The kinetics of the gas-phase reactions of selected monoterpenes and cyclo-alkenes with ozone and the NO3 radical

The relative rate method has been used to measure the room-temperature rate constants for the gasphase reactions of ozone and NO3 with selected monoterpenes and cyclo-alkenes with structural similarities to monoterpenes. Measurements were carried out at 298 ! 2 K and 760 ! 10 Torr. The following rate constants (in units of 10"18 cm3 molecule"1 s"1) were obtained for the reaction with ozone: methyl cyclohexene (132 ! 17), terpinolene (1290 ! 360), ethylidene cyclohexane (223 ! 57), norbornene (860 ! 240), t-butyl isopropylidene cyclohexane (1500 ! 460), cyclopentene (543 ! 94), cyclohexene (81 ! 18), cyclooctene (451 ! 66), dicyclopentadiene (1460 ! 170) and a-pinene (107 ! 13). For the reaction with NO3 the rate constants obtained (in units of 10"12 cm3 molecule"1 s"1) were: methyl cyclohexene (7.92 ! 0.95), terpinolene (47.9 ! 4.0), ethylidene cyclohexane (4.30 ! 0.24), norbornene (0.266 ! 0.029), cyclohexene (0.540 ! 0.017), cyclooctene (0.513 ! 0.029), dicyclopentadiene (1.20 ! 0.10) and a-pinene (5.17 ! 0.62). Errors are quoted as the root mean square of the statistical error (95% con!dence) and the quoted error in the rate constant for the reference compound. Combining these results with previous studies, new recommendations for the rate constants are presented. Molecular orbital energies were calculated for each alkene and the kinetic data are discussed in terms of the deviation from the structureeactivity relationship obtained from the rate constants for a series of simple alkenes. Lifetimes with respect to key initiators of atmospheric oxidation have been calculated suggesting that the studied reactions play dominant roles in the night-time removal of these compounds from the atmosphere.

Magnetic characterization of ferrihydrite nanoparticles synthesized by hydrolysis of Fe metal-organic precursor

We investigate the formation of ferrihydrite nanoparticles (NPs) by hydrolysis of the Fe(III) alkoxide Fe(O(t)Bu)(3). Controlled amounts of water, up to 3.0 vol%, were added to the precursor solution yielding a series of hydrolyzed samples ranging from P0.0 (the unreacted precursor) to P3.0. X-ray diffraction (XRD) analysis evidenced the formation of high-crystalline ferrihydrite NP in sample P3.0, with grain size estimate of about 3.2 nm. The transition from the molecular precursor to the formation of crystalline magnetic NPs was followed through magnetization measurements M(T) and M(H), as well as Mossbauer spectroscopy (MS). M(T) measurements indicate a paramagnetic (PM) behavior for sample P0.0, characteristic of binuclear Fe-O-Fe units, which evolves to a superparamagnetic (SPM) behavior, with an energy barrier for the blocking process estimated for sample P3.0 as E(a) = 4.9 x 10(-21) J (E(a)/k(B) = 355 K), resulting in a high effective anisotropy constant K(eff) = 290 kJ/m(3). Magnetization loops at 5 K progressively change from PM-like to ferromagnetic-like shape upon increasing the hydrolysis process, although hysteresis (H(c) approximate to 500 Oe) only is apparent for P2.0 and higher. MS spectra at room temperature are PM/SPM doublets for all samples, while the MS spectra at T = 4.2 K reveal increasingly well-defined magnetic ordering as hydrolysis of the precursor stepwise progresses until well-crystallized ferrihydrite particles are formed. (C) 2008 Elsevier B.V. All rights reserved.

Two-photon absorption spectrum of the photoinitiator Lucirin TPO-L

Two-photon absorption induced polymerization provides a powerful method for the fabrication of intricate three-dimensional microstructures. Recently, Lucirin TPO-L was shown to be a photoinitiator with several advantageous properties for two-photon induced polymerization. Here we measure the two-photon absorption cross-section spectrum of Lucirin TPO-L, which presents a maximum of 1.2 GM at 610 nm. Despite its small two-photon absorption cross-section, it is possible to fabricate excellent microstructures by two-photon polymerization due to the high polymerization quantum yield of Lucirin TPO-L. These results indicate that optimization of the two-photon absorption cross-section is not the only material parameter to be considered when searching for new photoinitiators for microfabrication via two-photon absorption.

Ability of Ru complexes for ROMP tuned through a combination of phosphines and amines

Polynorbonerne with high molecular weight was obtained via ring opening metathesis polymerization using catalysts derived from [RuCl(2)(PPh(2)Bz)(2) L] (1 for L = PPh(2) Bz; 2 for L = piperidine) type of complexes when in the presence of ethyl diazoacetate in CHCl(3). The polymer precipitated within a few minutes at 50 degrees C when using 1 with ca. 50% yield ([NBE]/[Ru] = 5000). Regarding 2, for either 30 min at 25 C or 5 min at 50 degrees C, more than 90% of yields are obtained; and at 50 C for 30 min a quantitative yield is obtained. The yield and PDI values are sensitive to the [NBE]/[Ru] ratio. The reaction of 1 with either isonicotinamide or nicotinamide produces six-coordinated complexes of [RuCl(2)(PPh(2)Bz)(2)(L)(2)] type, which are almost inactive and produce only small amounts of polymers at 50 C for 30 min. Thus, we Concluded that the novel complexes show very distinct reactivities for ROMP of NBE. This has been rationalized on account of a combination of synergistic effects of the phosphine-amine ancillary ligands. (C) 2009 Elsevier B.V. All rights reserved.

Síntese enzimática de ésteres de açúcar: surfactantes e polímeros como novos materiais ambientalmente seguros

Sugar esters are substances which possess surfactant, antifungical and bactericidal actions and can be obtained through two renewable sources of raw materials: sugars and vegetable oils. Their excellent biodegradability, allied to lhe fact that they are non toxic, insipid, inodorous, biocompatible, no-ionic, digestible and because they can resist to adverse conditions of temperature, pH and salinity, explain lhe crescent use of these substances in several sections of lhe industry. The objective of this thesis was to synthesize and characterize surfactants and polymers containing sugar branched in their structures, through enzymatic transesterification of vinyl esters and sugars, using alkaline protease from Bacillus subtilis as catalyst, in organic medium (DMF).Three types of sugars were used: L-arabinose, D-glucose and sucrose and two types of vinyl esters: vinyl laurate and vinyl adipate. Aiming to reach high conversions from substrates to products for a possible future large scale industrial production, a serie of variables was optimized, through Design of Experiments (DOE), using Response Surface Methodology (RSM).The investigated variables were: (1) enzyme concentration; (2) molar reason of substrates; (3) water/solvent rale; (4) temperature and (5) time. We obtained six distinct sugar esters: 5-0-lauroyl L-arabinose, 6-0-lauroyl D-glucose, 1'-O-lauroyl sucrose, 5-0-vinyladipoyl L-arabinose, 6-0-vinyladipoyl D-glucose and 1 '-O-vinyladipoyl sucrose, being lhe last three polymerizable. The progress of lhe reaction was monitored by HPLC analysis, through lhe decrease of sugar concentration in comparison to lhe blank. Qualitative analysis by TLC confirmed lhe formation of lhe products. In lhe purification step, two methodologies were adopted: (1) chromatographic column and (2) extraction with hot acetone. The acylation position and lhe chemical structure were determined by 13C-RMN. The polymerization of lhe three vinyl sugar esters was possible, through chemical catalysis, using H2O2 and K2S2O8 as initiators, at 60°C, for 24 hours. IR spectra of lhe monomers and respective polymers were compared revealing lhe disappearance of lhe vinyl group in lhe polymer spectra. The molar weights of lhe polymers were determined by GPC and presented lhe following results: poly (5-0-vinyladipoyl L-arabinose): Mw = 7.2 X 104; PD = 2.48; poly (6-0-vinyladipoyl D-glucose): Mw = 2.7 X 103; PD = 1.75 and poly (1'-O-vinyladipoyl sucrose): Mw = 4.2 X 104; PD = 6.57. The six sugar esters were submitted to superficial tension tests for determination of the critical micelle concentrations (CMC), which varied from 122 to 167 ppm. Finally, a study of applicability of these sugar esters, as lubricants for completion fluids of petroleum wells was' accomplished through comparative analysis of lhe efficiency of these sugar esters, in relation to three commercial lubricants. The products synthesized in this thesis presented equivalent or superior action to lhe tested commercial products

Soldiers initiate foraging activities in the subterranean termite, Heterotermes tenuis

Caste polyethism has been recorded in some termite species, however the foraging behavior of subterranean termites remains poorly known. Heterotermes tenuis Hagen (Isoptera: Rhinotermitidae) is a subterranean termite that is native to Brazil and is an agricultural and urban pest. The aim of this study was to investigate which caste acts as scouts when searching for food sources and determinate the percentages of each caste present in the foraging territories of field colonies of H. tenuis. Our results showed no significant differences among the caste proportions present in the foraging territories of the three colonies studied in the field. Laboratory experiments showed that minor soldiers were the most frequent initiators of foraging activities. This result suggests that the exploratory phase of the foraging behavior may be regulated by the number of soldiers present in the foraging territories of each colony.

Effect of cerium (IV) ions on the anticorrosion properties of siloxane-poly(methyl methacrylate) based film applied on tin coated steel

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

Dose- and sex-related carcinogenesis by N-bis(2-hydroxypropyl)nitrosamine in Wistar rats

An initiation-promotion medium-term bioassay for detection of chemical carcinogens, developed in the male F344 rat, uses 0.1% N-bis(2-hydroxypropyl)nitrosamine (DHPN) among five genotoxic chemicals for the initiation of carcinogenesis in multiple organs. To establish this bioassay in the Wistar strain, the effects of two dose levels of DHPN were evaluated on the main DHPN rat target organs: lung, thyroid gland, kidneys and liver. Four groups of male and female animals were studied: Control--untreated group; Multi-organ initiated group (also referred to as DMBDD, based on the initials of the five initiators)-treated sequentially with N-diethylnitrosamine (DEN, i.p.), N-methyl-N-nitrosourea (MNU, i.p.), N-butyl-N-(4-hydroxy butyl)nitrosamine (BBN, drinking water), N, N'-dimethylhydrazine (DMH, s.c.) and DHPN (drinking water) for 4 weeks; a third group treated with 0.1% DHPN in drinking water for 2 weeks and the last group treated with 0.2% DHPN in drinking water for 4 weeks. The animals were sacrificed after 30 weeks. DHPN at 0.2% induced preneoplasia in the liver and kidneys of rats of both sexes, the number and area of the putative preneoplastic liver glutathione S-transferase-positive hepatocyte foci being significantly increased in these animals. It also induced benign and malignant tumors in female and in male rats. However, there was no relationship between the increased incidence of preneoplastic lesions and tumor development in the 0.2% DHPN-exposed groups of both sexes. DHPN at 0.1% induced only a few preneoplastic lesions in the liver and kidney and no tumors in both male and female rats. A clear dose and sex-related carcinogenic activity of DHPN was registered, although Wistar rats of both sexes showed a relative resistance to the carcinogenic activity of this compound.

Organic-inorganic hybrids prepared by carboxylic acid solvolysis: Planar waveguides

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

Synthesis and functionalization of magnetite nanoparticles with different amino-functional alkoxysilanes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Nanocomposites of Styrene-Butadiene Rubber and Synthetic Anatase Obtained by a Colloidal Route and Their Photooxidation

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

Efeitos de ultradiluições de drogas carcinogênicas iniciadoras e da dexametasona na carcinogênese hepática de ratos

Pós-graduação em Ciências Biológicas (Biologia Celular e Molecular) - IBRC

Seleção de isolados de Bacillus thuringiensis Berliner em lagartas de Putella xylostella (L.) (Lepdoptera: Plutellidae)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Seleção assistida por marcadores moleculares microssatélites para resistência ao oídio em soja

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Lesões histológicas em ratos Wistar submetidos ao protocolo modificado do bioensaio DMBDD

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)