13C NMR/DFT/GIAO studies of phenylene bis(1,3-dioxolanium) dications and 2,4,6-triphenylene tris(1,3-dioxolanium) trication

The o-, m-, and p-phenylene bis(1,3-dioxolanium) dications (4-6) and 2,4,6-triphenylene tris(1,3-dioxolanium) trication (7) have been prepared by the ionization of the corresponding 2-methoxyethyl benzoates in FSO(3)H or CF(3)SO(3)H at 40 and 60 degrees C, respectively. The charge delocalization in these carbocations was probed by (13)C NMR chemical shifts and substantiated by GIAO/DFT calculations. Relatively less charge is delocalized into the aromatic ring of the carbotrication 7. The rotational barrier around the C(+)-Ar bond for carbodications 4 and 5 was also estimated to be 8-10 kcal/mol.     

Platinum complexes of diazo ligands. Studies of regioselective aromatic ring amination, oxidative halogen addition and reductive halogen elimination reactions

2-(Arylazo)pyridine ligands, L1a-1c react with the salt K2[PtCl4] to give the mononuclear complexes [PtCl2(L1)](1), which readily react with ArNH2 to yield the monochloro complexes of type [PtCl(L2)](HL2= 2-[(2-(arylamino)phenyl)azo]pyridine)(2) via regioselective ortho-amine fusion at the pendent aryl ring of coordinated L1. Oxidative addition of the electrophiles Y2(Y = Cl, Br, I) to the square-planar platinum(II) complex, has led to syntheses of the corresponding octahedral platinum(IV) complexes, [PtY3(L2)](3) in high yields. Ascorbate ion reductions of the platinum(IV) complexes, , resulted in reductive halogen elimination to revert to the platinum(II) complexes almost quantitatively. Isolation of products and X-ray structure determination of the representative complexes followed all these chemical reactions. In crystal packing, the compound [PtCl2(L1c)](1c) forms dimeric units with a Pt...Pt distance of 3.699(1) A. In contrast, the crystal packing of 2b revealed that the molecules are arranged in an antiparallel fashion to form a noncovalent 1D chain to accommodate pi(aryl)-pi(pyridyl) and Pt-pi(aryl) interactions. Notably, the oxidation of [Pt(II)Cl(L2a)](2a) by I2 produced a mixed halide complex [Pt(IV)ClI2(L2a)](5), which, in turn, is reduced by ascorbate ion to produce [Pt(II)I(L2a)] with the elimination of ClI. All the platinum(II) complexes are brown, the platinum(IV) complexes, on the other hand, are green. Low-energy visible range transitions in the complexes of the extended ligand [L2]- are ascribed to ligand basedpi-pi* transitions. Cyclic voltammetric behaviour of the complexes is reported.     

Honeycomb nets with interpenetrating frameworks involving iminodiacetato-copper(II) blocks and bipyridine spacers: syntheses, characterization, and magnetic studies

Three coordination polymers of copper(II), viz. ([Cu(ida)(4,4'-bipyH)]ClO(4))( proportional, variant ) (1), ([Cu(2)(ida)(2)(micro-4,4'-bipy)].2H(2)O)( proportional, variant ) (2), and [Cu(2)(ida)(2)(bpa)]( proportional, variant ) (3) have been synthesized by the process of self-assembly using Cu(ida) [ida = iminodiacetate(2-)] as the building block and 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane (bpa) as linkers. Crystals of 1 are orthorhombic, of space group Pna2(1), with a = 13.8956(12) A, b = 16.3362(16) A, c = 7.3340(12), and Z = 4. Both compounds 2 and 3 crystallize in monoclinic space group P2(1)/a with a = 10.1887(8) A (9.6779(10) A for 3), b = 8.0008(11) A (9.1718(10) A), c = 11.6684(9) A (12.9144(12) A), beta = 98.307(11) degrees (102.796(18) degrees ), and Z = 2 (2). Compound 1 has a zigzag chain structure with an extensive hydrogen-bonded network while compounds 2 and 3 are honeycomb (6,3) nets with interpenetrating structures. Variable temperature (2-300 K) magnetic study indicates the presence of weak antiferromagnetic interactions (J = 0.82 +/- 0.01 cm(-)(1)) in 1 and ferromagnetic in 2 (J = -0.45 +/- 0.05 cm(-)(1)) and 3 (J = -0.21 +/- 0.02 cm(-)(1)). The extent of planarity of the bridging "Cu-O-C-O-Cu" moiety, acting as the super-exchange pathway between the neighboring copper centers, probably controls the sign of the magnetic exchange coupling in these compounds.     

Polyphenolics with Strong Antioxidant Activity from Acacia nilotica Ameliorate Some Biochemical Signs of Arsenic-Induced Neurotoxicity and Oxidative Stress in Mice

Neurotoxicity is a serious health problem of patients chronically exposed to arsenic. There is no specific treatment of this problem. Oxidative stress has been implicated in the pathological process of neurotoxicity. Polyphenolics have proven antioxidant activity, thereby offering protection against oxidative stress. In this study, we have isolated the polyphenolics from Acacia nilotica and investigated its effect against arsenic-induced neurotoxicity and oxidative stress in mice. Acacia nilotica polyphenolics prepared from column chromatography of the crude methanol extract using diaion resin contained a phenolic content of 452.185 ± 7.879 mg gallic acid equivalent/gm of sample and flavonoid content of 200.075 ± 0.755 mg catechin equivalent/gm of sample. The polyphenolics exhibited potent antioxidant activity with respect to free radical scavenging ability, total antioxidant activity and inhibition of lipid peroxidation. Administration of arsenic in mice showed a reduction of acetylcholinesterase activity in the brain which was counteracted by Acacia nilotica polyphenolics. Similarly, elevation of lipid peroxidation and depletion of glutathione in the brain of mice was effectively restored to normal level by Acacia nilotica polyphenolics. Gallic acid methyl ester, catechin and catechin-7-gallate were identified in the polyphenolics as the major active compounds. These results suggest that Acacia nilotica polyphenolics due to its strong antioxidant potential might be effective in the management of arsenic induced neurotoxicity.     

Genericness of inflation in isotropic loop quantum cosmology

Nonperturbative corrections from loop quantum cosmology (LQC) to the scalar matter sector are already known to imply inflation. We prove that the LQC modified scalar field generates exponential inflation in the small scale factor regime, for all positive definite potentials, independent of initial conditions and independent of ambiguity parameters. For positive semidefinite potentials it is always possible to choose, without fine-tuning, a value of one of the ambiguity parameters such that exponential inflation results, provided zeros of the potential are approached at most as a power law in the scale factor. In conjunction with the generic occurrence of bounce at small volumes, particle horizon is absent, thus eliminating the horizon problem of the standard big bang model.     

Role of cleaning methods on bond quality of Ti coated glass/imidex system

Thin film materials are widely used in the fabrication of semiconductor microelectronic devices. In thin film deposition, cleanliness of substrate surface have become critically important as over 50% of yield losses in integrated circuit fabrication are caused by microcontamination [1]. There are many wafer cleaning techniques. The most successful approach for silicon wafer cleaning technique is RCA clean [2]. But for glass substrate it is still not known which procedure of cleaning is the best. This paper provides an understanding of the right way of glass wafer cleaning method, with a focus towards identifying good bond strength. Two wafer cleaning techniques have been used for cleaning glass substrates in the context of laser micro-joining of dissimilar substrates. First cleaning procedure involves two steps, first cleaning in acetone solution and then in DI water solution. After each step dried with N₂. Second cleaning procedure involves four steps, first cleaning with 1% Alconox solution, second in DI water, third in acetone solution and finally in a methanol solution and dried with N₂ after each step. Deposition of Ti thin film on top of these two types of substrate using DC magnetron sputtering method also showed better adhesion of Ti film on glass for the second type of cleaning method. Scanning electron microscopy (SEM) analyses of the lap shear tested failed surfaces for these two kinds of samples revealed strong bond for samples prepared by second cleaning method compared to first cleaning method. Characterization of these two sets of samples using X-ray photoelectron spectroscopy (XPS) has shown excellent contamination removal for the second cleaning method. This modification is believed to be due to reduction of carbon contamination.     

Rapid one-step synthesis, characterization and functionalization of silica coated gold nanoparticles

This paper describes a rapid, simple and one-step method for preparing silica coated gold (Au@SiO₂) nanoparticles with fine tunable silica shell thickness and surface functionalization of the prepared particles with different groups. Monodispersed Au nanoparticles with a mean particle size of 16 nm were prepared by citrate reduction method. Silica coating was carried out by mixing the as prepared Au solution, tetraethoxysilane (TEOS) and ammonia followed by microwave (MW) irradiation. Although there are several ways of coating Au nanoparticles with silica in the literature, each of these needs pre-coating step as well as long reaction duration. The present method is especially useful for giving the opportunity to cover the colloidal Au particles with uniform silica shell within very short time and forgoes the use of a silane coupling agent or pre-coating step before silica coating. Au@SiO₂ nanoparticles with wide range of silica shell thickness (5-105 nm) were prepared within 5 min of MW irradiation by changing the concentration of TEOS only. The size uniformity and monodispersity were found to be better compared to the particles prepared by conventional methods, which were confirmed by dynamic light scattering and transmission electron microscopic techniques. The prepared Au@SiO₂ nanoparticles were further functionalized with amino, carboxylate, alkyl groups to facilitate the rapid translation of the nanoparticles to a wide range of end applications. The functional groups were identified by XPS, and zeta potential measurements.     

A supramolecular spin crossover Fe(III) complex and its Cr(III) isomer: stabilization of water-chloride cluster within supramolecular host

The metal complexes, [M(Hdammthiol)(2)]Cl·3H(2)O [M = Cr(III) (1), Fe(III) (2)] [where H(2)dammthiol is the thiol form of the ligand, diacetylmonoxime morpholine N-thiohydrazone] were synthesized by metal template reactions of diacetylemonoxime with morpholine N-thiohydrazide in the presence of CrCl(3)·6H(2)O and FeCl(3)·6H(2)O. Both the complexes (1 and 2) were characterized by single crystal X-ray crystallography, spectroscopic (IR and UV-vis), M?ssbauer and TGA analyses. The single crystal X-ray studies of both complexes show that the supramolecular hosts, constructed by the discrete mononuclear complexes, form supramolecular channels along the c-axis which are filled up by water-chloride clusters. In both complexes, the 1D water-chloride chain with chair-like architecture within the supramolecular hosts presents novelty. The magnetic measurement study of Fe(III) complex shows a spin crossover from S = 1/2 at 2.5 K to S = 5/2 at 300 K. At very low temperature, the presence of strong cooperative hydrogen bonding interactions stabilizes the S = 1/2 state.     

Alkaline phosphatase-labeled macromolecular probe for sensitive chemiluminescence detection of proteins on a solid-phase membrane

In the present study, we synthesized dextran (MW = ca. 2,000 kDa)-based macromolecular probes containing multiple molecules of alkaline phosphatase (ALP) as a signal-trigger enzyme and of biotin as an assembly mediator. The ALP and biotin molecules were covalently attached into the dextran backbone after the formation of aldehyde groups into the macromolecule by periodate oxidation. The synthesized probes contained 27–31 molecules of ALP in their macromolecules when 50-fold molar ratio of ALP to the dextran was used for the synthesis. These probes provided 14–20 times stronger chemiluminescence (CL) than that of the equimolar free ALP adsorbed on a nylon membrane. The velocity of the CL reaction of ALP-catalyzed adamantlyl-1,2-dioxetane substrate was improved from a slower emission (glow type) of CL to a faster one (flash type). The CL signal integrated for 2 min under strongly alkaline conditions (pH 13.0) was about ten times greater than that obtained by the conventional conditions (pH 9.5). Therefore, the synthesized macromolecular probe could be successfully utilized for the high-throughput CL detection of biotin-conjugated anti-rabbit IgG antibody with a lower detection limit of 880 amol per spot on the nylon membrane. This study provides analytical strategy for the rapid, convenient, and sensitive detection of target proteins in immunoassays.