Threshold electrical switching in As45Te55-xInx and As50Te50-xInx glasses

The electrical switching behaviour of As₄₅Te_55-xIn_x (5≤x≤15) and As₅₀Te_50-xIn_x (2.5≤x≤11.5) has been studied over a wide range of compositions. These glasses are found to exhibit threshold switching. The composition dependence of switching voltage (V_t) has been found to exhibit a change in slope and a local minimum at compositions x=10 and 12.5 for As₄₅Te_55-xIn_x and x=7.5 and 10.8 for As₅₀Te_50-xIn_x, respectively. The slope change in V_t verses x and the local minimum have been identified using two network topological effects, namely the rigidity percolation threshold and the chemical threshold. Received: 23 August 2001 / Accepted: 27 August 2001 / Published online: 11 February 2002     

Furan ring oxidation strategy for the synthesis of macrosphelides A and B

By using the convenient protocol for conversion of 2-substituted furans into 4-oxo-2-alkenoic acids ((i) NBS, (ii) NaClO(2)), macrosphelide B (2) was synthesized from furyl alcohol 5 (>98% ee) and acid 6 (99% ee). The protocol was first applied to the PMB ether of 5 to afford acid 13b. On the other hand, DCC condensation of acid 6 with 5 gave 16 after deprotection of the TBS group. Condensation was again carried out between 13b and 16 to furnish the key ketone 17, which upon reduction with Zn(BH(4))(2) afforded anti alcohol 18 stereoselectively (15:1). After protection/deprotection steps, the furan 18 was converted to seco acid 3 by using the furan oxidation protocol mentioned above, and lactonization of 3 with Cl(3)C(6)H(2)COCl, Et(3)N, and DMAP afforded 22 (MOM ether of 2), which upon deprotection with TFA produced 2. Transformation of 22 to macrosphelide A (1) was then investigated. Although the chelation-controlled reduction of 22 should afford the desired anti alcohol 24, Zn(BH(4))(2) at <-90 degrees C gave a 2 approximately 1:1 mixture of anti/syn alcohols. On the contrary, reduction with NaBH(4) in MeOH at -15 degrees C produced the syn isomer 23 with >10:1 diastereoselectivity. Mitsunobu inversion of the resulting C(14)-hydroxyl group and deprotection of the MOM group with TFA afforded 1. Similarly, reduction of 2 with NaBH(4) afforded the C(14)-epimer of 1 stereoselectively. The observed stereoselectivity in the reductions of 22 and 2 could be explained on the basis of computer-assisted calculation, which showed presence of the low-energy conformers responsible for the stereoselective reduction. In addition, conversion of 2 to 1 was established, for the first time.     

Determination of mercury by radiochemical displacement method

A radiochemical displacement method for the determination of micro amounts of Hg(II) has been developed. 65Zn was displaced from the Zn-1-(2-pyridylazo-2-naphthol) complex at pH 5 in borate buffers by Hg (II). 10-80 micrograms of mercury could be determined. Interference of various metal ions and methods for suppression have also been carried out.     

An Observation on the Experimental Measurement of Dislocation Density

The common practice of ignoring the elastic strain gradient in measurements of geometrically necessary dislocation (GND) density is critically examined. It is concluded that the practice may result in substantial errors. Our analysis points to the importance of spatial variations of the elastic strain field in relation to its magnitude in inferring estimates of dislocation density from measurements.     

Trace element determination in high-purity aluminum clad samples by k 0-based internal monostandard instrumental neutron activation analysis

The k₀-based internal monostandard instrumental neutron activation analysis (IM-INAA) method was applied for quantification of trace impurities in seven high purity aluminum samples used as fuel cladding in a research reactor. Samples along with BCS CRM 182 (Si–Al alloy) were irradiated in high flux reactor neutrons for 10–15 h. In situ detection efficiency, needed in concentration calculation ratio by IM-INAA, was obtained using gamma rays of activation products produced in the samples. Elemental concentration ratios obtained with respect to Fe (used as internal monostandard) were converted to absolute concentrations by determining concentration of Fe by relative method of NAA. Concentrations of ten trace elements (Sc, Cr, Co, Zn, Ga, La, Ce, Sm, W and Hf) including major element Fe were determined in this work. The method used is non-destructive in nature and does not need multielement standards. Results of IM-INAA were compared with those obtained by relative method of INAA and inductively coupled plasma atomic emission spectrometry (ICP-AES). Details of methodologies and results obtained by all methods are discussed and compared in the paper.     

Trichloroisocyanuric Acid–KF as an Efficient Reagent for One-Pot Synthesis of Dialkylfluorophosphates from Dialkylphosphites

Trichloroisocyanuric acid–KF afforded dialkylfluorophosphates from dialkylphosphites at room temperature through a facile electrophilic–nucleophilic metathesis.     

Tween-80–n-Butanol–Diesel–Water Microemulsion System—A Class of Alternative Diesel Fuel

Tween-80–n–butanol–diesel–water microemulsion systems with various surfactant:cosurfactant (S:C) ratio have been reported as a class of alternative diesel fuel from their phase behavior, clouding phenomena, conductivity, turbidity, and inflammation studies. Temperature induced clouding of microemulsion containing 2% brine at an S:C ratio of 1:1 from a suitable turbid zone has been examined to see the stability of the diesel–water microemulsion systems. Regression models have been proposed to understand the impact of various components of the microemulsion on their cloud point (CP) values. Conductivity of the microemulsions at various S:C ratio increases with the volume of brine having two cut points depicting the presence of three microheterogenous phases within the system, whereas turbidity shows a linear increase. Dye-probed investigation of water-rich and oil-rich zones of the microemulsions indicates the involvement of a dynamic mass transfer process within the various zones. The intensities of flames produced during burning of the microemulsions with various O:E:W weight percentages selected from the isotropic regions of the phase diagrams have been estimated using MATLAB image processing method and the impacts of various components on the fuel use of the microemulsions have been analyzed.