Reagent-switch controlled metal-free intermolecular geminal diamination and aminooxygenation of vinylarenes

We report here the first general method for the geminal diamination and an intermolecular metal-free, geminal aminooxygenation of vinylarenes using hypervalent iodine reagent. A new m-CPBA mediated geminal aminooxygenation is also reported. A novel reagent-switch for the control of migrating group by controlling the two independent geminal addition paths is developed. Deuterium labelling studies and the control studies have provided unambiguous evidences for the phenyl migration and hydride migration in the oxidative geminal difunctionalization process mediated by Phl(OCOCF3)(2) and m-CPBA, respectively through a semi-pinacol rearrangement. (C) 2016 Elsevier Ltd. All rights reserved.

Characterization of silver-kaolinite (AgK): an adsorbent for long-lived I-129 species

Bentonite is a preferred buffer and backfill material for deep geological disposal of high-level nuclear waste (HLW). Bentonite does not retain anions by virtue of its negatively charged basal surface. Imparting anion retention ability to bentonite is important to enable the expansive clay to retain long-lived I-129 (iodine-129; half-life = 16 million years) species that may escape from the HLW geological repository. Silver-kaolinite (AgK) material is prepared as an additive to improve the iodide retention capacity of bentonite. The AgK is prepared by heating kaolinite-silver nitrate mix at 400 degrees C to study the kaolinite influence on the transition metal ion when reacting at its dehydroxylation temperature. Thermo gravimetric-Evolved Gas Detection analysis, X-ray diffraction analysis, X-ray photo electron spectroscopy and electron probe micro analysis indicated that silver occurs as AgO/Ag2O surface coating on thermally reacting kaolinite with silver nitrate at 400 degrees C.

Growth of bulk single crystals beta-FeSi2 by chemical vapour deposition

Bulk single crystals b-FeSi2, as a new photoelectric and thermoelectric material, has been successfully grown using chemical vapor transport technique by using iodine as transport agent in a sealed ampoule. The effects of crystal growth condition on quality and morphologies of the single crystals were studied. Both needle-like and grain-like single crystals were gained. By changing substrate temperature, tetrahedral high quality a-FeSi2 single crystals were also obtained.

用FLUENT软件计算化学氧碘激光流场

用计算流体动力学(CFD)软件FLUENT,数值研究化学氧碘激光喷管形线,碘喷孔位置,副流入口压力,O2(1△)初始产额,水蒸汽含量以及稀释气体对平均小信号增益系数沿流动方向分布的影响;并对大连化学物理研究所超音速化学氧碘激光的两次实验进行数值模拟,计算结果显示平均小信号增益系数与实验测试的摩尔功率趋势一致.

NUMERICAL ANALYSIS OF THE FLOWFIELD IN A SUPERSONIC COIL WITH AN INTERLEAVED JET CONFIGURATION AND ITS EFFECT ON THE GAIN DISTRIBUTION

In a supersonic chemical oxygen-iodine laser (COIL) operating without primary buffer gas, the features of flowfield have significant effects on the Laser efficiency and beam quality. In this paper three-dimensional, multi-species, chemically reactive CFD technology was used to study the flowfield in mixing nozzle implemented with a supersonic interleaving jet configuration. The features of the flowfield as well as its effect on the spatial distribution of small signal gain were analyzed.

Contos da Câmara 2 : depoimentos de servidores nos 180 anos do Legislativo

Reúne depoimentos de servidores da Câmara do Deputados sobre os acontecimentos que marcaram a história do parlamento brasileiro a partir da segunda metade do século XX. Coletados pelo Núcleo de História Oral da Câmara durante as comemorações dos 180 anos do Poder Legislativo em 2003, os textos retratam a realidade dos primeiros anos vividos no Planalto Central: a carência de infra-estrutura, a falta de opção de atividades de lazer e o profundo sentimento de saudade da antiga capital da República. Mas também levam a reminiscências de momentos divertidos, curiosidades e reflexões animadas e esperançosas sobre a mudança da capital para Brasília. O ponto alto são as experiências vivenciadas nos prédios do Congresso Nacional, a lembrança dos amigos, dos colegas e, especialmente, dos fatos marcantes, que sublinham as significativas mudanças nas rotinas de trabalho da Instituição para se adequar à modernização e às novas exigências da sociedade, no contexto de acontecimentos políticos que modificaram seguidas vezes o cenário do país.

化学反应与饱和模型对化学氧碘激光性能的影响

将速率方程(RE)模型与化学动力学模型相结合,讨论了增益饱和模型与化学反应系统对COIL性能的影响.流动为预混的一维模型,考虑了10种成分和21个化学反应,分析计算了未分解碘分子,激发态氧产率,水含量以及温度等因素对COIL性能的影响.计算结果表明,碘流量过多,混合和反应过程中消耗大量能量;碘流量过低,导致粒子数反转和增益过低,对于能量的提取不利.

L'aristocratie negriere, ou, reflexions philosophiques et historiques sur l'esclavage et l'affranchissement des noirs : par M. L'Abbé Sibire : ancien ami des Africains; et leur premier Missionnaire dans le royaume de Loango

Sibire foi o primeiro missionário do Reino de Loango, antigo estado africano, fundado provavelmente em 1485 pelo povo Vili. O reino de Loango tornou-se independente entre os séculos XVIl e XVIII, e em 1885 dividiu-se entre o Estado do Congo, Portugal e França . Sibire considerava-se grande amigo dos africanos. A obra ‘L'aristocratie negriere, ou, Réflexions philosophiques et hisloriques sur l'esclavage et l'affranchissemenl des noirs’ é composta de duas partes: a primeira traz a transcrição de um discurso proferido por Sibire na Assembleia Nacional africana; a segunda relata o conteúdo de uma carta dirigida aos colonos, negros, europeus, negociantes e agricultores. O tema dominante em toda a obra é o repúdio à escravidão e a defesa da liberdade do ser humano

Una nueva aproximación a la síntesis de heterociclos pirrolofusionados basada en la reacción de amidación de alquinos asistida por el reactivo de yodo hipervalente PIFA

458 p.

Iod in Fischen und Fischerzeugnissen

Germany is one of the iodine deficiency countries in Europe. Marine fish and its products can considerably contribute to the iodine supply via food. The short review gives an overview on the iodine content in fish and other marine species and discusses the influence of house hold cooking and other kitchen preparations. The iodine content in marine fish depends on the species and varies considerably at high level. Lean fish species have an average iodine content of more than 100 μg I / 100 g edible part. The recommended allowance for adults of dietary iodine of 180-200 μg can be covered by the consumption of one marine fish portion per day.

Reactivity of titanocene methylidene with metal halides, alkene sulfides, and alkene oxides

Titanocene metallacyclobutanes show a wide variety of reactivites with organic and inorganic reagents. Their reactions include methylene transfer to organic carbonyls, formation of enolates, electron transfer from activated alkyl chlorides, olefin metathesis, ring opening polymerization. Recently, preparations of heterobinuclear µ-methylene complexes were reported. In this thesis, mechanistic, synthetic, and structural studies of the heterobinuclear µ-methylene complexes will be described. Also, the reaction of titanocene methylidene trimethylphosphine complex with alkene sulfide and styrene sulfide will be presented.

Heterobinuclear µ-methylene-µ-methyl complexes C_(p2)Ti(µ-CH_2)( µ-CH_3)M(1,5-COD) have been prepared (M = Rh, Ir). X-ray crystallography showed that the methyl group of the complex was bonded to the rhodium and bridges to the titanium through an agostic bond. The ^(1)H,^(13)CNMR, IR spectra along with partial deuteration studies supported the structure in both solution and solid state. Activation of the agostic bond is demonstrated by the equilibration of the µ-CH_3 and µ-CH_2 groups. A nonlinear Arrhenius plot, an unusually large kinetic isotope effect (24(5)), and a large negative activation entropy (-64(3)eu) can be explained by the quantum-mechanical tunneling. Calculated rate constants with Bell-type barrier fitted well with the observed one. This equilibration was best explained by a 4e-4c mechanism (or σ bond metathesis) with the character of quantum-mechanical tunneling.

Heterobinuclear µ-methylene-µ-phenyl complexes were synthesized. Structural study of C_(p2)Ti(µ-CH_(2))(µ-p-Me_(2)NC_(6)H_(4))Rh(l,5-COD) showed that the two metal atoms are bridged by the methylene carbon and the ipso carbon of the p-N,N-dimethylarninophenyl group. The analogous structure of C_(p2))Ti(µ-CH_(2))(µ-o-MeOC_(6)H_(4))Rh(1,5-COD) has been verified by the differential NOE. The aromaticity of the phenyl group observed by ^(1)H NMR, was confirmed by the comparison of the C-C bond lengths in the crystallographic structure. The unusual downfield shifts of the ipso carbon in the ^(13)C NMR are assumed to be an indication of the interaction between the ipso carbon and electron-deficient titanium.

Titanium-platinum heterobinuclear µ-methylene complexes C_(p2)Ti(µ-CH_(2))(µ -X)Pt(Me)(PM_(2)Ph) have been prepared (X= Cl, Me). Structural studies indicate the following:(1) the Ti-CH2 bond possesses residual double bond character, (2) there is a dative Pt→Ti interaction which may be regarded as a π back donation from the platinum atom to the 'Ti=CH_(2)'' group, and (3) the µ-CH_3 group is bound to the titanium atom through a three-center, two-electron agostic bond.

Titanocene (η^(2)-thioformaldehyde)•PMe_3 was prepared from C_(p2)Ti=CH_(2)•PMe_3 and sulfur-containing organic compounds (e.g. alkene sulfide, triphenylphosphine sulfide) including elemental sulfur. Mechanistic studies utilizing trans-styrene sulfide-d_1 suggested the stepwise reaction to explain equimolar mixture of trans- and cis-styrene-d_1 as by-products. The product reacted with methyl iodide to produce cationic titanocene (η_(2)-thiomethoxymethyl) complex. Complexes having less coordinating anion like BF_4 or BPh_4 could be obtained through metathesis. Together with structural analyses, the further reactivities of the complexes have been explored.

The complex C_(p2)TiOCH_(2)CH(Ph)CH_2 was prepared from the compound C_(p2)Ti=CH_(2)-PMe_3 and styrene oxide. The product was characterized with ^(1)H-^(1)H correlated 2-dimensional NMR, selective decoupling of ^(1)H NMR, and differential NOE. Stereospecificity of deuterium in the product was lost when trans-styrene oxide-d_1 was allowed to react. Relative rates of the reaction were measured with varying substituents on the phenyl ring. Better linearity (r = -0.98, p^(+) = -0.79) was observed with σ_(p)^(+)than σ(r = -0.87, p = -1.26). The small magnitude of p^+ value and stereospecificity loss during the formation of product were best explained by the generation of biradicals, but partial generation of charge cannot be excluded. Carbonylation of the product followed by exposure to iodine yields the corresponding β-phenyl γ-lactone.

Electron energy-loss spectroscopy study of polyatomic molecular systems under pyrolytic conditions

The technique of variable-angle, electron energy-loss spectroscopy has been used to study the electronic spectroscopy of the diketene molecule. The experiment was performed using incident electron beam energies of 25 eV and 50 eV, and at scattering angles between 10° and 90°. The energy-loss region from 2 eV to 11 eV was examined. One spin-forbidden transition has been observed at 4.36 eV and three others that are spin-allowed have been located at 5.89 eV, 6.88 eV and 7.84 eV. Based on the intensity variation of these transitions with impact energy and scattering angle, and through analogy with simpler molecules, the first three transitions are tentatively assigned to an n → π* transition, a π - σ* (3s) Rydberg transition and a π → π* transition.

Thermal decomposition of chlorodifluoromethane, chloroform, dichloromethane and chloromethane under flash-vacuum pyrolysis conditions (900-1100°C) was investigated by the technique of electron energy-loss spectroscopy, using the impact energy of 50 eV and a scattering angle of 10°. The pyrolytic reaction follows a hydrogen-chloride α-elimination pathway. The difluoromethylene radical was produced from chlorodifluoromethane pyrolysis at 900°C and identified by its X^1 A_1 → A^1B_1 band at 5.04 eV.

Finally, a number of exploratory studies have been performed. The thermal decomposition of diketene was studied under flash vacuum pressures (1-10 mTorr) and temperatures ranging from 500°C to 1000°C. The complete decomposition of the diketene molecule into two ketene molecules was achieved at 900°C. The pyrolysis of trifluoromethyl iodide molecule at 1000°C produced an electron energy-loss spectrum with several iodine-atom, sharp peaks and only a small shoulder at 8.37 eV as a possible trifluoromethyl radical feature. The electron energy-loss spectrum of trichlorobromomethane at 900°C mainly showed features from bromine atom, chlorine molecule and tetrachloroethylene. Hexachloroacetone decomposed partially at 900°C, but showed well-defined features from chlorine, carbon monoxide and tetrachloroethylene molecules. Bromodichloromethane molecule was investigated at 1000°C and produced a congested, electron energy-loss spectrum with bromine-atom, hydrogen-bromide, hydrogen-chloride and tetrachloroethylene features.

Síntese, caracterização e avaliação da capacidade bactericida de copolímeros à base de 2-vinilpiridina funcionalizados

Neste trabalho, dois copolímeros à base de 2-vinilpiridina (2Vpy), estireno (Sty) e divinilbenzeno (DVB) foram sintetizados empregando a técnica de polimerização em suspensão aquosa via radical livre. Os copolímeros com diferentes características morfológicas foram preparados variando a composição da mistura diluente, constituída por tolueno e n-heptano, solventes solvatantes e não solvatantes para as cadeias poliméricas. A caracterização estrutural desses materiais foi feita através de medidas de área específica, volume de poros, diâmetro médio de poros e densidade aparente. Além disso, esses materiais foram avaliados por microscopia ótica e eletrônica de varredura, por espectroscopia na região do infravermelho (FTIR), análise termogravimétrica (TGA) e análise elementar. Os copolímeros Sty-DVB-2Vpy foram modificados quimicamente através de reação de quaternização das unidades de 2Vpy usando dois reagentes: iodeto de metila e acrilonitrila. A quaternização dos copolímeros Sty-DVB-2Vpy foi confirmada através de espectroscopia de infravermelho, pelo aparecimento das bandas de absorção características do íon peridíneo e do grupo nitrila e também pela análise do comportamento térmico. Os produtos dessas reações foram submetidos à avaliação da capacidade bactericida através do método de contagem em placas contra suspensão de Escherichia coli. O copolímero do tipo gel quaternizado com iodeto de metila apresentou a maior ação bactericida registrada, com eficiência até a concentração de 104 células/mL. Contudo, a maioria dos materiais quaternizados não apresentou ação biocida significativa. Com o objetivo de maximizar a atividade bactericida dos materiais preparados, os copolímeros quaternizados e não quaternizados foram impregnados com iodo por meio de duas metodologias: em solução e em fase vapor. O teor de iodo incorporado foi quantificado por análise gravimétrica. Foi possível observar que os copolímeros quaternizados e impregnados com iodo se mostraram mais eficientes como agentes bactericidas que os copolímeros não funcionalizados impregnados com iodo. De uma forma geral, foi possível perceber que a ação bactericida dos polímeros é fruto da associação entre as suas características de porosidade, o grau de quaternização alcançado e o teor de iodo incorporado. Para efeito de comparação foram feitos também ensaios bactericidas com uma resina comercial à base de Sty-DVB com grupo amônio quaternário, VP OC 1950. Os testes mostraram que a resina comercial não possui atividade bactericida. A impregnação de iodo a essa resina comercial forneceu um material com ação biocida semelhante à do copolímero do tipo gel, quaternizado com iodeto de metila e impregnado com iodo

Estudo da correlação entre as características da matéria-prima graxa e as propriedades físico-químicas do biodiesel

A possibilidade de utilização de várias matérias graxas na produção do biodiesel nacional é um fator diferencial em relação aos outros países e requer um conhecimento mais profundo das particularidades do biodiesel obtido a partir de matérias-primas tão distintas. Neste contexto, se insere a presente pesquisa, em que se buscou estabelecer correlações entre algumas propriedades do biodiesel e a fonte oleaginosa que lhe deu origem. O biodiesel foi obtido a partir da reação de transesterificação etílica de dez diferentes matérias-primas graxas (óleos refinados de soja, arroz, canola, girassol, milho, oliva, cyclus (mistura contendo óleos de canola, milho e girassol); óleos brutos de mamona e murumuru, além de resíduo de fritura), utilizando etanolato de potássio como agente catalítico, em um reator com sistema de refluxo a 70C durante uma hora. Após purificação, foram determinadas algumas propriedades do biodiesel (massa específica, viscosidade, índice de acidez e índice de iodo) e da matéria-prima (massa específica, viscosidade, índice de acidez, índice de iodo e composição) que lhe deu origem. Os resultados obtidos nas caracterizações geraram gráficos de correlações entre os diversos parâmetros e os dados foram analisados estatisticamente pelo método de correlações canônicas. Para todas as amostras de biodiesel, os valores obtidos nas caracterizações foram compatíveis com as especificações estabelecidas pela ANP para o produto, com exceção do biodiesel de murumuru (índice de acidez elevado e viscosidade baixa) e do biodiesel de mamona (viscosidade e massa específica elevadas). Os dados estatísticos demonstram altas correlações entre o biodiesel (massa específica (87,4%), viscosidade (98,5%) e índice de acidez (82,8%)) e as matérias-primas (massa específica (92,1%) e viscosidade (99,3%)). Além disso, existe uma grande correlação entre o índice de iodo (84,5%) do biodiesel e o índice de iodo (77,2%) e a massa molar dos ésteres na faixa de C16-C18 (MMTG) presentes na matéria-prima (89,1%). Estes resultados estatísticos ratificam as observações analíticas

Long-term natural acidification of upland sites in Cumbria: Evidence from post-glacial lake sediments

Studies by the Freshwater Biological Association over the last 25 years have supplied data relevant to the levels of acidity in local soils and water before the onset of industrial pollution and current interest in acid rain. This article reviews published analysis from cores of lake sediments, in or near the catchment of the River Duddon. Electron spin resonance spectra of humic acids and iodine values confirm evidence from pollen analysis for a history of progressive acidification of the source material of lake sediments since before 5000 radiocarbon years, in upland catchments of the Lake District. Processes involved included: removal of basic ions from soils by rainfall, the effects of which were intensified by removal by man of deciduous forest; acidification of soils and waters by decomposition products of Calluna and further acidification of waters by Sphagnum species which colonized habitats where drainage became impeded by paludification processes.