THE CHEMISTRY OF HETEROARYLPHOSPHORUS COMPOUNDS. PART XII.1 THE DIFFERENTIAL-PULSE POLAROGRAPHIC REDUCTION OF HETEROARYL-AND HETEROARYLMETHYLPHOSPHONIUM SALTS

Abstract

The polarographic reduction of series of heteroaryl- and heteroarylmethylphosphonium salts has been studied using a differential pulse polarographic technique, this having a number of advantages over classical dc polarography. For the salts Ar₃P⁺CH₂PhBr^-, the observed order of ease of reduction correlates with the electron-withdrawing ability of the heteroaryl group (i.e. Ar = 2-furyl > 2-thienyl > phenyl > 1-methylpyrrol-2-yl). In contrast, for the salts Ph₃P⁺CH₂ArBr^- (Ar = 2-furyl, 2-thienyl, phenyl, 1-methylpyrrol-2-yl, 3-thienyl and 3-furyl), the ease of reduction correlates best with the order of stability of the forming carbanions as established in earlier studies of the alkaline hydrolysis of these salts.     

Theoretical studies of smectic C liquid crystals confined in a wedge. Stability considerations and Frederiks transitions

Abstract

A general deformation of a smectic C liquid crystal is composed of five different distortions, each of which can be made independently. Here we show that to each of these distortions we can assign a simple vector operator. Use of these five basis operators enables us to write down the elastic free energy density as a quadratic form consisting of nine terms. We also discuss how the nine elastic constants defined by the elastic energy expansion must fulfil certain restrictions in terms of inequalities and a specific tilt angle dependence. Assuming the smectic layers to be incompressible, we examine how certain arrangements of the smectic layers can be stable due to an interplay between the incompressibility condition and the boundary conditions which we impose on the director. One such stable configuration is the wedge, where the smectic layers form parts of concentric cylinders with the common axis coinciding with the centre of the wedge. For such a system we discuss the different director configurations which can be achieved and their stability. We also discuss the possibility of inducing Frederiks transitions for some of these configurations and calculate the corresponding thresholds, thereby demonstrating the design of an experiment which would make it possible to measure those elastic constants which are related to the deformations of the smectic layers, constants which are normally difficult to determine experimentally.     

pH‐controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways

The reactions of dihydroxyfumarate with glyoxylate and formaldehyde exhibit a unique pH‐controlled mechanistic divergence leading to different product suites by two distinct pathways. The divergent reactions proceed via a central intermediate (2,3‐dihydroxy‐oxalosuccinate, 3 , in the reaction with glyoxylate and 2‐hydroxy‐2‐hydroxymethyl‐3‐oxosuccinate, 14 , in the reaction with formaldehyde). At pH 7–8, products ( 7 , 8 , and 15 ) exclusively from a decarboxylation of the intermediate are observed, while at pH 13–14, products ( 9 , 10 , and 16 ) solely derived from a hydroxide‐promoted fragmentation of the intermediate are formed. The decarboxylative and fragmentation pathways are mutually exclusive and do not appear to coexist under the range of pH (7–14) conditions investigated. Herein, we employ a combination of quantitative ¹³C NMR measurements and density functional theory calculations to provide a rationale for this pH‐driven reaction divergence. These rationalizations also hold true for the reactions of dihydroxyfumarate produced in situ by the catalytic cyanide‐mediated dimerization of glyoxylate. In addition, the non‐enzymatic decarboxylation and fragmentation transformations of these central intermediates ( 3 and 14 ) appear to have intriguing parallels to the enzymatic reactions of oxalosuccinate and formation of glyceric acid derivatives in extant metabolism – the high and low pH mimicking the precise control exerted by the enzymes over reaction pathways. Copyright © 2016 John Wiley & Sons, Ltd.     

Formation of collisionless high-beta plasmas by odd-parity rotating magnetic fields

Odd-parity rotating magnetic fields (RMFo) applied to mirror-configuration plasmas have produced average electron energies exceeding 200 eV at line-averaged electron densities of approximately 10(12) cm-3. These plasmas, sustained for over 10(3)tauAlfven, have low Coulomb collisionality, vc* triple bond L/lambdaC approximately 10(-3), where lambdaC is the Coulomb scattering mean free path and L is the plasma's characteristic half length. Divertors allow reduction of the electron-neutral collision frequency to values where the RMFo coupling indicates full penetration of the RMFo to the major axis.     

Substitution pattern elucidation of hydroxypropyl Pinus pinaster (Ait.) bark polyflavonoid derivatives by ESI(−)‐MS/MS

The structure of condensed tannins (CTs) from Pinus pinaster bark extract and their hydroxypropylated derivatives with four degrees of substitution (DS 1, 2, 3 and 4) has been characterized for the first time using negative‐ion mode electrospray ionization tandem mass spectrometry (ESI(?)‐MS/MS). The results showed that P. pinaster bark CTs possess structural homogeneity in terms of monomeric units (C₁₅, catechin). The oligomer sizes were detected to be dimers to heptamers. The derivatives showed typical phenyl‐propyl ether mass fragmentation by substituent elimination (58 amu) and inherent C₁₅ flavonoid fissions. The relative abundance of the product ions revealed a preferential triple, tetra‐/penta‐ and octa‐ hydroxypropylation substitution pattern in the monomer, dimer and trimer derivatives, respectively. A defined order of –OH reactivity towards propylene oxide was established by means of multistage experiments (A‐ring ≥ B‐ring > C‐ring). A high structural heterogeneity of the modified oligomers was detected. Copyright © 2014 John Wiley & Sons, Ltd.     

Peptide prefractionation is essential for proteomic approaches employing multiple‐reaction monitoring of fruit proteomic research

Off‐gel? IEF has become a popular tool in proteomics research to fractionate peptides or proteins. We conducted a detailed investigation on the fruit proteomics of apple, banana, and strawberry fruit employing Off‐gel? electrophoresis (OGE) as a crucial step to improve the proteome coverage and quantitative proteomic workflows including multiple‐reaction monitoring (MRM). We provide technical details concerning the application of Off‐gel?IEF, nano‐LC–MS detection, and MRM optimization and analysis. Our results demonstrated that the application of OGE is an effective method for peptide fractionation and increased significantly the number of proteins identified by at least ten times, with more total peptides detected and collected. Furthermore, we developed a protocol combining OGE and MRM studies to identify and quantitatively investigate monodehydroascorbate reductase, a key enzyme in the redox and antioxidant system of apple fruit during fruit ripening. Using this method, the quantitative changes in this protein during ripening and in response to ethylene treatment was investigated. Our results provide direct and comprehensive evidence demonstrating the benefits of OGE and its application for both shotgun and quantitative proteomics research.     

The structure of propadienone (CH2CCO)

A complete r_o structure has been obtained for propadienone (CH₂CCCO) with the aid of ab initio molecular-orbital calculations. The effect of electron correlation has been investigated using third order Møller-Plesset perturbation theory. The molecule is found to be planar bent (CCC145°) and the calculated structure yields rotational constants which are in good agreemant with experimental values.     

Studies in hydrogen bonding: simulation of the crystalline solids of ice, ammonia, and ammonia hydrate

The crystal structures of ice, ammonia and ammonia hydrate have been simulated with rigid molecules using the interatomic potential function EPEN/2 and the computer program WMIN. Structural parameters were adjusted to give structures with minimum energy. The hydrogen bonding in the simulated structures is compared with that in the experimental structures.