Kinetic study of the interaction of three glycine‐containing dipeptides with diaquaethylenediamineplatinum(II) in aqueous medium

The kinetics of the interaction of three glycine‐containing dipeptides, namely, glycine‐L‐leucine (Gly‐Leu), glycine‐L‐isoleucine (Gly‐Ile), and glycine‐valine (Gly‐Val) with [Pt(en)(H₂O)₂](ClO₄)₂ has been studied spectrophotometrically as a function of [substrate complex], [dipeptides] and temperature at a particular pH(4.0), where the substrate complex exists predominantly as the diaqua species and the dipeptides as a zwitterion. The substitution reaction shows two consecutive steps; the first is the ligand‐assisted anation and the second is the chelation step. The activation parameters for both the steps were evaluated using Eyring's equation. The low ΔH₁^≠ and large negative value of ΔS₁^≠ as well as ΔH₂^≠ and ΔS₂^≠ indicate an associative mode of activation for both the aqua ligand substitution processes. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 498–506, 2011     

Synthesis,characterization and reactivity of electrophilic mono- and binuclear nitrosyls of osmium(II)ketoximates

The reaction of [OsX₂(HL)(L)] (1) {X = Cl or Br; HL = PhC(O)C(=NOH)Ph (HL¹) or PhC(O)C(=NOH)Me (HL2)] with n-BuONO yields mononuclear [OsX(NO)(L¹)₂] (2) or binuclear [OsX₂(NO)(L²)]₂2 (3) nitrosyls depending on L. The complexes are also obtained by reacting (1) with NaNO₂ plus HCl. Molecular weight determinations are in agreement with mono- and binuclear formulations. The diamagnetic orange-red nitrosyls exhibit (NO) at ca. 1890 cm^–1 indicating NO⁺ character of the bound nitrogen monoxide. In ¹H-n.m.r. a single sharp L² methyl signal is in line with the centrosymmetric geometry (4) of the binuclear nitrosyls. The complexes display both spin-allowed and -forbidden charge transfer transitions in the 1000–200 nm range. Both (2) and (3) are electroactive and reductions characteristic of mono- and binuclear compositions are observable on the negative side of s.c.e. They react smoothly with acetylacetone (acacH) in the presence of K2CO3 yielding K[Os(acamo)(L1)2] (5) and K[Os(acac)(acamo)(L2)] (6) [acamo = deprotonated MeC(O)C(=NOH)C(O)Me] respectively.     

Ultrafast intermolecular electron transfer dynamics: Perylene in electron-accepting micellar medium

The dynamics of ultrafast photoinduced intermolecular electron transfer (ET) from the excited singlet (S1) state of perylene (Pe) to an electron-accepting cationic surfactant molecule, N-cetylpyridinium chloride (CPC), in aqueous micellar solutions has been investigated using the femtosecond transient absorption spectroscopic technique with temporal resolution of 120 fs. The Pe molecule is localized at or near the micellar surface, where it coexists with the pyridinium moieties (headgroups of the micelle) of the surfactant molecule. Following photoexcitation of Pe, an electron is transferred to the neat and geometrically restricted headgroup of the micelle. Dynamics of the forward ET process as well as the geminate recombination or back ET (BET) process have been followed by monitoring the temporal evolution of the S1 state of Pe and the cation radical of Pe (Pe*+), respectively. The multiexponential forward ET process indicates that the ET dynamics is highly correlated with the spatial distributions of the micellar headgroups around a donor Pe molecule and thus dependent on the donor-acceptor distance. The distance-dependent ET and BET rates have been calculated following the method of Weidemaier and Fayer (J. Chem. Phys. 1995, 102, 3820) to get the best fit parameters for the multiexponetial temporal profiles for the S1 state of Pe as well as Pe*+. Because the acceptor is a constituent of the neat micellar medium, their confinement on the surface of the microheterogeneous medium provides a very large concentration such that, even though the forward transfer rate is 0.06 ps(-1) at the distance of closest approach, the ET process is complete within a 200-ps time domain. If the concepts of distribution of ET distances are utilized, the possible role of material diffusion on the kinetics of forward ET is ruled out. This is an experimental study to show, for the first time, the ultrafast distance-dependent light-induced ET dynamics following both the excited state of the donor and the cation radical formed in an ET process using the transient absorption spectroscopic technique in a self-reactive restrictive environment.     

Extractive Spectrophotometric Determination of Titanium in Silicate Rocks, Soils and Columbite–Tantalite Minerals

2,3-Dihydroxynaphthalene forms a strong chelate with titanium over the pH range 4 to 9. At pH 4–5, titanium is extracted into ethyl acetate along with iron, leaving behind V, Nb, Mo, and a host of elements present in complex matrices of rock samples. In the extract, titanium is easily separated from iron after raising the pH of the medium and re-extracting. The method is free from any interference. The sensitivity of the method is 3.2×10⁴ L·mol^–1cm^–1. The method has been applied to a number of diverse samples including rocks and minerals. The precision of the Ti method is excellent. This method has been compared with tiron, chromotropic acid, diantipyrilmethane (DAM) and other existing spectrophotometric methods used in the analysis of rocks, ores and minerals. The proposed method has definite advantages over most spectrophotometric methods in terms of sensitivity, selectivity, reproducibility and simplicity.     

Basic alumina supported one-pot synthesis of structurally diverse pyridine/quinolinine-fused novel diazepanium, diazocanium, imidazodilinium and tetrahydro-pyrimidiniums

Basic alumina supported solvent-free one-pot synthesis of pyridine-fused polycyclic diazepaniums was achieved under microwave irradiation. The process was successfully extended to the synthesis of pyridine-fused bicyclic imidazolidiniums and tetrahydro-pyrimidiniums and also of tri- and tetracyclic diaza-heterocycle-fused quinoliniums. The dual characteristic of basic alumina, a solid support as well as a base, was successfully employed in the current investigation. The method emerged to be an effective route in terms of product yield, reaction time, and ease of purification and most importantly for environment friendly protocols.     

Optimal batch sizing in a multi-stage production system with rework consideration

In a production system, rework process plays an important role in eliminating waste and effectively controlling the cost of manufacturing. Determining the optimal batch size in a system that allows for rework is, therefore, a worthwhile objective to minimize the inventory cost of work-in-processes and the finished goods. In this paper, models for the optimum batch quantity in a multi-stage system with rework process have been developed for two different operational policies. Policy 1 deals with the rework within the same cycle with no shortage and policy 2 deals with the rework done after N cycles, incurring shortages in each cycle. The major components that play a role in minimizing this cost of the system are manufacturing setups, work-in-processes, storage of finished goods, rework processing, waiting-time, and penalty costs to discourage the generation of defectives. The mathematical structure of this rework processing model falls under a nonlinear convex programming problems for which a closed-form solution has been proposed and results are demonstrated through numerical examples, followed by sensitivity analyses of different important parameters. It is concluded that the total cost in policy 2 tends to be smaller than that in policy 1 at lower proportion of defectives if the in-process carrying cost is low. Policy 2 may be preferred when the work-in-process carrying cost is low and the penalty cost is negligible.     

Two highly unsymmetrical tetradentate (N3O) Schiff base copper(II) complexes: Template synthesis,structural characterization,magnetic and computational studies

Two new copper(II) complexes, [Cu₂(L¹)₂](ClO₄)₂ (1) and [Cu(L²)(ClO₄)] (2), of the highly unsymmetrical tetradentate (N₃O) Schiff base ligands HL¹ and HL² (where HL¹ = N-(2-hydroxyacetophenone)-bis-3-aminopropylamine and HL² = N-(salicyldehydine)-bis-3-aminopropylamine) have been synthesised using a template method. Their single crystal X-ray structures show that in complex 1 two independent copper(II) centers are doubly bridged through phenoxo-O atoms (O1A and O1B) of the two ligands and each copper atom is five-coordinated with a distorted square pyramidal geometry. The asymmetric unit of complex 2 consists of two crystallographically independent N-(salicylidene)-bis(aminopropyl)amine-copper(II) molecules, A and B, with similar square pyramidal geometries. Cryomagnetic susceptibility measurements (5–300 K) on complex 1 reveal a distinct antiferromagnetic interaction with J = ?23.6 cm^?1, which is substantiated by a DFT calculation (J = ?27.6 cm^?1) using the B3LYP functional. Complex 1, immobilized over highly ordered hexagonal mesoporous silica, shows moderate catalytic activity for the epoxidation of cyclohexene and styrene in the presence of TBHP as an oxidant.     

Photoactivated antimicrobial activity of carbon nanotube-porphyrin conjugates

We report the design of antimicrobial nanocomposite films based on conjugates of multiwalled carbon nanotubes (MWNT) and protoporphyrin IX (PPIX) that are highly effective against Staphylococcus aureus (S. aureus) upon irradiation with visible light. S. aureus infections can lead to life-threatening situations, especially when caused by antibiotic-resistant strains. While the light-activated antimicrobial activity of porphyrins against such pathogens is well-known, a facile way to incorporate porphyrins into coatings may lead to their more effective use. To that end, we decided to synthesize and characterize MWNT-PPIX conjugates which combine the biocidal capacity of porphyrins with the mechanical strength of MWNTs. The conjugates could effectively deactivate S. aureus cells in solution upon irradiation with visible light. We also designed large area nanocomposite films comprised of the MWNT-PPIX conjugates that showed potent antimicrobial activity. These MWNT-PPIX conjugates represent a facile strategy for the design of antimicrobial and antifouling coatings.     

Montmorillonite K-10 clay catalyzed solvent-free synthesis of bis-indolylindane-1,3-dione, 2-(1′,3′-dihydro-1H-[2,3′]biindolyl-2′-ylidene)-indan-1,3-dione and bisindolylindeno[1,2-b]quinoxaline under microwave irradiation

An environmentally benign protocol has been described for the synthesis of novel 2-(1′,3′-dihydro-1H-[2,3′]biindolyl-2′-ylidene)-indan-1,3-diones/bis-indolylindane-1,3-diones from ninhydrin and 3-substituted/unsubstituted indoles. It uses montmorillonite K-10 as catalyst in a solvent-free condition under microwave irradiation. The method was also used for the synthesis of novel bisindolylindeno[1,2-b]quinoxaline derivatives.     

Unprecedented copper(I)-catalyzed photochemical reaction of diethyl ether with vicinal diols and ketals

A novel Cu(I)-catalyzed photochemical reaction of diethyl ether with vicinal diols and their ketals is reported. The most remarkable feature is the transformation of 1,2-diols and their ketals to acetals of acetaldehyde under totally neutral condition without using acetaldehyde.