Pulse EPR Methods for Studying Chemical and Biological Samples Containing Transition Metals

This review discusses the application of pulse EPR to the characterization of disordered systems, with an emphasis on samples containing transition metals. Electron nuclear double‐resonance (ENDOR), electron‐spin‐echo envelope‐modulation (ESEEM), and double electron–electron resonance (DEER) methodologies are outlined. The theory of field modulation is outlined, and its application is illustrated with DEER experiments. The simulation of powder spectra in EPR is discussed, and strategies for optimization are given. The implementation of this armory of techniques is demonstrated on a rich variety of chemical systems: several porphyrin derivatives that are found in proteins and used as model systems, otherwise highly reactive aminyl radicals stabilized with electron‐rich transition metals, and nitroxide–copper–nitroxide clusters. These examples show that multi‐frequency continuous‐wave (CW) and pulse EPR provides detailed information about disordered systems.     

Chiral recognition applications of molecularly imprinted polymers: a critical review

Molecular imprinting technology offers the unique opportunity to tailor chiral stationary phases with predefined chiral recognition properties by employing the enantiomers of interest as binding-site-forming templates. Added advantages, such as ease of preparation, chemical robustness, low-cost production, and the possibility of shaping molecularly imprinted polymers (MIPs) in various self-supporting formats, render them attractive materials for a broad range of chiral recognition applications. In this review a critical overview on recent developments in the field of MIP-based chiral recognition applications is given, focusing on separation techniques and molecular sensing. Inherent limitations associated with the use of enantioselective MIP materials in high-performance separation techniques are outlined, including binding site heterogeneity and slow mass transfer characteristics. The prospects of MIP materials as versatile recognition elements for the design of enantioselective sensor systems are highlighted.     

An open-ended self-consistent field method. A simulation of a molecular orbital technique for small memory computers

The steps in a nonconventional algorithm for self-consistent field calculations are outlined, and calculations on cumulenes are given to demonstrate the convergence properties of the method. The approach is essentially open ended and is likely to be cost effective on computer systems with minimal core.     

Halogen dance reactions--a review

Halogen Dance (HD) reactions are a useful tool for synthetic chemists as they enable access to positions in aromatic and heteroaromatic systems for subsequent functionalization which are often difficult to address by other methods, hence, allowing entry to versatile scaffolds. While the method can be extremely useful, this transformation is often neglected upon designing synthetic sequences. This may be largely attributed to the lack of comprehensive reference works covering the general principles and outlining the versatility and limitations of the technique. The following review tries to present HD reactions in a clear and concise manner in order to convince more chemists of its advantages. It covers the field of HD reactions from their first observation in 1951 until the present. The important contributions leading to the elucidation of the mechanism are briefly outlined followed by a detailed mechanistic section and a discussion of factors which influence HD reactions. Finally, an overview of HD reactions on various carbocyclic and heterocyclic ring systems and its applications in the synthesis of complex compounds is given.     

Laser spectroscopy of molecules: State-of-the-art and possible trends

Summary A review is given on different techniques in laser spectroscopy of atoms and molecules, which allow high spectral resolution and a very high detection sensitivity of small samples. Analytical applications of the techniques are discussed for basic scientific research, as well as for environmental problems and technical processes. Possible trends of laser spectroscopy, in particular with respect to applications in biology and medicine are shortly outlined.     

Techniques for recording reconstituted ion channels

This review describes and discusses techniques useful for monitoring the activity of protein ion channels in vitro. In the first section the biological importance and the classification of ion channels are outlined in order to justify the strong motivation for dealing with this important class of membrane proteins. The expression, reconstitution and integration of recombinant proteins into lipid bilayers are crucial steps to obtain consistent data when working with ion channels. In the second section recording techniques used in research are presented. Since this review focuses on analytical systems bearing reconstituted ion channels the industrial most important patch-clamp techniques of cells are only briefly mentioned. In section three, artificial systems developed in the last decades are described while the emerging technologies using nanostructured supports or microfluidic systems are presented in section four. Finally, the remaining challenges of membrane protein analysis and its potential applications are briefly outlined.     

Scanning electrochemical microscopy: a new way of making electrochemical experiments

A short review is given on scanning electrochemical microscopy (SECM). The historic background of the technique is briefly summarized and the basic principles outlined. The three different directions of its use: chemical microscopic imaging, the measuring of physicochemical constants and coefficients, and use as a micromachining tool are briefly discussed. The general built-up of the SECM apparatus is described. Preparation and use of several different measuring tips are introduced. A few examples are given of the application of SECM measurement in different studies.     

Scanning electrochemical microscopy: a new way of making electrochemical experiments

A short review is given on scanning electrochemical microscopy (SECM). The historic background of the technique is briefly summarized and the basic principles outlined. The three different directions of its use: chemical microscopic imaging, the measuring of physicochemical constants and coefficients, and use as a micromachining tool are briefly discussed. The general built-up of the SECM apparatus is described. Preparation and use of several different measuring tips are introduced. A few examples are given of the application of SECM measurement in different studies.     

From organometallic and polymer chemistry to applied materials science: transition metal catalyzed synthesis of polyolefins and polyolefin-based high-performance materials

A brief history of the development of transition metal-catalyzed olefin polymerization including the present status of polyolefin chemistry is given. The entire evolution of polyolefin chemistry will be outlined, giving ample attention to the development in the catalytic systems. Starting with the first generation PP catalysts (TiCl₃/AlClEt₂), the success story of organometallic chemistry, which resulted in modern supported and unsupported single site systems and finally functional group-tolerant group VIII systems will be summarized. Where applicable, examples of technical application will be given. Additionally, organometallic chemistry responsible for selectivity but also for termination reactions as well as the various “living” systems and the adherent implications for materials science will be discussed. Finally, the impact of related transition metal-catalyzed metathesis chemistry on the area of specialty materials will be outlined.     

Durability of polymers—material property data

Some standardisation of input data is required for material property data bases. A brief review is given of developments of data bases of relevance to polymers and particular consideration given to the requirements for durability data. The measurements to be made in the Design Data Initiative Durability programme are outlined.     

Bioelectrocatalytic Synthesis: Concepts and Applications

Bioelectrocatalytic synthesis is the conversion of electrical energy into value-added products using biocatalysts. These methods merge the specificity and selectivity of biocatalysis and energy-related electrocatalysis to address challenges in the sustainable synthesis of pharmaceuticals, commodity chemicals, fuels, feedstocks and fertilizers. However, the specialized experimental setups and domain knowledge for bioelectrocatalysis pose a significant barrier to adoption. This review introduces key concepts of bioelectrosynthetic systems. We provide a tutorial on the methods of biocatalyst utilization, the setup of bioelectrosynthetic cells, and the analytical methods for assessing bioelectrocatalysts. Key applications of bioelectrosynthesis in ammonia production and small-molecule synthesis are outlined for both enzymatic and microbial systems. This review serves as a necessary introduction and resource for the non-specialist interested in bioelectrosynthetic research.     

Developments in coupled solid-phase extraction-capillary electrophoresis 2009-2011

This article presents an overview of the design and application of coupled solid-phase extraction-capillary electrophoresis (SPE-CE) systems that have been reported in the literature between January 2009 and July 2011. The present paper is an update of two previous review papers covering the years 2000-2009 (Electrophoresis 2008, 29, 108-128; Electrophoresis 2010, 31, 44-54). Both in-line and on-line SPE-CE approaches are treated and outlined. Attention is paid to emerging technological developments, such as the use of carbon nanotubes and magnetic particles for on-line extraction of sample components prior to CE analysis. Selected examples illustrate the applicability of SPE-CE in biomedical, pharmaceutical, environmental and food analysis. A full overview of recent SPE-CE studies is given in table format, providing information about sample type, SPE sorbent, coupling mode, detection mode and limit of detection. Finally, some general conclusions and future perspectives are given.     

Chelating polymers and related supports for separation and preconcentration of trace metals

This review is concerned mainly with the applications of chelating polymeric resins for the separation and concentration of trace metals from oceans, rivers, streams and other natural systems. Commercially available resins, specially prepared polymers and a selection of other sorbents are described and their uses outlined. Special emphasis is placed on the preconcentration of uranium from sea-water.     

The use of thermal analysis in studying catalysis and the chemisorption process

The term catalysis is examined closely and shown in application to a solid phase to be an approximation in that often not only the texture of the catalyst changes but also the composition. However, the action of catalysis still remains perfectly defined in that it opens up a new lower energy path for the reaction considered. The utilisation of thermal analysis tecniques in conjunction with textural studies is shown to be a specially suitable method of investigating catalytic systems. An outline of the necessary thermodynamic and kinetic considerations in catalysis systems is given. Examples of studies on inert supports are given, namely alumina and silica. The occurrence of catalysis in the thermal decomposition of oxysalts is illustrated by reference to oxalates and permanganates. Finally, thermal analysis methods suitable for studying catalysis systems are outlined.     

Photothermal spectrometry for detection in miniaturized systems: relevant features, strategies and recent applications

There is a growing interest in using miniaturized analytical devices because they allow to execute the different steps of an analytical process within very short times and with drastic reduction in the amounts of solvents, reagents and samples. As for capillary electrophoresis, these systems require detectors which are sensitive, versatile and adaptable to very small detection volumes. In this respect, photothermal spectrometry which is complementary to fluorescence seems to be a promising detection method. This review describes the basic principle of photothermal spectrometry along with the related methods based on colinear-beam or crossed-beam configuration of the pump and probe lasers. Two experimental set ups especially designed for microfluidic systems as well as for capillary electrophoresis are described. Their characteristics and key features are discussed and the main applications are outlined.     

Problems in data retrieval systems for analytical spectroscopy

Some of the existing retrieval systems for analytical purposes based on different spectrometric data are described and compared with systems under development. Requirements concerning input data, coding of fragments or complete chemical structures, preprocessing of input data, and evaluation of the retrieved results are discussed, and some examples are given. Some trends for future developments in this field are outlined.     

Quantum dynamics of the CH3 fragment: a curvilinear coordinate system and kinetic energy operators

A curvilinear coordinate system for AB(3) fragments is given. The corresponding exact kinetic energy operator is derived and a series of simpler, progressively more approximate kinetic energy operators are suggested. The operators are tailored for quantum dynamics simulations using the multiconfigurational time-dependent Hartree approach. It is outlined how these fragment coordinates can be utilized to set up coordinate systems for larger systems such as AB(3)C or AB(3)CD. Calculations of the vibrational levels of CH(3) and quantum dynamics studies investigate the accuracy of the different kinetic energy operators suggested.     

Post-Lithium-Ion Battery Era: Recent Advances in Rechargeable Potassium-Ion Batteries

Lithium shortage and the growing demand for electricity storage has encouraged researchers to look for new alternative energy-storage materials. Due to abundant potassium resources, similar redox potential to lithium metal, and low cost, potassium-ion batteries (PIBs), as one of the promising alternatives, have been applied in energy-storage research recently. However, PIBs do not have adequate competition in their electrochemical efficiency because the molar volume of potassium ions is higher than those in lithium and sodium ions. Therefore, for better application and development of PIBs, finding suitable anode and cathode materials is currently the most important task. The latest developments in electrode materials for PIBs have been outlined in depth in this review. It focuses on the structural design and synthetic methods for novel electrode materials, ingenious optimization and tuning strategies, and explains the intrinsic reaction mechanism. The effects of organic electrolytes and aqueous electrolytes on battery systems are compared and clarified. Finally, theoretical and viable insights are given to the challenges posed by the creation and practical application of PIBs in the future.