Reactions of oxygen containing ligands in the coordination sphere of permethylhafnocene and permethyltantalocene

A series of terl-butylperoxide complexes of hafnium, Cp*₂Hf(R)(OOCMe₃) (Cp* = ((η⁵-C₅Me₅); R = Cl, H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, CH₂CHMe₂, CH=CHCMe₃, C₆H₅, meta-C₆H₃(CH₂)2) and Cp*(η⁵-C₅(CH₃)₄CH₂CH₂CH₂)Hf(OOCMe₃), has been synthesized. One example has been structurally characterized, Cp*₂Hf(OOCMe₃)CH₂CH₃ crystallizes in space group P2₁/c, with a = 19.890(7)Å, b = 8.746(4)Å, c = 17.532(6)Å, β = 124.987(24)°, V = 2498(2)ų, Z = 4 and R_F = 0.054 (2222 reflections, I > 0). Despite the coordinative unsaturation of the hafnium center, the terl-butylperoxide ligand is coordinated in a mono-dentate ligand. The mode of decomposition of these species is highly dependent on the substituent R. For R = H, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, CH₂CHMe₂ a clean first order conversion to Cp*₂Hf(OCMe₃)(OR) is observed (for R CH₂CH₃, ΔHǂ = 19.6 kcal•mol^-1, ΔSǂ = -13 e.u.). These results are discussed in terms of a two step mechanism involving η²-coordination of the terl-butylperoxide ligand. Homolytic O-O bond cleavage is observed upon heating of Cp*₂Hf(OOCMe₃) R (R = C₆H₆, meta-C₆H₃(CH₃)₂). In the presence of excess 9,10-dihydroanthracene thermolysis of Cp*₂Hf(OOCMe₃)C₆H₆ cleanly affords Cp*₂Hf(C₆H₆)OH and HOCMe₃ (ΔHǂ = 22.6 kcal•mol^-1, ΔSǂ = -9 e.u.). The O-O bond strength in these complexes is thus estimated to be 22 kcal•mol^-1.

Cp*₂Ta(CH₂)H, Cp*₂Ta(CHC₆H₅)H, Cp*₂Ta(C₆H₄)H, Cp*₂Ta(CH₂=CH₂)H and Cp*₂Ta(CH₂=CHMe)H react, presumably through Cp*₂Ta-R intermediates, with H₂O to give Cp*₂Ta(O)H and alkane. Cp*₂Ta(O)H was structurally characterized: space group P2₁/n, a= 13.073(3)Å, b = 19.337(4)Å, c = 16.002(3)Å, β = 108.66(2)°, V = 3832(1)ų, Z = 8 and R_F = 0.0672 (6730 reflections). Reaction of terlbutylhydroperoxide with these same starting materials ultimately yields Cp*₂Ta(O)R and HOCMe₃. Cp*₂Ta(CH₂=CHR)OH species are proposed as intermediates in the olefin hydride reactions. Cp*₂Ta(O₂)R species can be generated from the reaction of the same starting materials and O₂. Lewis acids have been shown to promote oxygen insertion in these complexes.

Statistical and econometric analysis of the treatment of HIV/AIDS

The epidemic of HIV/AIDS in the United States is constantly changing and evolving, starting from patient zero to now an estimated 650,000 to 900,000 Americans infected. The nature and course of HIV changed dramatically with the introduction of antiretrovirals. This discourse examines many different facets of HIV from the beginning where there wasn't any treatment for HIV until the present era of highly active antiretroviral therapy (HAART). By utilizing statistical analysis of clinical data, this paper examines where we were, where we are and projections as to where treatment of HIV/AIDS is headed.

Chapter Two describes the datasets that were used for the analyses. The primary database utilized was collected by myself from an outpatient HIV clinic. The data included dates from 1984 until the present. The second database was from the Multicenter AIDS Cohort Study (MACS) public dataset. The data from the MACS cover the time between 1984 and October 1992. Comparisons are made between both datasets.

Chapter Three discusses where we were. Before the first anti-HIV drugs (called antiretrovirals) were approved, there was no treatment to slow the progression of HIV. The first generation of antiretrovirals, reverse transcriptase inhibitors such as AZT (zidovudine), DDI (didanosine), DDC (zalcitabine), and D4T (stavudine) provided the first treatment for HIV. The first clinical trials showed that these antiretrovirals had a significant impact on increasing patient survival. The trials also showed that patients on these drugs had increased CD4+ T cell counts. Chapter Three examines the distributions of CD4 T cell counts. The results show that the estimated distributions of CD4 T cell counts are distinctly non-Gaussian. Thus distributional assumptions regarding CD4 T cell counts must be taken, into account when performing analyses with this marker. The results also show the estimated CD4 T cell distributions for each disease stage: asymptomatic, symptomatic and AIDS are non-Gaussian. Interestingly, the distribution of CD4 T cell counts for the asymptomatic period is significantly below that of the CD4 T cell distribution for the uninfected population suggesting that even in patients with no outward symptoms of HIV infection, there exists high levels of immunosuppression.

Chapter Four discusses where we are at present. HIV quickly grew resistant to reverse transcriptase inhibitors which were given sequentially as mono or dual therapy. As resistance grew, the positive effects of the reverse transcriptase inhibitors on CD4 T cell counts and survival dissipated. As the old era faded a new era characterized by a new class of drugs and new technology changed the way that we treat HIV-infected patients. Viral load assays were able to quantify the levels of HIV RNA in the blood. By quantifying the viral load, one now had a faster, more direct way to test antiretroviral regimen efficacy. Protease inhibitors, which attacked a different region of HIV than reverse transcriptase inhibitors, when used in combination with other antiretroviral agents were found to dramatically and significantly reduce the HIV RNA levels in the blood. Patients also experienced significant increases in CD4 T cell counts. For the first time in the epidemic, there was hope. It was hypothesized that with HAART, viral levels could be kept so low that the immune system as measured by CD4 T cell counts would be able to recover. If these viral levels could be kept low enough, it would be possible for the immune system to eradicate the virus. The hypothesis of immune reconstitution, that is bringing CD4 T cell counts up to levels seen in uninfected patients, is tested in Chapter Four. It was found that for these patients, there was not enough of a CD4 T cell increase to be consistent with the hypothesis of immune reconstitution.

In Chapter Five, the effectiveness of long-term HAART is analyzed. Survival analysis was conducted on 213 patients on long-term HAART. The primary endpoint was presence of an AIDS defining illness. A high level of clinical failure, or progression to an endpoint, was found.

Chapter Six yields insights into where we are going. New technology such as viral genotypic testing, that looks at the genetic structure of HIV and determines where mutations have occurred, has shown that HIV is capable of producing resistance mutations that confer multiple drug resistance. This section looks at resistance issues and speculates, ceterus parabis, where the state of HIV is going. This section first addresses viral genotype and the correlates of viral load and disease progression. A second analysis looks at patients who have failed their primary attempts at HAART and subsequent salvage therapy. It was found that salvage regimens, efforts to control viral replication through the administration of different combinations of antiretrovirals, were not effective in 90 percent of the population in controlling viral replication. Thus, primary attempts at therapy offer the best change of viral suppression and delay of disease progression. Documentation of transmission of drug-resistant virus suggests that the public health crisis of HIV is far from over. Drug resistant HIV can sustain the epidemic and hamper our efforts to treat HIV infection. The data presented suggest that the decrease in the morbidity and mortality due to HIV/AIDS is transient. Deaths due to HIV will increase and public health officials must prepare for this eventuality unless new treatments become available. These results also underscore the importance of the vaccine effort.

The final chapter looks at the economic issues related to HIV. The direct and indirect costs of treating HIV/AIDS are very high. For the first time in the epidemic, there exists treatment that can actually slow disease progression. The direct costs for HAART are estimated. It is estimated that the direct lifetime costs for treating each HIV infected patient with HAART is between $353,000 to $598,000 depending on how long HAART prolongs life. If one looks at the incremental cost per year of life saved it is only $101,000. This is comparable with the incremental costs per year of life saved from coronary artery bypass surgery.

Policy makers need to be aware that although HAART can delay disease progression, it is not a cure and HIV is not over. The results presented here suggest that the decreases in the morbidity and mortality due to HIV are transient. Policymakers need to be prepared for the eventual increase in AIDS incidence and mortality. Costs associated with HIV/AIDS are also projected to increase. The cost savings seen recently have been from the dramatic decreases in the incidence of AIDS defining opportunistic infections. As patients who have been on HAART the longest start to progress to AIDS, policymakers and insurance companies will find that the cost of treating HIV/AIDS will increase.

Euskadi Irratiko (EITB) eta Radio nan Gàidheal-go (BBC ALBA) kazetarien profil eta jarreren alderaketa

337 p.

图像处理在光路自动准直系统中的应用

光路自动准直系统应用于惯性约束聚变的高功率激光装置中的光束自动调整。图像处理是光路自动准直的关键技术之一。针对神光Ⅲ原型装置，结合阈值化、重心法、中值滤波和圆拟合等多种不同的图像处理方法设计了一套合理的准直方案，并且在模拟实验平台上进行了实验验证。实验结果表明，光路自动准直系统能够在15min之内顺利完成光路的自动调整，光束近场调整精度优于近场光斑的±0．5％，光束远场调整精度≤±0．3″，满足了原型装置的总体要求。

Optimisation of the first principle code Octopus for massive parallel architectures: application to light harvesting complexes

150 p.

Impacto do consumo de alimentos fora do domicílio na dieta e no peso corporal da população brasileira

Esta tese é composta por quatro artigos que permitiram avaliar o impacto do consumo de alimentos fora do domicílio na dieta e no peso corporal da população brasileira. O primeiro artigo revisou de forma sistemática as evidências científicas da associação entre alimentação fora do domicílio e peso corporal com abordagem crítica dos artigos publicados na literatura. Foram avaliados 28 artigos e os resultados sugeriram uma associação positiva entre o consumo de alimentos fora do domicílio e o ganho de peso. A revisão mostrou que uma das limitações nessa área é a ausência de padronização nas definições e métodos de avaliação do consumo de alimentos fora do domicílio. Para o desenvolvimento dos demais artigos, utilizou-se dados do Inquérito Nacional de Alimentação (INA) do Brasil, uma subamostra da Pesquisa de Orçamentos Familiares (POF) 2008-2009, com o objetivo de caracterizar o consumo de alimentos fora do domicílio da população brasileira (artigo 2) e investigar a associação entre alimentação fora do domicílio e ingestão total de energia (artigo 3) e peso corporal (artigo 4). As análises foram realizadas com os dados de consumo de alimentos coletados por meio de registro alimentar de 34.003 indivíduos acima de 10 anos em dois dias não-consecutivos. Os registros incluíram descrição detalhada dos alimentos e quantidade consumida, tipo de preparação, horário e local de consumo (dentro ou fora do domicílio). Alimentação fora do domicílio foi definida como todo alimento adquirido e consumido fora de casa. O primeiro dia de registro foi utilizado nas análises, considerando o peso amostral específico do INA e o efeito do desenho amostral. O consumo de alimentos fora do domicílio no Brasil foi reportado por 40% dos entrevistados; diminuiu com a idade e aumentou com a renda em todas as regiões brasileiras; foi maior entre os homens e na área urbana. Os grupos de alimentos com maior percentual de consumo fora de casa foram bebidas alcoólicas, salgadinhos fritos e assados, pizza, refrigerantes e sanduíches. Entre indivíduos residentes nas áreas urbanas do Brasil (n=25.753), a média de energia proveniente dessa alimentação foi 337 kcal, representando 18% do consumo total de energia. Alimentação fora do domicílio foi positivamente associada ao consumo total de energia. Avaliando somente adultos entre 25 e 65 anos de idade das áreas urbanas (n=13.736) não foi encontrada associação entre o consumo de alimentos fora do domicílio e Índice de Massa Corporal (IMC). Indivíduos que consumiram alimentos fora do domicílio apresentaram menor ingestão de proteína; maior ingestão de gordura total, gordura saturada e açúcar livre; menor consumo de arroz, feijão e leite e maior consumo de salgadinhos fritos e assados, doces e açúcar, refrigerantes e bebidas alcoólicas do que não consumidores. Apesar da ausência de associação entre alimentação fora de casa e excesso de peso, o consumo de alimentos fora do domicílio influencia a qualidade da dieta dos indivíduos e em longo prazo pode ter um impacto no ganho de peso da população, portanto, deve ser considerado nas ações de saúde pública voltadas para a melhoria da alimentação dos brasileiros.

Super-resolution scanning laser microscopy with a third-order optical nonlinear thin film

In a configuration of optical far-field scanning microscopy, super-resolution achieved by inserting a third-order optical nonlinear thin film is demonstrated and analyzed in terms of the frequency response function. Without the thin film the microscopy is diffraction limited; thus, subwavelength features cannot be resolved. With the nonlinear thin film inserted, the resolution is dramatically improved and thus the microscopy resolves features significantly smaller than the smallest spacing allowed by the diffraction limit. A theoretical model is established and the device is analyzed for the frequency response function. The results show that the frequency response function exceeds the cutoff spatial frequency of the microscopy defined by the laser wavelength and the numerical aperture of the convergent lens. The main contribution to the improvement of the cutoff spatial frequency is from the phase change induced by the complex transmission of the nonlinear thin film. Experimental results are presented and are shown to be consistent with the results of theoretical simulations.

双调Q开关热退偏补偿全固态激光器

为了有效地补偿激光二极管(LD)侧向抽运1000 Hz重复率电光调Q Nd:YAG激光器棒状增益介质内存在的热致双折射损耗，设计了一种新颖的双调Q晶体开关复合谐振腔结构。实验结果表明，设计的双调Q晶体开关结构Nd:YAG激光器输出激光脉冲能量比单调Q晶体开关结构的非补偿腔输出能量提高了56%，当侧面抽运半导体激光器输出功率达到450 W时，激光输出达到30 mJ/pulse，输出光束偏振度优于10:1，激光脉冲宽度约14 ns。并获得6.7%的光-光转换效率。通过对双调Q开光激光谐振腔进行建模，并用求解速

Spatial-temporal excess mortality patterns of the 1918-1919 influenza pandemic in Spain

Background: The impact of socio-demographic factors and baseline health on the mortality burden of seasonal and pandemic influenza remains debated. Here we analyzed the spatial-temporal mortality patterns of the 1918 influenza pandemic in Spain, one of the countries of Europe that experienced the highest mortality burden. Methods: We analyzed monthly death rates from respiratory diseases and all-causes across 49 provinces of Spain, including the Canary and Balearic Islands, during the period January-1915 to June-1919. We estimated the influenza-related excess death rates and risk of death relative to baseline mortality by pandemic wave and province. We then explored the association between pandemic excess mortality rates and health and socio-demographic factors, which included population size and age structure, population density, infant mortality rates, baseline death rates, and urbanization. Results: Our analysis revealed high geographic heterogeneity in pandemic mortality impact. We identified 3 pandemic waves of varying timing and intensity covering the period from Jan-1918 to Jun-1919, with the highest pandemic-related excess mortality rates occurring during the months of October-November 1918 across all Spanish provinces. Cumulative excess mortality rates followed a south-north gradient after controlling for demographic factors, with the North experiencing highest excess mortality rates. A model that included latitude, population density, and the proportion of children living in provinces explained about 40% of the geographic variability in cumulative excess death rates during 1918-19, but different factors explained mortality variation in each wave. Conclusions: A substantial fraction of the variability in excess mortality rates across Spanish provinces remained unexplained, which suggests that other unidentified factors such as comorbidities, climate and background immunity may have affected the 1918-19 pandemic mortality rates. Further archeo-epidemiological research should concentrate on identifying settings with combined availability of local historical mortality records and information on the prevalence of underlying risk factors, or patient-level clinical data, to further clarify the drivers of 1918 pandemic influenza mortality.

Mechanisms and concentrations dependence of up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics

The up-conversion properties of Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980 nm excitation were investigated. Intense blue up-conversion luminescence due to the Tm3+: (1)G(4) -> H-3(6) transition was observed in the glass-ceramics. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The up-conversion mechanism is proposed. The reason for the intense Tm3+ up-conversion luminescence in the oxyfluoride glass-ceramics and the concentrations dependence of upconversion luminescence are also discussed. (c) 2005 Elsevier B.V. All rights reserved.