Kinetics and product distribution of p-nitrophenyl phosphate dianion solvolysis in ternary DMSO/alcohol/water mixtures are compatible with metaphosphate formation

The rate of solvolysis of p-nitrophenyl phosphate (PNPP) dianion in DMSO/water strongly decreases by increasing water concentration. Addition of linear alcohols (methanol, propanol, butanol, pentanol, and hexanol) at constant DMSO/water molar ratio produced an even sharper rate decrease. Alkyl phosphate formation, resulting from PNPP solvolysis in ternary DMSO/water/alcohol mixtures, increased with alcohol concentration and was essentially temperature independent. Methanol and hexanol were the poorest nucleophiles under all conditions. Activation energies and enthalpies for solvolysis in ternary mixtures were similar and entropies varied with alcohol concentration. Taken together these results can be best interpreted in terms of a dissociative mechanism with the intervention of metaphosphate. Copyright (C) 2011 John Wiley & Sons, Ltd.

Interaction of p-cymene with beta-cyclodextrin

In this investigation, the study of inclusion complexes formation between p-cymene and beta-cyclodextrin using the methods of physical mixture, paste (PC) and slurry (SC), was evaluated. The results of DSC and TG/DTG showed that the products prepared by PC and SC methods were able to incorporate greater amounts of p-cymene, as evidenced by the weight loss of 7.15 and 3.97%, respectively, which occurred between 120 and 270 A degrees C. SEM images showed decreased size of the household, especially in the SC product. The absorption bands in the IR spectrum, characteristic of p-cymene, were also identified in the preparations, indicating the presence of the compound in the complex.

GIDL behavior of p- and n-MuGFET devices with different TiN metal gate thickness and high-k gate dielectrics

This work studies the gate-induced drain leakage (GIDL) in p- and n-MuGFET structures with different TiN metal gate thickness and high-k gate dielectrics. As a result of this analysis, it was observed that a thinner TiN metal gate showed a larger GIDL due to the different gate oxide thickness and a reduced metal gate work function. In addition, replacing SiON by a high-k dielectric (HfSiON) results for nMuGFETs in a decrease of the GIDL On the other hand, the impact of the gate dielectric on the GIDL for p-channel MuGFETs is marginal. The effect of the channel width was also studied, whereby narrow fin devices exhibit a reduced GIDL current in spite of the larger vertical electric field expected for these devices. Finally, comparing the effect of the channel type, an enhanced GIDL current for pMuGFET devices was observed. (C) 2011 Elsevier Ltd. All rights reserved.

New species of Pseudanos Winterbottom, 1980 (Characiformes: Anostomidae), with notes on the taxonomy of P. gracilis and P. trimaculatus

A new species of Pseudanos (Characiformes, Anostomidae) is described from the Rio Negro in Brazil, and the Rio Casiquiare and Rio Atabapo, in Venezuela. Specimens of the new species were previously mistakenly identified as Pseudanos gracilis. The new species is diagnosed by having three branchiostegal rays (vs. four in P. gracilis and most specimens of P. winterbottomi), dark transversal bars on dorsum absent (vs. present in P. trimaculatus), dark spots present on the center of each body scale, forming conspicuous, straight dark lines (vs. dark spots absent in P. gracilis and in some specimens of P. trimaculatus), four midlateral dark blotches on body (vs. usually two, sometimes three or four in P. trimaculatus, or body lacking midlateral blotches and presenting instead a broad midlateral stripe in P. winterbottomi), angle of dorsal and ventralmost radii of body scales between 40 degrees and 90 degrees (vs. angle between 110 degrees and 180 degrees in P. gracilis and P. trimaculatus), and cranial fontanel opened along its entire length (vs. cranial fontanel partially closed in P. trimaculatus). Type specimens and extensive additional material of Pseudanos gracilis and P. trimaculatus were examined and comments on the taxonomy of both species are provided. Pseudanos irinae is herein considered a junior synonym of P. trimaculatus. In addition, an updated key to identification of valid species of Pseudanos is presented.

Stereoselective synthesis of novel diels-alder adducts of p-substituted Methyl Thiocinnamates and Cyclopentadiene

This article describes the Diels-Alder reaction between methyl thiocinnamates, substituted at the para position by electron-donating and electron-withdrawing groups, with cyclopentadiene in the presence of catechol boron bromide (CBB) as a Lewis acid catalyst. The adduct configuration was confirmed by H-1 NMR coupling constants and single-crystal x-ray diffraction. Total endo stereoselectivity was observed in all reactions and was attributed to the effective secondary interaction between the boron atom and the incipient double bond in the norbonene resulting from the planar geometry of the catalyst. C-13 NMR chemical shifts of the coordinated dienophile carbonyl carbons with CBB compared to those of the non coordinated thiocinammates suggest a strong complexation with the catalyst.