Adsorption kinetics of alkanes on TiO2 nanotubesarray - structure-activity relationship

Presented are thermal desorption spectroscopy (TDS) measurements of iso-/n-butane adsorption on a variety of TiO₂ nanotubes (TiNTs) samples which are characterized by different crystal structures. The results are compared with a prior study on anatase(0 0 1) thin films grown on SrTiO₃(0 0 1). A distinct kinetic structure-activity relationship was present, i.e., the binding energies of the alkanes depend on the polymorph (anatase vs. mixed anatase/rutile) of TiO₂. A direct-fitting procedure of the TDS data has been applied to extract the kinetics parameters. The binding energies in the limit of zero coverage decrease as anatase thin film > amorphous-TiNTs ∼ polycrystalline anatase TiNTs > polycrystalline mixed anatase/rutile TiNTs.     

XPS investigations of ruthenium deposited onto representative inner surfaces of nuclear reactor containment buildings

In the case of a hypothetical severe accident in a nuclear power plant, interactions of gaseous RuO₄ with reactor containment building surfaces (stainless steel and epoxy paint) could possibly lead to a black Ru-containing deposit on these surfaces. Some scenarios include the possibility of formation of highly radiotoxic RuO₄(g) by the interactions of these deposits with the oxidizing medium induced by air radiolysis, in the reactor containment building, and consequently dispersion of this species. Therefore, the accurate determination of the chemical nature of ruthenium in the deposits is of the high importance for safety studies. An experiment was designed to model the interactions of RuO₄(g) with samples of stainless steel and of steel covered with epoxy paint. Then, these deposits have been carefully characterised by scanning electron microscopy (SEM/EDS), electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). The analysis by XPS of Ru deposits formed by interaction of RuO₄(g), revealed that the ruthenium is likely to be in the IV oxidation state, as the shapes of the Ru 3d core levels are very similar with those observed on the RuO₂·xH₂O reference powder sample. The analysis of O 1s peaks indicates a large component attributed to the hydroxyl functional groups. From these results, it was concluded that Ru was present on the surface of the deposits as an oxyhydroxide of Ru(IV). It has also to be pointed out that the presence of “pure” RuO₂, or of a thin layer of RuO₃ or Ru₂O₅, coming from the decomposition of RuO₄ on the surface of samples of stainless steel and epoxy paint, could be ruled out. These findings will be used for further investigations of the possible revolatilisation phenomena induced by ozone.     

High-temperature measurements of the rates of the reactions CH2O + Ar → Products and CH2O + O2 → Products

The two-channel thermal decomposition of formaldehyde [CH₂O], (1a) CH₂O + Ar → HCO + H + Ar, and (1b) CH₂O + Ar → H₂ + CO + Ar, was studied in shock tube experiments in the 2258-2687 K temperature range, at an average total pressure of 1.6 atm. OH radicals, generated on shock heating trioxane-O₂-Ar mixtures, were monitored behind the reflected shock front using narrow-linewidth laser absorption. 1,3,5 trioxane [C₃H₆O₃] was used as the CH₂O precursor in the current experiments. H-atoms formed upon CH₂O and HCO decomposition rapidly react with O₂ to produce OH via H + O₂ → O + OH. The recorded OH time-histories show dominant sensitivity to the formaldehyde decomposition pathways. The second-order reaction rate coefficients were inferred by matching measured and modeled OH profiles behind the reflected shock. Two-parameter fits for k_1a and k_1b, applicable in this temperature range, are:

     

金属羰基化合物[CpFe(CO)_2]_2与金属氧化物表面作用的傅里叶变换漫反射和光声红外光谱研究

用漫反射红外光谱和光声红外光谱法研究了金属羰基化合物［ＣｐＦｅ（ＣＯ）２］２Ｃｐ＝η５—Ｃ５Ｈ５与酸性、中性和碱性Ａｌ２Ｏ３及ＴｉＯ２的相互作用。结果表明，在Ａｌ２Ｏ３表面生成的衍生物种类及浓度与Ａｌ２Ｏ３的酸碱度明显相关。在酸性Ａｌ２Ｏ３表面，主要存在衍生物［ＣｐＦｅ（ＣＯ）２Ｆｅ—Ｈ—Ｆｅ（ＣＯ）２Ｃｐ］＋及少量的ＣｐＦｅ（ＣＯ）２（—Ｏ—）；在中性Ａｌ２Ｏ３表面存在ＣｐＦｅ（ＣＯ）２（—Ｏ—）及较少的［ＣｐＦｅ（ＣＯ）］４；而在碱性Ａｌ２Ｏ３表面主要衍生物为［ＣｐＦｅ（ＣＯ）］４及少量ＣｐＦｅ（ＣＯ）２（—Ｏ—）。衍生物的相对浓度以酸性Ａｌ２Ｏ３表面最高，碱性Ａｌ２Ｏ３表面最低。在ＴｉＯ２表面，［ＣｐＦｅ（ＣＯ）２］２结构基本未变，在空气中比较稳定，没有观察到衍生物的生成。测定了［ＣｐＦｅ（ＣＯ）２］２及其在ＴｉＯ２表面近红外漫反射光谱，指认了大部分观察到的光谱为羰基振动的合频和倍频，并尝试指认了少数光谱为高级（三级）倍频和多元组频（合频）。     

Future pathways for combinatorial chemistry

Summary Investment in combinatorial chemistry (combichem) in the pharmaceutical industry is being driven by the need for increased efficiency. Results from pioneers in the field have demonstrated where mixture or discrete compound synthesis is useful, and what mixture sizes and compound concentrations are appropriate. To make the techniques of combichem of general utility in drug discovery, a broad range of advances is still required. Conversion of organic chemistry to solid phase conditions is key, as are developments in linkers and resins. Library design methodology requires further development. Combinatorial biosynthesis of focused libraries of natural products holds great promise for capitalising on hardwon natural product leads. Miniaturisation of screens is required to reduce the cost of screening combinatorial libraries. Developments in the processes preceding and following synthesis are required to enable the flow of increased numbers of compounds without new bottlenecks developing. The impact of combinatorial chemistry will be greatly enhanced by synergy with ongoing parallel developments in genetic technologies, screening technologies and bioinformatics.     

核科学百年讲座第五讲辐射化学与辐射加工

介绍辐射化学和辐射加工的发展与应用，以及基本原理，侧重介绍辐射加工在高分子辐射交联改性、食品的辐照处理和医疗用品消毒等方面的应用．     

高性能Ag/AgI红外空芯光纤的研究

采用液相化学镀膜法研制了内面镀有银膜和碘化银膜(Ag/AgI)的高性能空芯红外光纤.分析了绿色导航光和红外激光同时低损耗传输的光纤结构参量.长度1 m、内直径0.7 mm的Ag/AgI空芯光纤不仅在红外有低损耗传输特性,而且首次在波长530 nm处获得了7 dB/m的低传输损耗特性.满足可见光作为导航光的同轴传输要求.通过分析和改进实验工艺参量,有效降低Ag和AgI薄膜的表面粗糙度.给出了高性能Ag/AgI空芯光纤的介质镀膜的具体工艺参量.     

Optical and electrical characteristics of Al-doped ZnO thin films prepared by aqueous phase deposition

Transparent conducting Al-doped ZnO (AZO) thin films have been deposited by sol-gel route. Starting from an aqueous solution of zinc acetate by adding aluminum chloride as dopant, a c-axis oriented polycrystalline ZnO thin film 100 nm in thickness could be spin-coated on glass substrates via a two-step annealing process under reducing atmosphere. The effects of thermal annealing and dopant concentration on the structural, electrical and optical properties of AZO thin films were investigated. The post-treated AZO films exhibited a homogenous dense microstructure with grain sizes less than 10 nm as characterized by SEM photographs. The annealing atmosphere has prominent impact on the crystallinity of the films which will in turn influence the electrical conductivity. By varying the doping concentrations, the optical and electrical properties could be further adjusted. An optimal doping concentration of Al/Zn = 2.25 at.% was obtained with minimum resistivity of 9.90 × 10⁻³ Ω-cm whereas the carrier concentration and mobility was 1.25 × 10²⁰ cm⁻³ and 5.04 cm² V⁻¹ s⁻¹, respectively. In this case, the optical transmittance in the visible region is over 90%.     

A statistical dynamics approach to the study of human health data: Resolving population scale diurnal variation in laboratory data

Statistical physics and information theory is applied to the clinical chemistry measurements present in a patient database containing 2.5 million patients' data over a 20-year period. Despite the seemingly naive approach of aggregating all patients over all times (with respect to particular clinical chemistry measurements), both a diurnal signal in the decay of the time-delayed mutual information and the presence of two sub-populations with differing health are detected. This provides a proof in principle that the highly fragmented data in electronic health records has potential for being useful in defining disease and human phenotypes.     

Measuring the implantation depth of silver clusters in graphite

Scanning tunnelling microscopy (STM) and molecular dynamics (MD) simulations have been used to investigate the implantation of Ag₇ ^- clusters into the graphite surface. An experimental measure of the implantation depth of individual clusters is gained via thermal oxidation of the bombarded graphite surfaces. This process results in etching of the cluster-induced defects to form etch pits which grow laterally whilst retaining the depth of the implanted cluster. STM imaging of the etch pits reveals the distribution of implantation depths for deposition energies of 2 keV and 5 keV. Molecular dynamics simulations for clusters of 5 keV energy show that the implantation depth for Ag₇ ^- is largely independent of the impact site on the graphite surface and the cluster orientation. The implantation depth found by MD lies at the upper edge of the experimental depth distribution. Received 30 November 2000