Synthesis based on cyclohexadienes .21. Total synthesis of (+/-)-hinesol and (+/-)-10-epi-hinesol

An efficient strategy for the construction of the spiro[4,5]decane and eremane systems is described which involves an acid-catalysed rearrangement of an endo alcohol, followed by an oxidative cleavage resulting in the generation of a spiro-system, as the key step, This methodology is extended to the total synthesis of (+/-)-hinesol and (+/-)-10-epi-hinesol 2.

Synthesis based on cyclohexadienes .22. Formal syntheses of patchouli alcohol and norpatchoulenol

The preparation of 6-endo-formyl-1,3,3-trimethylbicyclo[2.2.2]octan-2-one 7 and 6-endo-acetyl-1,3,3-trimethylbicyclo[2.2.2]octan-2-one 8, the two key intermediates for the synthesis of patchouli alcohol 1 and norpatchoulenol 2, is reported by a simple and short method from 2-methylbenzoic acid.

N-3-benzoyl-2 ',3 '-di-O-benzoyluridine

The structure of N-3-benzoyl-2',3'-di-O-benzoyluridine, C30H24N2O9, has two molecules in the asymmetric unit. The uracil bases of both the molecules are in the anti conformation with respect to the ribose moiety and the furanosyl rings adopt a C3'-endo conformation. The orientation about the C4'-C5' bond is gauche-gauche. The two crystallographically independent molecules are linked through several C-H ... O hydrogen bonds. The nucleoside molecules pack as columns along the a axis and these columns repeat along the c axis.

N-4-anisoylcytidine dihydrate

The title compound, C17H19N3O7. 2H(2)O, has C2'-endo, C3'-exo puckering, The orientation of the base with respect to the sugar is anti and the geometry about C4'-C5' is gauche,trans. The angle between the cytidine base and the phenyl ring of the anisoyl group is 15.5(2)degrees.

N-6-anisoyladenosine monohydrate

The title compound, C18H19N5O6. H2O, has a syn conformation about the glycosidic bond. Its furanose ring shows a C2'-endo-C3'-exo twist conformation and trans-gauche geometry about the C4'-C5' bond. The angle between the adenine base and the phenyl ring of the anisoyl group is 22.9 degrees. Adenine and anisoyl groups stack along the b axis at a separation of 3.4 Angstrom.

Stereochemistry of the marine sesquiterpene 2-thiocyanatoneopupukeanane: Crystal structure of neopupukean-2-yl 4-nitrobenzoate

Single crystal X-ray diffraction analysis of neopupukean-2-yl p-nitrobenzoate unambiguously established the stereochemistry of the thiocyanate group as endo in the marine sesquiterpene 2-thiocyanatoneopupukeanane.

Investigating proline puckering states in diproline segments in proteins

In the current study, the puckering states of the Proline ring occurring in diproline segments (LPro-LPro) in proteins has been investigated with a segregation made on the basis of cis and trans states for the Pro-Pro peptide bond and the conformational states for the diproline segment to investigate the effects of conformation of the diproline segment on the corresponding puckering state of the Proline ring in the segment if any. The value of the endocyclic ring torsional angles of the pyrrolidine ring has been used for calculating and visualizing various puckering states using a proposed new sign convention (+/-) nomenclature. The results have been compared to that obtained in a previous study on peptides from this group. In this study, quite interestingly, the Planar (G) conformation that was present in 14.3% of the cases in peptides, appears to be nearly a rare conformation in the case of proteins (1.9%). The present study indicates that the (C-exo/C-exo), (C-exo/Twisted C-exo-C-endo) and (Twisted C-endo-C-exo/Twisted C-endo-C-exo) categories are the most preferred combinations. For Proline rings in proteins, the states C-exo, Twisted C-exo-C-endo and Twisted C-endo-C-exo are the most preferred states. Within diproline segments, the pyrrolidine ring conformations do not show a strong co-relation to the backbone conformation in which they are observed. It is likely that five-membered rings have a considerable plasticity of structure and are readily deformed to accommodate a variety of energetically preferred backbone conformations.

Energy Hyperspace for Stacking Interaction in AU/AU Dinucleotide Step: Dispersion-Corrected Density Functional Theory Study

Double helical structures of DNA and RNA are mostly determined by base pair stacking interactions, which give them the base sequence-directed features, such as small roll values for the purine-pyrimidine steps. Earlier attempts to characterize stacking interactions were mostly restricted to calculations on fiber diffraction geometries or optimized structure using ab initio calculations lacking variation in geometry to comment on rather unusual large roll values observed in AU/AU base pair step in crystal structures of RNA double helices. We have generated stacking energy hyperspace by modeling geometries with variations along the important degrees of freedom, roll, and slide, which were chosen via statistical analysis as maximally sequence dependent. Corresponding energy contours were constructed by several quantum chemical methods including dispersion corrections. This analysis established the most suitable methods for stacked base pair systems despite the limitation imparted by number of atom in a base pair step to employ very high level of theory. All the methods predict negative roll value and near-zero slide to be most favorable for the purine-pyrimidine steps, in agreement with Calladine's steric clash based rule. Successive base pairs in RNA are always linked by sugar-phosphate backbone with C3-endo sugars and this demands C1-C1 distance of about 5.4 angstrom along the chains. Consideration of an energy penalty term for deviation of C1-C1 distance from the mean value, to the recent DFT-D functionals, specifically B97X-D appears to predict reliable energy contour for AU/AU step. Such distance-based penalty improves energy contours for the other purine-pyrimidine sequences also. (c) 2013 Wiley Periodicals, Inc. Biopolymers 101: 107-120, 2014.

Oriented nanometric aggregates of partially inverted zinc ferrite: One-step processing and tunable high-frequency magnetic properties

In this work, it is demonstrated that the in situ growth of oriented nanometric aggregates of partially inverted zinc ferrite can potentially pave a way to alter and tune magnetocrystalline anisotropy that, in turn, dictates ferromagnetic resonance frequency (f(FMR)) by inducing strain due to aggregation. Furthermore, the influence of interparticle interaction on magnetic properties of the aggregates is investigated. Mono-dispersed zinc ferrite nanoparticles (<5 nm) with various degrees of aggregation were prepared through decomposition of metal-organic compounds of zinc (II) and iron (III) in an alcoholic solution under controlled microwave irradiation, below 200 degrees C. The nanocrystallites were found to possess high degree of inversion (>0.5). With increasing order of aggregation in the samples, saturation magnetization (at 5 K) is found to decrease from 38 emu/g to 24 emu/g, while coercivity is found to increase gradually by up to 100% (525 Oe to 1040 Oe). Anisotropy-mediated shift of f(FMR) has also been measured and discussed. In essence, the result exhibits an easy way to control the magnetic characteristics of nanocrystalline zinc ferrite, boosted with significant degree of inversion, at GHz frequencies. (C) 2015 AIP Publishing LLC.

Preliminary survey of parasites of Clarias in the Niger Delta area of Nigeria

A total of 160 Clarias lazera were collected with line hood between April and June 1984 from the Niger Delta area and observed for the presence of parasites. The results revealed the presence of three classes of endo-parasites: Trematodes (47%), nematodes (46%) and cestodes (7%). It was found that, the parasites have great affinity for the spleen (34%) and the liver (28.3%). Also, smaller fish habored more parasites than large fish. Though the investigation is still continuing, the study reveals the presence of parasites in Clarias and calls for measures to prevent wide-spread infestation in fish ponds and suggests treatment of infested fish

Investigations of the origin of stereocontrol in syndiospecific Ziegler-Natta polymerizations

In order to expand our understanding of the mechanism of stereocontrol in syndiospecific α-olefin polymerization, a family of Cs-symmetric, ansa-group 3 metallocenes was targeted as polymerization catalysts. The syntheses of new ansa-yttrocene and scandocene derivatives that employ the doubly [SiMe₂]- bridged ligand array (1,2-SiMe₂)₂{C₅H-3,5-(CHMe₂)₂} (where R = t- butyl, tBuThp; where R = i-propyl, iPrThp) are described. The structures of tBuThpY(µ-Cl)₂K(THF)₂, tBuThpSc(µ-Cl)₂K(Et₂O)₂, tBuThpYCH(SiMe₃)₂, Y₂{µ₂-(tBuThp)₂}(µ₂-H)₂, and tBuThpSc(µ-CH₃)₂ have been examined by single crystal X-ray diffraction methods. Ansa-yttrocenes and scandocenes that incorporate the singly [CPh₂]-bridged ligand array (CPh₂)(C₅H₄)(C₁₃H₈)(where C₅H₄ = Cp, cyclopentadienyl; where C₁₃H₈ = Flu, fluourenyl) have also been prepared. Select meallocene alkyl complexes are active single component catalysts for homopolymerization of propylene and 1-pentene. The scandocene tetramethylaluminate complexes generate polymers with the highes molecular weights of the series. Under all conditions examined atactic polymer microstructures are observed, suggesting a chain-end mechanism for stereocontrol.

A series of ansa-tantalocenes have been prepared as models for Ziegler-Natta polymerization catalysts. A singly bridged ansa-tantalocene trimethyl complex, Me₂Si(η⁵-C₅H₄)₂TaMe₃, has been prepared and used for the synthesis of a tantalocene ethylene-methyl complex. Addition of propylene to this ethylene-methyl adduct results in olefin exchange to give a mixture of endo and exo propylene isomers. Doubly-silylene bridged ansa-tantalocene complexes have been prepared with the tBuThp ligand; a tantalocene trimethyl complex and a tantalocene methylidene-methyl complex have been synthesized and characterized by X-ray diffraction. Thermolysis of the methylidene-methyl complex affords the corresponding ethylene-hydride complex. Addition of either propylene or styrene to this ethylene-hydride compound results in olefin exchange. In both cases, only one product isomer is observed. Studies of olefin exchange with ansa-tantalocene olefin-hydride and olefin-methyl complexes have provided information about the important steric influences for olefin coordination in Ziegler-Natta polymerization.

Relativistic laser channeling in plasmas for fast ignition

We report an experimental observation suggesting plasma channel formation by focusing a relativistic laser pulse into a long-scale-length preformed plasma. The channel direction coincides with the laser axis. Laser light transmittance measurement indicates laser channeling into the high-density plasma with relativistic self-focusing. A three-dimensional particle-in-cell simulation reproduces the plasma channel and reveals that the collimated hot-electron beam is generated along the laser axis in the laser channeling. These findings hold the promising possibility of fast heating a dense fuel plasma with a relativistic laser pulse.

Norbornenyl- and nortricyclyl free radicals

The number, symmetry, and product-forming capabilities of the intermediates in the photoinitiated reductions of endo- and exo-5- bromonorbornene and 2-bromonortricyclene with tri-n-butyltin hydride at temperatures between -10° and 22° were investigated.

Three mechanisms were evaluated:

1. The 5-norbornenyl- and 2-nortricyclyl radicals isomerize reversibly with the former producing nortricyclene by abstraction of hydrogen from tri-n-butyltin hydride.

2. The 5-norbornenyl- and 2-nortricyclyl radicals isomerize reversibly, but some norbornene can be formed from the 2-nortricyclyl radical or some nortricyclene can be formed from the 5-norbornenyl radical by abstraction of hydrogen.

3. There is intervention of a "bridged" radical which may be for med reversibly or irreversibly from the 5-norbornenyl- and 2-nortricyclyl radicals.

Within small error limits, the ratios of norbornene to nortricyclene as a function of the concentration of tri-n-butyltin hydride are consistent with the first mechanism.

In the reductions with tri-n-butyltin deuteride, primary deuterium isotope effects of 2. 3 and 2. 1 for the abstraction of deuterium by the 2-nortricyclyl- and 5-norbornenyl radicals, respectively, were found. The primary deuterium isotope effects were invariant with the concentration of tri-n-butyltin deuteride, although the ratios of norbornene to nortricyclene changed appreciably over this range. This is consistent with the first mechanism, and can accommodate the formation of either product from more than one intermediate only if the primary kinetic deuterium isotope effects are nearly equal for all reactions leading to the single product.

The reduction of endo-5-bromonorbornene-5, 6, 6-d₃ with tri-n-butyltin hydride or tri-n-butyltin deuteride leads to both unrearranged and rearranged norbornenes. The ratios of unrearranged to rearranged norbornene require that the 5-norbornenyl-5, 6, 6-d₃ radical isomerize to an intermediate with the symmetry expected of a nortricyclyl free radical. The results are consistent with mechanism 1, but imply a surprising normal secondary kinetic deuterium isotope effect of about 1.25 for the abstraction of hydrogen by the 5-norbornenyl- 5, 6, 6-d₃ radical.

Approximate calculations show that there does not appear to be any substantial difference in the stabilities of the 5-norbornenyl and 2-nortricyclyl radicals.

Although the results can not exclude a small contribution by a mechanism other than mechanism 1, no such contribution is required to adequately explain the results.

Estudo comparativo da citotoxicidade de cimentos obturadores sobre culturas de células endoteliais da linhagem ECV 304

Este estudo teve como objetivo avaliar, in vitro, a citotoxicidade dos cimentos endodônticos Densell Endo, Pulp-Fill, Endofill, Sealer 26, Pulp Canal Sealer e GuttaFlow após 12, 24 e 72 horas de tempo de contato, utilizando-se uma linhagem de células endoteliais ECV-304. Para a avaliação da viabilidade celular, utilizou-se o teste de citotoxicidade MTT. Para cada cimento foram preparados 12 corpos de prova que foram distribuídos em seis grupos experimentais de acordo com as marcas comerciais, sendo quatro para cada tempo. Foi criado um grupo controle que não foi submetido à ação de cimento. Para avaliação do efeito dos cimentos sobre as células endoteliais, os corpos de prova foram inseridos nos poços da placa cultura, incubados a 37C em presença de 5% de CO2 e 100% de umidade. Os testes MTT foram realizados, em quadruplicata, após 12, 24 e 72 horas de contato das amostras com o tapete celular. Foi utilizada a prova Two-Way Anova com o teste Post Hoc de Bonferroni com nível de significância de 5%. Na análise de 12 horas, foi possível observar que o cimento GuttaFlow apresentou média de absorbância de 0,055, seguido do Sealer 26 (média = 0,038). Os cimentos Pulp Canal Sealer e Densell Endo apresentaram a mesma média de absorbância (0,031). O Pulp Fill e o Endofill foram os cimentos que apresentaram maior citotoxicidade (média de absorbância = 0,024 e 0,021, respectivamente). O grupo controle apresentou média de absorbância de 0,158. Em 24 horas observou-se que os cimentos GuttaFlow e Sealer 26 apresentaram as maiores médias de absorbância (0,041 e 0,037, respectivamente), seguidos pelo cimento Pulp Canal Sealer que apresentou média de absorbância de 0,035. Já os cimentos Densell Endo e Pulp Fill apresentaram médias de absorbância de 0,033 e 0,032, respectivamente. O cimento Endofill apresentou uma média de 0,026 e o grupo controle de 0,086. Quando analisados em 72 horas, o cimento Pulp Canal Sealer obteve média de absorbância de 0,049, seguido dos cimentos GuttaFlow e Pulp Fill, ambos com 0,048. Os cimentos Densell Endo, Sealer 26 e Endofill apresentaram respectivamente, médias de 0,044, 0,040 e 0,036. O grupo controle diferenciou-se significativamente de todos os grupos em todos os tempos. Quando analisadas as médias gerais de absorbância dos grupos analisados observou-se que o cimento GuttaFlow se apresentou como o cimento com menor índice de citotoxicidade, apresentando média de absorbência de 0,048. Logo após, apresentando médias de absorbância iguais (0,038) encontraram-se os cimentos Pulp Canal Sealer e Sealer 26; seguidos do Densell Endo e do Pulp Fill, com 0,036 e 0,035, respectivamente. O grupo controle apresentou média de absorbância de 0,098. Portanto, tendo como base os resultados obtidos, pôde-se concluir que o cimento Endofill foi o que apresentou maior citotoxicidade e o cimento GuttaFlow, o menos citotóxico.

Avaliação da ingestão habitual de cálcio e sua associação com a concentração intracelular de cálcio, adiposidade corporal, perfil metabólico, biomarcadores inflamatórios, pressão arterial e função endotelial

A associação inversa da ingestão de cálcio dietético com adiposidade corporal e pressão arterial está documentada em estudos epidemiológicos. Achados experimentais sugerem que este fenômeno pode ser mediado por alterações na concentração intracelular de cálcio ([Ca]i). Existem poucos estudos relacionando o cálcio dietético com a [Ca]i. O objetivo do presente estudo foi avaliar a relação da ingestão habitual de cálcio dietético com a [Ca]i, adiposidade corporal, perfil metabólico, biomarcadores inflamatórios, pressão arterial e função endotelial em mulheres. Para tanto, foi desenvolvido estudo transversal, com 76 mulheres na pré-menopausa submetidas à avaliação: dietética (questionário de frequência alimentar validado); da [Ca]i em eritrócitos (espectrometria de absorbância atômica); da gordura corporal (GC) total [índice de massa corporal (IMC) e % GC por bioimpedância elétrica] e central [perímetro da cintura (PC), e razão cintura quadril (RCQ)]; do perfil metabólico (glicose, colesterol e frações, insulina e HOMA-IR); dos biomarcadores inflamatórios [adiponectina e proteína C-reativa (PCR)]; dos biomarcadores da função endotelial [molécula de adesão intracelular-1 (ICAM-1), molécula de adesão celular vascular-1 (VCAM-1) e E-Selectina]; da função endotelial avaliada pelo equipamento Endo-PAT2000; e da pressão arterial. Calcitriol, paratormônio, cálcio sérico e cálcio urinário completaram o metabolismo do cálcio. As participantes foram estratificadas em 2 grupos de acordo com a ingestão habitual de cálcio: Grupo com baixa ingestão de cálcio ou BIC (n=32; ingestão de cálcio <600mg/d) e Grupo com elevada ingestão de cálcio ou AIC (n=44; ingestão de cálcio ≥600mg/d). A média da idade foi semelhante entre os grupos (Grupo BIC: 31,41,4 vs Grupo AIC: 31,41,4anos; p=0,99). Após ajustes para fatores de confundimento (idade, ingestão de energia, bebida alcoólica, proteína, carboidratos e lipídios), o Grupo AIC, em comparação com o BIC, apresentou valores significativamente mais baixos de IMC (25,65,3 vs 26,9 6,0 kg/m; p=0,02), PC (84,413,6 vs 87,815,3cm; p=0,04), % GC (31,15,9 vs 33,35,6 %; p=0,003), pressão arterial diastólica (68,210,8 vs 72,411,2 mm Hg; p=0,04) e pressão arterial média (80,1310,94 vs 83,8611,70 mmHg; p=0,04); e significativamente mais altos de HDL-colesterol (58,612,2 vs 52,912,2 mg/dL; p=0,004) e adiponectina (34572,1 19472,8 vs 31910,319385,1 ng/mL; p=0,05). A [Ca]i e as outras variáveis avaliadas não diferiram entre os grupos, mesmo após ajustes. Neste estudo realizado com mulheres, o maior consumo de cálcio se associou com valores mais baixos de adiposidade corporal total e central, pressão arterial diastólica e média; além de valores mais elevados de HDL-colesterol e adiponectina