Reactions of cyclopalladated azobenzenes with xanthates and dithiocarbamates. Spectral characterisation and electrochemical studies of the products

Binuclear chloro-bridged cyclopalladated azobenzenes [Pd(A)Cl]₂ (A = ortho-metallated azobenzene or its derivatives) have been reacted with aqueous AgNO₃ to yield aquo-derivatives followed by the addition of xanthates, or dithiocarbamates (RCS₂ ^–) to synthesise ternary complexes, [Pd(A)(RCS₂)]. These complexes occur as configurational isomers and their compositions have been established by ¹H-n.m.r. spectroscopy. Cyclic voltammetric studies show azo reduction at negative and thiol oxidation at positive potentials relative to s.c.e., respectively. Dissociation of RCS₂ ^– under the electrode field is chemically supported by using a sulfide extractor, HgCl₂, Hg(OAc)₂, or AgOAc, to precipitate out the binuclear [Pd(A)Cl]₂/[Pd(A)(OAc)]₂ complexes.     

Synthesis and characterization of terbium doped TiO2 nanoparticles and their use as recyclable and reusable heterogeneous catalyst for efficient and environmentally sustainable synthesis of spiroannulated indolo[3,2-c]quinolines- mimetic scaffolds of isocryptolepine

An efficient and environmentally sustainable domino protocol has been presented for the synthesis of structurally diverse spiroannulated indolo[3,2-c]quinolines involving three component sequential reaction of phenylhydrazine, o-aminoacetophenone and cyclic ketones using nanostructured terbium doped TiO₂ as recyclable and reusable heterogeneous catalyst. The nanostructured catalyst was synthesized successfully and characterized by X-ray Diffraction (XRD), transmission electron microscopy (TEM), EDX and Fourier transform infra-red spectroscopy (FTIR). The substitution of Ti⁺⁴ with Tb⁺³ and the formation of Ti-O-Tb bonds as a result of doping of Terbium with TiO₂ NPs increases the catalytic efficiency and facilitates the reaction to provide the products in excellent yields. The present protocol with special features; operational simplicity, atom-economy, mild reaction conditions, environmental sustainability and high synthetic efficiency with recyclability and reusability of catalyst has been reported for the first time to synthesize spiroannulated indoloquinolines and expecting to provide the library of promising new leads in drug discovery research.     

The effect of aryl nitration on gas sorption and permeation in polysulfone

CO_2, CH_4, O_2, and N₂ permeability and solubility of unmodified and aryl-nitrated polysulfone were determined at 35°C and pressures up to 20 atm. The degree of nitration was varied from 0 to 2 nitro groups per repeat unit. The permeability and diffusion coefficients for all gases decreased with increasing degree of nitro substitution. The decrease in gas diffusivity is attributed to a combination of decreased fractional free volume and decreased torsional mobility with increasing degree of substitution. The solubilities of N_2, O_2, and CH₄ do not show a systematic dependence on degree of substitution. However, CO₂ solubility apparently goes through a minimum as the degree of substitution is increased. CO₂ solubility may be influenced by a competition between increases in polymer polarity (favoring higher solubility) and lower free volume (favoring lower solubility) that accompanies increases in the polar nitro substituent concentration. CO₂/CH₄ solubility selectivity increases monotonically as the degree of substitution increases. CO₂/CH₄ permselectivity and diffusivity selectivity increased with increasing degree of substitution. © 1995 John Wiley & Sons, Inc.     

Asymptotic distributions of M-estimators in a spatial regression model under some fixed and stochastic spatial sampling designs

In this paper, we consider M-estimators of the regression parameter in a spatial multiple linear regression model. We establish consistency and asymptotic normality of the M-estimators when the data-sites are generated by a class of deterministic as well as a class of stochastic spatial sampling schemes. Under the deterministic sampling schemes, the data-sites are located on a regular grid but may have aninfill component. On the other hand, under the stochastic sampling schemes, locations of the data-sites are given by the realizations of a collection of independent random vectors and thus, are irregularly spaced. It is shown that scaling constants of different orders are needed for asymptotic normality under different spatial sampling schemes considered here. Further, in the stochastic case, the asymptotic covariance matrix is shown to depend on the spatial sampling density associated with the stochastic design. Results are established for M-estimators corresponding to certain non-smooth score functions including Huber’s ψ-function and the sign functions (corresponding to the sample quantiles). Research of Lahiri is partially supported by NSF grant no. DMS-0072571. Research of Mukherjee is partially supported by the Academic Research Grant R-155-000-003-112 from the National University of Singapore.     

Hypochlorite‐Mediated Modulation of Photoinduced Electron Transfer in a Phenothiazine–Boron dipyrromethene Electron Donor–Acceptor Dyad: A Highly Water Soluble “Turn‐On” Fluorescent Probe for Hypochlorite

A highly water‐soluble phenothiazine (PTZ)–boron dipyrromethene (BODIPY)‐based electron donor–acceptor dyad ( WS‐Probe ), which contains BODIPY as the signaling antennae and PTZ as the OCl^? reactive group, was designed and used as a fluorescent chemosensor for the detection of OCl^?. Upon addition of incremental amounts of NaOCl, the quenched fluorescence of WS‐Probe was enhanced drastically, which indicated the inhibition of reductive photoinduced electron transfer (PET) from PTZ to ¹BODIPY*; the detection limit was calculated to be 26.7 nm . Selectivity studies with various reactive oxygen species, cations, and anions revealed that WS‐Probe was able to detect OCl^? selectively. Steady‐state fluorescence studies performed at varied pH suggested that WS‐Probe can detect NaOCl and exhibits maximum fluorescence in the pH range of 7 to 8, similar to physiological conditions. ESI‐MS analysis and ¹H NMR spectroscopy titrations showed the formation of sulfoxide as the major oxidized product upon addition of hypochlorite. More interestingly, when WS‐Probe was treated with real water samples, the fluorescence response was clearly visible with tap water and disinfectant, which indicated the presence of OCl^? in these samples. The in vitro cell viability assay performed with human embryonic kidney 293 (HEK 293) cells suggested that WS‐probe is non‐toxic up to 10 μm and implicates the use of the probe for biological applications.     

Soluble substituted poly-p-phenylenes—A new material for application in light-emitting diodes

Poly-p-phenylenes have attracted a great deal of attention with respect to their applications in displays, light-emitting devices, and batteries. However, the polymer poly-p-phenylene obtained by the Kovacic method is insoluble and intractable. The present study reports the preparation of soluble poly(p-phenylenes) by polymerization of derivatives of benzene in the presence of a specific aromatic nuclei. The resultant copolymer so obtained is soluble in common organic solvents such as chloroform and toluene. Preliminary studies have indicated that the polymer shows orange photoluminescence and electroluminescence when a potential of 7–10 V is applied to the device.     

Asymptotics of R-, MD- and LAD-estimators in linear regression models with long range dependent errors

Summary This paper establishes the uniform closeness of a weighted residual empirical process to its natural estimate in the linear regression setting when the errors are Gaussian, or a function of Gaussian random variables, that are strictly stationary and long range dependent. This result is used to yield the asymptotic uniform linearity of a class of rank statistics in linear regression models with long range dependent errors. The latter result, in turn, yields the asymptotic distribution of the Jaeckel (1972) rank estimators. The paper also studies the least absolute deviation and a class of certain minimum distance estimators of regression parameters and the kernel type density estimators of the marginal error density when the errors are long range dependent.Research of this author was partly supported by the NSF grant: DMS-9102041     

Synthesis of carbon nanotubes by catalytic vapor decomposition (CVD) method: Optimization of various parameters for the maximum yield

This paper describes an effect of flow rate, carrier gas (H₂, N₂ and Ar) composition, and amount of benzene on the quality and the yield of carbon nanotubes (CNTs) formed by catalytical vapour dcomposition (CVD) method. The flow and mass control of gases and precursor vapors respectively were found to be interdependent and therefore crucial in deciding the quality and yield of CNTs. We have achieved this by modified soap bubble flowmeter, which controlled the flow rates of two gases, simultaneously. With the help of this set-up, CNTs could be prepared in any common laboratory. Raman spectroscopy indicated the possibilities of formation of single-walled carbon nanotubes (SWNTs). From scanning electron microscopy (SEM) measurements, an average diameter of the tube/bundle was estimated to be about 70 nm. The elemental analysis using energy dispersion spectrum (EDS) suggested 96 at.wt.% carbon along with ca. 4 at.wt.% iron in the as-prepared sample. Maximum yield and best quality CNTs were obtained using H₂ as the carrier gas.      

Measurements of elastic scattering for 7Be, 7Li + 9Be systems and fusion cross sections for 7Li + 9Be system

Elastic scattering angular distributions have been measured for ⁷Be + ⁹Be system at E_lab = 17, 19 and 21 MeV in the angular range θ_cm=26^○–58°, and for ⁷Li + ⁹Be system at E_lab= 15.75, 24 and 30 MeV. An optical model (OM) analysis of these data have been carried out. For the ⁷Li + ⁹Be system fusion cross sections were obtained at E_lab = 15.75, 24 and 30 MeV by measuring the α-evaporation spectra from the compound nucleus at backward angles. The measured α-evaporation spectra were reproduced by the statistical model calculations and fusion cross sections were extracted therefrom. The ratios of the experimental fusion cross sections to the total reaction cross sections (obtained form OM analysis) were found to be rather small. This result suggests that break-up process has a strong influence on fusion process leading to a reduction in fusion cross section.