First dynamic kinetic resolution of selenium-containing chiral amines catalyzed by palladium (Pd/BaSO(4)) and Candida antartica lipase (CAL-B)

An efficient method for chemoenzymatic dynamic kinetic resolution of selenium-containing chiral amines (organoselenium-1-phenylethanamines) has been developed, leading to the corresponding amides in excellent enantioselectivities and high isolated yields. This one-pot procedure employs two different types of catalysts: Pd on barium sulphate (Pd/BaSO(4)) as racemization catalyst and lipase (CAL-B) as the resolution catalyst. (C) 2009 Elsevier Ltd. All rights reserved.

Subepithelial connective tissue graft for root coverage in smokers and non-smokers: A clinical and histologic controlled study in humans

Background: The aim of this study was to evaluate root coverage of gingival recessions and to compare graft vascularization in smokers and non-smokers. Methods: Thirty subjects, 15 smokers and 15 non-smokers, were selected. Each subject had one Miller Class I or II recession in a non-molar tooth. Clinical measurements of probing depth (PD), relative clinical attachment level (CAL), gingival recession (GR), and width of keratinized tissue (KT) were determined at baseline and 3 and 6 months after surgery. The recessions were treated surgically with a coronally positioned flap associated with a subepithelial connective tissue graft. A small portion of this graft was prepared for immunohistochemistry. Blood vessels were identified and counted by expression of factor VIII-related antigen-stained endothelial cells. Results: Intragroup analysis showed that after 6 months there a was gain in CAL, a decrease in GR, and an increase in KT for both groups (P<0.05), whereas changes in PD were not statistically significant. Smokers had less root coverage than non-smokers (58.02% +/- 19.75% versus 83.35% +/- 18.53%; P<0.05). Furthermore, the smokers had more GR (1.48 +/- 0.79 mm versus 0.52 +/- 0.60 mm) than the nonsmokers (P<0.05). Histomorphometry of the donor tissue revealed a blood vessel density of 49.01 +/- 11.91 vessels/200x field for non-smokers and 36.53 +/- 10.23 vessels/200x field for smokers (P<0.05). Conclusion: Root coverage with subepithelial connective tissue graft was negatively affected by smoking, which limited and jeopardized treatment results.

Efficacy of high intensity diode laser as an adjunct to non-surgical periodontal treatment: a randomized controlled trial

The high intensity diode laser has been studied in periodontics for the reduction of subgingival bacteria in non-surgical treatment. Our study evaluated the bacterial effect as well as changes in periodontal clinical parameters promoted by root scaling and planing associated with this wavelength. Twenty-seven patients randomly assigned in two groups underwent root scaling and planing on the tested sites, and only the experimental group received the diode laser irradiation. Among the clinical parameters studied, the clinical probing depth (CPD) and the clinical attachment level (CAL) resulted in significant enhancement in the control group when compared with the experimental group (P = 0.014 and P = 0.039, respectively). The results were similar for both groups regarding the plaque index (PI) and bleeding on probing (BP). No significant difference in the microbiological parameters was observed between the control and experimental groups. It was possible to conclude that the high power diode laser adjunct to the non-surgical periodontal treatment did not promote additional effects to the conventional periodontal treatment.

Anisotropy and chemical composition of ultra-high energy cosmic rays using arrival directions measured by the Pierre Auger Observatory

The Pierre Auger Collaboration has reported. evidence for anisotropy in the distribution of arrival directions of the cosmic rays with energies E > E(th) = 5.5 x 10(19) eV. These show a correlation with the distribution of nearby extragalactic objects, including an apparent excess around the direction of Centaurus A. If the particles responsible for these excesses at E > E(th) are heavy nuclei with charge Z, the proton component of the sources should lead to excesses in the same regions at energies E/Z. We here report the lack of anisotropies in these directions at energies above E(th)/Z (for illustrative values of Z = 6, 13, 26). If the anisotropies above E(th) are due to nuclei with charge Z, and under reasonable assumptions about the acceleration process, these observations imply stringent constraints on the allowed proton fraction at the lower energies.

Post-collisional lamprophyric event in Sierra Norte, Cordoba, Argentina: Mineralogical, geochemical and isotopic characteristics

Over 20 lamprophyre dykes, varying in width between a few centimeters and several meters, have been identified in central Sierra Norte - Eastern Pampean Ranges, Cordoba, Argentina. Their mineralogy and chemistry indicate that they are part of the calc-alkaline lamprophyres clan (CAL). They contain phenocrysts of magnesiohomblende +/- augite set in a groundmass of magnesiohornblende, calcic-plagioclase, alkali feldspar, and opaque minerals, which designate them as spessartite-type lamprophyres. Alteration products include chlorite, calcite and iron oxides after malfic phenocrysts, though some are partially replaced by actinolite. Feldspars are replaced by carbonate and clay minerals. The dykes are relatively primitive, and show restricted major element variation (SiO(2) 51.1-55.3 wt.%, Al(2)O(3) 12-16.6 wt.%, total alkalies 1.5-4.7 wt.%), high Mg# (55-77), high Cr contents (27-988 ppm) and moderate to high Ni contents (60-190 ppm). Lamprophyre LILE (e.g. Rb averages 110 ppm, Sr 211-387 ppm, Ba 203-452 ppm) are high relative to HFSE (e.g., Ta 0.2-1.6 ppm, Nb 4-11 ppm, Y 17-21 ppm), and are enriched in LREE (30-70 times chondrite). They are characterized by relatively high (208)Pb/(204)Pb (38.8-39.9), (207)Pb/(204)Pb(similar to 15.7), and (206)Pb/(204)Pb (18.7-20.1), combined with low (epsilon)epsilon(Nd) (-4.69 to -1.52) and a relative moderately high ((87)Sr/(86)Sr)(i) of 0.7055-0.7074. The Rb-Sr whole rock isochron indicates an Early Ordovician age of 485 +/- 25 Ma. The calculated T(DM) (1.7 Ga) suggests that these rocks appear to have originated from a reservoir that was created during a mantle metasomatism event related to the Pampean orogeny. The Sierra Norte lamprophyres show affinities with a subduction-related magma in an active continental margin. Their geochemical and isotopic features suggest a multicomponent source, composed of enriched mantle material variably contaminated by crustal components. The lamprophyric suite emplacement occurred at the dawning stage of the Pampean orogeny, in a regional post-collisional extensional setting developed in the Sierra Norte-Ambargasta batholith (SNAB) in Early Ordovician times. (C) 2008 Published by Elsevier Ltd.

Holocene fires in East Amazonia (Caraja`s), new evidences, chronology and relation with paleoclimate

Past studies have evidenced the presence of charcoal in soils and lacustrine sediments of Amazonia region and suggested occurrences of widespread fires during the Middle Holocene. However, the available records do not indicate the changes in fire regime with enough time resolution. We quantified charcoal fragments in lacustrine sediments in a lake of North Carajas plateau in East Amazonia (5 degrees 50`-6 degrees 35`S and 49 degrees 30`-52 degrees 00`W). The charcoal quantification was compared to other sediment proxies, allowing a connection between paleofires and climate changes. Large variations in sediment characteristics led to distinct stages of sedimentation. From 11,800 (base of CSN 93/4) to 4750 cal yr B.P., low accumulation rates of organic matter are observed. Between 7600 cal yr B.P. (base of CSN 93/3 core) and 4750 cal yr B.P., this initial phase of sedimentation is characterized by low chlorophyll derivate accumulation rates and high accumulation rates of Botryococcus braunii, an alga resistant to episodic drought. The first phase of sedimentation would therefore correspond to, a low take level and a drier climate than today. Large biomass burning events occurred between 7450 cal yr B.P. and 4750 cal yr B.P., as indicated by the high charcoal particle concentration. From 4750 cal yr B.P. to 2800 cal yr B.P., accumulation rates of charcoal particles decreased, and the accumulation rate of chlorophyll derivate was low. From 2800 cal yr B.P. to 1300 cal yr B.P., the charcoal accumulation rates reached their lowest values in the core and a rapid increase in lacustrine production is evidenced by the increase in chlorophyll derivates and carbon accumulation rate. From 1300 cal yr B.P. to the last century, the charcoal accumulation rates increased. During the most recent period, the record is characterized by high accumulation rates of chlorophyll derivates while the charcoal particle accumulation rate decreased. This region is still unaffected by the current increase of anthropogenic fires. (c) 2007 Elsevier B.V. All rights reserved.

Chemoenzymatic synthesis of boron-containing chiral amines and amides

The first application of lipases as catalysts to obtain optically active boron-containing amines and amides is described. We studied several reaction conditions to achieve the kinetic resolution of boron-containing amines via enantioselective acylation mediated by Candida antarctica lipase B (CAL-B). Excellent enantioselectivity (E>200) and high enantiomeric excess (up to >99%) of both the remaining amines and amides were obtained. (C) 2010 Elsevier Ltd. All rights reserved.

Direct Kinetic Observation of the Chemiexcitation Step in Peroxyoxalate Chemiluminescence

A high-energy intermediate in the peroxyoxalate reaction can be accumulated at room temperature under specific reaction conditions and in the absence of any reducing agent in up to micromolar concentrations. Bimolecular interaction of this intermediate, accumulated in the reaction of oxalyl chloride with hydrogen peroxide, with an activator (highly fluorescent aromatic hydrocarbons with low oxidation potential) added in delay shows unequivocally that this intermediate is responsible for chemiexcitation of the activator. Activation parameters for the unimolccular decomposition of this intermediate (Delta H(double dagger) = 11.2 kcal mol(-1); Delta S(double dagger) = -23.2 cal mol(-1) K(-1)) and for its bimolecular reaction with 9,10-diphenylanthracene (Delta H(double dagger) = 4.2 kcal mol(-1); Delta S(double dagger) = -26.9 cal mol(-1) K(-1)) show that this intermediate is much less stable than typical 1,2-dioxetanes and 1,2-dioxetanones and demonstrate its highly favored interaction with the activator. Therefore, it can be inferred that structural characterization of the high-energy intermediate in the presence of an activator must be highly improbable. The observed linear free-energy correlation between the catalytic rate constants and the oxidation potentials of several activators definitely confirms the occurrence of the chemically initiated electron-exchange luminescence (CIEEL) mechanism in the chemiexcitation step of the peroxyoxalate system.

Enzymatic kinetic resolution of organochalcogenides in supercritical CO(2)

1-(Phenylthio)-, 1-(phenylseleno)- and 1-(phenyltelluro)-propan-2-ol were efficiently resolved by CAL-B in sc-CO(2). (C) 2011 Elsevier Ltd. All rights reserved.

First chemoenzymatic synthesis of organoselenium amines and amides

A series of organoselenium amines have been synthesized and submitted to the enzymatic kinetic resolution by acetylation mediated by CAL-B (Novozym 435) to give the corresponding chiral amides in an enantiomerically pure form. After evaluating the appropriate lipase, solvent, temperature,and lipase/substrate ratio in the kinetic resolution, the chiral organoselenium amides were obtained with enantiomeric excess of up to 99%. (C) 2008 Elsevier Ltd. All rights reserved.