Synthesis of Unnatural Selenocystines and beta-Aminodiselenides via Regioselective Ring-Opening of Sulfamidates Using a Sequential, One-Pot, Multistep Strategy

A variety of N-alkyl-beta-aminodiselenides have been synthesized in high yield from sulfamidates under mild reaction conditions using potassium selenocyanate and benzyltriethylammonium tetrathiomolybdate ([BnNEt3](2)MoS4) in a sequential, one-pot, multistep reaction. The tolerance of multifarious protecting groups under the reaction conditions is discussed. The methodology was successfully extended to the synthesis of selenocystine,3,3'-dialkylselenocystine, and 3,3'-diphenylisoselenocystine and their direct incorporation into peptides.

Ultrasonic wave characteristics of nanorods via nonlocal strain gradient models

This paper studies an ultrasonic wave dispersion characteristics of a nanorod. Nonlocal strain gradient models (both second and fourth order) are introduced to analyze the ultrasonic wave behavior in nanorod. Explicit expressions are derived for wave numbers and the wave speeds of the nanorod. The analysis shows that the fourth order strain gradient model gives approximate results over the second order strain gradient model for dynamic analysis. The second order strain gradient model gives a critical wave number at certain wave frequency, where the wave speeds are zero. A relation among the number of waves along the nanorod, the nonlocal scaling parameter (e(0)a), and the length of the nanorod is obtained from the nonlocal second order strain gradient model. The ultrasonic wave characteristics of the nanorod obtained from the nonlocal strain gradient models are compared with the classical continuum model. The dynamic response behavior of nanorods is explained from both the strain gradient models. The effect of e(0)a on the ultrasonic wave behavior of the nanorods is also observed. (C) 2010 American Institute of Physics.

Possible use of self-calibration to reduce systematic uncertainties in determining distance-redshift relation via gravitational radiation from merging binaries

By observing mergers of compact objects, future gravity wave experiments would measure the luminosity distance to a large number of sources to a high precision but not their redshifts. Given the directional sensitivity of an experiment, a fraction of such sources (gold plated) can be identified optically as single objects in the direction of the source. We show that if an approximate distance-redshift relation is known then it is possible to statistically resolve those sources that have multiple galaxies in the beam. We study the feasibility of using gold plated sources to iteratively resolve the unresolved sources, obtain the self-calibrated best possible distance-redshift relation and provide an analytical expression for the accuracy achievable. We derive the lower limit on the total number of sources that is needed to achieve this accuracy through self-calibration. We show that this limit depends exponentially on the beam width and give estimates for various experimental parameters representative of future gravitational wave experiments DECIGO and BBO.

Folding a Polymer via Two-Point Interaction with an External Folding Agent: Use of H-Bonding and Charge-Transfer Interactions

A polymer containing electron-rich aromatic donors (1,5-dialkoxynaphthalene (DAN)) was coerced into a folded state by an external folding agent that contained an electron-deficient aromatic acceptor (pyromellitic diimide (PM)) unit. The donor-containing polymer was designed to carry a tertiary amine moiety in the linking segment, which served as an H-bonding site for reinforcing the interaction with the acceptor containing folding agent that also bore a carboxylic acid group. The H-bonding interaction of the carboxylic acid and the tertiary amine brings the PDI unit between two adjacent DAN units along the polymer backbone to induce charge-transfer (C-T) interactions, and this in turn causes the polymer chain to form a pleated structure. Evidence for the formation of such a pleated structure was obtained from NMR titration studies and also by monitoring the C-T band in their UV-visible spectra. By varying the length of the segment that links the PDI acceptor to the carboxylic acid group, we showed that the most effective folding agent was the one that had a single carbon spacer, as evident from the highest value of the association constant. Control experiments with propionic acid clearly demonstrated the importance of the additional C-T interactions for venerating the folded structures. Further, solution viscosity measurements in the presence of varying amounts of the folding agent revealed a gradual stiffening of the chain in the case of the PDI carrying carboxylic acid, whereas no such affect was seen in the case of simple propionic acid. These observations were supported by D FT calculations of the interactions of a dimeric model of the polymer with the various folding agents; here too the stability of the complex was seen to be highest in the case of the single carbon spacer.

Vapour phase synthesis of salol over solid acids via transesterification

The transesterification of methyl salicylate with phenol has been studied in vapour phase over solid acid catalysts such as ZrO2, MoO3 and SO42- or Mo(VI) ions modified zirconia. The catalytic materials were prepared and characterized for their total surface acidity, BET surface area and powder XRD patterns. The effect of mole-ratio of the reactants, catalyst bed temperature, catalyst weight, flow-rate of reactants, WHSV and time-on-stream on the conversion (%) of phenol and selectivity (%) of salol has been investigated. A good yield (up to 70%) of salol with 90% selectivity was observed when the reactions were carried out at a catalyst bed temperature of 200 degrees C and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of SO42- or Mo(VI) ions. The effect of poisoning of acid sites of SO42- or Mo(VI) ions modified zirconia on total surface acidity, powder XRD phases and catalytic activity was also studied. Possible reaction mechanisms for the formation of salol and diphenyl ether over acid sites are proposed.

Enantioselective formal total syntheses of Clavukerin A and isoclavukerin A via a ring-closing metathesis reaction

Enantioselective formal total syntheses of the marine trisnorsesquiterpenes clavukerin A and isoclavukerin A, starting from (R)-limonene employing an RCM reaction as the key step, are described.

COMMON-Sense net:Improved water management for resource-poor farmers via sensor networks

We describe the on-going design and implementation of a sensor network for agricultural management targeted at resource-poor farmers in India. Our focus on semi-arid regions led us to concentrate on water-related issues. Throughout 2004, we carried out a survey on the information needs of the population living in a cluster of villages in our study area. The results highlighted the potential that environment-related information has for the improvement of farming strategies in the face of highly variable conditions, in particular for risk management strategies (choice of crop varieties, sowing and harvest periods, prevention of pests and diseases, efficient use of irrigation water etc.). This leads us to advocate an original use of Information and Communication Technologies (ICT). We believe our demand-driven approach for the design of appropriate ICT tools that are targeted at the resource-poor to be relatively new. In order to go beyond a pure technocratic approach, we adopted an iterative, participatory methodology.

Phase diagram and dielectric studies of binary organic materials

The phase equilibrium studies of organic system, involving resorcinol (R) and p-dimethylaminobenzaldehyde (DMAB), reveal the formation of a 1:1 molecular complex with two eutectics. The heat of mixing, entropy of fusion, roughness parameter, interfacial energy, and the excess thermodynamic functions were calculated based on enthalpy of fusion data determined via differential scanning calorimetric (DSC) method. X-ray powder diffraction studies confirm that the eutectics are not simple mechanical mixture of the components under investigation. The spectroscopic investigations (IR and NMR) suggest the occurrence of hydrogen bonding between the components forming the molecular complex. The dielectric measurements, carried out on hot-pressed addition compound (molecular complex), show higher dielectric constant at 320 K than that of individual components. The microstructural investigations of eutectic and addition compound indicate dendritic and faceted morphological features. (C) 2000 Elsevier Science B.V. All rights reserved.

An alpha-aminomethyl carbanion equivalent via a novel Barbier reaction: (1H-naphtho[1,8-de]-1,2,3-triazin-2-yl)methyl anion

A novel sonication-promoted Barbier reaction putatively generated the titled species from the corresponding naphthotriazinylmethyl chloride and magnesium in THF: its formal addition to a variety of carbonyl compounds in situ occurred in excellent yields. Subsequent catalytic hydrogenolysis of the triazine moiety demasked the amine, thus defining a route to various phenylethylamines (including the alkaloid 'mescaline'), or ethanolamines (in two cases), in excellent overall yields. (C) 2000 Elsevier Science Ltd. All rights reserved.

Quantum Error Correction via Codes over GF(2)

It is well known that n-length stabilizer quantum error correcting codes (QECCs) can be obtained via n-length classical error correction codes (CECCs) over GF(4), that are additive and self-orthogonal with respect to the trace Hermitian inner product. But, most of the CECCs have been studied with respect to the Euclidean inner product. In this paper, it is shown that n-length stabilizer QECCs can be constructed via 371 length linear CECCs over GF(2) that are self-orthogonal with respect to the Euclidean inner product. This facilitates usage of the widely studied self-orthogonal CECCs to construct stabilizer QECCs. Moreover, classical, binary, self-orthogonal cyclic codes have been used to obtain stabilizer QECCs with guaranteed quantum error correcting capability. This is facilitated by the fact that (i) self-orthogonal, binary cyclic codes are easily identified using transform approach and (ii) for such codes lower bounds on the minimum Hamming distance are known. Several explicit codes are constructed including two pure MDS QECCs.

Attaching chelating ligands to polybenzimidazole via epoxidation to obtain metal selective sorbents

Microporous polybenzimidazole of 250–500 μm spherical bead size from Celanese has been reacted with epichlorohydrin and sodium hydroxide and the resulting product with pendant epoxy groups has been reacted with various chelating ligands in order to augment the metal sorption capacity and selectivity of the resin. The chelating ligands used include ethylenediamine, diethylenetriamine, diethanolamine, dimethylglyoxime, L-cysteine, thiourea, dithiooxamide, glyoxal-bis-2-hydroxyanil, salicylaldehyde-ethylenediimine, and glyoxal-bis-2-mercaptoanil. The aminolysis of the pendant epoxy groups with the oligoamines has been performed in pyridine under reflux conditions, while the addition reactions with the other ligands which are alkali soluble have been carried out at room temperature in a mixture of dioxane and aqueous KOH using tetra-n-butylammonium iodide as the phase transfer catalyst. The products are found to possess high capacity and selectivity in metal sorption depending on the ligand attached.

Conformations of three heterocyclicperhydropyrrolobenzofurans and polymeric assembly via co-operative inter-molecular C-H center dot center dot center dot O hydrogen bonds

In 1-cyclo-hexyl-6,6,8a-trimethyl-3a,6,7,8a-tetra-hydro-1H-1-benzofuro[2,3-b]pyrrole-2,4(3H,5H)-dione, C19H27NO3, (I), and the isomorphous compounds 6,6,8a-trimethyl-1-phenyl-3a,6,7,8a-tetra-hydro-1H-1-benzofuro[2,3-b]pyrrole-2,4(3H,5H)-dione, C19H21NO3, (II), and 6,6,8a-trimethyl-1-(3-pyridyl)-3a,6,7,8a-tetra-hydro-1H-1-benzofuro[2,3-b]pyrrole-2,4(3H,5H)-dione, C18H20N2O3, (III), the tetra-hydro-benzo-dihydro-furo-pyrrolidine ring systems are folded at the cis junction of the five-membered rings, giving rise to a non-planar shape of the tricyclic cores. The dihydro-furan and pyrrolidine rings in (I) are puckered and adopt an envelope conformation. The cyclo-hexene rings adopt a half-chair conformation in all the mol-ecules, while the substituent N-cyclo-hexyl ring in (I) assumes a chair form. Short intra-molecular C-HcO contacts form S(5) and S(6) motifs. The isomorphous compounds (II) and (III) are effectively isostructural, and aggregate into chains via inter-molecular C-HcO hydrogen bonds.

Structural, dielectric and ferroelectric properties of four-layer Aurivillius phase Na0.5La0.5Bi4Ti4O15

Monophasic Na0.5La0.5Bi4Ti4O15 powders were synthesized via the conventional solid-state reaction route. The X-ray powder diffraction (XRD), selected area electron diffraction (SAED) and high resolution transmission electron microscopy (HRTEM) studies carried out on the as synthesized powdered samples confirmed the phase to be a four-layer Aurivillius that crystallizes in an orthorhombic A2(1)am space group. The microstructure and the chemical composition of the sintered sample were examined by scanning electron microscope (SEM) equipped with an energy dispersive X-ray analyzer (EDX). The dielectric properties of the ceramics have been studied in the 27-700 degrees C temperature range at various frequencies (100 Hz to 1 MHz). A sharp dielectric anomaly was observed at 580 degrees C for all the frequencies corresponding to the ferroelectric to paraelectric phase transition. Saturated ferroelectric hysteresis loops were observed at 200 degrees C and the associated remnant polarization (P-r) and coercive field (E-c) were found to be 7.4 mu C/cm(2) and 34.8 kV/cm, respectively. AC conductivity analysis confirmed the existence of two different conduction mechanisms in the ferroelectric region. Activation energies calculated from the Arrhenius plots were similar to 0.24 eV and similar to 0.84 eV in the 300-450 degrees C and 450-580 degrees C temperature ranges, respectively. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis of S-functionalized thioesters using thioaroylate ions derived from carboxylic acids and tetrathiomolybdate via acyloxyphosphonium intermediates

Thioaroylate ions generated in situ from acyloxyphosphonium salts and tetrathiomolybdate upon Michael addition or ring opening of three membered systems led to a facile synthesis of S-funcationalized thioesters. While the ring opening of aziridines gave very good yield of the products, Micheal addition and epoxide ring opening gave moderate yields.(C) 2010 Elsevier Ltd. All rights reserved.