基元化学反应态态动力学研究

化学反应动力学是化学领域最基础的学科之一,量子态分辨的基元化学反应动力学在最为基本的原子与分子的层次上对化学反应的机制提供深刻的理解。该领域的科学家们通过精心设计的实验和高精度的理论计算,使得态态反应动力学在过去的半个多世纪中取得了长足的进步,实验和理论的相互结合极大地促进了我们对化学反应本质的认识。本文从实验研究的角度,通过对实验技术的发展和对H₂O光解离、H+H₂、F+H₂、Cl+H₂、OH+H₂、F+CH₄等具体实例的态态动力学研究的简介,概况介绍了过去二十年里态态化学反应动力学研究所取得的进展,希望借此为读者提供对化学反应动力学领域的一个概略认识。     

Experimental aspects of polymer adsorption at solid/solution interfaces

Several recent review articles have been concerned with the topic of polymers at interfaces from the theoretical standpoint. This reflects the extensive effort made in this area over the last 10 – 15 years. However, new experimental techniques for studying polymers at interfaces have also begun to appear in recent years; so have better defined model systems. This article is therefore directed more to a survey of these experimental aspects of the subject. However, a short review of the current state of the theory is given first as background and to define concepts. In the following chapter, details of the modern experimental methods are given. The last chapter comprises an extensive comparative review of results obtained using these techniques with model systems, covering homopolymers, copolymers and polyelectrolytes.     

New research areas inspired by sustainable development

More than 20 years after its birth, green chemistry has definitely entered its golden age. In this account, we highlight some of our progress made over the last 10 years towards the development of green methodologies. We investigated various aspects of green chemistry such as new reagents, catalysts, transformations and solvents and also the utilization of renewable resources. We report herein four mature projects illustrating our efforts in these fields: (1) polyhydrosiloxanes as new reducing agents; (2) glycerol as a new platform for amphiphilic molecules; (3) water, room-temperature ionic liquids and supercritical carbon dioxide as new solvents and (4) C(sp²)–H activation as new C–C bond formation methodology. An overview of each project is given and the potential applications are discussed.     

Surface tension of liquid metals and alloys — Recent developments

Surface tension measurements are a central task in the study of surfaces and interfaces. For liquid metals, they are complicated by the high temperatures and the consequently high reactivity characterising these melts. In particular, oxidation of the liquid surface in combination with evaporation phenomena requires a stringent control of the experimental conditions, and an appropriate theoretical treatment. Recently, much progress has been made on both sides. In addition to improving the conventional sessile drop technique, new containerless methods have been developed for surface tension measurements. This paper reviews the experimental progress made in the last few years, and the theoretical framework required for modelling and understanding the relevant physico-chemical surface phenomena.     

Liquid-liquid extraction in inorganic analysis: current status and prospects

This review surveys the progress in inorganic liquid-liquid extraction in the last 25 years. Achievements are emphasized in the theoretical foundations of the method, and in the synthesis, characterization and application of new extractants. Special attention is paid to the implementation of extraction methods and to the automation of extractive separation. The combination of liquid-liquid extraction as a method of preconcentration with the methods of subsequent determination of trace concentrations of elements is described in detail.     

Capillary electrophoresis - mass spectrometry: survey on developments and applications 2003-2004

The major developments and applications related to CE-MS over the last two years (2003-2004) and most of the reviews and applications found in the ISI Web of Science and publisher data bases are presented in a tabulated way. This article complements our previous review "Capillary electrophoresis - mass spectrometry: 15 years of developments and applications", Electrophoresis, 2003, 24, 3837-3867 for the last two years 2003-2004. All cited articles were analyzed in a way to illustrate (i) in which journals CE-MS-related papers were mostly found over the last decades and (ii) which commercial CE-, MS-instrumentations or CE-MS combinations were mostly used in the European, Asian, and American continent. Additionally, like it was done in our last review, the reader will rapidly find applications classified as forensics, environment, bioanalytics, pharmaceutics, and metabolites.     

Promoters in the hydrogenation of alkynes in mixtures: insights from density functional theory

Hydrogenation of alkyne-alkene mixtures of small sized hydrocarbons has been traditionally performed with Pd-based catalysts modified by a second metal. Over the last few years, this hydrogenation process has become a thriving field to understand selective processes that might be applicable to more complex molecules, for instance those derived from biomass. We summarize here the large body of experimental and open industrial documents to show the properties of different catalytic formulations, we concentrated on the role of the secondary metals employed. We compare these results to theoretical work performed over the last few years and to our new results based on Density Functional Theory. With this insight, we illustrate how secondary compounds behave under typical reaction conditions and how the reaction conditions might affect the stability of the catalyst.     

Recent developments in electrophoretic methods

13. Given the recent extended review by Vesterberg [J. Chromatogr., 480 (1989) 3-19] of electrokinetic methods, this survey has been restricted to the last decade, which has seen tremendous progress in several fields. DNA electrophoresis has experienced strong developments, both in the sequencing strategies (which have been largely automated with the use of fluorescent probes) and in pulsed field analysis of mega-DNA fragments, which has seen such developments as inverse-field, contour-clamped and rotating gel platforms, all allowing for straight band migration in each lane. Chromosome size mapping has now become a reality. Two-dimensional (2D) maps have also shown a dramatic improvement in performance, largely through the development of immobilized pH gradients, giving highly reproducible protein spots in the 2D plane and allowing the exploration of very narrow pH regions. Blotting techniques, combined with 2D mapping, allow sequence analysis and fingerprinting of a single polypeptide spot in a complex sample without resorting to lengthy chromatographic purification steps. Chromatophoresis generates a novel type of 2D mapping, based on hydrophobicity vs. size, rather than on charge vs. size, by direct coupling of a reversed-phase high-performance liquid chromatographic (HPLC) eluate to sodium dodecyl sulphate electrophoresis. The new rising star, capillary zone electrophoresis, offers speed, a large number of theoretical plates, selectivity and small sample requirements in a highly automated equipment.     

Principles and Applications of Miniaturized Near-Infrared (NIR) Spectrometers

This review article focuses on the principles and applications of miniaturized near-infrared (NIR) spectrometers. This technology and its applicability has advanced considerably over the last few years and revolutionized several fields of application. What is particularly remarkable is that the applications have a distinctly diverse nature, ranging from agriculture and the food sector, through to materials science, industry and environmental studies. Unlike a rather uniform design of a mature benchtop FTNIR spectrometer, miniaturized instruments employ diverse technological solutions, which have an impact on their operational characteristics. Continuous progress leads to new instruments appearing on the market. The current focus in analytical NIR spectroscopy is on the evaluation of the devices and associated methods, and to systematic characterization of their performance profiles.     

Square‐Wave Voltammetry: A Review on the Recent Progress

A review on the recent progress of square‐wave voltammetry is presented, covering the period of the last five years. The review addresses the new theoretical development of the technique as well as its application for mechanistic purposes, electrode kinetic measurements, biochemical and analytical applications. Besides, a few novel methodological modifications are proposed that might expand the scope and application of the technique.     

Determination of impurities and counterions of pharmaceuticals by capillary electromigration methods

The review presents a survey of recent applications of high‐performance capillary electromigration methods—capillary zone electrophoresis, nonaqueous capillary electrophoresis, capillary isotachophoresis, micellar electrokinetic chromatography, microemulsion electrokinetic chromatography and capillary electrochromatography—for the determination of impurities of pharmaceuticals, including chiral impurities, for the period 2007–2013. In addition, due to the missing evaluation of the determination of counterions of pharmaceuticals by capillary electromigration methods in the last 20 years, the publications dealing with this topic since 1995 are included in this review. General aspects of both these types of applications of capillary electromigration methods in pharmaceutical analysis are discussed, and detailed experimental conditions used for determination of various chemical impurities and counterions of many particular drugs are described.     

Separation of large DNA molecules by pulsed-field gel electrophoresis A review of the basic phenomenology

Pulsed-field gel electrophoresis is a method of separating large DNA molecules. The distinctive feature of this method is that the direction of the electric field is changed periodically. During the five years since Schwartz and Cantor introduced this technique, there has been dramatic progress in pulsed-field instrumentation and in associated electrophoretic methods. Progress has been driven by practical experience with little guidance from theory. In this review, the basic phenomenology of pulsed-field gel electrophoresis is summarized and some speculations are advanced about possible molecular mechanisms.     

Theory of DNA electrophoresis: a look at some current challenges

Although electrophoresis is one of the basic methods of the modern molecular biology laboratory, new ideas are being suggested at an accelerated rate, in large part because of the pressing demands of the biomedical community. Although we now have, at least for some methods, a fairly good theoretical understanding of the physical mechanisms that lead to the observed peak spacings, widths and shapes, this knowledge is often too qualitative to be used to guide further technical developments and improvements. In this article, we review some selected elements of the current state of our theoretical ignorance, focusing mostly on DNA electrophoresis, and we offer several suggestions for further theoretical investigations.     

New trends in light scattering

In this article we review some of the most important new developments in light scattering that have emerged over the past 10 years. Some of the new methods substantially extend the range of accessible time and length scales. Different cross-correlation methods are now available to suppress multiple scattering over a large concentration range. Novel low coherent light sources on the other hand have stimulated progress in the field of heterodyne detection. Many of these new approaches take advantage of the nowadays available area detectors such as high resolution CCD/CMOS video cameras. This has enabled large scale parallel processing of speckle intensity fluctuations and in consequence has provided a wealth of possibilities in dynamic light scattering such as multi-speckle detection and time resolved correlation analysis.     

Hydration of Lanthanoids(III) and Actinoids(III): An Experimental/Theoretical Saga

The latest experimental and theoretical studies on structural and dynamical properties of lanthanoid(III) and actinoid(III) ions in water have been reviewed. In the last years, most of the issues about lanthanoid(III) hydration have been resolved combining X-ray absorption experiments and different theoretical methods. Since 2008 an effort has been made to treat the entire series thus obtaining coherent sets of experimental and theoretical results that were lately put together in such a way that it was possible to derive new basic properties, such as effective ionic radii, across the series. While for the hydration of lanthanoids(III) many experiments and simulations have been reported, the hydration of actinoids(III) was less investigated. There are some experiments performed by different research groups and few simulations that we discuss in this review. Currently, there are enough results that it is possible to gain some understanding of the hydration behavior of lanthanoids(III) and actinoids(III). The ultimate goal of this review is to provide clues on the analogies and differences between the two series. These aspects are connected to several issues: 1)?technological: the separation of these elements that is necessary for recycling and stocking of nuclear waste, 2)?practical: because experiments on actinoids need particular care, the definition of possible analogies will give the possibility to use the correct lanthanoid when the information on a specific actinoid is needed, 3)?fundamental: related to chemical similarities between the two series.     

Recent Advances in the Synthesis of Ibuprofen and Naproxen

Herein, we review the recent progress in the synthesis of representative nonsteroidal anti-inflammatory drugs (NSAIDs), ibuprofen and naproxen. Although these drugs were discovered over 50 years ago, novel practical and asymmetric approaches are still being developed for their synthesis. In addition, this endeavor has enabled access to more potent and selective derivatives from the key frameworks of ibuprofen and naproxen. The development of a synthetic route to ibuprofen and naproxen over the last 10 years is summarized, including developing methodologies, finding novel synthetic routes, and applying continuous-flow chemistry.     

The pair-production channel in atomic processes

Assisted by the creation of electron–positron pairs, new channels for ionization, excitation, and charge transfer open in atomic collisions when the energy is raised to relativistic values. At extreme energies these pair-production channels usually dominate the “traditional” contributions to cross sections that involve only “positive-energy” electrons. An extensive body of theoretical and experimental work has been performed over the last two decades to investigate charge-changing processes catalyzed by pair production in relativistic heavy ion collisions. We review some of these studies.