Direct observation of hole transfer through DNA by hopping between adenine bases and by tunnelling.

The function of DNA during oxidative stress and its suitability as a potential building block for molecular devices depend on long-distance transfer of electrons and holes through the molecule, yet many conflicting measurements of the efficiency of this process have been reported. It is accepted that charges are transported over long distances through a multistep hopping reaction; this 'G-hopping' involves positive charges moving between guanines (Gs), the DNA bases with the lowest ionization potential. But the mechanism fails to explain the persistence of efficient charge transfer when the guanine sites are distant, where transfer rates do not, as expected, decrease rapidly with transfer distance. Here we show experimentally that the rate of charge transfer between two guanine bases decreases with increasing separation only if the guanines are separated by no more than three base pairs; if more bridging base pairs are present, the transfer rates exhibit only a weak distance dependence. We attribute this distinct change in the distance dependence of the rate of charge transfer through DNA to a shift from coherent superexchange charge transfer (tunnelling) at short distances to a process mediated by thermally induced hopping of charges between adenine bases (A-hopping) at long distances. Our results confirm theoretical predictions of this behaviour, emphasizing that seemingly contradictory observations of a strong as well as a weak influence of distance on DNA charge transfer are readily explained by a change in the transfer mechanism.     

DNA分子电荷输运的大极化机制探讨

近年来研究发现,与生命体密切相关的DNA损伤与修复过程伴随着DNA链内电荷的转移.在DNA中,极化子是重要的元激发,是DNA中电荷传递可能的载流子.为了更好的理解DNA的电荷输运的极化子机制,给出了能够准确估计电声耦合常数α数值的理论方法.利用确定的电声耦合常数α,计算了极化子宽度和极化子束缚能.计算结果显示,DNA中的电荷输运是通过大极化子的相干运动来实现的.     

Direct measurement of hole transport dynamics in DNA

Our understanding of oxidative damage to double helical DNA and the design of DNA-based devices for molecular electronics is crucially dependent upon elucidation of the mechanism and dynamics of electron and hole transport in DNA. Electrons and holes can migrate from the locus of formation to trap sites, and such migration can occur through either a single-step "superexchange" mechanism or a multistep charge transport "hopping" mechanism. The rates of single-step charge separation and charge recombination processes are found to decrease rapidly with increasing transfer distances, whereas multistep hole transport processes are only weakly distance dependent. However, the dynamics of hole transport has not yet been directly determined. Here we report spectroscopic measurements of photoinduced electron transfer in synthetic DNA that yield rate constants of approximately 5 x 10(7) s(-1) and 5 x 10(6) s(-1), respectively, for the forward and return hole transport from a single guanine base to a double guanine base step across a single adenine. These rates are faster than processes leading to strand cleavage, such as the reaction of guanine cation radical with water, thus permitting holes to migrate over long distances in DNA. However, they are too slow to compete with charge recombination in contact ion pairs, a process which protects DNA from photochemical damage.     

Direct measurement of electrical transport through DNA molecules

Attempts to infer DNA electron transfer from fluorescence quenching measurements on DNA strands doped with donor and acceptor molecules have spurred intense debate over the question of whether or not this important biomolecule is able to conduct electrical charges. More recently, first electrical transport measurements on micrometre-long DNA 'ropes', and also on large numbers of DNA molecules in films, have indicated that DNA behaves as a good linear conductor. Here we present measurements of electrical transport through individual 10.4-nm-long, double-stranded poly(G)-poly(C) DNA molecules connected to two metal nanoelectrodes, that indicate, by contrast, large-bandgap semiconducting behaviour. We obtain nonlinear current-voltage curves that exhibit a voltage gap at low applied bias. This is observed in air as well as in vacuum down to cryogenic temperatures. The voltage dependence of the differential conductance exhibits a peak structure, which is suggestive of the charge carrier transport being mediated by the molecular energy bands of DNA.     

含酯基和酰胺基支链的四苯基[a,c,h,j]蒽液晶电荷传输性质的理论研究

根据Marcus半经典模型,在B3LYP/6-31G**水平上,对支链中含酯基和酰胺基的四苯基[a,c,h,j]蒽衍生物的分子结构、电子结构及电荷传输性质进行理论研究.计算结果表明:支链中酯基和酰胺基排列的对称性对电荷传输矩阵元t和传输速率常数k影响不同.所研究的4个分子中,含酯基支链的非对称性分子(a-TRO)正电荷传输矩阵元t+(2.81 kJ/mol)与速率常数k+(4.17×1012s-1)最大,有利于正电荷传输,可设计为正电荷传输材料.含酰胺基支链的非对称性分子(a-TRN)的负电荷传输矩阵元t-(4.94kJ/mol)与速率常数k-(9.02×1012s-1)在4个分子中最大,有利于负电荷传输,可设计为负电荷传输材料.     

Intraprotein radical transfer during photoactivation of DNA photolyase

Amino-acid radicals play key roles in many enzymatic reactions. Catalysis often involves transfer of a radical character within the protein, as in class I ribonucleotide reductase where radical transfer occurs over 35 A, from a tyrosyl radical to a cysteine. It is currently debated whether this kind of long-range transfer occurs by electron transfer, followed by proton release to create a neutral radical, or by H-atom transfer, that is, simultaneous transfer of electrons and protons. The latter mechanism avoids the energetic cost of charge formation in the low dielectric protein, but it is less robust to structural changes than is electron transfer. Available experimental data do not clearly discriminate between these proposals. We have studied the mechanism of photoactivation (light-induced reduction of the flavin adenine dinucleotide cofactor) of Escherichia coli DNA photolyase using time-resolved absorption spectroscopy. Here we show that the excited flavin adenine dinucleotide radical abstracts an electron from a nearby tryptophan in 30 ps. After subsequent electron transfer along a chain of three tryptophans, the most remote tryptophan (as a cation radical) releases a proton to the solvent in about 300 ns, showing that electron transfer occurs before proton dissociation. A similar process may take place in photolyase-like blue-light receptors.     

Charge self-regulation upon changing the oxidation state of transition metals in insulators

Transition-metal atoms embedded in an ionic or semiconducting crystal can exist in various oxidation states that have distinct signatures in X-ray photoemission spectroscopy and 'ionic radii' which vary with the oxidation state of the atom. These oxidation states are often tacitly associated with a physical ionization of the transition-metal atoms--that is, a literal transfer of charge to or from the atoms. Physical models have been founded on this charge-transfer paradigm, but first-principles quantum mechanical calculations show only negligible changes in the local transition-metal charge as the oxidation state is altered. Here we explain this peculiar tendency of transition-metal atoms to maintain a constant local charge under external perturbations in terms of an inherent, homeostasis-like negative feedback. We show that signatures of oxidation states and multivalence--such as X-ray photoemission core-level shifts, ionic radii and variations in local magnetization--that have often been interpreted as literal charge transfer are instead a consequence of the negative-feedback charge regulation.     

电位滴定在憎液胶体表面电荷密度研究中的应用

首先讨论了进行电位滴定实验的时候,逐次加入的滴定剂中决定电位离子的数量与被分析憎液胶体分散相粒子表面电荷密度之间的定量关系式,比较了文献中几种不同的零电点的测定方法,进而肯定了其中盐滴定法的可行性.然后,文章介绍了滴定过程中,不溶于水的氧化物或含氧氢氧化物胶体分散相与电解质溶液之间的慢速质子迁移现象,介绍了这一过程的机理以及它对从电位滴定得到的表面电荷密度σ_0值的影响,提出防止这一影响,区分慢速质子迁移与表面电离、表面络合反应对表面电荷的贡献,研究表面吸附机理的实验方法.     

掺铋钇铁石榴石法拉第效应的增强机理研究

提出用电荷控制法研究ａ－ＳｉＣＣＤ电荷转移特性的理论模型，通过引入平均场效应迁移率的概念，推导出计算ａ－ＳｉＣＣＤ电荷转移损失率的解析解，理论计算与实验结果符合较好．该模型可以较好地反映热扩散、自感应电场和边缘电场的漂移机制对ａ－ＳｉＣＣＤ电荷转移特性的影响，分析结果表明，ａ－ＳｉＣＣＤ的电荷的转移主要是受电场漂移作用控制．     

R型半胱氨酸体系电荷转移百分数的理论计算

采用密度泛函理论中的CAM-B3LYP方法, 在6-31G(d)基组水平上优化气相条件下R型半胱氨酸(R-Cys)分子的几何构型, 理论研究电子激发过程中R-Cys体系片段间的电荷转移特征, 并基于弛豫与非弛豫激发态密度计算片段间的电荷转移百分数. 结果表明: 对于SH片段, S0到S3的电荷转移百分数为57.96%； 对于COOH片段, S0到S1~S5各激发态的电荷转移百分数均为负值, 二者电荷转移的定性结果一致； 对于NH2片段, S0到S1和S4的电荷转移百分数分别为6.98%和31.45%.     

电荷转移型导电配位化合物

介绍电荷转移型导电配合物的导电性的发现及导电机理、电荷转移型导电配合物研究的发展及类型、研究现状及热点 ,并讨论了提高电荷转移型导电配合物导电率的条件的优选及合成新的电荷转移型导电配合物的分子设计。     

不同价态的阴离子在DNA凝聚效应中的抑制作用

为了定量地研究阴离子对DNA凝聚和电荷中和过程的抑制作用，利用动态光散射和原子力显微镜研究了不同价态阴离子对阳离子介导的DNA凝聚效应的影响。在动态光散射实验中，阴离子可以使阳离子作用后的DNA的电泳迁移率变小，即对DNA的电荷中和有抑制作用，而且阴离子价态越高，对电泳迁移率的抑制作用越强。改变阳离子种类但控制相同的阳离子浓度，发现阴离子对DNA的电荷中和有同样的抑制作用及趋势，同时用原子力显微镜观察DNA的凝聚形态变化也得出一致的结果。在相同阳离子浓度下，高价阴离子相对低价态阴离子，对DNA凝聚的抑制作用更强，使DNA的凝聚形态变得更加松散，进一步证实了阴离子对阳离子导致的DNA凝聚有减弱作用。     

不同价态的阴离子在DNA凝聚效应中的抑制作用

为了定量地研究阴离子对DNA凝聚和电荷中和过程的抑制作用,利用动态光散射和原子力显微镜研究了不同价态阴离子对阳离子介导的DNA凝聚效应的影响。在动态光散射实验中,阴离子可以使阳离子作用后的DNA的电泳迁移率变小,即对DNA的电荷中和有抑制作用,而且阴离子价态越高,对电泳迁移率的抑制作用越强。改变阳离子种类但控制相同的阳离子浓度,发现阴离子对DNA的电荷中和有同样的抑制作用及趋势,同时用原子力显微镜观察DNA的凝聚形态变化也得出一致的结果。在相同阳离子浓度下,高价阴离子相对低价态阴离子,对DNA凝聚的抑制作用更强,使DNA的凝聚形态变得更加松散,进一步证实了阴离子对阳离子导致的DNA凝聚有减弱作用。     

基于多孔介质模型的火炮装药传热特性

在自行加榴炮的诸多战术指标之中,药温能够在很大程度上影响其发射初速及射程.以多孔介质传热模型为理论基础,建立火炮装药传热模型,利用有限容积法离散化处理所建立的数学模型,得到相应的差分计算格式,并对自行加榴炮的装药温度场进行模拟仿真.通过理论计算结果与试验测试数据的对比,表明所建的理论模型能够正确反映发射装药的温度变化规律,模拟结果具有一定的参考价值.     

C原子在Cu(200)表面吸附的第一原理研究

采用第一原理密度泛函理论研究了C原子在Cu(200)表面吸附后的几何结构和电子结构,计算了C原子在Cu(200)表面的吸附能、Cu(200)表面的局部结构变化、表面电荷分布以及C原子吸附后的差分电荷密度。研究结果表明Cu(200)表面的Hollow位是C原子的最优吸附位,C原子与Cu原子之间形成化学键,在C原子和Cu表面之间存在电荷转移。     

The mechanism of retroviral integration from X-ray structures of its key intermediates

To establish productive infection, a retrovirus must insert a DNA replica of its genome into host cell chromosomal DNA. This process is operated by the intasome, a nucleoprotein complex composed of an integrase tetramer (IN) assembled on the viral DNA ends. The intasome engages chromosomal DNA within a target capture complex to carry out strand transfer, irreversibly joining the viral and cellular DNA molecules. Although several intasome/transpososome structures from the DDE(D) recombinase superfamily have been reported, the mechanics of target DNA capture and strand transfer by these enzymes remained unclear. Here we report crystal structures of the intasome from prototype foamy virus in complex with target DNA, elucidating the pre-integration target DNA capture and post-catalytic strand transfer intermediates of the retroviral integration process. The cleft between IN dimers within the intasome accommodates chromosomal DNA in a severely bent conformation, allowing widely spaced IN active sites to access the scissile phosphodiester bonds. Our results resolve the structural basis for retroviral DNA integration and provide a framework for the design of INs with altered target sequences.     

基于原子电荷计算隐式溶剂下的甲硫氨酸电荷转移

计算隐式溶剂下左旋体甲硫氨酸(S-Met)手性对映体激发态的波函数, 并基于原子电荷计算片段间的电荷转移百分数. 结果表明： 原子偶极校正的Hirshfeld布居(ADCH)和Hirshfeld电荷方法计算的定性结果一致, 定量结果差异较大; 在隐式溶剂H₂O和甲醇下, S-Met分子体系片段电荷转移的计算结果基本相同, 各片段与分子其他部分连接原子间的Mayer键级变化基本相同.      

基于密度泛函理论对咔咯-吩噻嗪二元体激发态电荷转移的研究

采用密度泛函理论(DFT)对咔咯与吩噻嗪形成的F10C-PTZ供体-受体体系进行了计算,包括几何结构、前线分子轨道、电子-空穴分析、吸收光谱等基态和激发态性质;探讨了二元体间隔基和取代基位置对电荷转移激发态的影响.结果表明:F10C-PTZ二元体存在供体-受体间的电荷转移激发态;间隔基的C—C键会阻碍供体-受体的电荷转移,而间隔基的C—C键可增强体系的共轭性,有利于供体-受体的电荷转移;当供体取代位置与五氟苯基相邻时,咔咯上五氟苯基的拉电子效应使得供体-受体激发的电荷转移更易于发生.     

铁离子引起的DNA电荷逆转和凝聚

在生物体中,DNA会凝聚成紧密结构,对于遗传信息的储存和转录有重要意义。对于DNA的凝聚以及伴随的电荷逆转已经有了比较深入的研究,这些研究大多集中于一些水解性较弱的离子,而对于那些易水解对于溶液pH影响较大的金属离子（例如铁离子）的研究较少。本文系统地研究了铁离子引起的DNA电荷逆转和凝聚,通过与DNA在三氯六氨络合钴凝聚的对比,探索了铁离子引起的DNA的电荷逆转和凝聚的可能机制。     

Photoconductivity of fullerene derivatives

Two fullerene derivatives (compounds 1 and 2) have been synthesized. Their redox properties have been measured by cyclic voltammetry. The photoconductivities of poly(N_vinylcarbazo_le) (PVK) doped with fullerene and with their derivatives have been studied to explore the possible relationship between the reductibility of fullerenes and the photoconductivity of fullerenes_doped PVK. The charge generation efficiencies of PVK doped with fullerene and with its derivatives have changed remarkably: the diversity of charge generation efficiency is obvious in different doping systems. The result indicates that there is charge transfer between fullerenes and PVK.