2006年诺贝尔化学奖成果简介

简要介绍了2006诺贝尔化学奖的成果,获奖者美国科学家罗杰.科恩伯格在该成果的主要贡献在于对真核转录过程的分子研究,对于人们理解转录过程具有深远的意义。目前,基因转录的过程广泛应用在基因研究的实验室中。     

Current approach to design of high-power electron accelerators to match actual requirements of radiation technology in Poland

Existing and continuously emerging new applications of electron beam processing technologies evoke a constant interest in elaboration and design of accelerators’ solutions, matched to definite requirements of most-needed treatment procedures. In close collaboration with the Institute of Nuclear Chemistry and Technology, and the Andrzej So tan Institute for Nuclear Studies, the proposal for two types of technological accelerators has been formulated. In the present paper, basic features of these accelerators—10V, 10–20 kW and 10 MeV, 20–50 kW—are briefly described.     

生物可吸收高分子支架的研究进展

冠脉介入支架治疗技术发展至今已有30余年,从裸金属支架发展到药物洗脱支架乃至今天新兴的生物可吸收支架,不断的推动着冠心病介入治疗向前进步。生物可吸收支架的理念是治疗后无异物留体内。总的来讲,支架开通并保持狭窄或堵塞血管畅通的使命在血管修复后即完成,此后最理想的状态便是支架也随之消失。生物可吸收高分子支架(Bioresorbable Polymeric Scaffold,BRPS)由于使用的材料不仅可以人为地设计和改性,而且是药物的良好载体,因此成为该领域研究的热点。本文从材料、结构设计、加工工艺等方面介绍了BRPS的研究进展,重点讨论了激光切割和3D打印制备BRPS的两种方法,以及BRPS的降解性能及要求,最后对BRPS面临的挑战及发展方向做了展望。     

QED contributions to the atomic structure at strong central fields

Precise determination of the accurate structure of highly charged, very heavy ions is the basis for a detailed understanding of QED at strong fields. The experimental advances in this field will be reviewed with special emphasis given to H-, He- and Li-like very heavy ions. For the heaviest species, U, the ground-state Lamb shift for H-like ions is measured with an accuracy of about 1%, the two-electron QED terms for He-like system are just being touched, and for the Li-like species already two-loop QED terms have been probed with ultimate accuracy. The different approaches to measure the strong field QED contributions will be elucidated and the results compared to theory. Emphasis will be given to results from the heavy ion storage ring ESR.     

Structural Quantum Effects In Hydrogeneous Liquids And Glasses: Part I Review Of Early Methods And Experiments

The atomic or molecular structure of simple liquids may be studied experimentally through radiation scattering experiments. Normally, these experiments involve either beams of E-M radiation or of thermal neutrons, and frequently the samples included both hydrogenated and deuterated liquids. In order to interpret such data it has been assumed (frequently) that the liquid structure was unchanged when the H/D composition was changed. Similar comments apply to hydrogeneous glasses. As the quality of the data and of model calculations improved with passing years, limits to these assumptions were discovered. Part I of this review will cover both the background material and the research which led to an understanding of this field, and also determined the magnitude and shape of the observable effects. Subsequent research from the 90s onwards will be reviewed in Part II.     

非晶固体高分子表面的低温流动特性

高分子低温加工是材料领域重大挑战。相较于本体分子,位于材料表面高分子链的玻璃化转变温度降低、黏度减小、塑性增强,为高分子材料低温加工提供了可能途径。本文总结了近年来对非晶固体高分子表面分子运动的研究成果,从表面分子动力学的角度阐述了高分子表面低温流动性的起源及其影响因素,举例介绍了表面低温流动特性在高分子材料低温粘结、自愈合以及加工成型等方面的应用,并对未来研究及前景进行了展望。希望通过本文加深对高分子表面低温流动行为的认识和理解,促进高分子材料加工和成型新方法和新概念的发展。     

X-ray treatment at 5 MeV and above

There is agreement in the scientific community that X-ray treatment of food at 7.5 MeV can be safe. Possible process improvements for treating at higher than 5 MeV X-rays have been re-visited. Monte Carlo methods have been applied to simulate the X-ray conversion process and to calculate dose distributions in homogeneous phantoms. Experimental data obtained using X-rays produced with a Rhodotron TT200 at 5 and 10 MeV verifies a representative set of data which is calculated with the presented method.

With this qualified Monte Carlo tool, calculations at 7.5 MeV incident electron energy were performed. The analysis gives special attention to higher photon yield, improved product penetration, as well as surface and edge effects.     

Assessing long-range contributions to the charge asymmetry of ion adsorption at the air–water interface

Anions generally associate more favorably with the air–water interface than cations. In addition to solute size and polarizability, the intrinsic structure of the unperturbed interface has been discussed as an important contributor to this bias. Here we assess quantitatively the role that intrinsic charge asymmetry of water''s surface plays in ion adsorption, using computer simulations to compare model solutes of various size and charge. In doing so, we also evaluate the degree to which linear response theory for solvent polarization is a reasonable approach for comparing the thermodynamics of bulk and interfacial ion solvation. Consistent with previous works on bulk ion solvation, we find that the average electrostatic potential at the center of a neutral, sub-nanometer solute at the air–water interface depends sensitively on its radius, and that this potential changes quite nonlinearly as the solute''s charge is introduced. The nonlinear response closely resembles that of the bulk. As a result, the net nonlinearity of ion adsorption is weaker than in bulk, but still substantial, comparable to the apparent magnitude of macroscopically nonlocal contributions from the undisturbed interface. For the simple-point-charge model of water we study, these results argue distinctly against rationalizing ion adsorption in terms of surface potentials inherent to molecular structure of the liquid''s boundary.

Cations and anions have different affinities for the air-water interface. The intrinsic orientation of surface molecules suggests such an asymmetry, but the bias is dominated by solvent response that is spatially local and significantly nonlinear.

Counter to expectations from conventional theories of solvation, there is a large body of both computational and experimental evidence indicating that small ions can adsorb to the air–water interface.^1–9 Implications across the biological, atmospheric and physical sciences have inspired efforts to understand the microscopic driving forces for ions associating with hydrophobic interfaces in general.^10–21 A particular emphasis has been placed on understanding ion specificity, i.e., why some ions exhibit strong interfacial affinity while others do not. Empirical trends indicate that ion size and polarizability are important factors, as could be anticipated from conventional theory. More surprisingly, the sign of a solute''s charge can effect a significant bias, with anions tending to adsorb more favorably than cations.Here we examine the microscopic origin of this charge asymmetry in interfacial ion adsorption. We specifically assess whether the thermodynamic preference can be simply and generally understood in terms of long-range biases that are intrinsic to an aqueous system surrounded by vapor. By “long-range” and “nonlocal” we refer to macroscopically large scales, i.e., collective forces that are felt at arbitrarily long distance. Such a macroscopically long-range bias is expected from the air–water interface due to its average polarization, and by some measures the bias is quite strong. By contrast, “local” contributions comprise the entire influence of a solute''s microscopic environment, including electrostatic forces from molecules that are many solvation shells away – any influence that decays over a sub-macroscopic length scale.The importance of macroscopically nonlocal contributions has been discussed extensively in the context of ion solvation in bulk liquid water, which we review in Section 1 as a backdrop for interfacial solvation. The notion that such contributions strongly influence charge asymmetry of solvation at the air–water interface has informed theoretical approaches and inspired criticism of widely used force fields for molecular simulation.^22,23 A full understanding of their role in interfacial adsorption, however, is lacking.In the course of this study, we will also evaluate the suitability of dielectric continuum theory (DCT) to describe the adsorption process. DCT has provided an essential conceptual framework for rationalizing water''s response to electrostatic perturbations. But a more precise understanding of its applicability is needed, particularly for the construction of more elaborate models (e.g., with heterogeneous polarizability near interfaces^24–26) and for the application of DCT to evermore complex (e.g., nanoconfined^27,28) environments.     

Simulation of photon intensity distributions to facilitate the design of beamlines at accelerator-based IR/THz sources

Simulations with the software Synchrotron Radiation Workshop (SRW) for the ANKA infrared (IR) beamlines IR1 and IR2 have shown, that the far-IR and terahertz (THz) edge radiation can interact with the vacuum chamber walls very close to the electron beam. Unfortunately SRW cannot compute wavefronts at large angles of observation and at a close vicinity to the source. As we need to take into account these perturbations for the further propagation of the radiation through the entire beamline optics to the experimental station, we have started to develop our own code.This code can generate the electric and magnetic field vectors by solving Maxwell equations without approximations and without restrictions to the angles of observation or distance to the source. In particular the latter requires that also the magnetic field vectors have to be calculated, to obtain the corresponding photon intensity distribution for situations where the electron beam intersects the observation plane.Moreover it revealed that it is essential to correct for the Coulomb field prior to calculating the photon intensity in cases where the electron beam intersects the observation plane. Therefore our code is not limited to synchrotrons but can also be used for the development of new kinds of IR/THz radiation facilities.     

The effect of processing method on dry sliding performance of polyimides at high load/high velocity conditions

Polyimides can be processed by sintering or injection moulding, depending on their molecular structure. Raman spectroscopy shows differences in imide I (CO stretch), imide II (CNC axial vibration) and imide III (CNC transverse vibration) bands for both polyimide types, indicating that (i) further imidisation happens during sintering, while being amorphous and (ii) crystallisation happens during melt processing. Thermogravimetric analysis indicates no glass transition or melting temperatures until degradation at 592 °C after sintering, while moulded polyimides show a glass transition temperature at 250 °C. A dehydration reaction at 180 °C will importantly influence the sliding properties of both sintered and injection moulded polyimides. For sintered polyimide, friction and wear in cylinder-on-plate tests is mechanically controlled and mainly determined by normal loads. Overload for sintered polyimides is due to brittleness above 150 N, as also observed in debris morphology. For moulded polyimide, both normal loads and sliding velocity cause a decrease in friction and increase in wear. Overload for moulded polyimide is thermo-mechanically controlled. Sliding stability is controlled by smooth transfer, which is influenced by thermal action, plastic deformation or shear and promoted by elongation at break. Overload conditions are further discussed in relation to deformation of the Hertz line contact, recovery after sliding and the pv-limit (contact pressure × sliding velocity) related to frictional heating.     

Radiation doses at high altitudes and during space flights

There are three main sources of radiation exposure during space flights and at high altitudes—galactic cosmic radiation, solar cosmic radiation and radiation of the earth's radiation belt. Their basic characteristics are presented in the first part of this paper.Man's exposure during space flights is discussed in the second part of the paper. Particular attention is devoted to the quantitative and qualitative characteristics of the radiation exposure on near-earth orbits: both theoretical estimation as well as experimental data are presented. Some remarks on radiation protection rules on-board space vehicles are also given.The problems connected with the radiation protection of air crew and passengers of subsonic and supersonic air transport are discussed in the last part of the paper. General characteristics of on-board radiation fields and their variations with flight altitude, geomagnetic parameters of a flight and the solar activity are presented, both based on theoretical estimates and experimental studies. The questions concerning air crew and passenger radiation protection arising after the publication of ICRP 60 recommendation are also discussed. Activities of different institutions relevant to the topic are mentioned; strategies to manage and check this type of radiation exposure are presented and discussed. Examples of results based on the author's personal experience are given, analyzed and discussed.     

Synthesis of BaZrS3 and BaHfS3 Chalcogenide Perovskite Films Using Single-Phase Molecular Precursors at Moderate Temperatures

Chalcogenide perovskites have garnered interest for applications in semiconductor devices due to their excellent predicted optoelectronic properties and stability. However, high synthesis temperatures have historically made these materials incompatible with the creation of photovoltaic devices. Here, we demonstrate the solution processed synthesis of luminescent BaZrS₃ and BaHfS₃ chalcogenide perovskite films using single-phase molecular precursors at sulfurization temperatures of 575 °C and sulfurization times as short as one hour. These molecular precursor inks were synthesized using known carbon disulfide insertion chemistry to create Group 4 metal dithiocarbamates, and this chemistry was extended to create species, such as barium dithiocarboxylates, that have never been reported before. These findings, with added future research, have the potential to yield fully solution processed thin films of chalcogenide perovskites for various optoelectronic applications.     

On the origins of sudden adhesion loss at a critical relative humidity: examination of bulk and interfacial contributions

The origins for abrupt adhesion loss at a critical relative humidity (RH) for polymeric adhesives bonded to inorganic surfaces have been explored using a model poly(methyl methacrylate) (PMMA) film on glass. The interfacial and bulk water concentrations within the polymer film as a function of D 2O partial pressure were quantified using neutron reflectivity. Adhesion strength of these PMMA/SiO 2 interfaces under the same conditions was quantified using a shaft loaded blister test. A drop in adhesion strength was observed at a critical RH, and at this same RH, a discontinuity in the bulk moisture concentration occurred. The moisture concentration near the interface was higher than that in the bulk PMMA, and at the critical RH, the breadth of the interfacial water concentration distribution as a function of distance from the SiO 2/PMMA interface increased dramatically. We propose a mechanism for loss of adhesion at a critical RH based upon the interplay between bulk swelling induced stress and weakening of the interfacial bond by moisture accumulation at the PMMA/SiO 2 interface.     

Electrochemistry at High Pressures: A Review

High pressure electrochemical studies are potentially dangerous and less immediately implemented than conventional investigations. Technical obstacles related to properties of the working electrode material, preparation of its surface, availability of suitable reference electrodes, and the need for specially designed high pressure equipment and cells may account for the relative lack of experimental data on electrochemistry at high pressures. However, despite the stringent requirements for system and equipment stability, significant developments have been made in recent years and the combination of electrochemical methods with high hydrostatic pressure has provided useful insights into the thermodynamics, kinetics, and other physico‐chemical characteristics of a wide range of redox reactions. In addition to fundamental information, high pressure electrochemistry has also lead to a better understanding of a variety of processes under non‐classical conditions with potential applications in today's industrial environment from extraction and electrosynthesis in supercritical fluids to measurement of the pH at the bottom of the ocean. The purpose of this article is to detail the experimental pressurizing apparatus for electroanalytical measurements at high pressures and to review the relevant literature on the effect of pressure on electrode processes and on the properties of aqueous electrolyte solutions.     

Quantum chemical contributions on the reactivity of solids

The concept of reactivity is reviewed. Various reactivity indices are discussed. Different methods for the simulation of solids are systematically described. Applications for the reactivity of solids can be subdivided into three categories: surfaces, interfaces and bulk. Examples for the categories are presented with a special emphasis on diffusion processes in the bulk.     

Many-electron contributions in the auger spectrum of CO

The CO Auger electron spectrum has been re-investigated by means of ab initio MO LCAO calculations using a combined SCF CI procedure. The CI comprises internal and semi-internal contributions to the final double-hole Slate wave-functions. In particular, the latter contributions are found to be highly significant both with respect to energies and intensities of the Auger transitions. In order to compare with the experimental spectra, the intensities of the transitions have also been calculated using a simple one-center model.     

Effect of supercritical carbon dioxide treatment on structure and mechanical properties of β-nucleated polypropylene processed at different temperatures

Polypropylene (PP) was compounded with β-nucleating agent and injection-molded at 180 °C or 220 °C. The samples were subsequently treated by supercritical carbon dioxide (scCO₂) at different temperatures. Results show that processing temperature and scCO₂ treatment could strongly influence the tensile and impact properties of β-nucleated PP. In particular, the sample processed at 220 °C and treated at 120 °C exhibit much enhanced impact strength (4.8 times that of its untreated counterpart). FTIR, WAXD, SEM and DMA were performed to explore the effects of processing temperature and scCO₂ treatment on structure of the samples. Deformation-induced plastic flow and micro-voids were also evaluated to construct structure-property relations. It was found that the influence of processing temperature on mechanical properties is mainly associated with the β-form content and β-crystalline morphology, while the structural changes in the crystalline lamellar scale may be responsible for the toughening effect of scCO₂ treatment.     

A Critical Review of the Electrocatalysis Reported at C60 Modified Electrodes

Electrodes modified with C₆₀ have been reported to be electrocatalytic for a range of analytical targets. In this review we critically overview the recent explosion of interest in C₆₀ modified electrodes.