DNA as helical ruler: exciton-coupled circular dichroism in DNA conjugates

The structure and properties of oligonucleotide conjugates possessing stilbenedicarboxamide chromophores at both ends of a poly(dA):poly(dT) base-pair domain of variable length have been investigated using a combination of spectroscopic and computational methods. These conjugates form capped hairpin structures in which one stilbene serves as a hairpin linker and the other as a hydrophobic end-cap. The capping stilbene stabilizes the hairpin structures by ca. 2 kcal/mol, making possible the formation of a stable folded structure containing a single A:T base pair. Exciton coupling between the stilbene chromophores has little effect on the absorption bands of capped hairpins. However, exciton-coupled circular dichroism (EC-CD) can be observed for capped hairpins possessing as many as 11 base pairs. Both the sign and intensity of the EC-CD spectrum are sensitive to the number of base pairs separating the stilbene chromophores, as a consequence of the distance and angular dependence of exciton coupling. Calculated spectra obtained using a static vector model based on canonical B-DNA are in good agreement with the experimental spectra. Molecular dynamics simulations show that conformational fluctuations of the capped hairpins result in large deviations of the averaged spectra in both the positive and negative directions. These results demonstrate for the first time the ability of B-DNA to serve as a helical ruler for the study of electronic interactions between aligned chromophores. Furthermore, they provide important tests for atomistic theoretical models of DNA.     

DNA-mediated exciton coupling and electron transfer between donor and acceptor stilbenes separated by a variable number of base pairs

The synthesis, steady-state spectroscopy, and transient absorption spectroscopy of DNA conjugates possessing both stilbene electron donor and electron acceptor chromophores are described. These conjugates are proposed to form nicked DNA dumbbell structures in which a stilbenedicarboxamide acceptor and stilbenediether donor are separated by variable numbers of A-T or G-C base pairs. The nick is located either adjacent to one of the chromophores or between two of the bases. Thermal dissociation profiles indicate that stable structures are formed possessing as few as two A-T base pairs. Circular dichroism (CD) spectra in the base pair region are characteristic of B-DNA duplex structures, whereas CD spectra at longer wavelengths display two bands attributed to exciton coupling between the two stilbenes. The sign and intensity of these bands are dependent upon both the distance between the chromophores and the dihedral angle between their transition dipoles [Deltaepsilon approximately Rda(-2) sin(2theta)]. Pulsed laser excitation of the stilbenediamide results in creation of the acceptor-donor radical ion pair, which decays via charge recombination. The dynamics of charge separation and charge recombination display an exponential distance dependence, similar to that observed previously for systems in which guanine serves as the electron donor. Unlike exciton coupling between the stilbenes, there is no apparent dependence of the charge-transfer rates upon the dihedral angle between donor and acceptor stilbenes. The introduction of a single G-C base pair between the donor and acceptor results in a change in the mechanism for charge separation from single step superexchange to hole hopping.     

简析二氧化硫通入澄清石灰水的现象、反应及其它

把SO2通入澄清石灰水的现象、反应,是中学化学教学不可回避的问题。《化学教育》杂志先后发表过好几篇文章讨论这个问题。笔者认为,以下几个根本问题,在教学中至今仍然没有得到很好解决。1.把SO2通入澄清石灰水,到底有没有白色亚硫酸钙（CaSO3）沉淀生成? 2.SO2通入石灰水、跟把CO2通入石灰水,是不是有相似的化学反应现象和相同的化学反应过程?     

MoO_3电致变色薄膜的XPS研究

近年来 ,随着人们提倡节能和使用洁净能源 ,无机电致变色材料在建筑物采光控制系统和反射率可调表面的应用研究 ,已成为材料领域的一个新热点 .WO3、 MoO3等过渡金属氧化物薄膜具有良好的电致变色效应 ,是人们研究的重点 .其中 MoO3的电致变色效果要好于 IrO2、 TiOx、 CoO及 NiOx等电致变色材料 [1],而且它在可见光区有比 WO3更柔和的色彩 ,使人眼更易于适应其颜色变化 .着色态的 MoO3称为钼青铜 ,其开路记忆也好于钨青铜 [2].故 MoO3电致变色薄膜是极有潜力用于实用化的电致变色器件 .MoO3薄膜常用的制备方法有真空蒸 发、化学气…     

He—HF体系的结构和分析势能函数

利用Ｇｕａｓｓｉａｎ９４程序和ＱＣＩＳＤ／６－３１１＋＋Ｇ方法得到Ｈｅ－ＨＦ和Ｈｅ－ＦＨ两种线性平衡结构,计算出了这两种弱结合分子的结构参数、离解能和二阶力常数。在此基础上,利用多体项展式方法民出Ｈｅ－ＨＦ（Ｘ＾１Σ＾＋）体系的分析势能函数,得到的势能面准确地再现了Ｈｅ－ＨＦ和Ｈｅ－ＦＨ两种线性结构。     

鲁西南沿黄县区玉米中铅、镉、砷、铬的重金属含量及健康风险评价

为了评估鲁西南沿黄县区(东明县、牡丹区、鄄城县、郓城县)玉米中铅、镉、砷、铬重金属的污染风险,采集该地区玉米果穗,利用电感耦合等离子体质谱(ICP-MS)仪测定其玉米籽粒中铅、镉、砷、铬的含量,并使用单因子污染指数法、内梅罗综合多因子指数法和目标危险系数法开展玉米籽粒重金属污染评价和健康风险评价。结果表明,鲁西南沿黄县区玉米籽粒中重金属铅、镉、砷、铬的含量均未超出GB 2762—2017中规定的限量,重金属含量以Cr最高;鲁西南沿黄县区P_综和TTHQ均小于1,说明玉米籽粒中的重金属元素含量为清洁安全等级,食用该地区玉米对人体的健康风险较低。     

稀土氧化物提高中高碳钢堆焊试样抗开裂性机制的研究

采用5CrNiMo热锻模具钢作为研究对象，分析了堆焊试样上的裂纹形貌，测定了堆焊残余应力场并进行了数值模拟。在此基础上，分析了稀土氧化物改善堆焊金属结晶组织和变质夹杂物的作用。结果表明：堆焊裂纹主要在粗大的树枝晶之间、夹杂物和热影响区粗大奥氏体晶粒处形成，并且，在堆焊金属中心和热影响区残余拉应力作用下扩展。堆焊金属中加入稀土氧化物能细化一次柱状晶组织；变质夹杂物。同时，降低堆焊金属马氏体相变温度，从而降低上述危险部位的拉应力峰值。     

The discovery of nanometer fringes in laser self-mixing interference

We demonstrate the influences of optical feedback from an external mirror with high reflectivity in a He-Ne laser on self-mixing interference fringes and laser polarization states. When the external mirror is tilted to a certain level, the stable and uniform nanometer resolution fringes are generated. The fringe density is 40 times than that of the conventional self-mixing interference or two beam interference, and has still potential to be improved. Each self-mixing interference fringe corresponds to λ/80 displacement of the external mirror, i.e. 7.91 nm displacement of the external mirror. Moreover, when the movement direction of the external mirror is changed, the polarization flipping between two eigenstates will happen. The potential applications of the results are also discussed.     

仿真水晶成分的鉴定

介绍仿真水晶工艺品成分的鉴定过程。对常见阴、阳离子进行分组、分类检定，并用红外光谱法和差热分析法进行验证，最终确定仿真水晶样品的主要成分为含有部分硅酸盐杂质的铵明矾。鉴定结果对仿真水晶的制作有一定的借鉴意义。     

Ce^4+水解切籽5'-AMP,3'-AMPA和CAMP的原位增强 拉曼光谱研究

首次用原位增强拉曼光谱技术研究了Ce^4+水解切断核苷酸的过程,实验表明在粗糙化的银表面可以得到5'---AMP,3'－AMP和CAMP明显增强的拉曼光谱,Ce^4+水解切断5'--AMP时在2895cm^-1和2950cm^-1处分别出现CH~2的动振峰;3'---AMP中原有CH~2振动峰,当它的磷酸酯键被Ce^4+水解切断时,这些峰则明显减弱,甚至消失,把Ce^4+水解切断CAMP过程的原位拉曼光谱与5'---SAMP同Ce^4+反应以后的拉曼光谱相比较,推测Ce^4+断裂CAMP和3'--AMP时,首先切断CAMP中的一个磷酸酯键,生成5'--AMP和3'---AMP随着反应的进行Ce^4+再逐渐断裂5'--AMP和3'---AMP的磷酸酯键,生成最终产物腺苷。