Progress in dynamic study on the triplet excited states and radical ions of DNA and its components

Progress in dynamic study on the triplet excited states and radical ions of DNA and its components is reviewed. It has been found that acetone is the only effective sensitizer for the study of the triplet excited states of DNA components. The transient absorption spectrum of guanyl radical cation resulting from the interaction of triplet acetone and DNA was observed directly, and the original evidence for selective damage of DNA by excited photosensitizer was obtained for the first time, which offered a new pathway for obtaining the main transient species of selective damage of DNA by photonucleases and illustrating initial oxidation mechanism of DNA via electron transfer.     

Progress in dynamic study on the triplet excited states and radical ions of DNA and its components

Progress in dynamic study on the triplet excited states and radical ions of DNA and its components is reviewed. It has been found that acetone is the only effective sensitizer for the study of the triplet excited states of DNA components. The transient absorption spectrum of guanyl radical cation resulting from the interaction of triplet acetone and DNA was observed directly, and the original evidence for selective damage of DNA by excited photosensitizer was obtained for -the first time, which offered a new pathway for obtaining the main transient species of selective damage of DNA by photonucleases and illustrating initial oxidation mechanism of DNA via electron transfer.     

油页岩二硫化碳-丙酮混合溶剂萃取物的组成与结构分析

利用等体积的二硫化碳-丙酮混合溶剂对龙口(LK)和柳树河(LSH)油页岩进行超声萃取,对萃取物ELK和ELSH进行FTIR、GC/MS和DART-MS分析。结果表明,LK和LSH油页岩的萃取率分别为2.1 8%和9.71%;ELK和ELSH中均存在大量的正构烷烃并具有明显的奇碳优势,ELK含有较多的异构烷烃、稠环芳烃和含氮有机化合物,而ELSH含有较多的环烷烃、烯烃和含氧有机化合物;DART-MS分析表明ELK和ELSH中有大量分子量在520~850Da范围内的化合物无法由GC/MS检测出,并且ELK中化合物的种类多于ELSH。     

Resistless photochemical etching of a silicon wafer by UV laser with an H<Superscript>2</Superscript>O<Superscript>2</Superscript> and HF aqueous solution

A new resistless etching method has been developed for Silicon wafers. This new method uses an aqueous solution consisting of hydrogen peroxide (H₂O₂) and hydrogen fluoride (HF) as the activating etchants. A 193 nm ArF excimer laser and a 266 nm fourth harmonic generation Nd: YAG laser were used as the photon sources. Results showed that pattern etching has been achieved without any photoresist film. In the case of the 193 nm laser, the optimal etching appeared at a 1.3 H₂O₂÷HF ratio, where an etch depth of 210 nm was achieved with a fluence of 29 mJ/cm² and shot number of 10000. At the same conditions, the etch depth with H₂O₂ and HF solution was three times of that by using H₂O and HF mixture. In the case of the 266 nm Nd: YAG laser, the optimal etching appeared at twice ratio of H₂O₂/HF, where the etch depth of 420 nm was achieved with a fluence of 12 mJ/cm² and shot number of 30000. Results showed that the etch effect of the 266 nm Nd: YAG laser was more desirable than that of the 193 nm ArF excimer laser.     

Synthesis of layered LiMnO2 byin situ oxidation-intercalation and a study of the reaction mechanism and electrochemical performance

Using Mn(OH)₂ as precursor, LiOH as lithiating agent and (NH₄)₂S₂O₈ as oxidant, layeredo-LiMnO₂ was obtained by a novel method—in situ oxidation-intercalation under mild conditions (80 °C). The product was characterized by XRD, ICP, TEM and⁷Li-NMR. The results reveal that orthorhombic LiMnO₂ with high purity and good crystallinity can be obtained by this method. During electrochemical tests, a LiMnO₂/Li cell shows an initial reversible capacity of 208 mAh · g⁻¹ and a reversible capacity of 180 mAh · g⁻¹ after 30 cycles at room temperature.     

An effective novel reaction system for the photo-degradation of aqueous organic pollutants

A novel reaction system consisted of a supported TiO₂ film electrode, a Ru−Ti oxide film electrode and air (oxygen) electrode is reported. The air (oxygen) electrode can provide H₂O₂ continuously for homogeneous photochemical oxidation reaction on the spot. In this reactor, degradation reaction of aniline occur from interface of TiO₂ film to all solution which is irradiated by ultraviolet ray. The degradation rate of aniline was characterized by measuring the change of chemical oxygen demand (COD) in solution under different conditions. It was found that the degradation rate of aniline in the novel system increased apparently as compared with single heterogeneous photocatalysis and homogeneous photochemistry system. It can be explained in terms of combining acts of heterogeneous photocatalysis and homogeneous photochemistry. Foundation item: Supported by the National Natural Science Foundation of China (10791033) Biography: CAI Nai-cai (1946-), male, Associate professor, Research direction: electrochemical catalysis and photocatalysis.     

载Pt纳米TiO2抑制滇池蓝藻生长的研究

 对蓝藻样品的叶绿素含量、光合速率、呼吸速率、氧化物岐化酶(SOD)活性以及超氧阴离子含量进行测定.比较研究纳米TiO₂和负载Pt纳米TiO₂对蓝藻生长抑制的影响.结果表明,与纳米TiO₂相比,在太阳光下负载Pt纳米TiO₂对蓝藻的抑制效果更好.另外,研究表明,载Pt纳米TiO₂的载Pt量选择1.5%为最佳.     

CeO2(111)表面的氧物种对Au的活化吸附

采用第一性原理的经过库仑力修正的密度泛函方法,研究了CeO_2(111)表面不同氧空穴附近形成的不同的活性O_2物种.在此基础上,研究这些O_2物种对Au原子的吸附能力,得到过氧O_2-2对Au吸附能为1.8eV,吸附较强;超氧O-2对Au的吸附能为0.4eV,吸附较弱.研究结果为Au/CeO_2催化CO氧化提供了重要理论思路.     

An in-situ DRIFTS study in the reaction between NO x and soot on BaAl2O4

The interactions between NO, O2 and their mixture on BaAl2O4, as well as the reaction of NOx with soot in the presence of O2, have been investigated using Diffuse Reflectance Infrared Fourier Transform Spectroscopy （DRIFTS）. NO adsorption produces only nitrites species in the absence of O2. NO2 adsorption produces nitrates species besides nitrites species. The produced nitrites will further react with O2, Osurf^-. and Olattice^2- to form nitrates. The reaction of NOx with soot begins with the reaction of nitrates with soot oxygenated complex （C（O））, which is regarded as the key and rate determining step. A reaction pathway is proposed for the catalyzed reaction of NOx with soot in the presence of O2.     

同步辐射XANES方法对FeCl3 水溶液的研究

利用X 射线近边吸收谱学(X-ray Absorption Near Edge Structure, XANES)方法研究了不同浓度的FeCl₃ 水溶液中Fe³⁺离子的电子结构和近邻结构. 在不同浓度的FeCl₃ 水溶液的XANES 谱中, XANES 谱的形状随着FeCl₃ 浓度的不同而发生改变. 在XANES 谱的边前结构中观测到边前锋的分裂, 其分裂的能量差约为1.6 eV, 随着浓度的降低约有0.2 eV 的高能方向的位移, 此边前结构由1s-3d 轨道的电子跃迁引起, 双峰分裂来源于配位体配位引起的3d 轨道分裂. 随着FeCl₃ 浓度的改变, XANES 谱的主峰也发生变化, 此变化来源于溶液中Fe—Cl 配位与Fe—O 配位的比例变化. 另外, 利用量子化学计算的方法对于Fe³⁺与不同数目的H₂O 和Cl^?配位体络合时的构型进行了计算, 得到了Fe³⁺在水溶液中近邻结构的信息, 从另一方面解释了FeCl₃ 溶液中Fe³⁺离子3d 轨道分裂能的变化     

Simulation experiments on the reaction system of CH4-MgSO4-H2O

H2S-rich gas in carbonate reservoirs is usually attributed to thermochemical sulfate reduction （TSR）. In this paper, thermal simulation experiments on the reaction system of CH4-MgSO4-H2O were carried out using autoclave at 425℃--525℃. The threshold temperature for initiating TSR is much lower than our previous studies （550℃）. Properties of the reaction products were analyzed by microcoulometry, gas-chromatography （GC）, Fourier transform-infrared spectrometry （FT-IR） and X-ray diffraction （XRD） methods. Thermodynamics and reaction kinetics of TSR processes were investigated on the basis of the experimental data. The results show that thermochemical reduction of magnesium sulfate with methane can proceed spontaneously to produce magnesium oxide, hydrogen sulfur, and carbon dioxide as the main products, and high temperature is thermodynamically favorable to the reaction. Ac- cording to the reaction model, the calculated activation energy of TSR is 101.894 kJ/mol, which is lower than that by most previous studies. Mg^2＋ may have played a role of catalytic action in the process of TSR. The elementary steps of TSR and reaction mechanism were discussed tentatively. The study can provide important information on the explanation of geochemical depth limit for natural gas and on the generation of high H2S gas in deep carbonates reservoirs.     

广西柳州市主城区主要绿化植物叶片的全硫氮含量特征

通过测试,找出柳州市主城区吸收SO2、NO2能力强的植物,为今后城市生态修复和功能型园林绿化提供素材.以广西柳州市主城区内61种绿化植物为对象,采用HNO3-HClO4、H2SO4-H2O2消煮法,对其叶片的全硫、全氮含量进行测定.结果表明,所选61种绿化植物的全硫含量为0.024％-0.711％,全氮含量为0.007...     

挥发性油藏酸气回注的最小混相压力与组分优化

高含H_2S和CO_2酸性气体的低渗透挥发性油藏在开发过程中,H_2S和CO_2会以溶解气的形式被采出,并占有较高的摩尔分数。分离器条件下的气态轻烃通过回注地层,在油藏压力高于最小混相压力(MMP)时达到混相驱动,一方面可以显著提高驱油效率,另一方面可以起到减缓压力衰竭的目的。H_2S和CO_2作为污染气体,分离和回收成本较高;而与烃气一同回注地层势必会对MMP产生影响。因此,需要研究酸性气体对溶解气回注MMP的影响规律并且合理地优化回注气组分。在对目标区块原油组分拟合重组的基础上,通过混合单元格法预测MMP,研究了溶解气主要组分的混相能力以及H_2S和CO_2对烃气驱MMP的影响规律,通过正交试验方法优化了注入气比例。结果表明:作为酸性杂质气体H_2S和CO_2具有较强的混相能力,可以降低注气MMP;最优注气形式为溶解气直接回注地层。     

氟代次甲基与氧气的反应机理研究

在B3LYP/6-311G(d,p)水平上研究了CF自由基与O2反应的微观机理.对反应势能面上的各反应物、过渡态、中间体和产物的几何结构进行了全参数优化,且在QCISD/6-311G(d,p)水平上计算了它们的能量.研究发现CF+O2反应在高温过程中重要,有3个产物通道,即F+CO2、FCO+O和FO+CO,其中最有竞争力的通道为F+CO2,其次为FCO+O通道,FO+CO通道可能难发生.与CH+O2反应比较发现两者有相似的地方,如第一步都是CX(X=H或F)自由基进攻O2分子中的一个氧原子形成链状过氧化物XCOO.两反应机理也存在很多不同之处,如HCO+O和FCO+O通道的形成过程有很大的不同;两反应速率也相差较大.CH+O2反应快,CF+O2反应慢.     

基于体积平均法的NH4 Cl水溶液凝固行为研究

根据合金凝固理论和体积平均多相模型,对NH4 Cl-70%H2 O凝固过程进行了数值模拟和实验验证。虽然研究者已研究过NH4 Cl-70%H2 O凝固过程,但是只针对单个现象进行分析,比如通道偏析的形成、对流形式以及晶粒的形成。在前人研究的基础上,本文首次通过数值模拟和实验对比两种手段相结合的方式全面地研究了氯化铵水溶液凝固整个计算域的全部现象,尤其再现了等轴晶在铸锭中的下落漂移现象以及由此引起的对流,并且更深入地探究了偏析的形成原因。通过计算发现等轴晶从型壁处沉降并逐渐向铸型底部积聚,直到体积分数达到一临界值后,柱状晶停止生长,完成柱状晶向等轴晶转化过程。由于溶质再分配,底部晶粒集中的区域形成了负偏析,在尚未凝固的上部区域形成较大范围的正偏析。通过实验验证发现,等轴晶在铸锭中的下落漂移现象和对流形式的预测值与实验值较为一致,从而全面揭示出凝固过程中固相的移动和对流是产生宏观偏析的关键因素。     

盆地气候条件下成都城区O_3与NO_2相互作用的时间尺度分析

应用去趋势互相关分析法对比分析了成都市2013年7月1日至8月31日和2014年1月1日至2月28日等2个时间段4个大气环境监测站点近地面O3与前体物(NO2)小时平均浓度的相关性及其时空演化尺度特征.研究表明,成都市4个监测站点近地面O3与NO2小时平均浓度波动的相关性在一定时间尺度内具有长期持续特征.并对成都市夏季和冬季近地面O3与NO2相关性进行了对比分析,探讨了导致此种差异的原因.结果表明,不同的气象条件下成都市O3与NO2相互作用的时间尺度存在显著差异.其差异性可能与成都市独特的盆地气候特点以及当地夏季与冬季太阳光辐射、日照数、气温等气象因子有关.研究结果有助于进一步加深对盆地气候条件下成都市O3污染特征的认识.     

WO3-ZrO2/SBA-15的制备及其可见光催化分析

通过溶胶凝胶法,分别制备了不同负载量的WO_3/SBA-15和WO_3-ZrO_2/SBA-15介孔材料,利用XRD、BET和TEM等表征手段对其进行表征,并对其光降解染料罗丹明B的活性进行比对研究分析。结果表明:Wx/SBA-15(x=20,30,40,50)和W_(40)Zry/SBA-15(y=3,5,7,9)均能在可见光下光降解罗丹明B,光催化活性W_(40)/SBA-15W_(50)/SBA-15W_(30)/SBA-15W_(20)/SBA-15;引入ZrO_2后,光催化活性W_(40)Zr_5/SBA-15W_(40)Zr_9/SBA-15W_(40)Zr_7/SBA-15W_(40)Zr_3/SBA-15。其中,W_(40)/SBA-15和W_(40)Zr_5/SBA-15的光降解效率最高,分别为73.4%和86.6%,ZrO_2的引入提高了光降解效率;同时,WO_3/SBA-15和WO_3-ZrO_2/SBA-15也具有很好的循环价值,可多次使用。     

水溶液体系电积砷的析AsH3过程分析

计算了水溶液中As(Ⅲ)的理论溶解度, 分析了电沉积过程 AsH3的形成机理.研究指出, As( (Ⅲ) 在碱性水溶液中的溶解度比在酸性或中性水溶液中大得多, 因此,在碱性溶液中电沉积砷更有利, 防止产生 AsH₃的有效途径是提高氢的析出电势.     

镀镍碳纳米管对Mo_2FeB_2基金属陶瓷组织与性能的影响

采用化学镀法对碳纳米管进行表面镀镍处理,再利用真空液相烧结法制备出以镀镍碳纳米管为增强体的Mo_2FeB_2基金属陶瓷复合材料,借助SEM、EDS、硬度计等研究了添加镀镍碳纳米管对Mo_2FeB_2基金属陶瓷微观组织及力学性能的影响。结果表明,添加适量镀镍碳纳米管可细化Mo_2FeB_2基金属陶瓷组织并控制其孔洞尺寸及数量,显著提高其硬度及断裂韧性。当镀镍碳纳米管添加量为0.5%时,所得试样的晶粒最为细小,晶粒尺寸大约为1.2μm,材料的力学性能最佳,其硬度和断裂韧性分别达到1228.4HV0.3及15.90MPa·m12,相应增韧机制为裂纹偏转、桥接增韧、撕裂棱增韧和微孔洞增韧。     

碱金属K对铁焦与CO_2气化反应的影响

将铁焦置于K_2CO_3水溶液中煮沸,通过调节煮沸时间获得不同增碱量的试样。采用热重天平和气体分析仪研究铁焦在增碱处理前后几个不同温度下与CO_2气化反应时的失重和废气成分变化情况,确定了铁焦的气化开始温度,并基于未反应核模型进行铁焦的气化反应动力学分析。结果表明,碱金属K使铁焦气化开始温度明显降低;碱金属K对铁焦的气化反应有促进作用,降低了化学反应活化能和内扩散活化能,这种正催化作用在低温下比高温下更明显;铁焦气化反应在开始阶段主要受界面化学反应的控制,随后逐渐变为内扩散和界面化学反应的混合控制。