A facile C-C bond cleavage in the epoxides and its use for the synthesis of oxygenated heterocycles by a ring expansion strategy

The bicyclic epoxy alcohols when treated with DAST gave a new class of rearranged organofluorine compounds, by a ring expansion via C-C bond cleavage of the oxirane ring. The outcome of this reaction with respect to ring size and stereochemical relation between the functionalities is presented here.     

Active-site models for the nickel-iron hydrogenases: effects of ligands on reactivity and catalytic properties

Described are new derivatives of the type [HNiFe(SR)(2)(diphosphine)(CO)(3)](+), which feature a Ni(diphosphine) group linked to a Fe(CO)(3) group by two bridging thiolate ligands. Previous work had described [HNiFe(pdt)(dppe)(CO)(3)](+) ([1H](+)) and its activity as a catalyst for the reduction of protons (J. Am. Chem. Soc. 2010, 132, 14877). Work described in this paper focuses on the effects on properties of NiFe model complexes of the diphosphine attached to nickel as well as the dithiolate bridge, 1,3-propanedithiolate (pdt) vs 1,2-ethanedithiolate (edt). A new synthetic route to these Ni-Fe dithiolates is described, involving reaction of Ni(SR)(2)(diphosphine) with FeI(2)(CO)(4) followed by in situ reduction with cobaltocene. Evidence is presented that this route proceeds via a metastable μ-iodo derivative. Attempted isolation of such species led to the crystallization of NiFe(Me(2)pdt)(dppe)I(2), which features tetrahedral Fe(II) and square planar Ni(II) centers (H(2)Me(2)pdt = 2,2-dimethylpropanedithiol). The new tricarbonyls prepared in this work are NiFe(pdt)(dcpe)(CO)(3) (2, dcpe = 1,2-bis(dicyclohexylphosphino)ethane), NiFe(edt)(dppe)(CO)(3) (3), and NiFe(edt)(dcpe)(CO)(3) (4). Attempted preparation of a phenylthiolate-bridged complex via the FeI(2)(CO)(4) + Ni(SPh)(2)(dppe) route gave the tetrametallic species [(CO)(2)Fe(SPh)(2)Ni(CO)](2)(μ-dppe)(2). Crystallographic analysis of the edt-dcpe compund [2H]BF(4) and the edt-dppe compound [3H]BF(4) verified their close resemblance. Each features pseudo-octahedral Fe and square pyramidal Ni centers. Starting from [3H]BF(4) we prepared the PPh(3) derivative [HNiFe(edt)(dppe)(PPh(3))(CO)(2)]BF(4) ([5H]BF(4)), which was obtained as a ～2:1 mixture of unsymmetrical and symmetrical isomers. Acid-base measurements indicate that changing from Ni(dppe) (dppe = Ph(2)PCH(2)CH(2)PPh(2)) to Ni(dcpe) decreases the acidity of the cationic hydride complexes by 2.5 pK(a)(PhCN) units, from ～11 to ～13.5 (previous work showed that substitution at Fe leads to more dramatic effects). The redox potentials are more strongly affected by the change from dppe to dcpe, for example the [2](0/+) couple occurs at E(1/2) = -820 for [2](0/+) vs -574 mV (vs Fc(+/0)) for [1](0/+). Changes in the dithiolate do not affect the acidity or the reduction potentials of the hydrides. The acid-independent rate of reduction of CH(2)ClCO(2)H by [2H](+) is about 50 s(-1) (25 °C), twice that of [1H](+). The edt-dppe complex [2H](+) proved to be the most active catalyst, with an acid-independent rate of 300 s(-1).     

Electrostatic and Non‐covalent Interactions in Dicationic Imidazolium–Sulfonium Salts with Mixed Anions

A series of thioether‐functionalised imidazolium salts have been prepared and characterized. Subsequent reaction of the thioether‐functionalised imidazolium salts with iodomethane affords imidazolium–sulfonium salts composed of doubly charged cations and two different anions. Imidazolium–sulfonium salts containing a single anion type are obtained either by a solvent extraction method or by anion exchange. The imidazolium–sulfonium salts undergo a methyl‐transfer reaction on exposure to water, giving rise to a new, singly charged imidazolium salt with iodide introduced at the 2‐position of the imidazolium ring. Crystal structures of some of the imidazolium–sulfonium salts were determined by X‐ray crystallography providing the topology of the interactions between the dications and the anions. Electrospray ionization mass spectrometry and quantum‐chemical calculations were used to rationalise the relative strength of these interactions.     

Laser frequency noise immunity in multiplexed displacement sensing

Digitally enhanced interferometry (DI) can be used to distinguish between interferometric signals and simultaneously monitor in-line object displacements with subnanometer sensitivity. In contrast to conventional interferometry-where these signals interfere with each other and degrade performance-we experimentally show that by using DI, each of these signals can be isolated and measured at the same time. We present what we believe to be the first demonstration of DI's signal multiplexing capabilities, showing simultaneous length sensing of three sections of an optical fiber. The cross talk between length measurements was less than 2.6×10(-3) with a displacement noise floor of 200 pm/√Hz, which corresponds to a strain sensitivity of less than 80 picostrain(p?) in each sensor. We also enhance our system's displacement sensitivity at low frequencies by combining information from multiple lengths to suppress errors due to laser frequency noise.     

Detection of Synthetic Antioxidants: What Factors Affect the Efficiency in the Chromatographic Analysis and in the Electrochemical Analysis?

Antioxidants are food additives largely employed to inhibit oxidative reactions in foodstuffs rich in oils and fat lipids, extending the shelf life of foodstuffs and inhibiting alterations in color, flavor, smell, and loss of nutritional value. However, various research has demonstrated that the inadequate use of synthetic antioxidants results in environmental and health problems due to the fact that some of these compounds present toxicity, and their presence in the human body, in high concentrations, is related to the development of some cancer types and other diseases. Therefore, the development of analytical methods for identifying and quantifying synthetic antioxidants in foodstuffs is fundamental to quality control and in ensuring consumer food safety. This review describes the recent chromatographic and electrochemical techniques used in the detection of synthetic phenolic antioxidants in foodstuffs, highlighting the main characteristics, advantages and disadvantages of these methods, and specific typical features, which include extraction methods for sample preparation and materials used in the working electrode construction, considering chromatographic and voltammetric methods, since these specific features influence the efficiency in the analysis.     

On an asymptotic distribution of dependent random variables on a 3-dimensional lattice

We define conditions under which sums of dependent spatial data will be approximately normally distributed. A theorem on the asymptotic distribution of a sum of dependent random variables defined on a 3-dimensional lattice is presented. Examples are also presented.     

A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils

Photoinduced processes in thiouracil derivatives have lately attracted considerable attention due to their suitability for innovative biological and pharmacological applications. Here, sub-20 fs broadband transient absorption spectroscopy in the near-UV are combined with CASPT2/MM decay path calculations to unravel the excited-state decay channels of water solvated 2-thio and 2,4-dithiouracil. These molecules feature linear absorption spectra with overlapping ππ* bands, leading to parallel decay routes which we systematically track for the first time. The results reveal that different processes lead to the triplet states population, both directly from the ππ* absorbing state and via the intermediate nπ* dark state. Moreover, the 2,4-dithiouracil decay pathways is shown to be strongly correlated either to those of 2- or 4-thiouracil, depending on the sulfur atom on which the electronic transition localizes.     

Starch Nanocrystal Fillers in an Acrylic Polymer Matrix

Aqueous suspensions of nanocrystals can be obtained by acid hydrolysis of native waxy maize starch granules. The disruption of waxy maize starch granules by 2.2N HCl hydrolysis has been followed by scanning and transmission electron microscopy and laser granulometry. The mechanical properties of composite materials made of poly(styrene-co-butyl acrylate) filled with starch nanocrystals were characterized by dynamic mechanical analysis. These nanocrystals appeared to be an interesting reinforcing phase in a thermoplastic matrix.     

ChemInform Abstract: Theoretical Study of the Relative Stabilities of the α/β3‐[XW11O39]m‐ Lacunary Polyoxometalates (X: P,Si).

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