外源水杨酸对TMV侵染后辣椒幼苗生理特性的影响

采用烟草花叶病毒侵染辣椒植株,用不同浓度水杨酸处理感病的辣椒植株,测定叶绿素、丙二醛等生理指标,分析其生理生化变化.结果表明：烟草花叶病毒侵染后辣椒叶片叶绿素含量降低、丙二醛含量升高、脯氨酸含量下降、过氧化物酶活性和超氧化物歧化酶活力值明显下降,100μ rnol/L水杨酸处理后生理特性的变化影响较显著,叶绿素含量升高、丙二醛含量降低、脯氨酸含量升高、过氧化物酶和超氧化物歧化酶活性升高,而500μmol/L的水杨酸对辣椒形成胁迫效应.表明外源水杨酸（＜500μmol/L）可以显著提高感染TMV辣椒的抗病性,有利于辣椒幼苗对逆境的适应.     

阴离子取代合成Sr3LaAxV3-xO12:Eu3+(A=Mo,W)白光荧光粉

通过高温固相法合成Sr₃LaA_xV_3-xO₁₂:Eu³⁺（A=Mo,W）荧光粉,利用MoO₄^2-和WO₄^2-取代基质中部分VO₄^3-,改变基质组成和结构,进而影响基质和激活剂Eu³⁺离子的发光性能。采用X射线衍射（XRD）、扫描电子显微镜（SEM）和荧光分光光度计对所合成样品的物相、形貌、荧光性能及荧光寿命进行表征。研究表明,MoO₄^2-和WO₄^2-的部分掺杂对基质发光位置和强度均有影响,能明显减弱VO₄^3-的发光,但对Eu³⁺离子发光影响不大,添加电荷补偿剂F^-可以加强VO₄^3-对Eu³⁺离子的能量传递。通过调整基质VO₄^3-发光和Eu³⁺离子发光,可以得到单一基质的白光荧光粉。初步探讨了阴离子掺杂对Eu³⁺离子红光发射增强的机理。     

光谱分析和延迟荧光检测研究外源水杨酸对拟南芥光合作用的影响

外源水杨酸在影响植物活性氧代谢以及光合作用等方面起着重要作用.该文以野生型拟南芥和胁迫条件下内源水杨酸含量较高的cpr5突变体和内源水杨酸含量较低的eds-4突变体为材料,采用光谱分析和延迟荧光检测分析手段,研究了不同浓度的外源水杨酸对三种拟南芥离体叶片光合能力的影响,实验发现100和300 μmol·L-1较低浓度的外源水杨酸对野生型拟南芥离体叶片,eds-4叶片的光合作用都有一定的促进作用,而对cpr5叶片的光合会产生抑制,形成一种胁迫.500μmol·L-1较高浓度的外源水杨酸对三种拟南芥离体叶片均形成了一种胁迫,进而阻抑和降低了叶片的光合效能.DCF(dichloro fluorescein)标记活性氧检测了外源水杨酸作用下叶片活性氧产生量的变化,发现在500μmol·L-1外源水杨酸作用下60min内叶片组织中活性氧产生了明显的积累.     

羟自由基与水杨酸反应机理的初探

探讨羟自由基与水杨酸的反应动力学过程。水杨酸与Fenton反应产生的的羟自由基反应,采用紫外-可见分光光度法（UV）和质谱法（MS）,考察反应物的浓度、反应时间、反应温度、溶剂pH值等对反应产物的浓度以及反应速率的影响。水杨酸与.OH反应生成的紫色产物在波长530nm处有最大UV吸收峰,但仅于pH=4.51的缓冲溶液和水中有吸收峰;且该产物的吸光度值,随着反应物浓度的增加而增加;随反应时间的延长而减少;随着反应温度的升高而减少。反应速率t=5s达到最大值,其后随着反应时间的延长而逐渐降低,1min时达到平衡。通过MS分析,可得到质荷比（m/Z）=153,248,249,288,289,304,328,329,344,345的离子峰。推测羟自由基与水杨酸反应的中间产物是紫色的大分子自由基,而最终产物为二羟基苯甲酸,该反应可能是加成反应和聚合反应同时进行。     

水杨酸与牛血清蛋白相互作用的荧光光谱研究

应用荧光光谱研究了水杨酸与牛血清蛋白 (BSA)分子间的相互作用。研究表明 :水杨酸对BSA内源荧光的猝灭机制属于形成化合物所引起的静态猝灭 ,猝灭常数Ksv 为 1 0 97× 10 4 (mol·L- 1 ) - 1 ;水杨酸与BSA反应的结合常数为 7 377× 10 4 ,结合位点数为 1,当水杨酸浓度较低 (摩尔比小于 1∶1)时 ,它与Trp残基或其附近基团结合但并不引起Trp残基微环境的改变 ;根据F rster非辐射能量转移理论 ,计算了授体 受体间的结合距离和能量转移效率     

水杨酸与人血清白蛋白相互作用的荧光光谱研究

在ｐＨ９．５０含０．０１ｍｏｌ／ＬＫＣｌ的硼砂缓冲溶液中,人血清白蛋白（ＨＳＡ）与水杨酸发生相互作用,而导致两者的荧光谱发生变化。采用不同的方法测得这一反应的解离常数。     

A DFT/TD-DFT study of effect of different substituent on ESIPT fluorescence features of 2-(2'-hydroxyphenyl)-4-chloro- methylthiazole derivatives

Based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT), the effects of substituent on the excited-state intramolecular proton transfer (ESIPT) process and photophysical properties of 2-(2'-hydroxyphenyl)-4-chloromethylthiazole (HCT) are studied. The electron-donating group (CH₃, OH) and electron-withdrawing group (CF₃, CHO) are introduced to analyze the changes of intramolecular H-bond, the frontier molecular orbitals, the absorption/fluorescence spectra, and the energy barrier of ESIPT process. The calculation results indicate that electron-donating group strengthens the intramolecular H-bond in the S₁ state, and leads to an easier ESIPT process. The electron-withdrawing group weakens the corresponding H-bond and makes ESIPT process a little harder. Different substituents also affect the photophysical properties of HCT. The electron-withdrawing group (CF₃, CHO) has a little effect on electronic spectra. The electron-donating group (CH₃, OH) red-shifts both the absorption and fluorescence emission peaks of HCT, respectively, which causes the Stokes shift to increase.     

氯离子对银胶的宽波段光吸收光谱的影响

本文借助紫外-可见-近红外吸收光谱、透射电子显微镜技术,研究灰银胶中加入氯离子后此体系的宽波段吸收光谱的变化,旨在探索氯离子对纳米银颗粒表面特性的影响。实验结果表明,氯离子的加入会引起胶体中银颗粒的凝聚和银纳米颗粒的聚集体形态的变化,造成银颗粒的本征吸收光谱的"蓝移"和近红外区新吸收带的出现。最后我们初步分析了此现象产生的机制。     

分子内氮原子上亲核取代反应的理论研究

在MP2(full)/631+G(d,p)理论水平上,以-CHR-(CH2)3-NFCH3(R=H,CH3,CH2CF3,CHO,COCH3)为计算模型,对分子内可能发生的两条反应路径—氮原子上的亲核取代反应及消去反应进行了理论研究.结果表明,当进攻基团-CHR为碱性较强的基团,即R=H、CH3、CH2CF3时,有利于发生消去反应而生成直链化合物R-CH2-(CH2)3N=CH2;而当R为吸电子基团-CHO、-COCH3时,主要发生分子内氮原子上的亲核取代反应,产物为含氮的五员杂环化合物.这些理论预测与已有的实验结果吻合.     

Photophysical properties of substituted intramolecularly hydrogen bonded compounds: A combined experimental and theoretical study

Photophysical properties of prototype excited state intramolecular proton transfer (ESIPT) system 4-methyl-2,6-diformyl phenol (MFOH) and its derivatives were studied by steady state and time-resolved fluorescence spectroscopy as well as by ab-initio quantum chemical calculation. It has been found that nonradiative decay process is the most important deactivation channel in all the cases and the hydrogen bonded enol conformer is stable in the ground state whereas, the proton transferred keto form is energetically favoured in the S₁(ππ^*) state. However, the net gain in stabilization in the process of ESIPT is almost unaffected by the substitution. The reversal of stability in the excited state was explained on the basis of the nature of frontier molecular orbital in all the cases. Intrinsic reaction coordinate analysis showed that drastic change in nonbonded interoxygen distance R(O-O) in the proton transfer pathway causes the switch over from the enol to keto configuration. A close comparison of several properties like molecular geometry, hydrogen bond strength and atomic charge in different derivatives of MFOH were found to be consistent and in good agreement with the experimental results obtained from time-resolved fluorescence experiments.     

甲基乙基亚硫酸与亚氨基负离子多组分反应及机理的理论研究

采用分子动力学方法研究了一系列同比例(5:5,10:10,20:20,50:50)和不同比例(20:30,20:40,20:50和30:20,40:20,50:20)的亚氨基负离子与甲基乙基亚硫酸的反应显示,有较多的亚氨基转化为氨气,同时甲基乙基亚硫酸分解为甲醇、乙醇和一些小的碳化合物等物质.通过密度泛函的B3lyp和Bhandhlyp两种方法,在6-311++G(3df, 3pd)水平下对其反应机理进行研究表明,此反应为多通道多步骤的反应体系,无论主反应还是次反应均为放热反应,其中生成产物为P1(CH₃OSO₂~-+NH₃+C₂H₄),P2(CH₃OSO₂~-+NH₂CH₂CH₃),P3(CH₂O+SO₂+NH₃+C₂H₅~-)的路径为最佳反应通道,而生成P4...     

紫外光谱法监测阿司匹林合成体系中的阿司匹林和水杨酸

建立一种同时快速定量分析阿司匹林合成体系中阿司匹林和水杨酸的方法。通过均匀设计构造样本并采集其紫外光谱,结合偏最小二乘法（PLS）建立同时测定混合体系中阿司匹林和水杨酸的校正模型,阿司匹林和水杨酸模型的校正均方根误差分别为1.708μg/mL和0.435μg/mL。该模型用于预测氨基磺酸催化合成过程中阿司匹林和水杨酸含量,二组分回收率在93.48%—108.37%之间,相对标准偏差（RSD）分别为3.45%和4.80%。结果表明,紫外光谱法结合PLS模型实现氨基磺酸催化合成阿司匹林过程的实时监测是可行的。     

紫外光谱法同时测定制药废水中苯酚和水杨酸的研究

本文用系数倍率紫外光谱法同时测定了制药废水中苯酚和水杨酸的含量 ,取得了满意的结果。苯酚测量回收率为 97.33%— 1 0 0 .77%、相对标准偏差 0 .83%。水杨酸测量回收率为 98.1 5 %— 1 0 0 .83%、相对标准偏差 0 .5 2 %。     

水杨酸功能化聚苯乙烯包覆硅胶复合微粒对银的分离富集性能研究

制备了水杨酸功能化聚苯乙烯包覆硅胶复合微粒,填充微柱后,测定了微柱的穿透曲线和洗脱曲线。将微柱用于低浓度Ag（I）的分离富集测定,研究了各影响因素,优化了实验条件。测定Ag（I）的线性范围为0.020—0.50μg/mL。方法可用于水样中痕量银的测定。     

General and Specific Solvent Effects in Optical Spectra of <Emphasis Type="Italic">ortho</Emphasis>-Aminobenzoic Acid

We describe studies about solvent effects on the absorption and emission properties of o-aminobenzoic acid (o-Abz), interpreting the results within the framework of general and specific solute-solvent interactions. Measurements were performed in several solvents and analysis of the absorption and emission wavelengths were made based on Lipperts model for general solvent effects and on the use of different parameters to describe the ability of the solvent to promote specific interactions with the solute. We observed low sensitivity of the Stokes shift upon changes in the medium polarity, and large deviation from the linearity predicted by Lipperts equation when the solvents were characterized as Bronsted acid in the Kamlet-Taft ^* scale. Quantum yield and fluorescence lifetimes were best interpreted based on the AN+DN scale used to describe the electron donor/acceptor properties of the solvent. The results indicated that non-radiative deexcitation processes are favoured in solvents which promote the formation of intramolecular hydrogen bond, while interactions with electron acceptor solvents lead to enhancement of fluorescence.     

Influence of Isotope Substitution Helium Atom on Partial Cross Sections in He-HF Collisions

Close-coupling equation and anisotropic potential developed in our previous research are applied to HE-SHe （4He, 6He, 8He,10He） collision system, and partial cross sections （PCSs） at the incident energy of 40 me V are calculated. By analyzing the differences of these PCSs, change rules of PCSs with the increase of partial wave number, and with the change of the mass of isotope substitution helium atom are obtained. The results show that excitation PCSs converge faster than elastic PCSs for collision energy and each of systems considered here. Also excitation PCSs converge more rapidly for high-excited states. Tail effect is present only in elastic scattering and low-excited states but not in high- excited states. With the increase of the mass of isotope substitution helium atom, converging speed of elastic, total inelastic, and state-to-state excitation PCS slows down, and the maxima of these PCSs undergoes a regular change.     

Substitution Effects on MgB2 Superconductivity

With the help of supercell method, the first-principle calculations were performed for the study of doping crystal Mg_1-xAl_xB₂ and Mg(B_1-yC_y)₂. Analyzing the variations of the charge distribution and the partial densities of states, we found that the compounds with doping Al to MgB₂ compound and/or replacing boron by carbon exhibit new covalent bond effects and unexpected electronic properties, related to superconductivity. The study of the density of states indicates that superconductivity decreases with the increase of Al fraction and carbon concentration. There exists a transition of superconductor to non-superconductor with the change of Al doping fraction. The substitution of boron by carbon results in the decrease of the transition temperature since the decrease of the electron concentration and the lattice constant. The theoretical predictions agree with experimental observations.     

尿嘧啶核苷酸阴离子液相中的过电子附着和电离

本文采用QM/MM方法研究液相尿嘧啶核苷酸阴离子的过电子附着和电离过程. 从分子动力学模拟的轨线抽取了40个采样结构,并计算了在这些采样点的垂直电子亲合势、绝热电子亲合势、垂直电子剥离能、垂直电离能和绝热电离能,分析了过电子附着和电离过程中的过电子及空穴分布. 模拟的垂直电子亲合势和绝热电子亲合势的平均值分别为-0.31 eV和2.13 eV,表明过电子很容易附着到尿嘧啶核苷酸阴离子上. 在尿嘧啶碱基上,垂直和绝热过电子分布的平均值分别为-0.50 eV和-0.62 eV,证明大多数的过电子局域在尿嘧啶碱基上. 双阴离子结构弛豫后,在几个抽样中发现过电子分布也可能会在碱基/糖环或者糖环/磷酸根上非局域化. 2.78 eV的垂直电子剥离能平均值表明,过电子附着后形成的尿嘧啶核苷酸双阴离子非常稳定. 液相尿嘧啶核苷酸阴离子的垂直电离能平均值为8.13 eV,与以前采用溶剂模型模拟的结果一致. 电离中,空穴主要分布在尿嘧啶碱基上,表明其最容易被电离. 在垂直电离中,几个抽样下的空穴会非局域分布在尿嘧啶碱基和糖环上. 绝热的空穴分布表明,在特定结构下,电离后的结构弛豫会导致磷酸根上电子和碱基上空穴转移到糖环上.     

Influence of Isotope Substitution Helium Atom on Partial Cross Sections in He-HF Collisions

Close-coupling equation and anisotropic potential developed in our previous research are applied to HF - ³He (⁴He, ⁶He, ⁸He, ¹⁰He) collision system, andpartial cross sections (PCSs) at the incident energy of 40 meV are calculated. By analyzing the differences of these PCSs, change rules of PCSs with the increase of partial wave number, and with the change of the mass of isotope substitution helium atom are obtained. The results show that excitation PCSs converge faster than elastic PCSs for collision energy and each of systems considered here. Also excitation PCSs converge more rapidly for high-excited states. Tail effect is present only in elastic scattering and low-excited statesbut not in high-excited states. With the increase of the mass of isotope substitution helium atom, converging speed of elastic, total inelastic, and state-to-state excitation PCS slows down, and the maxima of these PCSs undergoes a regular change.     

Anion effect on the conformational equilibrium of sulfamide and its N,N′‐diindolyl derivative: Insights on anion transportation

The relatively high acidity of the sulfamide hydrogens suggests a potential for the development of sulfamide derivatives as novel anion receptors. The interactions of sulfamide with F^?, Cl^?, CH₃COO^?, and H₂PO₄^? anions were spectroscopically (¹H and ¹⁹F NMR) and theoretically (density functional theory) analyzed, and the complexation through hydrogen bonds was confirmed by changes in the NMR signals and theoretical calculations. The replacement of 2 sulfamide hydrogens with indolyl groups yields the N,N′‐diindolylsulfamide ( DIS , N‐1H‐indol‐4‐yl‐N′‐1H‐indol‐7‐ylsulfuric diamide), whose bond rotations allow the interaction of 4 H(N) atoms with anions. The conformational preferences of DIS change upon the presence of anions, but they are practically insensitive to the anion type. According to the quantum theory of atoms in molecules, natural bond orbital analysis, and NMR chemical shifts, as well as to a thermodynamic cycle, the complex with fluoride is the most stable, followed by the oxoanion‐derived models.