Study of the reaction of chalcone analogs of dehydroacetic acid and o-aminothiophenol: synthesis and structure of 1,5-benzothiazepines and 1,4-benzothiazines

Treatment of α,β-unsaturated carbonyl compounds, obtained by the reaction of DHA and aromatic (or heteroaromatic) aldehydes, with o-aminothiophenol results in the formation of 1,5-benzothiazepines and/or 1,4-benzothiazines depending upon the reaction conditions and structure of the aldehydes. The products were characterized by the combined use of multinuclear 1D and 2D NMR and GIAO/DFT calculations of ¹H, ¹³C and ¹⁵N chemical shifts. The tautomerism of these compounds in solution was determined, they have an exocyclic CC double bond.     

Trifluoroacetic acid: a more effective and efficient reagent for the synthesis of 3-arylmethylene-3,4-dihydro-1H-quinolin-2-ones and 3-arylmethyl-2-amino-quinolines from Baylis-Hillman derivatives via Claisen rearrangement

Trifluoroacetic acid has been discovered to be a highly effective and efficient reagent for the tandem Claisen rearrangement and cyclization reaction to yield 3-arylmethylene-3,4-dihydro-1H-quinolin-2-ones from compounds obtained from the S_N2 reaction between anilines and acetyl derivatives of Baylis-Hillman adducts of acrylates in the presence of DABCO. In contrast, similar compounds obtained from the acetyl derivatives of Baylis-Hillman adduct of acrylonitrile on treatment with trifluoroacetic acid directly furnish 3-arylmethyl-2-amino-quinoline via tandem Claisen rearrangement, cyclization and isomerization.     

Substituted Diorganotin(IV) O,O’-Alkylene Dithiophosphates: Synthesis and Spectral Aspects

Six new substituted diphenyltin(IV) O,O′-alkylene dithiophosphates, (C₆H₅)₂Sn(X)S(S) POGO [G = —CH₂C(CH₃)₂CH₂—, X = Cl (1), SCN (3), ClO₄ (5); G = —CH₂C (C₄H₉)(C₂H₅)CH₂—, X = Cl (2), SCN (4), ClO₄ (6)], were synthesized by the reaction of the corresponding ammonium salts of the O,O’-alkylene dithiophosphates with an appropriate organotin(IV) chloride. The compounds were characterized on the basis of elemental and spectral analyses (ESI mass spectrometry, IR, ¹H, ¹³C, ³¹P, and ¹¹⁹Sn NMR). The presence of a four-coordinated Sn atom and monodentate O,O’-alkylene dithiophosphate moiety in compounds 1–4 as well as bidentate O,O’-alkylene dithiophosphate unit in compounds 5,6 is established.     

Comparative Antioxidant Study of Stem and Stem Induced Callus of Phyllanthus fraternus Webster—An Important Antiviral and Hepatoprotective Plant

Phyllanthus fraternus is widely used in the cure of various liver diseases and possess antiviral properties especially against hepatitis virus. In the present study, evaluation of the antioxidant activity of stem and calli induced from stem has been done by different assays. Extraction was done by standard method in water and ethanol. Total antioxidant capacity was measured by 1, 1-diphenyl-2-picrylhydrazyl free radical scavenging method. Lipid peroxidation was measured in terms of thiobarbituric acid-reactive substances (TBARS) by using egg yolk homogenates as lipid-rich media, and superoxide radical scavenging activity was measured using riboflavin–light–nitro blue tetrazolium assay. Reducing power was determined on the basis of Fe³⁺–Fe²⁺ transformation in the presence of the extract. In addition to the antioxidant activity, polyphenolic compounds like total phenolics and flavonoids were also measured by spectroscopic method. Results showed that the ethanolic extract of stem is more potent in antioxidant activity than its aqueous extract and ethanolic extract of calli. A significant correlation between antioxidant capacity and polyphenolic content and reducing potential was observed, indicating that phenolic compounds and reducers present in extract are major contributors to the antioxidant potential. Thus, this plant extract could be used as a potent natural antioxidant.     

Novel Tripod Amphiphiles for Membrane Protein Analysis

Integral membrane proteins play central roles in controlling the flow of information and molecules across membranes. Our understanding of membrane protein structures and functions, however, is seriously limited, mainly due to difficulties in handling and analysing these proteins in aqueous solution. The use of a detergent or other amphipathic agents is required to overcome the intrinsic incompatibility between the large lipophilic surfaces displayed by the membrane proteins in their native forms and the polar solvent molecules. Here, we introduce new tripod amphiphiles displaying favourable behaviours toward several membrane protein systems, leading to an enhanced protein solubilisation and stabilisation compared to both conventional detergents and previously described tripod amphiphiles.     

Inversion of the Kirkwood–Buff theory of solutions: application to binary systems

Kirkwood–Buff (K–B) integrals play an important role in characterizing the properties and interactions of various liquid mixtures. However, there exists no method to calculate directly the K–B integrals from the easily available experimental data of ultrasonic velocity and density. An attempt has been made to evaluate the same using these initial parameters. A statistical mechanical theory advanced by Arakawa et al. has been used here, in combination with a semi-empirical formula to compute K–B parameters in the whole concentration range for six binary systems at atmospheric pressure and at 298.15 K.     

Principal eigenvector field segmentation for reproducible diffusion tensor tractography of white matter structures

The study was aimed to test the feasibility of utilizing an algorithmically determinable stable fiber mass (SFM) map obtained by an unsupervised principal eigenvector field segmentation (PEVFS) for automatic delineation of 18 white matter (WM) tracts: (1) corpus callosum (CC), (2) tapetum (TP), (3) inferior longitudinal fasciculus (ILF), (4) uncinate fasciculus (UNC), (5) inferior fronto-occipital fasciculus (IFO), (6) optic pathways (OP), (7) superior longitudinal fasciculus (SLF), (8) arcuate fasciculus (AF), (9) fornix (FX), (10) cingulum (CG), (11) anterior thalamic radiation (ATR), (12) superior thalamic radiation (STR), (13) posterior thalamic radiation (PTR), (14) corticospinal/corticopontine tract (CST/CPT), (15) medial lemniscus (ML), (16) superior cerebellar peduncle (SCP), (17) middle cerebellar peduncle (MCP) and (18) inferior cerebellar peduncle (ICP). Diffusion tensor imaging (DTI)-derived fractional anisotropy (FA) and the principal eigenvector field have been used to create the SFM consisting of a collection of linear voxel structures which are grouped together by color-coding them into seven natural classes to provide PEVFS signature segments which greatly facilitate the selection of regions of interest (ROIs) for fiber tractography using just a single mouse click, as compared with a manual drawing of ROIs in the classical approach. All the 18 fiber bundles have been successfully reconstructed, in all the subjects, using the single ROIs provided by the SFM approach, with their reproducibility characterized by the fact that the ROI selection is user independent. The essentially automatic PEVFS method is robust, efficient and compares favorably with the classical ROI methods for diffusion tensor tractography (DTT).     

Thiol–Ene “Click” Reaction Triggered by Neutral Ionic Liquid: The “Ambiphilic” Character of [hmim]Br in the Regioselective Nucleophilic Hydrothiolation

Thiol–ene “click” chemistry has emerged as a powerful strategy to construct carbon–heteroatom (C? S) bonds, which generally results in the formation of two regioisomers. To this end, the neutral ionic liquid [hmim]Br has been explored as a solvent cum catalyst for the synthesis of linear thioethers from activated and inactivated styrene derivatives or secondary benzyl alcohols and thiols without the requirement of using a metal complex, base, or free radical initiator. Furthermore, detailed mechanistic investigations using ¹H NMR spectroscopy and quadrupole time‐of‐flight electrospray ionization mass spectrometry (Q‐TOF ESI‐MS) revealed that the “ambiphilic” character of the ionic liquid promotes the nucleophilic addition of thiol to styrene through an anti‐Markovnikov pathway. The catalyst recyclability and the extension of the methodology for thiol–yne click chemistry are additional benefits. A competitive study among thiophenol, styrene, and phenyl acetylene revealed that the rate of reaction is in the order of thiol–yne>thiol–ene>dimerization of thiol in [hmim]Br.