Mixed-ligand and binuclear complexes of oxovanadium(IV)

Summary Mixed ligand complexes of the type [VOLA]ClO₄ where L=5-bromosalicylaldehyde (L) or 5-nitrosalicylaldehyde (L) and A=2, 2-dipyridyl (A) or 1, 10-phenanthroline (A) have been prepared. Treatment of the mononuclear complexes, [VOLA]ClO₄, withp-phenylenediamine (ppd) orm-phenylenediamine (mpd) yielded homobinuclear [VOLA-NC₆H₄N-LAVO](ClO₄)₂, complexes, which were characterised by elemental analyses, spectra, magnetic susceptibility and molar conductance measurements.     

Synthesis of crescent shaped heterocycle-fused aromatics via Garratt-Braverman cyclization and their DNA-binding studies

Three crescent shaped heterocycle-fused phenanthrene based systems 1–3 have been synthesized starting from benzene (or substituted benzene) 1,2-bis-propargyl alcohols. Bis-alkylation with propargylic bromides provided the key intermediate, the bis-propargyl bis-ethers. In spite of the possibility of many competing reactions, the latter underwent facile double Garratt-Braverman cyclization to provide compounds 1–3 in near quantitative yield, in a striking reaction involving the formation of four C–C bonds in a single step. Compounds 1–3 showed binding interaction with DNA, predominantly, via groove binding along with partial intercalation (combilexins). Molecular docking study supported the proposed binding modes.     

Ternary complexes of substituted catechols and catecholamines

Stability constants of the ternary complexes [CuAL] whereA = 5-Nitro-1,10-phenanthroline, bis(2-pyridyl) ketone (DPK) orbis(2-pyridyl)amine (DPA) andL is the dianion of catechol, tiron, protocatechic acid, pyrogallol, 1,8-dihydroxynaphthalene, catecholaldehyde, 2,3-dihydroxynaphthalene, dopamine or adrenaline have been determined by potentiometric titration in dioxane water (1:1 v/v) medium using a SCOGS computer programme. The observed trend of stability is explained on the basis of the nature of substitution over the ligands, chelate ring size and also the composition of mixed solvent in case of DPK. Structural changes in DPK have also been discussed as a function of pH, composition of medium and coordinating mode of the secondary ligand in the ternary complexes.     

Functionalization of polyesters with maleic anhydride by reactive extrusion

Maleic anhydride (MAn) was grafted onto aliphatic and aromatic/aliphatic copolyesters by reactive extrusion in the presence of a free radical initiator using a twin‐screw extruder. The grafting reaction was confirmed by spectroscopic analyses. The presence of succinic anhydride groups was shown by FT‐IR spectroscopy, and NMR spectra indicate that the grafts consist of single succinic anhydride units. The 2D ¹H‐NMR spectra (COSY) indicate that grafting reactions take place at aliphatic dicarboxylic acid units of copolyesters. The graft content was determined by a nonaqueous titration method. The effects of concentration of initiator and monomer and reaction temperature on the graft content and intrinsic viscosity were studied. The low percentage grafting in poly(lactic acid) was observed due to the presence of limited free radical sites in the polymer backbone. Temperature and monomer and initiator concentrations affect the graft content, and the desired graft content with minimal degradation can be obtained by controlling these factors. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1693–1702, 1999     

Recent advances in Garratt-Braverman cyclization: Mechanistic and synthetic explorations

Garratt-Braverman cyclization has emerged as one of the simplest synthetic tool to construct two consecutive CC bonds leading to the formation of various important structural scaffolds having significance in the field of therapeutics and material science. The strategic design of suitable precursor for this cycloaromatization reaction involves the deep understanding of reaction pathways involving diradicals and ions. On the other hand, the reaction offers an unprecedented mechanistic paradox for the chemists to solve. This report aims at outlining the recent mechanistic and synthetic developments with special emphasis on the research outcomes from our laboratory.     

Use of Solar Power for Heat Generation for Household Application

The requirement of getting continuous electricity at low cost is essential but challenging. Especially in the undeveloped countries there is no sufficient electricity for the people to do their daily regular works. In order to overcome this problem different renewable energy sources are sought and being explored. One of the approaches is to have a cooking system that is energized from the solar power, not directly using a solar cooker but by storing the energy in the form of heat that can be utilized as per requirement. This paper reports the design and fabrication of an alternative system to generate heat using solar radiation. This chulha is helpful in effective heating with the help of solar radiations at lower costs. A cooking technology is presented consisting of a solar panel directly connected to an electric heater inside of a well-insulated chamber. An insulated container with fixed amount of oil is heated up. The heat is found to be retained in the chamber even after sun set which is sufficient for heating water for making tea. The possible causes of temperature drop and possible remedy has been pointed out and discussed in this paper.     

Kinetics and mechanism for the aquation of bismalonatoethylenediaminecobaltate(III) ion in acid perchlorate media

Summary The title complex aquates in acid media, first to [Co(mal)-(H₂O)₂(en)]⁺ (1) (Step 1) and subsequently to [Co(H₂O)₄(en)]³⁺ (2) (Step 2). Complex species (1) has been separated and characterised in solution. While Step 1 involves only a second-order acid catalysed path, Step 2 involves both a first-order acid independent path and a second-order acid catalysed path. The rate constants and activation parameters evaluated for these reaction paths have been compared with those for similar carboxylato-cobalt(III) complexes. This, together with an observed isokinetic relation, indicates that the rate-determining step involves opening of the unprotonated (in the spontaneous acid independent path) or the protonated (for the acid catalysed path) chelate ring of the malonate ligand and insignificant solvation of the central metal ion.     

Effect of finite energy of intravalley acoustic phonons on the temperature of non-equilibrium electrons in a quantum surface

The effect of finite energy of intravalley acoustic phonons on the electric field dependence of the temperature of the non-equilibrium carriers in a quantum surface has been studied here. The calculations have been made, for a rather pure material, at low lattice temperature. Numerical results are obtained for GaAs and Si. The results are interesting being significantly different from what one obtains by neglecting the phonon energy.     

On a Theorem of Dubins and Freedman

Under a notion of splitting the existence of a unique invariant probability, and a geometric rate of convergence to it in an appropriate metric, are established for Markov processes on a general state space S generated by iterations of i.i.d. maps on S. As corollaries we derive extensions of earlier results of Dubins and Freedman;⁽¹⁷⁾ Yahav;⁽³⁰⁾ and Bhattacharya and Lee⁽⁶⁾ for monotone maps. The general theorem applies in other contexts as well. It is also shown that the Dubins–Freedman result on the necessity of splitting in the case of increasing maps does not hold for decreasing maps, although the sufficiency part holds for both. In addition, the asymptotic stationarity of the process generated by i.i.d. nondecreasing maps is established without the requirement of continuity. Finally, the theory is applied to the random iteration of two (nonmonotone) quadratic maps each with two repelling fixed points and an attractive period-two orbit.