Synthesis and spectral studies of cobalt(II), nickel(II) and copper(II) complexes of 1-(2-hydroxy-1-naphthyl)-3-(4-X-phenyl)-2-propen-1-ones and their pyridine adducts

Transition Metal Chemistry - Metal(II) chelates of the type ML2nB [M = CoII, NiII and CuII; L = 1-(2-hydroxy-1-naphthyl)-3-(4-X-phenyl)-2-pro-pen-1-one, (X = H, Cl or Me); B = H2O or Py; n = 0, 2]...     

Rh2(OAc)4-catalyzed reactions of alpha-diazoimides: a simple and novel synthesis of mono- and bis(2,3-fused perhydrooxazol-4-one) systems

Simply, trapping the intermediate isomünchnone 1,3-dipoles by the external oxygen nucleophiles resulted in new heterocyclic systems and the use of diols led to the formation of four carbon-oxygen bonds in a single operation which eventually delivered bis(2,3-fused perhydrooxazol-4-one) systems.     

Potential functions for hydrogen bond interactions

A careful comparison of the distribution in the (R, θ)-plane of all NH … O hydrogen bonds with that for bonds between neutral NH and neutral C=O groups indicated that the latter has a larger mean R and a wider range of θ and that the distribution was also broader than for the average case. Therefore, the potential function developed earlier for an average NH … O hydrogen bond was modified to suit the peptide case. A three-parameter expression of the form \(V_{hb} = V_{min} + p_1 \Delta ^2 + q_1 e^{p_3 \Delta } \theta ^2 \) , with △ = R - R_min, was found to be satisfactory. By comparing the theoretically expected distribution in R and θ with observed data (although limited), the best values were found to bep ₁ = 25,p ₃ = ? 2 andq ₁ = 1 × 10^?3, with R_min = 2·95 Å and V_min = ? 4·5 kcal/mole. The procedure for obtaining a smooth transition from V_hb to the non-bonded potential V_nb for large R and θ is described, along with a flow chart useful for programming the formulae. Calculated values of ΔH, the enthalpy of formation of the hydrogen bond, using this function are in reasonable agreement with observation. When the atoms involved in the hydrogen bond occur in a five-membered ring as in the sequence a different formula for the potential function is needed, which is of the form V_hb = V_min +p ₁△² +q ₁ x ² wherex = θ ? 50° for θ ≥ 50°, withp ₁ = 15,q ₁ = 0·002, R_min = 2· Å and V_min = ? 2·5 kcal/mole.     

Electrochemical rectification at electrode surface modified with poly (acrylic acid) and decane thiol

Gold surface modified with a two-component system consisting of poly (acrylic acid) (PAA) by electropolymerizing acrylic acid (AA) and decane thiol (DT), further functionalized with ferrocene monocarboxylic acid (FMC) through covalent linkage, was used to demonstrate mediated electron transfer resulting in a unidirectional flow of current. The electrode surface was modified using two different configurations. In Configuration 1 (Config. 1), electrode surface modified with FMC showed rectification behavior when contacted with a solution containing methylene blue (MB). In Configuration 2, redox-active bilayer was constructed using polyvinyl pyrollidone (PVP) and hexaamineruthernium (II) chloride [Ru(NH₃)₆]²⁺ showed rectification characteristics. The continuous rectification property of the redox-active bilayer is achieved by releasing the trapped [Ru(NH₃)₆]³⁺ in the outer layer using a reductant (ascorbic acid). Spectroelectrochemical measurements were made to study the reduction property of the ascorbic acid. Atomic force microscopic images and impedance measurements were also made on the modified electrode surfaces to explore the compactness of the first layer (PAA and PAA/DT).     

The first total synthesis of cytopiloyne, an anti-diabetic, polyacetylenic glucoside

The first total synthesis of cytopiloyne 1, a novel bioactive polyacetylenic glucoside isolated from the extract of Bidens pilosa, is described. The structure of cytopiloyne was determined to be 2-β-D-glucopyranosyloxy-1-hydroxytrideca-5,7,9,11-tetrayne by using various spectroscopic methods, but the chirality of the polyyne moiety was unknown. Herein, the convergent synthesis of two diastereomers of cytopiloyne by starting from commercially available 4-(2-hydroxyethyl)-2,2-dimethyl-1,3-diozolane is described. The synthetic sequence involved two key steps: stereoselective glycosylation of the glucosyl trichloroacetimidate with 1-[(4-methoxybenzyl)oxy]hex-5-yn-2-ol to give the desired β-glycoside and the construction of the glucosyl tetrayne skeleton by using a palladium/silver-catalyzed cross-coupling reaction to form the alkyne-alkyne bond, the first such use of this reaction. Comparison between the observed and published characterization data showed the 2R isomer to be the natural product cytopiloyne.     

Ruthenium catalyzed hydroboration of terminal alkynes to z-vinylboronates

The nonclassical ruthenium hydride pincer complex [Ru(PNP)(H)(2)(H(2))] 1 (PNP = 1,3-bis(di-tert-butyl-phosphinomethyl)pyridine) catalyzes the anti-Markovnikov addition of pinacolborane to terminal alkynes yielding Z-vinylboronates at mild conditions. The complex [Ru(PNP)(H)(2)(HBpin)] 2 (HBpin = pinacolborane), which was identified at the end of the reaction and prepared independently, is proposed as the direct precursor to the catalytic cycle involving rearrangement of coordinated alkyne to Z-vinylidene as a key step for the apparent trans-hydroboration.     

Spatial and temporal variations of radon concentrations in groundwater of hard rock aquifers in Madurai district,India

Radon (²²²Rn) and other radionuclides in groundwater can lead to health problems if present in higher concentrations. A study was carried out in Madurai district of Tamilnadu by collecting groundwater samples for four different seasons and aims to identify the regions with higher ²²²Rn concentration along with their spatial and seasonal variations. ²²²Rn has been compared with field parameters, log pCO₂, major ions and uranium to detect the factors responsible for the higher concentration in groundwater. The weathering process induces the release of higher uranium ions from the granitic terrain from the rock matrix which enhances the ²²²Rn levels in groundwater.     

The influence of monovalent cations on the stability of electrochemically formed nickel fluoride films

The stability of electrochemically formed NiF₂ film in 1.0 M perchloric acid containing monovalent fluorides namely, NH₄F, HF, NaF, KF and LiF, is investigated using cyclic voltammetry, chronoamperometry, atomic absorption spectroscopy and scanning electron microscopy. In addition to direct dissolution of nickel and dissolution through the oxide layer, a new mode of dissolution of NiF₂ film as NiF₃ ⁻ and NiF₄ ²⁻ through complex formation is proposed. This process is significantly influenced by the alkali metal fluorides. On a comparative basis the stability of NiF₂ decreases in the order NH₄F > HF > KF > LiF. Received: 29 July 1998 / Accepted: 3 November 1998     

A study of the thermal properties of single jersey fabrics of cotton, bamboo and cotton/bamboo blended-yarn vis-a-vis bamboo fibre presence and yarn count

In this study, the thermal properties of 100% cotton, 50/50 cotton/bamboo and 100% bamboo single jersey fabrics with differing yarn linear density are evaluated and analysed. The linear densities of the yarns composing the fabrics are 20^s, 25^s, 30^s Ne_c and the twist level in the yarns is kept the same. An increasing the presence of bamboo fibre in the fabric causes a reduction in fabric thickness and GSM for all linear densities of yarn. Air permeability and water-vapour permeability also increase with increase in bamboo fibre content while both thermal conductivity and thermal resistance show a decreasing trend. As the constituent yarn gets finer, fabric air and water-vapour permeability both increase in value while the thermal conductivity falls.