Photoluminescence study of InGaN/GaN quantum dots grown on passivated GaN surface

We have measured photoluminescence (PL) and time-resolve photoluminescence (TRPL) from InGaN/GaN quantum dots (QDs) grown on passivated GaN surfaces by metalorganic chemical vapor deposition (MOCVD). Strong PL emission was observed from the QDs structure even at room temperature. By comparing the PL and TRPL dependence on temperature, a significant difference between the QD and wetting layer emissions was revealed. The QD emission is characterized by a strong exciton localization effect, which leads to a larger thermal activation energy, a nearly constant radiative lifetime independent of temperature and an unusual temperature behavior of the PL peak energy. (C) 2003 Elsevier B.V. All rights reserved.

In-plane stray field induced spin-filtering in a two-dimensional electron gas under the modulation of surface ferromagnetic dual-gate

Based upon a hybrid ferromagnet/semiconductor structure consisting of two-dimensional electron gas and a pair of surface ferromagnetic stripes on top, we have theoretically investigated the effect of in-plane stray field omitted frequently in previous studies on the spin-dependent ballistic transport properties in hybrid structure. It is demonstrated here that, in combination with an external-controllable electrostatic modulation, the concerned structure shows a similar function as a lateral spin-polarized resonant tunneling device, where the strong spin-filtering effect occurs and nearly single-mode polarization is anticipated for the proper modulation. More importantly, the spin polarity of transmission electron can be easily transferred from one extreme to the other by switching the magnetization of stripes, showing the promising application as an efficient spin aligner in the developing semiconductor spintronics.

Color center formation in silica glass induced by high energy Fe and Xe ions

Silica glass samples were implanted with 1.157 GeV Fe-56 and 1.755 GeV Xe-136 ions to fluences range from 1 x 10(11) to 3.8 x 10(12) ions/cm(2). Virgin and irradiated samples were investigated by ultraviolet (UV) absorption from 3 to 6.4 eV and photoluminescence (PL) spectroscopy. The UV absorption investigation reveals the presence of various color centers (E' center, non-bridging oxygen hole center (NBOHC) and ODC(II)) appearing in the irradiated samples. It is found that the concentration of all color centers increase with the increase of fluence and tend to saturation at high fluence. Furthermore the concentration of E' center and that of NBOHC is approximately equal and both scale better with the energy deposition through processes of electronic stopping, indicating that E' center and NBOHC are mainly produced simultaneously from the scission of strained Si-O-Si bond by electronic excitation effects in heavy ion irradiated silica glass. The PL measurement shows three emissions peaked at about 4.28 eV (alpha band), 3.2 eV (beta band) and 2.67 eV (gamma band) when excited at 5 eV. The intensities of alpha and gamma bands increase with the increase of fluence and tend to saturation at high fluence. The intensity of beta band is at its maximum in virgin silica glass and it is reduced on increasing the ions fluence. It is further confirmed that nuclear energy loss processes determine the production of alpha and gamma bands and electronic energy loss processes determine the bleaching of beta band in heavy ion irradiated silica glass. (c) 2009 Elsevier B.V. All rights reserved.

快重离子在SiO2基材料中引起的强电子激发效应研究

具有特殊结构的SiO2基材料与Si平面工艺具有好的兼容性，在光电技术中的发光二极管、固体显示屏等器件的研制方面有巨大的潜在应用价值。本论文以快重离子与物质相互作用的特点为依据，选择具有重要应用价值的SiO2基材料，研究快重离子辐照在SiO2基材料中引起的强电子激发效应，特别是辐照相变等现象，探索制备具有特殊功能的新型材料的方法，主要开展了如下研究： 1）在单晶Si衬底上通过高温湿法氧化一层SiO2薄膜，制备出SiO2/Si样品；在室温条件下，用能量为100 keV的碳离子注入样品，注入剂量分别为2.0×1017、5.0×1017和1.2×1018 ions/cm2，使样品SiO2薄膜中一定区域内C、Si和O原子达到适当的原子浓度配比；再用能量为308 MeV的Xe和853 MeV的Pb离子在室温下对注碳后的SiO2/Si样品进行辐照，Xe离子辐照是在兰州重离子加速器国家实验室的扇聚焦回旋加速器（HIRFL-SFC）的重离子辐照终端上完成，辐照剂量分别为1.0×1012、5.0×1012、1.0×1013、1.0×1014 Xe-ions/cm2，Pb离子辐照实验是在法国重离子激光交叉学科研究中心(CIRIL,Caen)的中能离子辐照终端（IRASME）完成的，辐照剂量分别为5.0×1011、1.0×1012、2.0×1012、5.0×1012 Pb-ions/cm2；最后用荧光光谱、红外吸收光谱、拉曼光谱和透射电子显微镜分析等技术对样品进行了表征。研究了样品发光与注碳剂量、辐照剂量和离子在薄膜中电子能损值的依赖关系，辐照引起SiO2薄膜中微结构改变与实验参数的依赖关系。发现快重离子辐照能显著改变注碳SiO2/Si样品的发光特性，如在5.0×1012 Pb-ions/cm2辐照的注碳2.0×1017 ions/cm2的样品中，探测到了很强的位于456、484和563nm的发光；在电镜照片中观察到了8H-SiC纳米晶及其他微结构的形成。基于实验结果，对薄膜发光特性与微结构改变之间的关系进行了初步探讨。 2）利用磁控溅射在单晶SiO2表面沉积Ni薄膜，制备了Ni/SiO2样品；在室温下用能量为308MeV的Xe和853MeV的Pb离子辐照Ni/SiO2样品，离子穿透Ni薄膜和Ni/SiO2界面，Xe、Pb离子辐照分别在HIRFL-SFC和法国CIRIL的IRASME辐照终端上完成，辐照剂量为1.0×1012、5.0×1012 Xe/cm2和5.0×1011Pb/cm2；用卢瑟福背散射技术和X射线衍射谱对样品进行了分析，研究了界面原子混合及相变效应与辐照剂量、电子能损值的依赖关系。发现快重离子辐照能引起Ni/SiO2样品界面处原子的混合，并导致界面形成NiSi2或Ni3Si新相，且原子扩散量随辐照剂量和电子能损值的增大而增大。 3）以热峰模型原理为基础，对实验观测到的快重离子辐照效应特别是电子能损效应的产生机理进行了探讨

Facile fabrication of large area of aggregated gold nanorods film for efficient surface-enhanced Raman scattering

An effective and facile method for fabrication of large area of aggregated gold nanorods (AuNRs) film was proposed by self-assembly of AuNRs at a toluene/water interface for the first time. It was found that large area of aggregated AuNRs film could be formed at the interface of toluene and water due to the interfacial tension between the two phases. The obtained large area of aggregated AuNRs film exhibits strong surface-enhanced Raman scattering (SERS) activity with 4-aminothiophenol (4-ATP) and 2-aminothiophenol (2-ATP) as the probe molecules based on the strong electromagnetic coupling effect between the very adjacent AuNRs.

金川矿山岩体移动规律及竖井变形、破坏机理研究

The Jinchuan Nickel Mine is the largest underground mine with cut-and-fill mining in China. It is very difficult to be exploited for very low safety stability of rock mass caused by complex geological conditions, developed faults, cracked rock mass and high stress. In this paper, the laws of rock mass movement、mechanics of shaft deformation and destroy were analyzed based on the collection of date, the detailed field engineering investigations, ground movement monitoring by GPS, theoretical analysis and numerical simulation. According to the GPS monitoring result of ground surface movement, there are different ground movement characteristics among the three Mine area of Jinchuan Nickel Mine. In No. 2 Mine area, the ground movement funnel with apparent asymmetry is developing, the influence scope is larger in the up faulted block than in the down faulted block, and the centre of ground movement is moving along the up faulted block direction with increasing depth of mining. Moreover, the tunnels in the corresponding area with the centre of ground movement are damaged seriously. In Longshou Mine area, the ground movement funnel is also developing, but the moving path and the nonlinear characters are more sophisticated because of the long-term effects of open excavating and the effects of underground mining together. In No. 3 Mine area, the underground mining impact on surface is not serious for the time of mining activity is not for long, but the ground movement funnel is also forming now. The underground mining has caused widespread land subsidence in Jinchuan Nickel Mine area, but the phenomena of surface raise appeared in some partial areas of Longshou Mine area and No. 3 Mine area. Analysis proved that the reason for the open pit bottom raise is the slope deformation activation caused by the excavation from open pit into underground mine; and that the raise of surface in No.3 Mine area is caused by the effect of elastic foundation due to underground mining. Although the GPS Monitoring results show the amount of subsidence is increasing constantly, the subsidence rate has a descending tendency with fluctuation in Jinchuan No. 2 Mine area. The subsidence rate curve is a time function and exists an extreme point, the rate increasing before extreme point and decreasing after the extreme point ,but the scale of decreasing rate will be very small after the rate decreasing up to a certain degree, moreover, the characteristics is different among different areas, which have some relation with the distance to the mining section and the dip of the ore body. ArcView is GIS software, which we adopted as a development platform, and made secondary development by its development language “avenue”, through which we developed a ground movement analysis and forecast System for Jinchuan Nickel Mine, which contain three modules : management of ground movement information; analysis and evaluation of ground movement; and ground movement forecast. In the module of evaluation, using the technique of MATLAB6.5 program with VB6.0, the system can achieve the ANN prediction model for GPS monitoring data, data preparation results analysis and model integrated was realized by Avenue programming. Finally, the author analyzed the mechanical of deformation and destroy of the No. 14 shaft, and its repair and artificial-support effectiveness also given detailed demonstration in various aspect. The result showed that the reason for the destroy of No. 14 shaft is underground mining, and being the case, the destroy of the shaft also has its special features, which mainly contains forked stress contour for mining steep ore and fault effect caused by mining activities. The repair and artificial-support played some restrictions on the rock mass movement and deformation, but did not show a strong or marked effect. With the increasing of mining depth and large-scale, the closure rock of the shaft will still deformed, even be destroyed.

Disparity Gradients and Depth Scaling

The binocular perception of shape and depth relations between objects can change considerably if the viewing direction is changed only by a small angle. We explored this effect psychophysically and found a strong depth reduction effect for large disparity gradients. The effect is found to be strongest for horizontally oriented stimuli, and stronger for line stimuli than for points. This depth scaling effect is discussed in a computational framework of stereo based on a Baysian approach which allows integration of information from different types of matching primitives weighted according to their robustness.

Density Functional study of the photoactive yellow protein's chromophore

We have investigated the structural and electronic properties of p-coumaric acid, the chromophore of the photoactive yellow protein (PYP), by means of first-principles molecular dynamics based on density functional theory (DFT). We have studied the chromophore both in the vacuum and in an extended model which includes the nearest residues in the binding pocket of PYP, as derived from crystallographic data. We have characterized the ground state of the isolated chromophore in its protonated and deprotonated forms and computed the energy barrier involved in the trans to cis isomerization process around the carbon-carbon double bond. A comparison of the optimized structures of the chromophore in the vacuum and in the extended protein model, both in the trans (ground state of PYP in the dark) and cis (first light-activated intermediate) configuration, shows how the protein environment affects the chromophore in the first step of the photocycle. Our model gives an energy storage of 25 kcal/mol associated with the trans-to-cia photoisomerization. Finally, we have elucidated the nature of the electronic excitation relevant for the photochemistry of PYP by means of time-dependent DFT calculations.

Automated versus non-automated weaning for reducing the duration of mechanical ventilation for critically ill adults and children: a cochrane systematic review and meta-analysis

IntroductionAutomated weaning systems may improve adaptation of mechanical support for a patient’s ventilatory needs and facilitate systematic and early recognition of their ability to breathe spontaneously and the potential for discontinuation of ventilation. Our objective was to compare mechanical ventilator weaning duration for critically ill adults and children when managed with automated systems versus non-automated strategies. Secondary objectives were to determine differences in duration of ventilation, intensive care unit (ICU) and hospital length of stay (LOS), mortality, and adverse events.MethodsElectronic databases were searched to 30 September 2013 without language restrictions. We also searched conference proceedings; trial registration websites; and article reference lists. Two authors independently extracted data and assessed risk of bias. We combined data using random-effects modelling.ResultsWe identified 21 eligible trials totalling 1,676 participants. Pooled data from 16 trials indicated that automated systems reduced the geometric mean weaning duration by 30% (95% confidence interval (CI) 13% to 45%), with substantial heterogeneity (I2 = 87%, P <0.00001). Reduced weaning duration was found with mixed or medical ICU populations (42%, 95% CI 10% to 63%) and Smartcare/PS™ (28%, 95% CI 7% to 49%) but not with surgical populations or using other systems. Automated systems reduced ventilation duration with no heterogeneity (10%, 95% CI 3% to 16%) and ICU LOS (8%, 95% CI 0% to 15%). There was no strong evidence of effect on mortality, hospital LOS, reintubation, self-extubation and non-invasive ventilation following extubation. Automated systems reduced prolonged mechanical ventilation and tracheostomy. Overall quality of evidence was high.ConclusionsAutomated systems may reduce weaning and ventilation duration and ICU stay. Due to substantial trial heterogeneity an adequately powered, high quality, multi-centre randomized controlled trial is needed.

Structure and Catalytic Activity of Gold in Low-Temperature CO Oxidation

Structures and catalytic activities of Au thin films supported at anatase TiO(2)(101)) and a Au substrate are studied by using density functional theory calculations. The results show that O(2) can hardly adsorb at flat and stepped Au thin films, even supported by fully reduced TiO(2)(101) that can highly disperse Au atoms and offer strong electronic promotion. Interestingly, in both oxide-supported and pure Au. systems, wire-structured Au can adsorb both CO and O(2) rather strongly, and kinetic analysis suggests its high catalytic activity for low-temperature CO oxidation. The d-band center of Au at the catalytic site is determined to account for the unusual activity of the wire-structured film. A generalized structural model based on the wire-structured film is proposed for active Au, and possible support effects are discussed: Selected oxide surfaces can disperse Au atoms and stabilize the formation of a filmlike structure; they may also serve as a template for the preferential arrangement of Au atoms in a wire structure under low Au coverage.

Latent vs. Observed Variables: Analysis of Irrigation Water Efficiency Using SEM and SUR

In this paper we compare conceptualising single factor technical and allocative efficiency as indicators of a single latent variable, or as separate observed variables. In the former case, the impacts on both efficiency types are analysed by means of structural equation modeling (SEM), in the latter by seemingly unrelated regression (SUR). We compare estimation results of the two approaches based on a dataset on single factor irrigation water use efficiency obtained from a survey of 360 farmers in the Guanzhong Plain, China. The main methodological findings are that SEM allows identification of the most important dimension of irrigation water efficiency (technical efficiency) via comparison of their factor scores and reliability. Moreover, it reduces multicollinearity and attenuation bias. It thus is preferable to SUR. The SEM estimates show that perception of water scarcity is the most important positive determinant of both types of efficiency, followed by irrigation infrastructure, income and water price. Furthermore, there is a strong negative reverse effect from efficiency on perception.

Microstructure design of Titanate-based electroceramics

Electrocerâmicos são uma classe de materiais avançados com propriedades eléctricas valiosas para aplicações. Estas propriedades são geralmente muito dependentes da microestrutura dos materiais. Portanto, o objectivo geral deste trabalho é investigar o desenho da resposta dieléctrica de filmes espessos obtidos por Deposição Electroforética (EPD) e cerâmicos monolíticos, através do controlo da evolução da microestrutura durante a sinterização de electrocerâmicos à base de titanatos. Aplicações sem fios na indústria microelectrónica e de comunicações, em rápido crescimento, tornaram-se um importante mercado para os fabricantes de semicondutores. Devido à constante necessidade de miniaturização, redução de custos e maior funcionalidade e integração, a tecnologia de filmes espessos está a tornar-se uma abordagem de processamento de materiais funcionais cada vez mais importante. Uma técnica adequada neste contexto é EPD. Os filmes espessos resultantes necessitam de um passo subsequente de sinterização que é afectada pelo substrato subjacente, tendo este um forte efeito sobre a evolução da microestrutura. Relacionado com a miniaturização e a discriminação do sinal, materiais dieléctricos usados como componentes operando a frequências das microondas em aplicações na industria microelectrónica de comunicações devem apresentar baixas perdas dieléctricas e elevadas permitividade dieléctrica e estabilidade com a temperatura. Materiais do sistema BaO-Ln2O3- TiO2 (BLnT: Ln = La ou Nd), como BaLa4Ti4O15 (BLT) e Ba4.5Nd9Ti18O54 (BNT), cumprem esses requisitos e são interessantes para aplicações, por exemplo, em estações de base para comunicações móveis ou em ressonadores para telefones móveis, onde a miniaturização dos dispositivos é muito importante. Por sua vez, o titanato de estrôncio (SrTiO3, STO) é um ferroeléctrico incipiente com constante dieléctrica elevada e baixas perdas, que encontra aplicação em, por exemplo, condensadores de camada interna, tirando partido de fronteiras de grão altamente resistivas. A dependência da permitividade dieléctrica do campo eléctrico aplicado torna este material muito interessante para aplicações em dispositivos de microondas sintonizáveis. Materiais à base de STO são também interessantes para aplicações termoeléctricas, que podem contribuir para a redução da actual dependência de combustíveis fósseis por meio da geração de energia a partir de calor desaproveitado. No entanto, as mesmas fronteiras de grão resistivas são um obstáculo relativamente à eficiência do STO para aplicações termoeléctricas. Para além do efeito do substrato durante a sinterização constrangida, outros factores, como a presença de fase líquida, a não-estequiometria ou a temperatura de sinterização, afectam significativamente não apenas a microestrutura dos materiais funcionais, mas também a sua resposta dieléctrica. Se adequadamente compreendidos, estes factores podem ser intencionalmente usados para desenhar a microestrutura dos electrocerâmicos e, desta forma, as suas propriedades dieléctricas. O efeito da não-estequiometria (razão Sr/Ti 0.995-1.02) no crescimento de grão e resposta dieléctrica de cerâmicos de STO foi investigado neste trabalho. A mobilidade das fronteiras de grão aumenta com a diminuição da razão Sr/Ti. A resistividade do interior dos grãos e das fronteiras de grão é sistematicamente diminuída em amostras não-estequiométricas de STO, em comparação com o material estequiométrico. O efeito é muito mais forte para as fronteiras de grão do que para o seu interior. Dependências sistemáticas da não-estequiometria foram também observadas relativamente à dependência da condutividade da temperatura (muito mais afectada no caso da contribuição das fronteiras de grão), à capacitância do interior e fronteiras de grão e à espessura das fronteiras de grão. Uma anomalia no crescimento de grão em cerâmicos de STO ricos em Ti foi também observada e sistematicamente analisada. Foram detectadas três descontinuidades na dependência do tipo Arrhenius do crescimento de grão relativamente à temperatura com diminuições no tamanho de grão a temperaturas em torno de 1500, 1550 e 1605 °C. Além disso, descontinuidades semelhantes foram também observadas na dependência da energia de activação relativamente à condutividade das fronteiras de grão e na espessura das fronteiras de grão, avaliadas por Espectroscopia de Impedância. Estas notáveis coincidências suportam fortemente a formação de diferentes complexos de fronteira de grão com transições entre os regimes de crescimento de grão observados, que podem ser correlacionados com diferentes mobilidades de fronteira de grão e propriedades dieléctricas. Um modelo é sugerido, que se baseia na diminuição da fase líquida localizada nas fronteiras de grão, como o aumento da temperatura de sinterização, um cenário compatível com um fenómeno de solubilidade retrógrada, observado anteriormente em metais e semicondutores, mas não em cerâmicos. A EPD de filmes espessos de STO em substratos de folha de Pt e a sinterização constrangida dos filmes fabricados foram também preliminarmente tratadas. Filmes espessos de STO foram depositados com êxito por EPD sobre substratos de Pt e, depois de sinterizados, atingiram densidades elevadas. Um aumento da densificação e do tamanho de grão assim como o alargamento da distribuição de tamanho do grão foram observados com a diminuição da razão Sr/Ti, tal como anteriormente observado em amostras cerâmicas. Grãos equiaxiados foram observados para todas as composições, mas um certo grau de anisotropia na orientação dos poros foi detectado: os poros revelaram uma orientação vertical preferencial. Este trabalho focou-se também na sinterização constrangida do sistema BLnT (Ln = La ou Nd), nomeadamente de filmes espessos de BLT e BNT sobre substratos de folha de platina, e na relação do desenvolvimento de anisotropia microestrutural com as propriedades dieléctricas. As observações durante a sinterização constrangida foram comparadas com cerâmicos monolíticos equivalentes sinterizados livremente. Filmes espessos de BLnT (Ln = La ou Nd) com elevada densidade foram obtidos por EPD e subsequente sinterização constrangida. A anisometria cristalográfica do material em conjunto com um passo de sinterização constrangida resultou em grãos alongados e microestruturas anisotrópicas. O efeito do stress do substrato durante a sinterização constrangida originou graus mais elevados de anisotropia (grãos e poros alongados e orientação preferencial, bem como textura cristalográfica) nos filmes sinterizados relativamente aos cerâmicos equivalentes sinterizados livremente, não obstante o estado equivalente das amostras em verde. A densificação dos filmes de BLnT (Ln = La ou Nd) é retardada em comparação com os cerâmicos, mas depois de longos tempos de sinterização densidades semelhantes são obtidas. No entanto, em oposição a observações na sinterização constrangida de outros sistemas, o crescimento do grão em filmes de BLnT (Ln = La ou Nd) é favorecido pelo constrangimento causado pelo substrato. Além disso, grãos e poros alongados orientados paralelamente ao substrato foram desenvolvidos durante a sinterização constrangida de filmes espessos. Verificou-se uma forte correlação entre a evolução de grãos e poros, que começou assim que o crescimento do grão se iniciou. Um efeito da tensão do substrato no aumento do crescimento de grão, bem como um forte “Zener pinning”, origina microestruturas altamente texturizadas, o que também é observado a nível cristalográfico. Efeitos marcantes da anisotropia microestrutural foram também detectados nas propriedades dieléctricas dos filmes de BLnT (Ln = La ou Nd). Juntamente com o aumento da razão de aspecto dos grãos, do factor de orientação e do grau de textura cristalográfica, a permitividade relativa é ligeiramente diminuída e o coeficiente de temperatura da permitividade evolui de negativo para positivo com o aumento do tempo isotérmico de sinterização. Este trabalho mostra que a não-estequiometria pode ser usada para controlar a mobilidade das fronteiras de grão e, portanto, desenhar a microestrutura e as propriedades dieléctricas de electrocerâmicos à base de STO, com ênfase nas propriedades das fronteiras de grão. O papel da não-estequiometria no STO e dos complexos de fronteira de grão no desenvolvimento microestrutural é discutido e novas oportunidades para desenhar as propriedades de materiais funcionais são abertas. As observações relativamente à sinterização constrangida apontam para o efeito de tensões mecânicas desenvolvidas devido ao substrato subjacente no desenvolvimento da microestrutura de materiais funcionais. É assim esperado que a escolha adequada de substrato permitia desenhar a microestrutura de filmes espessos funcionais com desempenho optimizado. “Stress Assisted Grain Growth” (SAGG) é então proposto como uma técnica potencial para desenhar a microestrutura de materiais funcionais, originando microestruturas anisotrópicas texturizadas com propriedades desejadas.

Growing Up in Taiwan: Counterfactual Models of Part-Time Work, Romantic Relationships, and Crime among Taiwanese Youth

Thesis (Ph.D.)--University of Washington, 2015

Vacuum-ultraviolet photochemically initiated modification of polystyrene surfaces: morphological changes and mechanistic investigations

Vacuum-ultraviolet (VUV) irradiation (kexc: 172 ± 12 nm) of polystyrene films in the presence of oxygen produced not only oxidatively functionalized surfaces, but generated also morphological changes. Whereas OH- and C=O-functionalized surfaces might be used for e.g. secondary functionalization, enhanced aggregation or printing, processes leading to morphological changes open new possibilities of microstructurization. Series of experiments made under different experimental conditions brought evidence of two different reaction pathways: introduction of OH- and C=O-groups at the polystyrene pathways is mainly due to the reaction of reactive oxygen species (hydroxyl radicals, atomic oxygen, ozone) produced in the gas phase between the VUV-radiation source and the substrate. However, oxidative fragmentation leading to morphological changes, oxidation products of low molecular weight and eventually to mineralization of the organic substrate is initiated by electronic excitation of the polymer leading to C–C-bond homolysis and to a complex oxidation manifold after trapping of the C-centred radicals by molecular oxygen. The pathways of oxidative functionalization or fragmentation could be differentiated by FTIR-ATR analysis of irradiated polystyrene surfaces before and after washing with acetonitrile and microscopic fluorescence analysis of the surfaces secondarily functionalized with the N,N,N-tridodecyl-triaza-triangulenium (TATA) cation. Ozonization of the polystyrene leads to oxidative functionalization of the polymer surface but cannot initiate the fragmentation of the polymer backbone. Oxidative fragmentation is initiated by electronic excitation of the polymer (contact-mode AFM analysis), and evidence of the generation of intermediate C-centred radicals is given e.g. by experiments in the absence of oxygen leading to cross-linking (solubility effects, optical microscopy, friction-mode AFM) and disproportionation (fluorescence).

Conformations of poly{G}-poly{C} π stacks with high hole mobility

Charge transfer properties of DNA depend strongly on the π stack conformation. In the present paper, we identify conformations of homogeneous poly-{G}-poly-{C} stacks that should exhibit high charge mobility. Two different computational approaches were applied. First, we calculated the electronic coupling squared, V2, between adjacent base pairs for all 1 ps snapshots extracted from 15 ns molecular dynamics trajectory of the duplex G15. The average value of the coupling squared 〈 V2 〉 is found to be 0.0065 eV2. Then we analyze the base-pair and step parameters of the configurations in which V2 is at least an order of magnitude larger than 〈 V2 〉. To obtain more consistent data, ∼65 000 configurations of the (G:C)2 stack were built using systematic screening of the step parameters shift, slide, and twist. We show that undertwisted structures (twist<20°) are of special interest, because the π stack conformations with strong electronic couplings are found for a wide range of slide and shift. Although effective hole transfer can also occur in configurations with twist=30° and 35°, large mutual displacements of neighboring base pairs are required for that. Overtwisted conformation (twist38°) seems to be of limited interest in the context of effective hole transfer. The results may be helpful in the search for DNA based elements for nanoelectronics