Interaction of protonated merocyanine dyes with amines in organic solvents

2,6-Diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (1a) and 4-[(1-methyl-4(1H)-pyridinylidene)-ethylidene]-2,5-cyclohexadien-1-one (2a) were protonated in organic solvents (dichloromethane, acetonitrile, and DMSO) to form 1b and 2b, respectively. The appearance of the solvatochromic bands of 1a and 2a was studied UV-vis spectrophotometrically by deprotonation of 1b and 2b in solution in the presence of the following amines: aniline (AN), N-methylaniline (NMAN), N,N-dimethylaniline (NDAN), n-butylamine (BA), diethylamine (DEA), and triethylamine (TEA). Titrations of 1b and 2b with the amines were carried out and the binding constants were determined from the titration curves in each solvent, using a mathematical model adapted from the literature which considers the simultaneous participation of two dye: amine stoichiometries, 1:1 and 1:2. The data obtained showed the following base order for the two compounds in DMSO: BA>DEA>TEA, while aromatic amines did not cause any effect. In dichloromethane, the following base order for 1b was verified: TEA>DEA>BA?NDAN, while for 2b the order was: TEA>DEA>BA, suggesting that 1b is more acidic than 2b. The data in acetonitrile indicated for 1b and 2b the following order for the amines: DEA>TEA>BA. The diversity of the experimental data were explained based on a model that considers the level of interaction of the protonated dyes with the amines to be dependent on three aspects: (a) the basicity of the amine, which varies according to their molecular structure and the solvent in which it is dissolved, (b) the molecular structure of the dye, and (c) the solvent used to study the system.     

Natural Small Molecules in Gastrointestinal Tract and Associated Cancers: Molecular Insights and Targeted Therapies

Gastric cancer is one of the most common cancers of the gastrointestinal tract. Although surgery is the primary treatment, serious maladies that dissipate to other parts of the body may require chemotherapy. As there is no effective procedure to treat stomach cancer, natural small molecules are a current focus of research interest for the development of better therapeutics. Chemotherapy is usually used as a last resort for people with advanced stomach cancer. Anti-colon cancer chemotherapy has become increasingly effective due to drug resistance and sensitivity across a wide spectrum of drugs. Naturally-occurring substances have been widely acknowledged as an important project for discovering innovative medications, and many therapeutic pharmaceuticals are made from natural small molecules. Although the beneficial effects of natural products are as yet unknown, emerging data suggest that several natural small molecules could suppress the progression of stomach cancer. Therefore, the underlying mechanism of natural small molecules for pathways that are directly involved in the pathogenesis of cancerous diseases is reviewed in this article. Chemotherapy and molecularly-targeted drugs can provide hope to colon cancer patients. New discoveries could help in the fight against cancer, and future stomach cancer therapies will probably include molecularly formulated drugs.     

Calibration transfer between electronic nose systems for rapid In situ measurement of pulp and paper industry emissions

Electronic nose systems when deployed in network mesh can effectively provide a low budget and onsite solution for the industrial obnoxious gaseous measurement. For accurate and identical prediction capability by all the electronic nose systems, a reliable calibration transfer model needs to be implemented in order to overcome the inherent sensor array variability. In this work, robust regression (RR) is used for calibration transfer between two electronic nose systems using a Box–Behnken (BB) design. Out of the two electronic nose systems, one was trained using industrial gas samples by four artificial neural network models, for the measurement of obnoxious odours emitted from pulp and paper industries. The emissions constitute mainly of hydrogen sulphide (H₂S), methyl mercaptan (MM), dimethyl sulphide (DMS) and dimethyl disulphide (DMDS) in different proportions. A Box–Behnken design consisting of 27 experiment sets based on synthetic gas combinations of H₂S, MM, DMS and DMDS, were conducted for calibration transfer between two identical electronic nose systems. Identical sensors on both the systems were mapped and the prediction models developed using ANN were then transferred to the second system using BB–RR methodology. The results showed successful transmission of prediction models developed for one system to other system, with the mean absolute error between the actual and predicted concentration of analytes in mg L⁻¹ after calibration transfer (on second system) being 0.076, 0.1801, 0.0329, 0.427 for DMS, DMDS, MM, H₂S respectively.     

Instrumentation for beam-foil spectroscopic studies in the UV-visible region

A facility for carrying out beam-foil spectroscopic studies in the UV and visible region using the 400 kV electrostatic ion accelerator at Tata Institute of Fundamental Research, Bombay is described.     

Chiral discrimination in biomimetic systems: Phenylalanine

Chiral discrimination and recognition is important in peptide biosynthesis, amino acid synthesis and drug designing. Detailed structural information is available about the peptide synthesis in ribosome. However, no detailed study is available about the discrimination in peptide synthesis. We study the conformational energy variation of neutral methoxy phenyl alanine molecule as a function of its different dihedral angle to locate the minimum energy conformation using quantum chemical theory. We compared the intermolecular energy surfaces of phenyl alanine molecule in its neutral and zwitterionic state using quantum chemical theory as a function of distance and mutual orientation. The energy surfaces are studied with rigid geometry by varying the distance and orientation. The potential energy surfaces of L-L and D-L pairs are found to be dissimilar and reflect the underlying chirality of the homochiral pair and racemic nature of the heterochiral pair. The intermolecular energy surface of homochiral pair is more favourable than the corresponding energy surface of heterochiral pair.     

Metal chelates in vinyl polymerization. II. Mechanism of initiation by Fe(DPM)3

The nature of the interaction between the unsaturated monomer and the chelate, Fe(DPM)₃, is studied in detail. The interaction is found to occur only in solution. The stoichiometry of interaction and the equilibrium constant are evaluated. With the help of spectral evidence, attempts are made to point out the specific sites of interaction.     

Mechanisms of the aquation of tris-(substituted) malonatochromate(III) complexes

Summary Investigations on the aquation of tris-(substituted)malonatochromate(III)ion, between 25°–40° in the presence of acid (I=1.0M) show that the mono- and dimethyl substituted complexes aquate by a two term rate law, only one of which is acid dependent. All other complexes aquate by a one term rate law which is first-order with respect to acid concentration; the unsubstituted malonato complex behaves in this way. Aquation of the first two complexes is dissociative, while for others appreciable associative character has been observed.