Reações de Cp'(CO)2MnPPH2H com CH3COCl e CH3S(O)2Cl em THF/trietilamina: evidências da primeira estabilização por complexação de um fósforo-homólogo das sulfonamidas

Cp'Mn(CO)3 (Cp'=h5-C5H4-CH 3) reacts with P(C6H5)2H in THF to give Cp'(CO)2MnPPh2H (Ph = Phenyl) (1), by substitution of one CO ligand. The reaction of 1 with CH3COCl and CH3S(O)2Cl in the presence of triethylamine occurs under electrophilic substitution on the diphenylphosphan ligand to yield the acetyl- and sulfonylphosphane complexes of manganese(I) Cp'(CO)2MnPPh2COCH3 (2) and Cp'(CO)2MnPPh2S(O)2 CH3 (3). The complex stabilisation of these molecules, wich are hitherto unknown in the free state, is only accomplished by blocking the free electron pair on phosphorus by coordination. The new complexes 1, 2 and 3 were analysed by IR, ¹H-NMR and 31P-MNR spectroscopy and their similar structures are discusssed.

An expeditious and consistent procedure for tetrahydrofuran (THF) drying and deoxygenation by the still apparatus

Despite the availability of alternative methods for drying tetrahydrofuran (THF), the use of the still apparatus, wherein a THF solution containing Na-bezophenone ketyl is heated to reflux, remains widespread. We herein propose a set of procedures to solve the problems usually faced in applying this drying technique. Moreover, a discussion is made on the chemical knowledge underlying such procedures. Safety and economy issues concerned with the operation of the THF still apparatus are also discussed.

The molecular structure and one-pot synthesis of [Li(thf)3·Sn(SiMe3)3]

The molecular structure of [Li(thf)3 · Sn(SiMe3)3], prepared by a new, one-pot synthesis in 44% yield, has been determined by a single crystal X-ray diffraction study using synchrotron radiation and a CCD detector. The +Li(thf)3 and −Sn(SiMe3)3 moieties are joined by a Li–Sn bond, 2.865(5) Å in length. [Li(thf)3 · Sn(SiMe3)3] is isomorphous with its germanium analogue.

Estudo de N-metilformamida em meio aquoso e não aquoso (THF)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Mesure de sections efficaces absolues vibrationnelles pour la collision d’électrons de basse énergie (1-19 eV) avec le tétrahydrofurane (THF) condensé

Résumé: Ce mémoire de maîtrise est une étude des probabilités d’interactions (sections efficaces) des électrons de basse énergie avec une molécule d’intérêt biologique. Cette molécule est le tétrahydrofurane (THF) qui est un bon modèle de la molécule constituant la colonne vertébrale de l’ADN; le désoxyribose. Étant donné la grande quantité d’électrons secondaires libérés lors du passage des radiations à travers la matière biologique et sachant que ceux-ci déposent la majorité de l’énergie, l’étude de leurs interactions avec les molécules constituant l’ADN devient rapidement d’une grande importance. Les mesures de sections efficaces sont faites à l’aide d’un spectromètre à haute résolution de pertes d’énergie de l’électron. Les spectres de pertes d’énergie de l’électron obtenus de cet appareil permettent de calculer les valeurs de sections efficaces pour chaque vibration en fonction de l’énergie incidente de l’électron. L’article présenté dans ce mémoire traite de ces mesures et des résultats. En effet, il présente et explique en détail les conditions expérimentales, il décrit la méthode de déconvolution qui est utilisée pour obtenir les valeurs de sections efficaces et il présente et discute des 4 résonances observées dans la dépendance en énergie des sections efficaces. En effet, cette étude a permis de localiser en énergie 4 résonances et celles-ci ont toutes été confirmées par des recherches expérimentales et théoriques antérieures sur le sujet des collisions électrons lents-THF. En outre, jamais ces résonances n’avaient été observées simultanément dans une même étude et jamais la résonance trouvée à basse énergie n’avait été observée avec autant d’intensité que cette présente étude. Cette étude a donc permis de raffiner notre compréhension fondamentale des processus résonants impliqués lors de collisions d’électrons secondaires avec le THF. Les valeurs de sections efficaces sont, quant à elles, très prisées par les théoriciens et sont nécessaires pour les simulations Monte Carlo pour prédire, par exemple, le nombre d’ions formées après le passage des radiations. Ces valeurs pourront justement être utilisées dans les modèles de distribution et dépôt d’énergie au niveau nanoscopique dans les milieux biologiques et ceux-ci pourront éventuellement améliorer l’efficacité des modalités radiothérapeutiques.

Metodologia analítica para determinação de folatos e ácido fólico em alimentos

The aim of this work was to develop and to validate a methodology using HPLC for the simultaneous determination of folates and folic acid in foods. The limits of detection and the recovery rates for the vitamins in the certified reference materials were respectively 5 pg/mL and 94-108% for 5-MTHF, 7 pg/mL and 97-102% for THF, 30 pg/mL and 97.9-104% for 5-FTHF, 30 pg/mL and 95-107 for 10-FFA, 5 ng/mL and 97-102% for FA and 5 ng/mL and 98-103% for 10-MFA. Repeatability showed a coefficient of variation below 3.9% for all the vitamins. The proposed methodology was shown to be efficient when applied to different certified reference materials, namely pig's liver (BCR487), powdered milk (BCR421) and a vegetable mixture (BCR485).

Synthesis, characterization, DFT and Td-dfT study of the [Fe(mnt)(L)(t-BuNC) 2] octahedral complex (L = phen, bipy)

FeBr2 has reacted with an equivalent of mnt2- (mnt = cis-1,2-dicyanoethylene-1,2-dithiolate) and the α-diimine L (L = 1,10'-phenantroline, 2,2'-bipyridine) in THF solution, and followed by adding of t-butyl-isocyanide to give [Fe(mnt)(L)(t-BuNC)2] neutral compound. The products were characterized by infrared, UV-visible and Mössbauer spectroscopy, besides thermogravimetric and conductivity data. The geometry in the equilibrium was calculated by the density functional theory and the electronic spectrum by the time-dependent. The experimental and theoretical results in good agreement have defined an octahedral geometry with two isocyanide neighbours. The π→π* intraligand electronic transition was not observed for cis-isomers in the near-IR spectral region.

Quantum yield excitation spectrum (UV-visible) of CdSe/ZnS core-shell quantum dots by thermal lens spectrometry

A recently developed thermal lens spectrometry configuration has been used to study CdSe/ZnS core-shell quantum dots (QDs) suspended in toluene and tetrahydrofuran (THF) solvents. The special features of this configuration make it very attractive to measure fluorescence quantum yield (eta) excitation spectrum since it simplifies the measurement procedure and consequently improve the accuracy. Furthermore, the precision reached is much higher than in conventional photoluminescence (PL) technique. Two methods, called reference sample and multiwavelength have been applied to determine eta, varying excitation wavelength in the UV-visible region (between 335-543 nm). The eta and PL spectra are practically independent of the excitation wavelength. For CdSe/ZnS QDs suspended in toluene we have obtained eta=76 +/- 2%. In addition, the aging effect on eta and PL has been studied over a 200 h period for QDs suspended in THF. (C) 2010 American Institute of Physics. [doi:10.1063/1.3343517]

Direct Zincation of Functionalized Aromatics and Heterocycles by Using a Magnesium Base in the Presence of ZnCl(2)

A wide range of polyfunctional aryl and heteroaryl zinc reagents were efficiently prepared in THF by using (TMP)(2)Mg center dot 2LiCl (TMP = 2,2,6,6-tetramethylpiperamidyl) in the presence of ZnCl(2). The possible pathways of this metalation procedure as well as possible reactive intermediates are discussed. This experimental protocol expands the tolerance of functional groups and allows an efficient zincation of sensitive heterocycles such as quinoxaline or pyrazine. The zincated arenes and heteroarenes react with various electrophiles providing the expected products in 60-95 % yield.

The radical homopolymerization of N-phenylmaleimide, N-n-hexylmaleimide and N-cyclohexylmaleimide in tetrahydrofuran

The kinetics and mechanisms of thermally initiated (using 2,2'-azobisisoburyronitrile (AIBN) as initiator) radical homopolymerizations of a series of maleimides, including N-phenymaleimide (PHMI) [l-phenyl-1H-pyrrole-2,5-dione]; N-n-hexylmaleimide (nHMI) [l-(n-hexyI)-1H-pyrrole-2,5-dione]; and N-cyclohexylmaIeimide (CHMI) [l-cyclohexyl- 1H-pyrrole-2,5-dione] have been investigated in THF solution by an on-line FT-NIR technique. It was found that the order of the activation energies for the three N-sub-MIs is: E-a PHMI < E-a (PHMI) < E-a (CHMI). The overall polymerization rate parameter k and the pre-exponential factor A were calculated. The kinetic order with respect to the N-sub-MIs was in the range of 0.71 < m < 0.75 for the initiator and n = 1.0 for the monomer. Radical transfer to solvent was found to be the key factor in determining the apparent order with respect to the initiator. All of the homopolymers had a relatively low molecular weight. The end groups of the polymer chains were characterized by MALDI-TOF, GPC and NMR methods and the results clearly indicate that the polymerization was initiated by THF radicals, and that the termination reaction is mainly controlled by chain transfer to solvent through an hydrogen abstraction mechanism. (C) 2001 Elsevier Science Ltd. All rights reserved.

Novel neutral iron(II) isocyanide maleonitrile dithiolate [Fe(S2C2(CN)2)(t-BuNC) 4] compound

FeBr2 reacts with the S2C2(CN)22- ion (1:1 ratio) in the presence of an excess of t-BuNC in THF to give the mixed ligand [Fe(S2C2(CN)2)(t-BuNC) 4] compound. This neutral product with a formal oxidation state of two for the iron atom was characterized by conductivity measurements, and, i.r., Mössbauer, 13C and 1H n.m.r. spectroscopy. There is a Fe-C p back-donation strengthened towards isocyanide ligands, according to the data of 13C, 1H n.m.r. and Mössbauer spectroscopy.

Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.

Influence of commercially available polyimide and formation conditions on the performance and structure of asymmetric polyimide organic solvent nanofiltration membranes

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Engenharia Química e Bioquímica

The role of electron transfer in DNA building blocks: evaluation of strand breaks and their implications

Dissertação para obtenção do Grau de Doutor em Engenharia Física

Soil CO2 efflux in central Amazonia: environmental and methodological effects

Soil respiration plays a significant role in the carbon cycle of Amazonian rainforests. Measurements of soil respiration have only been carried out in few places in the Amazon. This study investigated the effects of the method of ring insertion in the soil as well as of rainfall and spatial distribution on CO2 emission in the central Amazon region. The ring insertion effect increased the soil emission about 13-20% for sandy and loamy soils during the firsts 4-7 hours, respectively. After rainfall events below 2 mm, the soil respiration did not change, but for rainfall greater than 3 mm, after 2 hours there was a decrease in soil temperature and respiration of about 10-34% for the loamy and sand soils, with emissions returning to normal after around 15-18 hours. The size of the measurement areas and the spatial distribution of soil respiration were better estimated using the Shuttle Radar Topographic Mission (SRTM) data. The Campina reserve is a mosaic of bare soil, stunted heath forest-SHF and tall heath forest-THF. The estimated total average CO2 emissions from the area was 3.08±0.8 µmol CO2 m-2 s-1. The Cuieiras reserve is another mosaic of plateau, slope, Campinarana and riparian forests and the total average emission from the area was 3.82±0.76 µmol CO2 m-2 s-1. We also found that the main control factor of the soil respiration was soil temperature, with 90% explained by regression analysis. Automated soil respiration datasets are a good tool to improve the technique and increase the reliability of measurements to allow a better understanding of all possible factors driven by soil respiration processes.