Complete infrared spectroscopic characterization of phenol-borane-trimethylamine dihydrogen-bonded complex in the gas phase

In the paper we report the first observation of the vibrational spectrum in the B-H stretching region in the gas phase for a dihydrogen bonded complex. The appearance of three transitions for the B-H stretching modes of a (di)hydrogen-bonded complex involving borane-trimethylamine indicates the lowering of the symmetry on the BH3 group upon interaction with phenol. Further, the shift in the O-H stretching frequency indicates that phenol is hydrogen bonded to borane-trimethylamine. The two sets of the present data establish, unequivocally, the formation of O-H...H-B dihydrogen-bonded complex between phenol and borane-trimethylamine.     

Characterization of N‐methylated amino acids by GC‐MS after ethyl chloroformate derivatization

Methylation is an essential metabolic process in the biological systems, and it is significant for several biological reactions in living organisms. Methylated compounds are known to be involved in most of the bodily functions, and some of them serve as biomarkers. Theoretically, all α‐amino acids can be methylated, and it is possible to encounter them in most animal/plant samples. But the analytical data, especially the mass spectral data, are available only for a few of the methylated amino acids. Thus, it is essential to generate mass spectral data and to develop mass spectrometry methods for the identification of all possible methylated amino acids for future metabolomic studies. In this study, all N‐methyl and N,N‐dimethyl amino acids were synthesized by the methylation of α‐amino acids and characterized by a GC‐MS method. The methylated amino acids were derivatized with ethyl chloroformate and analyzed by GC‐MS under EI and methane/CI conditions. The EI mass spectra of ethyl chloroformate derivatives of N‐methyl ( 1–18 ) and N,N‐dimethyl amino acids ( 19–35 ) showed abundant [M‐COOC₂H₅]⁺ ions. The fragment ions due to loss of C₂H₄, CO₂, (CO₂ + C₂H₄) from [M‐COOC₂H₅]⁺ were of structure indicative for 1–18 . The EI spectra of 19–35 showed less number of fragment ions when compared with those of 1–18 . The side chain group (R) caused specific fragment ions characteristic to its structure. The methane/CI spectra of the studied compounds showed [M + H]⁺ ions to substantiate their molecular weights. The detected EI fragment ions were characteristic of the structure that made easy identification of the studied compounds, including isomeric/isobaric compounds. Fragmentation patterns of the studied compounds ( 1–35 ) were confirmed by high‐resolution mass spectra data and further substantiated by the data obtained from ¹³C₂‐labeled glycines and N‐ethoxycarbonyl methoxy esters. The method was applied to human plasma samples for the identification of amino acids and methylated amino acids. Copyright © 2016 John Wiley & Sons, Ltd.     

Modify SRS-induced crosstalk with variety of fiber in SCM–WDM transmission links

In this paper, the SRS-induced crosstalk has been evaluated in a SCM–WDM communication links at different modulation frequencies and transmission lengths for variety of fiber. Results show that SRS-induced crosstalk dominates at low frequency. As the dispersion and effective area of fiber (A_eff) decreases, initially the crosstalk remains high and then it decreases with increase in modulation frequency. The present work shows that out of five different types of fiber, standard single mode fiber (SMF) has minimum crosstalk (−78 to −38) dB, (−55 to −33) dB and (−46 to −34) dB at modulation frequencies, transmission lengths and optical powers. Dispersion compensation fiber (DCF) has maximum crosstalk (−60 to −12) dB, (−37 to −12) dB and (−27 to −12) dB at modulation frequencies and transmission lengths.     

An efficient synthesis of novel 2,4-disubstituted tetrahydroquinolines and quinolines

A series of novel tetrahydroquinolines have been synthesized via the acid-catalyzed reaction of an azaflavan-4-ol with a variety of reactive nucleophiles. The tetrahydroquinolines were found to undergo oxidation in the presence of iodine as catalyst to generate the corresponding novel 2,4-disubstituted quinolines.     

Characterization of amino acid‐derived betaines by electrospray ionization tandem mass spectrometry

Betaines belong to the naturally occurring osmoprotectants or compatible solutes present in a variety of plants, animals and microorganisms. In recent years, metabolomic techniques have been emerging as a fundamental tool for biologists because the constellation of these molecules and their relative proportions provide with information about the actual biochemical condition of a biological system. Therefore, identification and characterization of biologically important betaines are crucial, especially for metabolomic studies. Most of the natural betaines are derived from amino acids and related homologues. Although, theoretically, all the amino acids can be converted to corresponding betaines by simple methylation of the amine group, only a few of the amino acid‐derived betaines were fully characterized in the literature. Here, we report a combined electrospray ionization tandem and high‐resolution mass spectrometry study of all the betaines derived from amino acids, including the isomeric betaines. The decomposition pathway of protonated, sodiated and potassiated molecule ions that enable unambiguous characterization of the betaines including the isomeric betaines and overlapping ionic species of different betaines is distinctive. Copyright © 2012 John Wiley & Sons, Ltd.     

On the equivalence of the Einstein–Hilbert and the Einstein–Palatini formulations of general relativity for an arbitrary connection

In the framework of the Einstein–Palatini formalism, even though the projective transformation connecting the arbitrary connection with the Levi-Civita connection has been floating in the literature for a long time and perhaps the result was implicitly known in the affine gravity community, yet as far as we know Julia and Silva were the first to realise its gauge character. We rederive this result by using the Rosenfeld–Dirac–Bergmann approach to constrained Hamiltonian systems and do a comprehensive self contained analysis establishing the equivalence of the Einstein–Palatini and the metric formulations without having to impose the gauge choice that the connection is symmetric. We also make contact with the the Einstein–Cartan theory when the matter Lagrangian has fermions.     

An Improved Process for the Enantioselective Synthesis of HCV NS5A Inhibitor Elbasvir (MK-8742) Chiral Amine Intermediate

Russian Journal of General Chemistry - Large-scale enantioselective synthesis of the chiral amine unit of HCV NS5A inhibitor Elbasvir has been accomplished in six steps, with 55% overall yield. The...     

Isothermal fluid sphere: Uniqueness and conformal mapping

We prove the theorem: A necessary and sufficient condition for a spacetime to represent an isothermal fluid sphere (linear equation of state with density falling off as inverse square of the curvature radius) without boundary is that it is conformal to a spacetime of zero gravitational mass (‘minimally’ curved).     

Synthesis of dipyrrolo[2,3-a:1′,2′,3′-fg]acridin-12(1H)-ones

Acylation reactions of 4,6-dimethoxyindoles with glyoxyloyl chlorides were achieved by the use of graphite powder in 1,2-dichloroethane at reflux. The products were monoketones as a result of decarbonylation, rather than the expected 1,2-diketones. Treatment of these monoketones with base led to their cyclisation and elimination of methanol to afford the novel dipyrrolo[2.3-a:1′,2′,3′-fg]acridin-12(1H)-ones.