974 resultados para Boîte homéo
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A produção acadêmica motivada pela epidemia de HIV e Aids impulsionou as pesquisas relativas à sexualidade configurando novos campos de investigação, em especial sobre os gays. No entanto, não é significativa no Brasil a produção acadêmica que aborde a vulnerabilidade às DSTs a partir da identidade lésbica. A saúde sexual das mulheres presumidamente heterossexuais tendeu a permanecer subsumida à exclusiva preocupação com a reprodução ao longo da trajetória das políticas de atenção à saúde das mulheres, mesmo frente à Aids. De forma ainda mais acentuada que a sexualidade feminina heterossexual, a homossexualidade feminina tendeu à invisibilidade na sociedade brasileira e frente ao discurso médico-ginecológico. O advento da epidemia contribuiu para a manutenção desta invisibilidade por força da crença de que o corpo lésbico seria o único infenso à infecção pela via sexual. Nesta tese busca-se compreender a transformação discursiva do corpo lésbico dos primeiros tempos da epidemia até hoje. Mais especificamente, como um corpo imune à epidemia está calcada na idéia de que a vulnerabilidade das lésbicas é o passaporte para a afirmação/inclusão de um dado marco identitário na agenda de políticas públicas. Nesse sentido, o campo em que se desenha a disputa do corpo lésbico face às DST/Aids é marcado pela tensão entre prática sexual e identidade sexual.
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Humans perform fascinating science experiments at home on a daily basis when they undertake the modification of natural and naturally-derived materials by a cooking process prior to consumption. The material properties of such foods are of interest to food scientists (texture is often fundamental to food acceptability), oral biologists (foods modulate feeding behavior), anthropologists (cooking is probably as old as the genus Homo and distinguishes us from all other creatures) and dentists (foods interact with tooth and tooth replacement materials). Materials scientists may be interested in the drastic changes in food properties observed over relatively short cooking times. In the current study, the mechanical properties of one of the most common (and oldest at 4,000+ years) foods on earth, the noodle, were examined as a function of cooking time. Two types of noodles were studied, each made from natural materials (wheat flour, salt, alkali and water) by kneading dough and passing them through a pasta-making machine. These were boiled for between 2-14 min and tested at regular intervals from raw to an overcooked state. Cyclic tensile tests at small strain levels were used to examine energy dissipation characteristics. Energy dissipation was >50% per cycle in uncooked noodles, but decreased by an order of magnitude with cooking. Fractional dissipation values remained approximately constant at cooking times greater than 7 min. Overall, a greater effect of cooking was on viscoplastic dissipation characteristics rather than on fracture resistance. The results of the current study plot the evolution of a viscoplastic mixture into an essentially elastic material in the space of 7 minutes and have broad implications for understanding what cooking does to food materials. In particular, they suggest that textural assessment by consumers of the optimally cooked state of food has a definite physical definition. © 2007 Materials Research Society.
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Cross-species painting (fluorescence in situ hybridization) with 23 human (Homo sapiens (HSA)) chromosome-specific painting probes (HSA 1-22 and the X) was used to delimit regions of homology on the chromosomes of the golden mole (Ghrysochloris asiaticus) and elephant-shrew (Elephantulus rupestris). A cladistic interpretation of our data provides evidence of two unique associations, HSA 1/19p and 5/21/3, that support Afrotheria. The recognition of HSA 5/3/21 expands on the 3/21 synteny originally designated as an ancestral state for all eutherians. We have identified one adjacent segment combination (HSA2/8p/4) that is supportive of Afroinsectiphillia (aardvark, golden mole, elephant-shrew). Two segmental combinations (HSA 10q/17 and HSA 3/20) unite the aardvark and elephant-shrews as sister taxa. The finding that segmental syntenies in evolutionarily distant taxa can improve phylogenetic resolution suggests that they may be useful for testing sequence-based phylogenies of the early eutherian mammals. They may even suggest clades that sequence trees are not recovering with any consistency and thus encourage the search for additional rare genomic changes among afrotheres.
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Multidirectional chromosome painting with probes derived from flow-sorted chromosomes of humans (Homo sapiens, HSA, 2n = 46) and galagos (Galago moholi, GMO, 2n = 38) allowed us to map evolutionarily conserved chromosomal segments among humans, galagos, a
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Detecting receptor dimerisation and other forms of clustering on the cell surface depends on methods capable of determining protein-protein separations with high resolution in the ∼10-50 nm range. However, this distance range poses a significant challenge because it is too large for fluorescence resonance energy transfer and contains distances too small for all other techniques capable of high-resolution in cells. Here we have adapted the technique of fluorophore localisation imaging with photobleaching to measure inter-receptor separations in the cellular environment. Using the epidermal growth factor receptor, a key cancer target molecule, we demonstrate ∼10 nm resolution while continuously covering the range of ∼10-80 nm. By labelling the receptor on cells expressing low receptor numbers with a fluorescent antagonist we have found inter-receptor separations all the way up from 8 nm to 59 nm. Our data are consistent with epidermal growth factor receptors being able to form homo-polymers of at least 10 receptors in the absence of activating ligands. © 2013 Needham et al.
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The power-conversion efficiency of solid-state dye-sensitized solar cells can be optimized by reducing the energy offset between the highest occupied molecular orbital (HOMO) levels of dye and hole-transporting material (HTM) to minimize the loss-in-potential. Here, we report a study of three novel HTMs with HOMO levels slightly above and below the one of the commonly used HTM 2,2′,7,7′- tetrakis(N,N-di-p-methoxyphenylamino)-9,9′- spirobifluorene (spiro-OMeTAD) to systematically explore this possibility. Using transient absorption spectroscopy and employing the ruthenium based dye Z907 as sensitizer, it is shown that, despite one new HTM showing a 100% hole-transfer yield, all devices based on the new HTMs performed worse than those incorporating spiro-OMeTAD. We further demonstrate that the design of the HTM has an additional impact on the electronic density of states present at the TiO2 electrode surface and hence influences not only hole- but also electron-transfer from the sensitizer. These results provide insight into the complex influence of the HTM on charge transfer and provide guidance for the molecular design of new materials. © 2013 American Chemical Society.
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Endogenous yolk nutrients are crucial for embryo and larval development in fish, but developmental behavior of the genes that control yolk utilization remains unknown. Apolipoproteins have been shown to play important roles in lipid transport and uptake through the circulation system. In this study, EcApoC-I, the first cloned ApoC-I in teleosts, has been screened from pituitary cDNA library of female orange-spotted grouper (Epinephelus coioides), and the deduced amino acid sequence shows 43.5% identity to one zebrafish (Danio rerio) hypothetical protein similar to ApoC-I, and 21.2%, 21.7%, 22.5%, 20%, and 22.5% identities to Apo C-I of human (Homo sapiens), house mouse (Mus musculus), common tree shrew (Tupaia glis), dog (Canis lupus familiaris) and hamadryas baboon (Papio hamadryas), respectively. Although the sequence identity is low, amphipathic alpha-helices with the potential to bind to lipid were predicted to exist in the EcApoC-I. RT-PCR analysis revealed that it was first transcribed in gastrula embryos and maintained a relatively stable expression level during the following embryogenesis. During embryonic and early larval development, a very high level of EcApoC-I expression was in the yolk syncytial layer, indicating that it plays a significant role in yolk degradation and transfers nutrition to the embryo and early larva. By the day 7 after hatching, EcApoC-I transcripts were observed in brain. In adult, EcApoC-I mRNA was detected abundantly in brain and gonad. In transitional gonads, the EcApoC-I expression is restricted to the germ cells. The data suggested that EcApoC-I might play an important role in brain and gonad morphogenesis and growth.
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By the use of partial least squares (PLS) method and 27 quantum chemical descriptors computed by PM3 Hamiltonian, a statistically significant QSPR were obtained for direct photolysis quantum yields (Y) of selected Polychlorinated dibenzo-p-dioxins (PCDDs). The QSPR can be used for prediction. The direct photolysis quantum yields of the PCDDs are dependent on the number of chlorine atoms bonded with the parent structures, the character of the carbon-oxygen bonds, and molecular polarity. Increasing bulkness and polarity of PCDDs lead to decrease of log Y values. Increasing the frontier molecular orbital energies (E-lumo and E-homo) and heat of formation (HOF) values leads to increase of log Y values. (C) 2001 Elsevier Science Ltd. All rights reserved.
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The configurations, stability, and electronic structure of AuSin (n = 1-16) clusters have been investigated within the framework of the density functional theory at the B3PW91/LanL2DZ and PW91/DNP levels. The results show that the Au atom begins to occupy the interior site for cages as small as Si-11 and for Si-12 the Au atom completely falls into the interior site forming Au@Si-12 cage. A relatively large embedding energy and small HOMO-LUMO gap are also found for this Au@Si-12 structure indicating enhanced chemical activity and good electronic transfer properties. All these make Au@Si-12 attractive for cluster-assembled materials.
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Optical refrigeration of semiconductors is encountering efficiency difficulties caused by nonradiative recombination and luminescence trapping. A commonly used approach for enhancing luminescence efficiency of a semiconductor device is coupling a lens with the device. We quantitatively study the effects of a coupling lens on optical refrigeration based on rate equations and photon recycling, and calculated cooling efficiencies of different coupling mechanisms and of different lens materials. A GaAs/GaInP heterostructure coupled with a homo-epitaxial GaInP hemispherical lens is recommended.
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并苯类化合物和噻吩齐聚物是目前研究最广泛的两类p型高迁移率有机半导体材料,晶态下强分子间电子相互作用的特点使它们具有优异的电荷传输性质,作为电荷传输层制备的有机薄膜晶体管(OTFT)的器件性能已经可以和非晶硅器件(α- Si:H)相比拟(0.1~1.0 cm2/V.s)。但是,由于这两类材料具有较窄的能隙和较高的最高被占分子轨道(HOMO) 能级,容易与空气中的水、氧发生反应,而且并苯类化合物对光也非常敏感,因此它们的器件性能在空气中衰减很快。可以说,如何设计与合成兼具高迁移率和优异稳定性的OTFT材料依然是目前有机光电子研究领域面临的挑战之一。 在本论文中,我们采用较稳定的芳香基团和噻吩单元构造了三个系列杂化共轭齐聚物,通过改变芳香基团结构和引入方式,对共轭齐聚物的HOMO能级做了有效的调节,不仅提高了分子的热稳定性和化学稳定性,而且使分子的HOMO能级与金电极功函相匹配,有利于电荷的注入,获得了稳定的高迁移率有机半导体材料。 1、设计并合成了一系列含不同苯类(苯、联苯、芴和菲)中心单元的噻吩类共轭齐聚物,表征了它们基本的光谱、电化学和热行为,并作为传输层用于顶电极结构的OTFT,获得了较高的场致迁移率((1-6.7)×10-2 cm2/V.s)。引入平面刚性芳香基团有利于获得稳定的高迁移率材料。噻吩/菲杂化共轭齐聚物,即2,7二(5'正己基2,2'二噻吩5)菲(DH-TTPhTT)综合性能最佳,与在相同条件下制备的DH6T具有相当的场致迁移率(μFET = 0.065 cm2/V.s)。 2、设计并合成了一系列含菲共轭齐聚物,研究了它们的基本物理和化学性质。[2,2';7',2''] 三联菲(Ph3)可通过真空蒸镀形成高度有序的薄膜,其OTFT μFET达0.01 cm2/V.s。但是,由于其HOMO能级太低,导致器件阈值电压很高,很难进一步优化器件性能。因此,为了调节分子的HOMO能级,合成了2 ,5二(2菲基) [3,2-b]并二噻吩(PhTT)和5,5'二(2菲基) 2,2'二噻吩(PhT2)两个含噻吩化合物,成功的应用于顶电极结构的OTFT,使器件性能大幅提高。其中PhT2的μFET > 0.1 cm2/V.s; Ion/Ioff > 1×105。更重要的是,器件在空气、自然光条件下保存一个月后,μFET 、Ion/Ioff和阈值电压三个性能指标都基本没有变化,说明PhT2是目前最好的OTFT材料之一。 3、设计并合成了六个萘和硫茚封端的噻吩齐聚物,研究了它们的基本物理和化学性质。为了对分子结构—堆积方式—器件性能的关系有所认识,解析了5,5'二(2萘基) 2,2'二噻吩(NaT2),5,5''二(2萘基) 2,2':5',2''三噻吩(NaT3),5,5'二(2硫茚基) 2,2'二噻吩(TNT2)和5,5''二(2硫茚基) 2,2':5',2''三噻吩(TNT3) 的单晶结构。所有六个化合物均可形成高度有序的多晶薄膜,而且薄膜有序性随噻吩单元数的增加而提高。取决于分子长度和端基结构,它们的μFET介于0.01-0.39 cm2/V.s。和TNTn系列分子(n = 2-4)相比,NaTn系列齐聚物(n = 2-4)具有更好的器件性能。齐聚物5,5'''二(2萘基) 2,2':5',2'':5'',2'''四噻吩(NaT4)具有最好的器件性能,其场致迁移率为0.39 cm2/V.s;VT = -5 V; Ion/Ioff > 1×105,是目前性能最好的OTFT材料之一。
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和共轭聚合物相比,单分散共轭齐聚物具有结构确定、易提纯等优点,不仅是建立共轭体系结构与性能关系的最佳模型,而且是一类高纯度光电子材料,还是构造具有规整结构嵌段共聚物和超分子体系的理想构造单元。鉴于基于芴单元的共轭齐聚物与聚合物具有优异的光电性能,引入不同端基能够有效调节共轭齐聚物的性能,本论文以端基官能化齐聚芴为研究对象,设计与合成了具有不同端基结构的系列单分散齐聚芴,研究了它们基本的物理化学性质,主要成果与创新点如下: 1、利用Horner-Wadsworth-Emmons反应、Wittig反应和Heck偶联反应,交替引入极性、非极性反应端基,成功解决了发散法合成较长单分散共轭齐聚物过程中产物难以提纯的技术问题,合成了系列芴撑乙烯撑共轭齐聚物。其中,最长的齐聚物含11个芴单元,光谱外推得到的有效共轭长度可达19个重复单元。DSC和偏光显微镜研究表明,芴单元数大于5的齐聚物可形成向列型液晶相。含7个芴单元以上的齐聚物可用于制备有机发光二极管,含11个芴单元的齐聚物电致发光效率是相应聚合物的5倍。 2、通过Hagigara-Sonogashira偶联、Diels-Alder环加成等反应合成了一系列端基为刚性的苯乙炔基和五苯基苯的单分散齐聚芴。但典型Scholl反应条件不能实现完全氧化脱氢,获得六苯并晕苯封端的齐聚芴。光谱研究表明苯乙炔基的引入导致吸收光谱和荧光光谱有1-2 nm的红移。五苯基苯结构的引入能显著提高齐聚芴的Tg,从而提高齐聚物的形态稳定性。 3、利用Yamamoto反应,采用端基溴代的齐聚芴大分子单体聚合结合制备色谱分离,成功地制备了分子量超过20000 Da的单分散共轭聚合物,说明大分子单体聚合结合制备色谱分离制备单分散共轭聚合物是可行的。 4、通过Horner-Wadsworth-Emmons反应合成一系列端基为三苯胺乙烯撑的单分散齐聚芴,其中,最长的齐聚物含9个芴单元。光谱研究表明,随芴单元数的增加,两个三苯胺乙烯撑端基间共轭作用显著减弱,最大吸收波长蓝移;当芴的单元数≥3时,最大发射波长均位于450 nm,和聚芴和齐聚芴相比,这类共轭齐聚物的蓝光发光峰位更佳。电化学研究表明三苯胺乙烯撑单元的氧化还原过程不受齐聚芴单元长度的影响,该封端齐聚芴的HOMO能级主要是由三苯胺乙烯撑单元决定。 关键词:端基官能化,齐聚芴,单分散共轭聚合物
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本论文以改善有机/高分子电致发光器件的载流子注入与传输平衡为目的,以具有良好成膜性、热稳定性及氧化还原性的氮硫共扼聚合物为母体,通过在氮上引入不同的侧基来研究所得聚合物的空穴传输性能,发光性能及其在电致发光器件中佩的应用。1.设计与合成出一系列不同链长的烷基取代的氮硫共扼聚合物,所得聚合物具有规整的结构,高的分子量,可溶于常见的有机溶剂且具有良好的成膜性。电化学研究表明,它们具有良好的氧化还原可逆性及稳定性,其HOMO值在5.02一5.16eV之间,与阳极ITO具有较好的匹配,说明它们有着良好的空穴注入性能。通过对“hole-only"器件(ITO/PPSA-R/C u )的研究表明随着烷基侧链的增长,所得聚合物的空穴传输能力逐渐下降。双层器件(TO/PPSA-R/Alq3几佩F/AI)研究结果表明与传统的高分子空穴传输材料聚乙烯咔叫含(PVK)相比,器件的启动电压降低,发光效率明显提高,说明烷基取代氮硫共扼聚合物具有优良的空穴传输性能。2.设计与合成出侧链悬挂有三芳胺类空穴传输小分子的氮硫共辆单体,在强酸体系下聚合后,通过核磁表征发现由于醚键断裂导致部分三芳1}5}小分子脱落,聚合物中三芳胺小分子含量降低。电化学研究表明它们具有良好的氧化还原可逆性,其HOMO值在-5.18eV左右,大于未引入二芳服时的氮硫共扼聚合物。双层器件(ITO/PPSA-TPA/Alq3/LiF/Al)研究结果表明,与未引入三芳l}}C的氮硫共扼聚合物相比,器件的启动电压升高,发光效率降低。3.设计与合成出侧链悬挂有高荧光效率的蓝色发光二苯葱小分子的氮硫单体,并通过其与可合成出高性能的空穴传输材料一的乙基取代的氮硫单体以不同比例共聚获得一系列新型的主链传输空穴而侧链发光的聚合物。它们具有高的热稳定性,良好的溶解性及成膜性,电化学研究表明它们具有良好的氧化还原可逆 性及低的起始氧化电位。通过对其发光性质的研究,我们发现在溶液荧光光谱中短波长的发射归结于二苯葱单体的发射,而长波长的发射则归结于分子内或分子间受激分子的发射;在固体膜的荧光光谱中,主要表现为激基缔合物发光,并随着二苯葱基元含量的减少光致发光亮度增加,且发光蓝移。4.设计与合成出含有N一烷基咔吟或N一芳基咔畔和不同发光中心的小分子发光材料,我们发现含葱环的发光小分子发光颜色向长波移动,含联苯结构的发光小分子的发光颜色则向短波移动。电化学研究表明,11卜畔的存在提高了发光小分子的空穴传输性能。通过将含有电子传输层的发光小分子双层器件与单层器件对比,我们发现双层器件的各项性能远高于单层器件,进一步说明了发光小分子传输性能的改善。
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本论文以合成聚荀及其衍生物电致发光材料为目的。通过光谱性质、电化学性质的表征及聚合物单层电致发光器件的测试来评价所合成的聚合物的性能。经过研究不同分子结构的共聚合单体及其含量对聚合物光电性能的影响及相关机理,为设计高性能的电致发光聚合物材料探索切实可行的途径。1.设计并合成了在侧链中带有嗯二哇类电子注入和传输基团的聚(9,9-二烷芴)系列聚合物,详细讨论了嗯二哇侧基含量对聚合物的分子量、溶解性、热性能的影响。嗯二哇侧基使聚合物有较大的空间位阻,限制了聚(9,9-二烷芴)的分子间的堆积,破坏了其晶相的形成。由于不同含量的唔二哇的引入,提高了聚合物的LUMO值,降低了电子的注入势垒。聚合物单层电致发光器件的性能数据表明,嗯二哇侧基的引入可以提高器件的效率和亮度,且含嗯二哇侧基的单体含量的最佳范围为27%左右。嗯二哇侧基的加入,导致电致发光出现较强的激基复合物发光,器件的电致发光表现为蓝白色荧光。2.设计和合成了在侧链中带有三苯胺基团的芴类系列聚合物,详细讨论了三苯胺侧基对聚合物的分子量、溶解性、热性能进行的影响。三苯胺侧基使聚合物有较大的位阻,限制了聚合物分子间的堆积,破坏了晶相的形成。三苯胺的引入降低了聚合物的HOMO值,因此空穴的注入势垒较小。聚合物单层电致发光器件的研究结果表明,三苯胺侧基的引入可以提高器件的效率和亮度,且三苯胺侧基的单体的含量的最佳范围为13%左右。加入三苯胺侧基后,聚合物保持了聚药本身的蓝光发光特性,并在一定程度上可以抑制激基复合物的形成。3.设计并合成了一类新的N-苯基取代吩噬嗦与9,9-二烷芴的具有空穴注入和传输功能的共聚物发光材料。N一苯基取代的吩唆嗓使聚合物发光有较大的红移,且光谱变宽。N-苯基取代的吩唆嗦与9,9-二烷芴交替共聚物显示出比三苯胺和咔哇类单体与9,9-二烷芴交替共聚物更低的HOMO值,是一类潜在的空穴注入和传输材料。在共聚含量低于30%时,吩噬啧单体的引入可以提高器件的效率。其电致发光光谱显示出与光致发光光谱相同的变化规律。4.本章基于“蓝光和橙光二原色”协同形成白光的物理思想,采用聚芴为蓝光构造基元,蔡酞亚胺衍生物为橙光构造基元,设计合成了将蔡酞亚胺衍生物共聚到聚荀及其衍生物主链的系列聚合物,实现蓝光和橙光发射基元在单一高分子中共同发光。通过调节蔡酰亚胺衍生物单体的含量,调控蓝光发射与橙光发射的相对强度,实现单一高分子的白光发射。利用能量转移和电荷转移(或电荷捕获)提高了聚合物器件性能,来达到提高白光器件电致发光光谱稳定性的目的。本章制备的白色电荧光聚合物是目前世界上器件结构和制备工艺最简单,效率最高的白光电致发光聚合物材料。
Resumo:
The structure and frequencies of C12B24N24 have been calculated by means of an ab initio method. By comparing the average bond energies with C-60, the calculated results predict that the cage C12B24N24 is a stable molecule. The calculated results indicate that the cage molecule C12B24N24 has a relative large HOMO-LUMO energy gap and a low rigidity The structures and stability of six possible isomers of C2B4N4 are used to suggest a possible transformation path from the pentagon CB2N2 to the C12B24N24 materials. (C) 2001 John Wiley & Sons, Inc.