The Jahn-Teller effect: a case of incomplete theory for d4 complexes?

We present relativistic calculations at the four-component Dirac-DFT level for the geometries of the series of group 9 monoanionic hexafluorides MF(6)(-), M = Co, Rh, Ir. Highly correlated four-component relativistic CCSD(T) energies were also calculated for the optimized geometries. Spin-orbit coupling effects influence the geometrical preferences for molecular structures: relativistic calculations predict ground states with octahedral symmetries O(h)* for all hexafluorides in this study, while at the nonrelativistic limit, a structural deviation toward D(4h) ground state symmetries is predicted. Our findings suggest that relativistic effects have an important role in molecular structure preferences for the title hexafluorides.     

The Use of Boron‐Doped Diamond Electrodes for the Amperometric Determination of Flavonoids in a Flow Injection System

Abstract

This paper describes the use of boron‐doped diamond electrode for the amperometric detection and quantification of flavonoids in tea samples using a flow injection system. Flavonoids are phenol derivates widely distributed in fruits, nuts, seeds, flowers, vegetable peels, and beverages; they are known to exhibit high antioxidative activities. After optimization, the experiments were performed at a fixed potential of 0.42 V vs Ag/AgCl with a flow rate of 2.5 ml min^?1 in a Britton‐Robinson buffer at pH 5.0. The results revealed that the peak current increases linearly with rutin concentration in the interval 0.1–2.5×10^?4 mol L^?1 and the detection limit was 7.7×10^?6 mol L^?1. The method was used for the determination of rutin in three different green tea (Camellia sinensis) infusions by the direct addition of 150 µL of untreated sample. The repeatability of current responses for injections of 150 µL rutin was evaluated to be 2.1% (n=20) and the analytical frequency was 100 Hz h^?1. The results were compared with the results obtained by high‐performance liquid chromatrography‐diode ray detector.     

Ionic Liquid-salt Aqueous Two-phase System, a Novel System for the Extraction of Abused Drugs

Extraction of drugs from complex sample is a crucial step for determination of drugs. However, most of existing extraction methods use poisonous volatile solvents1. The traditional aqueous two-phase system (ATPS) might be an alternative, but most of phase-forming polymers have high viscidity and form an opaque solution. Recently, ionic liquids (ILs) are gaining attention for their potential use as green solvents and possible replacements for common volatile organic solvents2,3. In this work…     

Transient violation of Le Chatelier��s principle for a network of water molecules

For a process in a small chemical system observed for short periods of time, the probability that it proceeds in the opposite direction to that found in the thermodynamic limit can be significant. We demonstrate this using simulations of a hydrogenbonded network of water molecules whose temperature is changed from 300 K to 310 K. It is shown that for this system, and finite periods (up to tenths of picoseconds), the change during an individual observation period might be in either direction which satisfies the transient fluctuation theorem for a temperature change (Journal of Chemical Physics, 131, 214503 (2009)).     

The In-cell iR Compensation Using a Four-electrode System

It is well known that the iR compensation is very important in electrochemistry, especially in fast, ultra-fast and transient voltammetry for kinetic and mechanistic studies. The modern design of potentiostat is usually of the three-electrode system, in w…     

Microelectrodes for voltammetry��a personal historical perspective

Since the 1950s, the field of electrochemistry has undergone rejuvenation numerous times, attributed to such developments as the three-electrode potentiostat, the integrated circuit operational amplifier, surface modified electrodes, computer-based instrumentation, (ultra)microelectrodes, scanning microelectrode techniques, nanostructured materials, and powerful computational packages (such as COMSOL Multiphysics) that facilitate solution of complex diffusion problems. My own career has spanned nearly all of these renaissances in electrochemistry, but for this discourse, I select the development of microelectrodes as an example of how serendipity can alter the direction of one??s research career. This is not a complete historical account of the development of microelectrodes but rather a personal perspective focusing on my own group??s contributions to this area.     

The Synthesis of a New Class of Potential Inhibitors for Glycoside Hydrolases†

Some attempts toward the synthesis of novel inhibitors of glycosyl transferases are described. More successfully, the synthesis of an activated cyclopropacyclohexene and an amide and an amine of a cyclopropa‐fused pyranose are described. None of these three novel compounds proved to be a significant inhibitor of a retaining α‐glucosidase from barley.     

Chalcogen-Containing π-Complexes of Lanthanides: Crystal-Chemical Analysis and a System of Descriptors for Intermolecular Contacts

A sample comprising 241 -complexes LnC _n H _m Z _k (Z = O, S, Se, Te) was used to analyze the influence of the nature, the oxidation state, and the coordination number of the central atom and the nature of the Z atom on the activity area of the lanthanide (Ln). A new system of criteria based on the concepts of the atomic and molecular Voronoi–Dirichlet polyhedra is proposed for the quantitative analysis of intermolecular contacts. This system was used to analyze the influence of steric factors on the stability of complex groups and the presence or absence of agostic interactions in the structures of 475 complexes LnC _n H _m , LnC _n H _m X _k (X = F, Cl, Br), and LnC _n H _m Z _k .     

The search for a new model structure of β-Factor XIIa

We present the search for a new model of -factor XIIa, a blood coagulation enzyme, with an unknown experimental 3D-structure. We decided to build not one but three different models using different homologous proteins as well as different techniques and different modellers. Additional studies, including extensive molecular dynamics simulations on the solvated state, allowed us to draw several conclusions concerning homology modelling, in general, and -factor XIIa, in particular.     

A semi-empirical method for calculation of true coincidence corrections for the case of a close-in detection in γ-ray spectrometry

In this paper, a semi-empirical method is proposed to determine true coincidence-summing (TCS) correction factors for high resolution γ-ray spectrometry. It needs the knowledge of both full energy peak (FEP) efficiency and total-to-peak (TTP) efficiency curves. The TTP efficiency curve is established from the measurements with a set of coincidence-free point sources. Whereas for a volume source, the coincidence-free FEP efficiency curve is obtained iteratively by using the peaks from almost the coincidence-free nuclides and those from the coincident nuclides in the mixed standard sources. Then the fitting parameters obtained for both TTP and FEP efficiency curves are combined in a freely-available TCS calculation program called TrueCoinc, which yields the TCS correction factors required for any nuclide. As an application, the TCS correction factors were determined for the particular peaks of ²³⁸U, ²²⁶Ra and ²³²Th in the reference materials, measured in the case of a close-in detection geometry using a well-type Ge detector. The present TCS correction method can be applied without difficulty to all Ge detectors for any coincident nuclide.     

The determination of a π-sigma constant for substituents attached to silicon

The proton, ¹³C, and ²⁹Si chemical shifts and the ¹³C¹H coupling constants of a series of compounds of the type (CH₃)₃SiX were measured and correlated with inductive and resonance σ constants. In order to provide a comparison with a homologous series in which π-bonding is absent, shifts and coupling constants were obtained for the t-butyl series, (CH₃)₃CX. Only the coupling constants gave significant correlations with σ_I. A series of σ constants, presumably reflective of the amount of π-bonding, were obtained from the deviations from the J vs. σ_I plot. The magnitudes of these values indicate that oxygen is a better π-donor than nitrogen and chlorine.     

Chemistry-structure-simulation or chemistry-simulation-structure sequences? The case of MIL-34, a new porous aluminophosphate

A new aluminophosphate, MIL-34, is investigated from its as-synthesized structure to its calcined microporous form. Single-crystal X-ray diffraction measurements on the as-synthesized MIL-34 (Al(4)(PO(4))(4)OH x C(4)H(10)N, space group P-1, a = 8.701(3) A, b = 9.210(3) A, c = 12.385(3) A, alpha = 111.11(2) degrees, beta = 101.42(2) degrees, gamma = 102.08(2) degrees, V = 863.8(4) A(3), Z = 2, R = 3.8%) reveal a 3-D open framework where Al atoms are in both tetrahedral and trigonal bipyramidal coordinations. It contains a 2-D pore system defined by eight rings where channels along [100] cross channels running along [010] and [110]. CBuA molecules are trapped at their intersection. (27)Al, (31)P, and (1)H MAS NMR spectroscopies corroborate these structural features. Calcination treatments of a powder sample of the as-synthesized MIL-34 indicate its transformation into the related template-free structure that is stable up to 1000 degrees C. Lattice energy minimizations are then used in order to anticipate the crystal structure of the calcined MIL-34, starting with the knowledge of the as-synthesized structure exclusively. Energy minimizations predict a new regular zeotype structure (AlPO(4), space group P-1, a = 8.706 A, b = 8.749 A, c = 12.768 A, alpha = 111.17 degrees, beta = 97.70 degrees, gamma = 105.14 degrees, V = 846.75 A(3), Z = 2) together with a thermodynamic stability similar to that of existing zeotype AlPOs. Excellent agreement is observed between the diffraction pattern calculated from the predicted calcined MIL-34 and the experimental X-ray powder diffraction pattern of the calcined sample. Finally, the atomic coordinates and cell parameters of the calcined MIL-34 predicted from the simulations are used to perform the Rietveld refinement of the calcined sample powder pattern, further corroborated by (27)Al and (31)P NMR measurements. This unique combination of experiment and simulation approaches is an interesting and innovative strategy in materials sciences, where simulations articulate the prediction of a possible template-free framework from its as-synthesized templated form. This is especially valuable when straightforward characterizations of the solid of interest with conventional techniques are not easy to carry out.     

Evidence for a Proton-Coupled Electron Transfer Mechanism in a Biomimetic System for Monoamine Oxidase B Catalysis

Mechanistic studies with 5-ethyl-3-methyllumiflavinium (Fl⁺) perchlorate, a biomimetic model for flavoenzyme monoamine oxidase B (MAO-B) catalysis, and the tertiary, allyl amine 1-methyl-4-(1-methyl-1 H-pyrrol-2-yl)-1,2,3,6-tetrahydropyridine (MMTP) reveal that proton-coupled electron transfer (PCET) may be an important pathway for MAO catalysis. The first step involves a single-electron transfer (SET) leading to the free radicals Fl^. and MMTP^., the latter produced by deprotonation of the initially formed and highly acidic MMTP^.+. Molecular oxygen (O₂) is found to play a hitherto unrecognized role in the early steps of the oxidation. MMTP and several structurally similar tertiary amines are the only tertiary amines oxidized by MAO, and their structural/electronic properties provide the key to understanding this behavior. A general hypothesis about the role of SET in MAO catalysis, and the recognition that PCET occurs with appropriately substituted substrates is presented.     

Why take chemistry stoically? The case of Posidonius

This paper analyzes views of the Stoic philosopher Posidonius (1st century BC) in the light of modern Chemistry. I propose that Posidonius’ account on “generation and destruction” bears noteworthy similarities to the scientific notions of chemical elements, chemical species, nuclear reactions, and the law of conservation of mass. I find that his views compare favorably also with our understanding of chemical change at solid surfaces. Provided his thought is correctly placed in the cultural context of his day, I argue that Posidonius deserves a previously un-acknowledged consideration in the historical background of modern Chemistry.

The strange case of the “oscillating” catalysts

The field of stereoselective propene polymerization has been dramatically innovated by the discovery of homogeneous metallocene-based catalysts with well-defined and tunable molecular structure. Of all, “oscillating” metallocenes are probably the most ingenious and challenging example of catalyst design. Their catalytic species were built to “flip-flop” between a chiral and an achiral conformation, at a rate intermediate between those of monomer insertion and chain transfer. The result of this molecular switching would be a polypropylene with an isotactic/atactic stereoblock structure, performing as a thermoplastic elastomer. This essay discusses how the real polymerization mechanism differs from what the catalyst inventors had in mind, but also how - through fortunate circumstances -their optimism has been rewarded.     

Are crystal polymorphs predictable? The case of sexithiophene

Using sexithiophene as a benchmark compound, we present a very effective strategy for searching the potential energy minima of a crystalline material, described in terms of rigid molecules with Coulombic and atom-atom interactions. The strategy involves uniform sampling of the many-body energy hypersurface, mechanical identification of all constraints deriving from the crystallographic symmetry, and a "sight-resight" method, originally introduced in wildlife ecology, for assessing the completeness of the search. Thousands of distinct potential energy minima, with a surprising variety of structural arrangements, are identified for sexithiophene. Despite the large number of competing minima, the system presents a small number of deep minima, with very different structures and not particularly congested in energy or density. The two deepest minima correspond to the structures of the two known experimental polymorphs, which are satisfactorily described.     

The Synthesis of a Novel Lignan

Lignans have attracted much interest over the years on account of their widespread ocurrence in nature1, and on account of their broad range of biological activity2. Thus, several lignans are known to exhibit anti-tumor activity3-7, while others function as growth inhibitors and antifungal agents8,9. The importance is the isolation of lignans from animals, including human beings10-12, which has led to the suggestion that such compounds may be an example of a novel class of hormone controlling …     

The Review of the Catalyst System of Poly（ethylene oxide）

聚氧化乙烯（PEO）是环氧乙烷经开环聚合而成的一种多功能水溶性聚合物,性能优异,用途广泛。本文简述了聚氧化乙烯的典型特征和国内外研究进展,综述了聚氧化乙烯制备的各类催化剂体系,描述了催化剂聚合环氧乙烷的聚合机理,重点介绍了几种具有工业应用前景的催化剂体系：烷基金属催化剂体系、烷氧基金属催化剂体系和碱土金属氨化物催化痢体系。并对其技术发展和应用进行了展望。