Sensitivity of charge transfer reactions to hydrocarbon ion structures

Charge transfer reactivities of hydrocarbon ions have been measured with time-of-flight techniques, and results correlated with theoretical structures computed by self-consistent field molecular orbital methods. Recombination energies, ion structures, heats of formation, reaction energetics and relative charge transfer cross-sections are presented for molecular and fragment ions produced by electron bombardment ionization of CH4, C2H4, C2H6, C3H8 and C4H10 molecules. Even-electron bridged cations have low ion recombination energies and relatively low charge transfer cross-sections as compared with odd-electron hydrocarbon cations.

Application of headspace solid phase microextraction to qualitative and quantitative analysis of tobacco additives in cigarettes

Cigarettes may contain up to 10% by weight additives which are intended to make them more attractive. A fast and rugged method for a cigarette-screening for additives with medium volatility was developed using automatic headspace solid phase microextraction (HS-SPME) with a 65 microm carbowax-divinylbenzene fiber and gas chromatography-mass spectrometry (GC-MS) with standard electron impact ionisation. In three runs, each cigarette sample was extracted in closed headspace vials using basic, acidic and neutral medium containing 0.5 g NaCl or Na2SO4. Furthermore, the method was optimized for quantitative determination of 17 frequently occurring additives. The practical applicability of the method was demonstrated for cigarettes from 32 brands.

A quantitiative LC-MS/MS method for the measurement of arachidonic acid, prostanoids, endocannabinoids, N-acylethanolamines and steroids in human plasma.

Free arachidonic acid is functionally interlinked with different lipid signaling networks including those involving prostanoid pathways, the endocannabinoid system, N-acylethanolamines, as well as steroids. A sensitive and specific LC-MS/MS method for the quantification of arachidonic acid, prostaglandin E2, thromboxane B2, anandamide, 2-arachidonoylglycerol, noladin ether, lineoyl ethanolamide, oleoyl ethanolamide, palmitoyl ethanolamide, steroyl ethanolamide, aldosterone, cortisol, dehydroepiandrosterone, progesterone, and testosterone in human plasma was developed and validated. Analytes were extracted using acetonitrile precipitation followed by solid phase extraction. Separations were performed by UFLC using a C18 column and analyzed on a triple quadrupole MS with electron spray ionization. Analytes were run first in negative mode and, subsequently, in positive mode in two independent LC-MS/MS runs. For each analyte, two MRM transitions were collected in order to confirm identity. All analytes showed good linearity over the investigated concentration range (r>0.98). Validated LLOQs ranged from 0.1 to 190ng/mL and LODs ranged from 0.04 to 12.3ng/mL. Our data show that this LC-MS/MS method is suitable for the quantification of a diverse set of bioactive lipids in plasma from human donors (n=32). The determined plasma levels are in agreement with the literature, thus providing a versatile method to explore pathophysiological processes in which changes of these lipids are implicated.

Phytol and phytyldiol concentrations at DYFAMED time series station and sediment trap

Particulate samples from the water column were collected monthly from depths of 5-150 m, between May 1996 and March 1997, in the northwestern Mediterranean Sea (Ligurian Sea) as part of the DYFAMED project within the French JGOFS program. These samples were analyzed by gas chromatography-electron impact mass spectrometry for their phytol and 3-methylidene-3,7,11-trimethylhexadecan-1,2-diol (phytyldiol) content. The corresponding Chlorophyll Phytyl side chain Photodegradation Index, molar ratio of phytyldiol to phytol, was calculated and the mean amount of chlorophyll photodegraded within the euphotic zone estimated. Seasonal differences in the chlorophyll photodegradation process appear in the one-year study. The chlorophyll appeared more photodegraded in the surface water (generally more than 40% photodegraded at 5-10 m) than at the deep chlorophyll maximum (DCM) (40-50 m) observed in the summer stratified waters (about 20% photodegraded). This difference was attributed to the healthy state of the phytoplankton community (coincidence with the highest primary production levels) and to the lower intensity of irradiance at the DCM level. On the other hand, the bulk of the detrital chlorophyll (chlorophyll associated with phytodetritus, phaeopigments) undergoes photodegradation before it sinks out of the photic zone. However, in January (winter mixed water) the pigments exported towards the sea floor were less photodegraded. This is thought to result from a shorter period of residence of the pigments in the photic zone due to vertical convection and grazing activity of macrozooplankton (salps), which are producers of rapid sinking fecal pellets.

A mutant of Mycobacterium smegmatis defective in the biosynthesis of mycolic acids accumulates meromycolates

Mycolic acids are a major constituent of the mycobacterial cell wall, and they form an effective permeability barrier to protect mycobacteria from antimicrobial agents. Although the chemical structures of mycolic acids are well established, little is known on their biosynthesis. We have isolated a mycolate-deficient mutant strain of Mycobacterium smegmatis mc2-155 by chemical mutagenesis followed by screening for increased sensitivity to novobiocin. This mutant also was hypersensitive to other hydrophobic compounds such as crystal violet, rifampicin, and erythromycin. Entry of hydrophobic probes into mutant cells occurred much more rapidly than that into the wild-type cells. HPLC and TLC analysis of fatty acid composition after saponification showed that the mutant failed to synthesize full-length mycolic acids. Instead, it accumulated a series of long-chain fatty acids, which were not detected in the wild-type strain. Analysis by 1H NMR, electrospray and electron impact mass spectroscopy, and permanganate cleavage of double bonds showed that these compounds corresponded to the incomplete meromycolate chain of mycolic acids, except for the presence of a β-hydroxyl group. This direct identification of meromycolates as precursors of mycolic acids provides a strong support for the previously proposed pathway for mycolic acid biosynthesis involving the separate synthesis of meromycolate chain and the α-branch of mycolic acids, followed by the joining of these two branches.

Scientific report : RF Project 464 /

1. The determination and interpretation of electronic collision cross sections -- 2. An electron spectrometer for the study of inelastic collision cross sections -- 3. The inelastic scattering of electrons by helium -- 4. Inelastic collision cross sections of carbon monoxide -- 5. An electron impact study of nitrogen in the kinetic energy range 400 to 600 volts -- 6. Electronic collision cross sections and oscillator strengths for oxygen in the Schumann-Runge region -- 7. Electronic collision cross sections for oxygen at excitation energies above 10 volts -- 8. Electronic collsion cross sections for nitrogen at excitation energies from 10 to 80 electron volts -- 9. Additional collision cross sections for helium, especially in the ionized continuum -- 10. A collision cross section study of CO₂, with a theoretical study of two transitions -- 11. Further developments in the theory and use of the electron spectrometer -- 12. Electronic collision cross sections of water vapor.

Synthesis and characterization of triazolotriazines

The Dimroth rearrangement in ring-fused 1,2,4-triazoles has been reviewed in detail in Part I and the synthesis of all known triazolo-triazines is described in Part II. Experimental investigations concerned the establishinent of the skeletal arrangement of a variety of triazolotriazines formed by several synthetic routes. Interaction of 3-amino-5-hydrazino-12,4-triazole and benzilafforded 2-amino-6, 7-diphenyl-1, 2,4-triazolo[ 5, 1-c-]-1,2,4-triazine,whereas cyclization of 5,6-diphenyl-3-hydrazino-1,2,4-triazine withcyanogen bromide resulted in the isomeric 3-amino-6,7-diphenyl,-1,2,4-triazolo [4, 3-b]-1,2,4-triazine: both amines were deaminated with amyl nitrite in boiling tetrahydrofuran without rearrangement of the heterocyclic skeleton. 6,7-Diphenyl-1,2,4-triazolo[5,1-cJ-1,2.4-triazine, synthesized from 3-hydrazino-1,2,4-triazole and benzil, formed a covalent hydrate which could be detected spectroscopically in solution, and a covalemt methanolate and ethanolate which could be isolated. A new route to 3-amino-5-hydrazino-pyrazole is described and cyclization to 7-amino-3,4-diphenyl-pyrazolo[ 5,1-.c]-1,2,4-triazine was achieved with benzil. The diazonium nitrate of 3-amino-1,2,4-triazole coupled with ethyl cyanoacetate to yield a mixture of two geometrical isomers of ethyl 2-(2H-1,2,4-triazol-3-ylhydrazono) cyanoacetate.Recrystallization of the crude coupling mixture from aqueous ethanol gave a single hydra-zone which cyclized predominantly to ethyl 7-amino-1,2,4-triazolo[5,1-c]-1,2,4-triazine-6-carboxylate in acid conditions and 6-cyano-1,2,4-triazolo[ 5,1-c]-1,2,4~triazin-7(4H)-one under basic conditions. The nature of the cyclizing medium also controlled the cyclization of .the (pyrazol-ylhydrazono) cyanoacetate hut the corresponding (tetrazol- ylhydrazono) cyanoacetate gave only ethyl 7-aminotetrazolo[ 5,1-cJ-1,2,4- -triazine-6-carboxylate. 2-( 2H-1,2,4-Triazol-3-:ylhydrazono) malonitrile cyclized unambiguously to 7-amino-6-cyano-1,2,4-triazolo-[ 5,1-c]-1,2,4- triazine. Drastic hydrolysis of ethyl 2-(2H-1,2,4-triazol-3-yllhydrazono)-cyanoacetate, ethyl 7-amino-1, 2,4-triazolo[ 5,1-c]-1,2,4-triazine-6-carboxylate, 6-cyano-1,2,4-triazolo[ 5,1-c]-1,2,4-triazin-7{ 4H)-one and 7-amino-6- cyano-1,2,4-triazolo[5,1-c]-1,2,4-triazine gave a hydrate of 1,2,4-triazo1o[5,1-c ]-1,2,4-triazin-7(4H)-one. Mass spectral fragmentations of 7-aminoazolo-[5,1-c]-1,2,4-triazinesconfirm that the azole ring is more stable than the 1,2,4-triazine ring on electron impact.

Benchmarking a modified version of the civ3 nonrelativistic atomic-structure code within Na-like-tungsten R -matrix calculations

In this work we explore the validity of employing a modified version of the nonrelativistic structure code civ3 for heavy, highly charged systems, using Na-like tungsten as a simple benchmark. Consequently, we present radiative and subsequent collisional atomic data compared with corresponding results from a fully relativistic structure and collisional model. Our motivation for this line of study is to benchmark civ3 against the relativistic grasp0 structure code. This is an important study as civ3 wave functions in nonrelativistic R-matrix calculations are computationally less expensive than their Dirac counterparts. There are very few existing data for the W LXIV ion in the literature with which we can compare except for an incomplete set of energy levels available from the NIST database. The overall accuracy of the present results is thus determined by the comparison between the civ3 and grasp0 structure codes alongside collisional atomic data computed by the R-matrix Breit-Pauli and Dirac codes. It is found that the electron-impact collision strengths and effective collision strengths computed by these differing methods are in good general agreement for the majority of the transitions considered, across a broad range of electron temperatures.

Chemical profile and antifungal potential of essential oils from leaves and flowers of Salvia algeriensis (Desf.): A comparative study

Salvia is a plant genus widely used in folk medicine in the Mediterranean area since antiquity. A large number of Salvia essential oils have been reported against diverse microorganisms. In the current study, chemical composition of essential oils from leaves and flowers of Salvia algeriensis (Desf.) was determined using gas chromatography-electron impact mass spectrometry (GC-EIMS) as well as their antifungal activity against phytopathogenic fungi Alternaria solani and Fusarium oxysporum exploring disk method. The GC-EIMS analysis identified 59 compounds (84.8%) in the essential oil obtained from leaves of S. algeriensis. Its major constituents were benzaldehyde (9.7%), eugenol (8.7%) and phenylethyl alcohol (8.4%). In flowers oil, 34 compounds (92.8%) were detected. The main ones were viridiflorol (71.1%) and globulol (8.6%). The essential oil obtained from leaves exhibited the highest antifungal activity, where the effective dose inhibiting 50% of mycelial fungal (ED50) against A. solani was 0.90 μL mL-1 with minimum inhibitory concentration (MIC) equal to 2 μL mL-1, whereas the ED50 and MIC in F. oxysporum culture was 1.84 μL mL-1 and 3 μL mL-1 respectively. The mycelial inhibition by flowers oil varies from 1.77 μL mL-1 (ED50) with A. solani culture (MIC 6.5 μL mL-1) to the lowest effect recorded (ED50 3.00 μL mL-1 and MIC 9.33 μL mL-1) against F. oxysporum. To our best knowledge, this is the first report on S. algeriensis, their leaves oil can constitute an alternative biocontrol against phytopathogenic fungi commonly controlled by chemical fungicides.

Flowers of Gomphrena globosa L. as an alternatve source of betacyanins: optimization of the extraction using response surface methodology

Betacyanins are betalain pigments that display a red-violet colour which have been reported to be three times stronger than the red-violet dye produced by anthocyanins [1]. The applications of betacyanins cover a wide range of matrices, mainly as additives or ingredients in the food industry, cosmetics, pharmaceuticals and livestock feed. Although, being less commonly used than anthocyanins and carotenoids, betacyanins are stable between pH 3 to 7 and suitable for colouring in low acid matrices. In addition, betacyanins have been reported to display interesting medicinal character as powerful antioxidant and chemopreventive compounds either in vitro or in vivo models [2]. Betacyanins are obtained mainly from the red beet of Beta vulgaris plant (between I 0 to 20 mg per I 00 g pulp) but alternative primary sources are needed [3]. In addition, independently of the source used, the effect of the variables that affect the extraction of betacyanins have not been properly described and quantified. Therefore, the aim of this study was to identifY and optimize the conditions that maximize betacyanins extraction using the tepals of Gomphrena globosa L. flowers as an alternative source. Assisted by the statistical technique of response surface methodology, an experimental design was developed for testing the significant explanatory variables of the extraction (time, temperature, solid-liquid ratio and ethanolwater ratio). The identification was performed using high-performance liquid chromatography coupled with a photodiode array detector and mass spectrometry with electron spray ionization (HPLC-PDAMS/ ESI) and the response was measured by the quantification of these compounds using HPLC-PDA. Afterwards, a response surface analysis was performed to evaluate the results. The major betacyanin compounds identified were gomphrenin 11 and Ill and isogomphrenin IJ and Ill. The highest total betacyanins content was obtained by using the following conditions: 45 min of extraction. time, 35•c, 35 g/L of solid-liquid ratio and 25% of ethanol. These values would not be found without optimizing the conditions of the betacyanins extraction, which moreover showed contrary trends to what it has been described in the scientific bibliography. More specifically, concerning the time and temperature variables, an increase of both values (from the common ones used in the bibliography) showed a considerable improvement on the betacyanins extraction yield without displaying any type of degradation patterns.

Synthesis and antibacterial study of some s-substituted aliphatic analogues of 2-mercapto-5-(1-(4-toluenesulfonyl) piperidin-4-yl)-1,3,4-oxadiazole

Purpose: To synthesize a series of analogues of 1,3,4-oxadiazole and to evaluate their antibacterial activity. Methods: Ethyl piperidin-4-carboxylate (1) was mixed with 4-toluenesulfonyl chloride (2) in benignant conditions to yield ethyl 1-(4-toluenesulfonyl)piperidin-4-carboxylate (3) and then 1-(4- toluenesulfonyl)piperidin-4-carbohydrazide (4). Intermolecular cyclization of 4 into 2-mercapto-5-(1-(4- toluenesulfonyl) piperidin-4-yl)-1,3,4-oxadiazole (5) was obtained on reflux with CS2 in the presence of KOH. Molecule 5 was stirred with alkyl halides, 6a-i, in DMF in the presence of LiH to synthesize the final compounds, 7a-i. The structures of these molecules were elucidated by Fourier transform infra-red (FTIR) spectroscopy, proton nuclear magnetic resonance (1H-NMR) and electron impact mass spectrometry (EI-MS). Antibacterial activity was evaluated against five bacterial strains, namely, Salmonella typhi, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Bacillus subtilis, with ciprofloxacin used as standard antibacterial agent. Results: Out of nine synthesized derivatives, compound 7a was the most active against three bacterial strains, S. typhi, E. coli and P. aeruginosa, with minimum inhibitory concentration (MIC) of 9.11 ± 0.40, 9.89 ± 0.45 and 9.14 ± 0.72 μM, respectively, compared with 7.45 ± 0.58, 7.16 ± 0.58 and 7.14 ± 0.18 μM, respectively, for the reference standard (ciprofloxacin). Similarly, compounds 7a - 7c showed relatively good antibacterial activity against B. subtilis strain while compound 7e - 7g revealed good results against S. typhi bacterial strain. Conclusion: The results indicate that S-substituted derivatives of the parent compound are more effective antibacterial agents than the parent compound, even with minor differences in substituents

Physical modeling and numerical simulations of degradation mechanisms in devices and insulators for power applications

In this thesis, a TCAD approach for the investigation of charge transport in amorphous silicon dioxide is presented for the first time. The proposed approach is used to investigate high-voltage silicon oxide thick TEOS capacitors embedded in the back-end inter-level dielectric layers for galvanic insulation applications. In the first part of this thesis, a detailed review of the main physical and chemical properties of silicon dioxide and the main physical models for the description of charge transport in insulators are presented. In the second part, the characterization of high-voltage MIM structures at different high-field stress conditions up to the breakdown is presented. The main physical mechanisms responsible of the observed results are then discussed in details. The third part is dedicated to the implementation of a TCAD approach capable of describing charge transport in silicon dioxide layers in order to gain insight into the microscopic physical mechanisms responsible of the leakage current in MIM structures. In particular, I investigated and modeled the role of charge injection at contacts and charge build-up due to trapping and de-trapping mechanisms in the oxide layer to the purpose of understanding its behavior under DC and AC stress conditions. In addition, oxide breakdown due to impact-ionization of carriers has been taken into account in order to have a complete representation of the oxide behavior at very high fields. Numerical simulations have been compared against experiments to quantitatively validate the proposed approach. In the last part of the thesis, the proposed approach has been applied to simulate the breakdown in realistic structures under different stress conditions. The TCAD tool has been used to carry out a detailed analysis of the most relevant physical quantities, in order to gain a detailed understanding on the main mechanisms responsible for breakdown and guide design optimization.

Distorted-wave calculation of cross sections for inner-shell ionization by electron and positron impact

The relativistic distorted-wave Born approximation is used to calculate differential and total cross sections for inner shell ionization of neutral atoms by electron and positron impact. The target atom is described within the independent-electron approximation using the self-consistent Dirac-Fock-Slater potential. The distorting potential for the projectile is also set equal to the Dirac-Fock-Slater potential. For electrons, this guarantees orthogonality of all the orbitals involved and simplifies the calculation of exchange T-matrix elements. The interaction between the projectile and the target electrons is assumed to reduce to the instantaneous Coulomb interaction. The adopted numerical algorithm allows the calculation of differential and total cross sections for projectiles with kinetic energies ranging from the ionization threshold up to about ten times this value. Algorithm accuracy and stability are demonstrated by comparing differential cross sections calculated by our code with the distorting potential set to zero with equivalent results generated by a more robust code that uses the conventional plane-wave Born approximation. Sample calculation results are presented for ionization of K- and L-shells of various elements and compared with the available experimental data.

Monte Carlo simulations for dosimetric verification in photon and electron beam radiotherapy

Dissertação para obtenção do Grau de Doutor em Engenharia Biomédica