989 resultados para Suzuki-Miyaura cross-coupling reaction
Resumo:
Bound and resonance states of HO2 have been calculated quantum mechanically by the Lanczos homogeneous filter diagonalization method [Zhang and Smith, Phys. Chem. Chem. Phys. 3, 2282 (2001); J. Chem. Phys. 115, 5751 (2001)] for nonzero total angular momentum J = 1,2,3. For lower bound states, agreement between the results in this paper and previous work is quite satisfactory; while for high lying bound states and resonances these are the first reported results. A helicity quantum number V assignment (within the helicity conserving approximation) is performed and the results indicate that for lower bound states it is possible to assign the V quantum numbers unambiguously, but for resonances it is impossible to assign the V helicity quantum numbers due to strong mixing. In fact, for the high-lying bound states, the mixing has already appeared. These results indicate that the helicity conserving approximation is not good for the resonance state calculations and exact quantum calculations are needed to accurately describe the reaction dynamics for HO2 system. Analysis of the resonance widths shows that most of the resonances are overlapping and the interferences between them lead to large fluctuations from one resonance to another. In accord with the conclusions from earlier J = 0 calculations, this indicates that the dissociation of HO2 is essentially irregular. (C) 2003 American Institute of Physics.
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Phosphine (hydrogen phosphide, PH3) is the fumigant most widely used to protect stored products from pest infestation. Despite the importance of this chemical, little is known about its mode of action. We have created three phosphine-resistant lines (pre-1, pre-7, pre-33) in the model organism C. elegans, with LC50 values 2, 5, and 9 times greater than the fully susceptible parental strain. Molecular oxygen was shown to be an extremely effective synergist with phosphine as, under hyperoxic conditions, 100% mortality was observed in wild-type nematodes exposed to 0.1 mg/l phosphine, a nonlethal concentration in air. All three mutants were resistant to the synergistic effects of oxygen in proportion to their resistance to phosphine with one mutant, pre-33, showing complete resistance to this synergism. We take the proportionality of cross-resistance between phosphine and the synergistic effect of oxygen to imply that all three mutants circumvent a mechanism of phosphine toxicity that is directly coupled to oxygen metabolism. Compared with the wild-type strain, all three mutants have an extended average life expectancy of from 12.5 to 25.3%. This is consistent with the proposed involvement of oxidative stress in both phosphine toxicity and ageing. Because the wild-type and mutant nematodes develop at the same rate, the longevity is unlikely to be caused by a clk-type reduction in oxidative metabolism, a potential alternative mechanism of phosphine resistance.
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Early pregnancy factor (EPF) is a secreted protein, present in serum during early pregnancy and essential for maintaining viability of the embryo. It is a homologue of chaperonin 10 (Cpn10) but, unlike Cpn10, it has an extracellular role. EPF has immunosuppressive and growth regulatory properties. Previously we have reported the preparation of recombinant EPF (rEPF) and shown that treatment with rEPF will suppress clinical signs of MBP-EAE in Lewis rats and PLP-EAE in SJL/J mice. In the present study, these findings have been extended to investigate possible mechanisms involved in the action of EPF. Following treatment of mice with rEPF from the day of inoculation, there were fewer infiltrating CD3+ and CD4+ cells in the parenchyma of the spinal cord during the onset of disease and after the initial episode, compared with mice treated with vehicle. Expression of the integrins LFA-1, VLA-4 and Mac-1 and of members of the immunoglobulin superfamily of adhesion molecules ICAM-1 and VCAM-1 was suppressed in the central nervous system (CNS) following rEPF treatment. The expression of PECAM-1 was not affected. To determine if rEPF suppressed T cell activation in the periphery, the delayed-type hypersensitivity (DTH) reaction of normal BALB/c mice to trinitrochlorobenzene (TNCB) following treatment with rEPF was studied. The results showed that treatment with rEPF suppressed the DTH reaction, demonstrating the ability of EPF to downregulate the cell-mediated immune response. These results indicate that suppression of immunological mechanisms by rEPF plays a major role in the reduction of clinical signs of disease in experimental autoimmune encephalomyelitis (EAE). (C) 2003 Elsevier Science B.V. All rights reserved.
Resumo:
In 1997 the United Nations adopted the UNCITRAL Model Law on Cross-Border Insolvency and recommended that member states adopt it as part of domestic legislation. In 2002 Australia, an active participant in UNCITRAL's Working Group on Insolvency Law, announced that the next phase of the Commonwealth Government's Corporate Law Economic Reform Program would be a review of cross-border insolvency law. CLERP 8 seeks feedback on the proposed enactment of the Model Law by a separate Commonwealth statute. This article places such a development within the context of Australian cross-border insolvency law as it has evolved from early English bankruptcy legislation through case law arising from the banking collapses of the late 19th century to the more recent jurisprudence produced by corporate collapses of the late 1980s to early 1990s and current high-profile insolvencies.
Resumo:
Two experiments using a temporal occlusion paradigm (the first with expert and novice participants and the second with participants of intermediate skill) were conducted to examine the capability of tennis players to predict the direction of an opponent's service in situ. In both experiments two different response conditions, reflecting differing degrees of perception-action coupling, were employed. In a coupled condition players were required to make a movement-based response identical to that which they would use to hit a return of service in a game situation, whereas in an uncoupled condition a verbal prediction of service direction was required. Experiment 1 provided clear evidence of superior prediction accuracy under the coupled response condition when ball flight was available, plus some limited evidence to suggest that superior prediction accuracy under uncoupled response conditions might hold true if only advance (pre-contact) information was available. Experiment 2 showed the former finding to be a robust one, but was unable to reveal any support for the latter. Experiment 1 also revealed that expert superiority is more apparent for predictions made under natural (coupled) than uncoupled response-mode conditions. Collectively, these findings suggest that different perceptual processes may be in operation in anticipatory tasks which depend on skill level, the type of information presented, and degree of perception-action coupling inherent in the task requirements.
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Objective: To explore relationships between physical activity and mental health cross-sectionally and longitudinally in a large cohort of older Australian women. Method: Women in their 70s participating in the Australian Longitudinal Study on Women's Health responded in 1996 (aged 70-75) and in 1999 (aged 73-78). Cross-sectional data were analyzed for 10,063 women and longitudinal data for 6472. Self-reports were used to categorize women into four categories of physical activity at each time point as well as to define four physical activity transition categories across the 3-year period. Outcome variables for the cross-sectional analyses were the mental health component score (MCS) and mental health subscales of the Medical Outcomes Study Short Form (SF-36). The longitudinal analyses focused on changes in these variables. Confounders included the physical health component scale (PCS) of the SF-36, marital status, body mass index (BMI) and life events. Adjustment for baseline scores was included for the longitudinal analyses. Results: Cross-sectionally, higher levels of physical activity were associated with higher scores on all dependent variables, both with and without adjustment for confounders. Longitudinally, the effects were weaker, but women who had made a transition from some physical activity to none generally showed more negative changes in emotional well-being than those who had always been sedentary, while those who maintained or adopted physical activity had better outcomes. Conclusion: Physical activity is associated with emotional well-being among a population cohort of older women both cross-sectionally and longitudinally, supporting the need for the promotion of appropriate physical activity in this age group. (C) 2003 Elsevier Science Inc. All rights reserved.
Resumo:
Background : Femoral shaft fracture incidence increases in older adults and is associated with low-energy trauma. Apart from bone density, the distribution and size of bone contributes to its strength. Aim : To examine if bone geometry and density of the femoral mid-shaft in older adults differs by sex and race, we studied 197 White women, 225 Black women, 242 White men, and 148 Black men aged 70-79 years participating in the Health, Aging, and Body Composition study; a prospective cohort study in the USA. A secondary purpose of the study was to examine the association of site-specific muscle and fat to bone geometry and density. Subjects and methods : Subjects were community-dwelling and reported no difficulty walking one-quarter of a mile or climbing stairs. Mid-femoral volumetric bone mineral density (vBMD, mg cm -3 ), total area (TA), cortical area (CA), medullary area (MA), cross-sectional moments of inertia (CSMI: I x , I y , J ), and muscle and fat areas (cm 2 ) were determined by computed tomography (CT; GE CT-9800, 10 mm slice thickness). Results : vBMD was greater in men than women with no difference by race ( p < 0.001). Bone areas and area moments of inertia were also greater in men than women ( p < 0.001), with Black women having higher values than White women for TA and CA. Standardizing geometric parameters for body size differences by dividing by powers of femur length did not negate the sex difference for TA and MA. Significant differences ( p < 0.05) among the four groups also remained for I x and J . Mid-thigh muscle area was an independent contributor to TA in all groups (Std beta = 0.181-0.351, p < 0.05) as well as CA in women (Std beta = 0.246-0.254, p < 0.01) and CSMI in White women (Std beta = 0.175-0.185, p < 0.05). Further, muscle area was a significant contributor to vBMD in Black women. Conclusion : These results indicate that bone geometry and density of the femoral diaphysis differs primarily by sex, rather than race, in older well-functioning adults. In addition, site-specific muscle area appears to have a potential contributory role to bone geometry parameters, especially in women.
Spread-F/sporadic E coupling at Chung-Li, especially for postsunset periods of sunspot maximum years
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The effect of electron beam radiation on a perfluoroalkoxy (PFA) resin was examined using solid-state high-speed magic angle spinning F-19 NMR spectroscopy and FT-IR spectroscopy. Samples were prepared for analysis by subjecting them to electron beam radiation in the dose range 0.5-2.0 MGy at 633 K, which is above the crystalline melting temperature. The new structures were identified and include new saturated chain ends, short and long branches, unsaturated groups, and cross-links. The radiation chemical yield (G value) of new long branch points was greater than the G value of new chain ends, suggesting that cross-linking is the net radiolytic process. This conclusion was supported by an observed decrease in the crystallinity and an increase in the optical clarity of the polymer.
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The synthesis of helium in the early Universe depends on many input parameters, including the value of the gravitational coupling during the period when the nucleosynthesis takes place. We compute the primordial abundance of helium as function of the gravitational coupling, using a semi-analytical method, in order to track the influence of G in the primordial nucleosynthesis. To be specific, we construct a cosmological model with varying G, using the Brans-Dicke theory. The greater the value of G at nucleosynthesis period, the greater the predicted abundance of helium. Using the observational data for the abundance of primordial helium, constraints for the time variation of G are established.
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Introdução: O parto pretermo (PPT) é um dos principais determinantes da morbimortalidade neonatal, acarretando consequências adversas para saúde. As causas são multifatoriais, sendo a infecção intrauterina a razão mais provável para explicar a maioria destes desfechos. Acredita-se que a infecção por Chlamydia trachomatis (CT) também esteja envolvida no PPT e rotura prematura de membranas (ROPREMA). Objetivo: Determinar a prevalência de CT em parturientes e os possíveis fatores de risco relacionados com os casos de partos prematuros atendidos no Hospital Universitário Cassiano Antonio Moraes. Métodos: Estudo de corte transversal, realizado entre parturientes que apresentaram PPT em um Hospital Universitário em Vitória - ES, entre junho de 2012 e agosto de 2013. As participantes responderam a um questionário contendo dados sóciodemográficos, comportamentais e clínicos. Foi coletada uma amostra de urina para rastreio de CT usando reação em cadeia da polimerase. Resultados: A prevalência de PPT durante o período do estudo foi de 26%. Um total de 378 casos de PPT foram registrados, entre eles 323 mulheres foram testadas para o CT; quarenta e cinco (13,9%) tiveram um resultado positivo, sendo que 31,6% possuiam até 24 anos e as mulheres infectadas pela CT eram mais jovens do que as demais (p = 0,022). Um total de 76,2% eram casadas/em união estável, e CT foi mais frequente entre as solteiras (p = 0,018); 16,7% relataram primeira relação sexual com menos de 14 anos de idade. As causas de PPT foram materno-fetais em 40,9%, ROPREMA em 29,7% e trabalho de parto prematuro em 29,4%. Na análise multivariada, ser casada foi um fator de proteção [OR = 12:48 (IC 95%: 0,24-0,97)]. Nenhuma das demais características foram associadas com a infecção por CT. Conclusões: Este estudo evidencia uma alta prevalência de infecção por CT entre parturientes com PPT. Essa alta prevalência reforça a necessidade da definição de estratégias de rastreamento e assistência durante o pré-natal.
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What are Indian and Japanese reactions to China's rise in economic, political and military terms? According to realist tradition, their option would be between balancing and bandwagoning. Applying Stephen Walt's balance of threats approach, this work aims to analyze Indian and Japan responses to an increasingly powerful China; its conclusions point to an evolving relationship between India and Japan, in military terms, especially after 2005.
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A numeric model has been proposed to investigate the mechanical and electrical properties of a polymeric/carbon nanotube (CNT) composite material subjected to a deformation force. The reinforcing phase affects the behavior of the polymeric matrix and depends on the nanofiber aspect ratio and preferential orientation. The simulations show that the mechanical behavior of a computer generated material (CGM) depends on fiber length and initial orientation in the polymeric matrix. It is also shown how the conductivity of the polymer/CNT composite can be calculated for each time step of applied stress, effectively providing the ability to simulate and predict strain-dependent electrical behavior of CNT nanocomposites.
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Biocompatibility is a major challenge for successful application of many biomaterials. In this study the ability to coat chemically and enzymatically activated poly(L-lactic acid) (PLA) membranes with heat denatured human serum albumin to improve biocompatibility was investigated. PLA membranes hydrolyzed with NaOH or cutinase and then treated with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, hydrochloride (EDAC) as a heterobifunctional cross-linker promoted the coupling single bondCOOH groups on PLA membranes and single bondNH2 groups of heat denatured human serum albumin. This resulted in increased hydrophilicity (lowest water contact angles of 43° and 35°) and highest antioxidant activity (quenching of 79 μM and 115 μM tetramethylazobisquinone (TMAMQ) for NaOH and cutinase pretreated membranes, respectively). FTIR analysis of modified PLA membranes showed new peaks attributed to human serum albumin (amide bond, NH2 and side chain stretching) appearing within 3600–3000 cm−1 and 1700–1500 cm−1 (Fig. 3). MTT studies also showed that osteoblasts-like and MC-3T3-E1 cells viability increased 2.4 times as compared to untreated PLA membranes. The study therefore shows that this strategy of modifying the surfaces of PLA polymers could significantly improve biocompatibility.