Role of hydrogen bonding on the spectroscopic properties of thiazolidinedione derivatives in homogeneous solvents

In this work, three newly synthesized derivatives of thiazolidinediones, with potential for application as drugs in pharmaceutical industry and free radical scavenging activity, have been taken up to investigate their behaviour in different homogeneous solvents. The purpose of this work is to study the solvation characteristics in ground and excited states of the derivatives by monitoring the absorbance and fluorescence band maxima. The steady state and time resolved fluorescence studies in protic and aprotic solvents have been rationalized on the basis of solute–solvent interaction and substituent effect on these photophysical processes have been analyzed. Substituents at different positions of the aryl moiety affect the hydrogen bond formation ability of the probes.     

Single, binary, and multicomponent sorption of iron and manganese on lignite

Acid mine drainage (AMD) has long been a significant environmental problem resulting from the microbial oxidation of iron pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. The main objective of this study was to remove metal ions [Fe(II), Fe(III), Mn(II), Zn(II)] from AMD using lignite, a low-cost adsorbent. The lignite sorbent was utilized for the sorption of ferrous, ferric, manganese, zinc, and calcium ions in aqueous solutions. Studies were performed at different pH to find optimum pH. Equilibrium isotherms were determined to assess the maximum adsorption capacity of lignite for different metal ions. Sorption capacities were compared in single, binary, ternary, and multicomponent systems. The sorption data are correlated with Freundlich and Langmuir isotherms in each system. Both Freundlich and Langmuir isotherms fit the data reasonably well in terms of regression coefficients. Sorption studies were also performed at different temperatures to obtain the thermodynamic parameters of the process. The maximum lignite adsorption capacities at 25 degrees C were 34.22, 25.84, and 11.90 mg/g for Fe(II), Mn(II), and Fe(III), respectively. Adsorption of Fe(2+) (24.70 mg/g at 10 degrees C and 46.46 mg/g at 40 degrees C) increased with increased temperature, while Mn(2+) adsorption (28.11 mg/g at 10 degrees C and 7.70 mg/g at 40 degrees C) decreased with increased temperature.     

Indium(I) iodide promoted cleavage of diphenyl diselenide and disulfide and subsequent palladium(0)-catalyzed condensation with vinylic bromides. A simple one-pot synthesis of vinylic selenides and sulfides

[reaction: see text] Diphenyl diselenide (and disulfide) undergo facile reaction with indium(I) iodide and the corresponding intermediate complex condenses in situ with a variety of substituted vinyl bromides in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4] in THF at room temperature to produce vinylic selenides and sulfides in good yields. The conversion of (E)-vinyl bromides is remarkably stereoselective giving (E)-vinyl selenides (and sulpfides) whereas the stereoselectivity in reaction of (Z)-vinyl bromides is not very good.     

Total syntheses of 28,29-diepi-arenamide A, 29-epi-arenamide A, and 28-epi-arenamide A

This communication describes the synthesis of stereochemical analogs of arenamide A, a 19-membered cytotoxic depsipeptide isolated from the fermentation broth of a marine bacterial strain Salinispora arenicola. The key steps are diastereoselective aldol reaction, Mitsunobu reaction, and HATU mediated macrolactamization.     

Spectrophotometric Investigation of the Charge–Transfer Interaction of 2,3-Dicyano-1,4-naphthoquinone with N-Ethylaniline in Chlorinated Solvents

The charge?Ctransfer interaction between 2,3-dicyano-1,4-naphthoquinone (DCNQ) and N-ethylaniline was studied in the halocarbons chloroform and dichloromethane and a 1:1 (v/v) mixture of these two solvents. A rapid interaction between DCNQ and N-ethylaniline results in the formation of the monosubstituted final product. The reaction is found to proceed through an initial charge?Ctransfer (CT) complex intermediate. The equilibrium constants of the ??-complex, in all the three media, were evaluated along with first-order and second-order rate constants for the appearance and disappearance of the ??- and ??-complexes. The final product was isolated and characterized by IR, NMR and elemental analysis. Based on the kinetic results a mechanism was proposed for the reaction.     

Ionic liquid/PPh3 promoted cleavage of diphenyl disulfide and diselenide: a straight-forward metal-free one-pot route to the synthesis of unsymmetrical sulfides and selenides

A metal-free cleavage of diphenyl disulfide and diphenyl diselenide has been achieved using ionic liquid/triphenyl phosphine (PPh₃) and a convenient protocol for the one-pot synthesis of unsymmetrical sulfides and selenides by condensing ‘in situ’ generated thiolate or selenate anion with alkyl halides has been developed. In addition, 1,4-conjugate addition of the generated thiolate anions to activated alkenes has also been demonstrated. The ionic liquid, 1-methyl-3-pentyl imidazolium bromide, [pmIm]Br plays a crucial role in promoting the course of the reactions and shows superior activity and selectivity compared to other solvents. The [pmIm]Br has been reused for at least five times without appreciable loss of activity.     

Catalytic Activity and Morphological Properties of Ni/MgO Catalysts for the Oxidative Coupling of Methane

The catalytic activity of Ni/MgO catalysts was studied for the oxidative coupling of methane (OCM). The catalysts were characterized using transmission electron microscope (TEM) and XRD. The increase in C2+ selectivity of Ni/MgO was attributed to the presence of bulk dislocations and MgNiO₂ phase. This revised version was published online in June 2006 with corrections to the Cover Date.     

Rectangular Tiling in Multidimensional Arrays

We study the following tiling problem in d dimensions: given a d-dimensional rectangular array of nonnegative numbers and an integer p, partition the array into at most p rectangular subarrays so that the maximum weight of any subarray is minimized; the weight of a subarray is the sum of its elements. The rectangular tiling problem is motivated by applications in data mining, data partitioning, and video compression. Recently, Khanna, Muthukrishnan, and Paterson [SODA '98], showed that the tiling problem is NP-complete and gave a 2.5-approximation algorithm for d = 2.In this paper, we extend their result to multidimensional arrays and give an algorithm with approximation ratio , for d ≥ 2. The algorithm can be implemented to run in worst-case time O(N + p log N) time, where N is the size of the array, and the constant is of the order d!. We also obtain a similar algorithm for the dual tiling problem, where the goal is to compute a tiling of weight at most W using as few tiles as possible. Our algorithm yields an approximation factor (2d + 1).We implemented our algorithm and ran simulation tests on multidimensional arrays with random data. In our limited experiments, the algorithm always produced approximations that were no worse than factor two from the optimal.     

Off-Line Maintenance of Planar Configurations

We achieve anO(log n) amortized time bound per operation for the off-line version of the dynamic convex hull problem in the plane. In this problem, a sequence ofninsert,delete, andqueryinstructions are to be processed, where each insert instruction adds a new point to the set, each delete instruction removes an existing point, and each query requests a standard convex hull search. We process the entire sequence in totalO(n log n) time andO(n) space. Alternatively, we can preprocess a sequence ofninsertions and deletions inO(n log n) time and space, then answer queries in history inO(log n) time apiece (a query in history means a query comes with a time parametert, and it must be answered with respect to the convex hull present at timet). The same bounds also hold for the off-line maintenance of several related structures, such as the maximal vectors, the intersection of half-planes, and the kernel of a polygon. Achieving anO(log n) per-operation time bound for theon-lineversions of these problems is a longstanding open problem in computational geometry.     

A Three-Stage Quantum Cryptography Protocol

We present a three-stage quantum cryptographic protocol based on public key cryptography in which each party uses its own secret key. Unlike the BB84 protocol, where the qubits are transmitted in only one direction and classical information exchanged thereafter, the communication in the proposed protocol remains quantum in each stage. A related system of key distribution is also described.