Dichloro(cyclohexilidene-1-methylene)(phenyl)Te(IV). Looking for the theoretical treatment

C(13)H(16)Cl(2)Te,M(r)=370.76,P2(1)/a, a = 8.1833(8), b = 8.4163(8), c = 20.787(2) A, beta = 99.52(1)degrees, Z = 4, R(1) = 0,0275. The primary coordination around the Te(IV) atom is consistent with a pseudo-trigonal bipyramidal bond configuration with two Cl atoms occupying axial positions while the C atoms and the lone pair of electrons occupy the equatorial positions. The Te(IV) atom is involved in an intermolecular secondary interaction resulting in the self assembly of zigzag-chains supramolecular array. In order to determine the theoretical basis set for the Te atom which leads to the best agreement with the experimental data, a large series of geometry optimizations were performed on dichloro dimethyl Te(IV), as a model compound, and the results compared with the mean distances and angles obtained from 45 X-ray structures. The Ahlrichs basis set plus the Hay & Wadt ECP was selected and used for a series of calculations performed on the title compound.

Automated NMR structure determination and disulfide bond identification of the myotoxin crotamine from Crotalus durissus terrificus

Crotamine is one of four major components of the venom of the South American rattlesnake Crotalus durissus terrificus. Similar to its counterparts in the family of the myotoxins, it induces myonecrosis of skeletal muscle cells. This paper describes a new NMR structure determination of crotamine in aqueous solution at pH 5.8 and 20 degrees C, using standard homonuclear (1)H NMR spectroscopy at 900 MHz and the automated structure calculation software ATNOS/CANDID/DYANA. The automatic NOESY spectral analysis included the identification of a most likely combination of the six cysteines into three disulfide bonds, i.e. Cys4-Cys36, Cys11-Cys30 and Cys18-Cys37; thereby a generally applicable new computational protocol is introduced to determine unknown disulfide bond connectivities in globular proteins. A previous NMR structure determination was thus confirmed and the structure refined. Crotamine contains an alpha-helix with residues 1-7 and a two-stranded anti-parallel beta-sheet with residues 9-13 and 34-38 as the only regular secondary structures. These are connected with each other and the remainder of the polypeptide chain by the three disulfide bonds, which also form part of a central hydrophobic core. A single conformation was observed, with Pro13 and Pro21 in the trans and Pro20 in the cis-form. The global fold and the cysteine-pairing pattern of crotamine are similar to the beta-defensin fold, although the two proteins have low sequence homology, and display different biological activities. (c) 2005 Elsevier Ltd. All rights reserved.

Er:YAG-Laser and Sodium Hypochlorite Influence on Bond to Dentin

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Fluoride release and secondary caries inhibition by adhesive systems on root dentine

This study tested the fluoride-release rate and the root caries inhibitory effect of dental adhesives. In phase 1, the fluoride released from samples (n = 5) of the adhesives A (Optibond Solo), B (One-up Bond F), C (Prime & Bond NT), D (Tenure Quick), and also of the controls [+] (glass-ionomer cement) and [-] (non-fluoride releasing adhesive), was quantified on a daily basis during a pH-cycling, caries-simulating phenomenon. In phase 2, restorations were made in bovine root dentine slabs (n = 16) with the same adhesives associated with a non-fluoridated composite. Control [+] restorations were made entirely with glass-ionomer cement. Specimens were thermocycled and submitted to the pH-cycling regimen. Demineralization areas and the presence of the wall lesion (WL) and the inhibition zone (IZ) were determined by polarizing light microscopy in dentine adjacent to the restoration. The highest concentration of fluoride was released by the control [+]; adhesives A, B and C, also released fluoride. No detectable amount of fluoride was released by D or [-]. Smaller areas of demineralization were found with control [+], whereas the demineralization areas of adhesives A-D and [-] did not differ from each other. No WL was detected, and higher percentages of IZ were recorded to [+] and to adhesive A. Although some dental adhesives were able to release fluoride, they could not inhibit secondary caries development as well as the glass-ionomer cement.