of the alkyl substituent. Intermediates range from open-ions with the positive charge on carbon-2, to various bridged species, to open-ions on the terminal carbon.     

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.     

Rh-promoted methanol decomposition on cerium oxide thin films

Methanol adsorption and reaction have been studied on Rh-deposited cerium oxide thin films under UHV conditions using temperature-programmed desorption and synchrotron soft X-ray photoelectron spectroscopy. The methanol behavior was examined as a function of the Ce oxidation state, methanol exposure, and Rh particle size and coverage. When Rh nanoparticles were deposited on the ceria films, methanol decomposed on Rh to CO and H below 200 K. H atoms recombined and desorbed between 200 and 300 K. CO evolved from Rh deposited on fully oxidized ceria between 400 and 500 K. However, on reduced ceria films, the CO on Rh further decomposed to atomic C. Methanol adsorbed on the ceria films deprotonated to form methoxy as the only intermediate on the surface. This methoxy decomposed and desorbed as CO and H2 at higher temperatures regardless of the ceria oxidation state. Compared with the methanol reaction on Rh-free ceria thin films, formaldehyde formation from methoxy was completely suppressed after Rh deposition. Our results indicate that Rh can promote the decomposition of methoxy adsorbed on the ceria and that decomposition of methoxy intermediates occurred at the metal/oxide interfaces. On the other hand, the reduced ceria can promote total methanol decomposition on Rh.     

多相聚合物体系相界面研究进展

综述了多相聚合物体系相界面的形成、界面层状态的表征、界面层性质及其对体系性能的影响。重点论述了不同类型增容剂对界面行为的影响，其中对嵌段型增容剂的分子量、浓度等因素对界面行为的影响建立了定量关系；而对接枝型和无规增容剂对界面行为的影响研究较少，有待发展。指出了在界面张力、界面层厚度与多相聚合物体系性能，尤其是力学性能之间建立量化关系是高分子物理领域一个可以期待的发展方向。     

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.     

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。     

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.     

Hydrodynamic effects on the extension of stars and dendrimers in external fields

We assess the influence of hydrodynamic interactions on the extension of branched polymers subjected to external forces. We envisage that the macromolecules move under external applied fields, exemplified by mechanical or electrical micromanipulations. We focus our attention on the difference of the results obtained using the Rouse and the Zimm models, both of which represent an extreme situation, so that the realistic behavior is encompassed by the two models. We focus on the mean displacement of a specified monomer, on the shape which the macromolecule attains and on the structural average of the displacements involved. We discuss how these dynamic properties depend on the underlying topology, such as the number of branches and their length for the stars and on the number of generations for the dendrimers. Interestingly, although there exist quantitative differences between the results of the Rouse and of the Zimm model, in both models there appear typical dynamical features which depend on the topology only. This stresses the role of the structure on the dynamics and offers the possibility of tracking it under realistic, experimental conditions.