Self‐Assembled Heteroleptic Zn(II) Dithiocarbamate‐Based 2D‐Interwoven Supramolecular Giant Macrocycles and Their Redox Properties

This article presents a new heteroleptic Zn(II) dithiocarbamate ( 1 ) having molecules linked together via H···H and π···π interactions to form a giant hexanuclear macrocycle. These macrocycles are connected together through S···H interactions to offer a unique two‐dimensional cloth‐like interwoven architecture in the solid state. The redox behavior of the complex deposited on the surface of a glassy carbon electrode was investigated in different pH media. The analyte was found to oxidize and reduce in a pH‐dependent irreversible manner. On the basis of the electrochemical findings, redox mechanistic pathways were proposed.     

Synthesis of Air and Light Sensitive Cis-phenolic Cyclopropane Derivatives

The synthesis of several cis-phenolic cyclopropanes, 6, 7, 8, and 13 is described. These cyclopropanes are new potential antiestrogens. A hydrogenolysis study of precursors, 5b, 5c, 5d, 10 11, and 12 and a novel method for the prevention of gem-dichlorocyclopropane ring-opening during hydrogenolysis are discussed.     

采用燃烧技术制备CuO纳米粒子:一种高效且环境友好的用于芳族醛合成芳族腈催化剂(英文)

CuO nanoparticles were synthesized using an energy-efficient and rapid solution combustion technique with malic acid employed as a fuel. The combustion-derived CuO nanoparticles were used as catalysts in a one-pot synthesis of aromatic nitriles from aromatic aldehydes and hydroxylamine hydrochloride. The catalyst was characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, transmission electron microscopy, and Brunauer-Emmett-Teller surface area analysis. The catalytic activity of the CuO nanoparticles in the synthesis of aromatic nitriles from aromatic aldehydes was evaluated. The present protocol offers the advantages of a clean reaction, simple methodology, short reaction duration (1-2 min), and high yield (85%-98%). The catalytic activity of the CuO nanoparticles was found to be higher than that of bulk CuO powder under the same conditions. The catalyst can also be recovered and reused up to four times with no significant loss of catalytic activity. The present approach is inexpensive and is a convenient technique suitable for industrial production of CuO nanoparticles and nitriles.     

Redox Mechanism and Evaluation of Kinetic and Thermodynamic Parameters of 1,3‐Dioxolo[4,5‐g]pyrido[2,3‐b]quinoxaline Using Electrochemical Techniques

The electrochemical behavior of a biologically important heterocyclic compound, 1,3‐dioxolo[4,5‐g]pyrido[2,3‐b]quinoxaline was investigated by cyclic, square wave and differential pulse voltammetry in solutions of different pH. Kinetic and thermodynamic parameters like standard rate constant, diffusion coefficient, apparent energy of activation_, standard Gibbs free energy and enthalpy and entropy changes were evaluated. Limits of detection and quantification were determined by square wave voltammetry. The redox mechanism of the compound was proposed on the basis of experimental results. Computational chemistry was used as a tool for the verification of experimental outcomes and assessment of different theoretical parameters     

Surface characterization and heats of adsorption of chromatographic alumina gel

The porous nature of chromatographic alumina gel has been investigated by adsorption/condensation processes and electron microscopy. Having 63% porosity, the gel is very porous. Total pore volume as determined by the fluid-displacement method is 0.497 cm³ g^–1. Its specific surface area, as determined by water vapor adsorption, is 225 m² g^–1. Micropore volume, as determined by utilizing Gurwitsch's rule, turns out to be 0.262 cm³ g^–1. The greater portion of the surface area and pore volume occurs in small and transitional pores, with average pore radii (hydraulic) less than 2.1 nm.Organic vapors, such as methyl ethyl ketone, acetone, methyl acetate, and methyl alcohol, were adsorbed on the gel between 0 and 36°C under vacuum, and the data were recorded on a Cahn-1000 electrobalance device. Isosteric heats of adsorption were calculated by applying the Clausius Clapeyron equation to the adsorption isosters at different surface coverages. Two types of adsorption processes, one with low activation energy and other with high activation energy can be distinguished. The increase in values ofq _st indicates that increasing temperature changes physical adsorption into chemisorption.     

Estimation of titanium and iron in uranium by EDXRF using microdroplets on filter paper

Uranium, Fe and Ti solutions have been analyzed by EDXRF spectrometry after dispensing microdroplets of the simulated solution on filter paper fixed on a scotch tape. Precision of intensity measurements has been studied and the change in intensity with concentration behaviour is observed and discussed.     

The natural hedge of a gas-fired power plant

Electricity industries worldwide have been restructured in order to introduce competition. As a result, decision makers are exposed to volatile electricity prices, which are positively correlated with those of natural gas in markets with price-setting gas-fired power plants. Consequently, gas-fired plants are said to enjoy a “natural hedge.” We explore the properties of such a built-in hedge for a gas-fired power plant via a stochastic programming approach, which enables characterisation of uncertainty in both electricity and gas prices in deriving optimal hedging and generation decisions. The producer engages in financial hedging by signing forward contracts at the beginning of the month while anticipating uncertainty in spot prices. Using UK energy price data from 2006 to 2011 and daily aggregated dispatch decisions of a typical gas-fired power plant, we find that such a producer does, in fact, enjoy a natural hedge, i.e., it is better off facing uncertain spot prices rather than locking in its generation cost. However, the natural hedge is not a perfect hedge, i.e., even modest risk aversion makes it optimal to use gas forwards partially. Furthermore, greater operational flexibility enhances this natural hedge as generation decisions provide a countervailing response to uncertainty. Conversely, higher energy-conversion efficiency reduces the natural hedge by decreasing the importance of natural gas price volatility and, thus, its correlation with the electricity price.     

A new simple sensitive differential pulse polarographic method for the determination of acrylamide in aqueous solution

A new simple sensitive differential pulse polarographic (DPP) method was investigated for the determination of acrylamide (AA) directly in a neutral aqueous solution. The AA showed a well-defined and well-resolved peak in pure aqueous LiCl at −1.84 V in the potential range from −1.6 V to −1.97 V at nitrogen pressure of 0.5 kg cm⁻². Among the various electrolytes studied, the AA showed good DPP response in the presence of LiCl and tetra methyl ammonium iodide, while it showed poor response in the presence of tetra butyl ammonium hydroxide and tetra butyl ammonium bromide due to their strong adsorption on the surface of electrode which hindered its reduction. The effect of LiCl concentration, the cyclic voltammetric response and the drop time study showed that AA exhibited an irreversible adsorptive electrochemical behavior. The good electrochemical response in pure aqueous medium suggested that hydrogen bonding might be involved which may favor the electrode reaction. Under optimized conditions, the peak current was linear in the entire concentration range from 0.2 mg L⁻¹ to 20 mg L⁻¹ with the correlation coefficient of R² = 0.9998. The method showed good reproducible results with R.S.D. of 0.3% (n = 16). The detection limit (LOD) was 27 μg L⁻¹. The influence of various interfering agents was also studied. The method was applied successfully for the quantification of AA in water samples without any interference effect from alkali metals.     

Hyphenation in sample preparation: advancement from the micro to the nano world

Analysis at trace levels, an ideal area of application for hyphenated techniques, is steadily gaining importance. Many sample pre-concentration and clean-up methods have been hyphenated with core analytical techniques to accomplish the task of low level detection. The present article describes the state of the art of hyphenation of various techniques such as solid phase extraction, micro-solid phase extraction, dialysis, and chromatographic modalities etc. with liquid chromatography, gas chromatography, capillary electrophoresis, and spectroscopic methods. Besides, attempts have been made to address the hyphenation approach in microfluidic devices.     

Polymers imprinted with PAH mixtures—comparing fluorescence and QCM sensors

Molecular imprinting with binary mixtures of different polycyclic aromatic hydrocarbons (PAH) is a tool for design of chemically highly sensitive layers for detection of these analytes. Sensor responses increase by one order of magnitude compared with layers imprinted with one type of template. Detection limits, e.g. for pyrene, reach down to 30 ng L(-1) in water, as could be observed with a naphthalene and pyrene-imprinted polyurethane. Comparing sensor characteristics obtained by QCM and fluorescence reveals different saturation behaviours indicating that, first, single PAH molecules occupy the interaction centres followed by gradual excimer incorporation at higher concentrations finally leading to substantial quenching, when all accessible cavities are occupied. The plateau in the mass-sensitive measurements suggests that up to 80% of the cavities generated in the MIP are re-occupied. Displacement measurements between chrysene and pyrene revealed that for imprinted layers with very high pyrene sensitivities the signals of both PAH are additive, whereas in materials with lower pyrene uptake the two analytes replace each other in the interaction sites of the polymer.