新型中位取代七甲川菁染料的合成及光稳定性研究

本文合成了两种新型中位取代近红外七甲川菁染料,采用核磁1 HN-MR和HRMS质谱对其结构进行了表征.并测试了染料在不同溶剂中的吸收光谱和荧光发射光谱性质.染料3b、3c在甲醇中的最大吸收波长和最大荧光发射波长分别为677/790nm和647/786nm,斯托克斯位移分别为113 nm、139nm.经过光降解实验测试得到3种染料3a—3c在乙醇中的光降解速率常数分别为1.21×10-3 mol/min、1.81×10-3 mol/min和2.14×10-3 mol/min.循环伏安法测得染料3a—3c的氧化电位分别在0.729V、0.624V和0.598V.光降解实验表明:七甲川菁染料中位亚甲基链上吸电基取代增强染料光稳定性,供电基取代减弱染料的光稳定性;供-吸电子能力强弱决定了染料的光稳定性强弱;同时中位氯原子取代与共轭链上的氢键作用有利于染料的稳定性增强,中位氮原子取代无法形成很好的氢键作用,不利于染料稳定性的提高.     

DFT Investigation on the Trans-cis Photoisomerization of Pentamethine Cyanine Dye Model Molecule

The trans-cis photoisomerization of pentamethine cyanine dye (Cy5) has been theoretically investigated by the analysis on an analogical molecule model. All possible isomers have been searched by rotating the different bridge C-C bonds of the model. The relative stability of the isomers for the ground and first excited states as well as the corresponding excitation mechanism has been envisaged by DFT and time-dependent DFT method. The results show different conjugation degree of the isomers resulting in different absorption energy upon the different C-C bridge bond rotation. From the analyses of electronic density distribution of the frontier orbitals, it is predicted that there is charge transfer besides the π-π* excitation for the cyanine dye model, which makes the mechanism and photo-properties different form those of other conjugated molecules.     

Synthesis,Crystal Structure,and Spectral Properties of a Cobalt(II) Complex with N‐Salicylidene‐p‐Toluidine

The complex Co(C₁₄H₁₃NO)₂Cl₂ with the protonated N‐salicylidene‐p‐toluidine ligand was synthesized from an ethanolic solution of CoCl₂·6H₂O and N‐salicylidene‐p‐toluidine. The crystal structure was determined from X‐ray single crystal data (monoclinic, space group Cc, a = 1496.2(3) pm, b = 1257.4(4) pm, c = 1544.6(3) pm, β = 115.01(1)°, Z = 4). Co²⁺ adopts a distorted tetrahedral geometry. The UV‐Vis and IR spectra of the complex are discussed.     

苯并噻唑类核酸分子荧光探针的合成及光谱性质

设计合成了3种两端杂环氮原子上具有不同取代基的苯并噻唑类不对称三甲川菁染料,并对染料的结构进行了表征。 测试了染料在乙醇中的吸收和荧光发射光谱,染料的最大吸收值和荧光发射值分别在629~635 nm和656~672 nm之间。 染料8、9和10的斯托克斯位移分别为23、37和27 nm。 染料在溶剂中基本无荧光,荧光量子产率小于0.021,可以极大的降低染料自身的荧光背景干扰。 染料的光降解实验表明,两端杂环氮原子苄基取代后可以明显增强染料的光稳定性。 测试循环伏安曲线得到染料的氧化电位分别为0.535、0.456和0.399 V,氧化电位越大,光降解速率常数越小,与光降解实验得到的降解速率常数结果一致。     

四甲川苯乙烯菁染料的合成及其激光性能

合成了一系列四甲川苯乙烯菁染料。以Nd:YAG锁模激光倍频(532nm)作泵浦源,测定了染料的激光性能,包括激光调谐范围、中心激光波长、激光转换效率及稳定性。探讨了该类分子结构与其激光性能之间的关系。     

一种若丹宁蓝光份菁染料的合成、晶体结构及光谱性质

以N-甲基-2-吡咯甲醛和若单宁为原料,在哌啶催化下合成了一种若单宁蓝光份菁染料:5-(1-甲基-2-吡咯次甲基)若丹宁,采用1HNMR,IR,UV-vis及元素分析对染料进行了结构表征,并采用X射线单晶衍射法测定了该染料的晶体结构.研究了该染料在不同溶剂中的紫外-可见吸收光谱和荧光光谱.实验结果表明:该染料属于单斜晶系,为C2/c空间群,其晶胞参数为a=1.6736(3)nm,b=0.74588(11)nm,c=1.6567(3)nm,F(000)=928,V=2.0637(6)nm3,Z=8,Dc=1.444g/cm3,μ=0.482mm-1.染料分子中的π…π作用、N—H…O氢键及弱的S…S作用使分子在晶胞中密集堆积排列.该染料在常规溶剂(氯仿、二甲亚砜、水、丙酮、乙醇和甲醇)中的最大吸收波长及摩尔消光系数分别在428.0～443.5nm和1.8×104～2.1×104dm3·mol-1·cm-1范围内,显示出该染料在蓝光区有较强的吸收.     

含碲唑杂环的不对称碳菁及方酸菁的合成与性质

以苯并碲唑季铵碘盐为原料，将其与３－乙基－２－（β－乙酰苯胺）乙烯工噻唑磺化季铵盐在无水吡啶中回流，得到４个含碲不对称碳菁染料，上述季铵盐与方酸的反应不 般杂环碱，只能发生１：１缩合反应，缩合产物与苯并噻唑碘盐在正丁醇／吡啶中反应即得含碲不对称方酸菁染料，该法避免了通常制备不对称方酸菁所带来的分离纯化的困难，从而提供了制备不对称方酸碲菁染料的通用方法，研究了不对称碲碳菁的“Ｂｒｏｏｋｅｒ偏差”，结     

Synthesis,Crystal Structure and Properties of RbMnO2

RbMnO₂ was prepared via the azide/nitrate route. Stoichiometric mixtures of the precursers (Mn₂O₃, RbN₃ and RbNO₃) were heated in a special regime up to 600 °C and annealed at this temperature for 30 h in specially designed silver crucibles. Single crystals have been grown by annealing a 1:1 mixture of Rb₂O and MnO_x at 585 °C for 1200 h. According to the crystal structure determination Mn³⁺ is in a square‐pyramidal coordination by oxygen. These [MnO₅] units form double chains extending along the crystallographic c‐axis. RbMnO₂ shows Curie‐Weiss behaviour down to ～ 100 K. A fit of the susceptibility data yields an average value of the magnetic moment (per manganese atom) of μ_eff = 5.33 μ_B, and θ_p = –820 K. At 50 K and low field strength onset of ferromagnetic order due to spin canting has been observed.     

Synthesis and Characterization of a Squarylium Cyanine Dye with Two [60]Fullerene Units

Fullerene derivatives containing two or more [60]fullerene units may exhibit interesting properties1. There have been reported a limited number of organofullerenes with two or more cages, and the synthetic procedures are an oxidative coupling reaction of terminal alkynes2, bifunctional cycloaddition reactions such as diazo compounds3, dienes4 or (-amino acids and aldehydes 1, 3-dipolar cycloaddtion5, cyanogen di-N-oxide as a double 1, 3-dipole6. Oxo- and methylene-bridged [60]fullerene dimers …     

近红外菁染料敏化的准固态太阳电池的光电化学研究

一个新型的近红外五甲川菁染料敏化剂(Cy)通过3,3-二甲基-1-乙基-2-[4-(N-苯乙酰氨基]-1,3-丁二烯-1-基]-3H-苯并[e]吲哚碘盐和5-羧基-1-丁基-2,3,3-三甲基-3H-吲哚碘盐的Knoevenagel缩合反应合成, 其结构用核磁、质谱和紫外等方法进行了确定; 使用疏水性气相法纳米SiO2 R974固化1-丁基-3-丙基咪唑碘离子液体制备了一种新的准固态电解质, 将其应用于菁染料(Cy)敏化的太阳电池, 对该染料敏化的准固态太阳电池的光电化学性能进行了研究. 在AM1.5G标准光源下, 得到1.49%的光电转换效率. 此方法对拓展准固态染料敏化太阳电池的研究具有一定的意义.     

1,3-二-(3,3-二甲基-2-甲烯假吲哚)方酸菁染料的合成及其晶体

合成了两个新型方酸菁染料3和5。在酸催化下,2,3,3-三甲基假吲哚不需N-烷基化,可直接与方酸反应。反应过程中发生了明显的质子转移。结晶学数据表明,分子3的整体位于同一平面;溶剂苯规则地排布在方酸四碳环的周围,后者酷似电子陷阱。染料5有良好的水溶性。     

新型花菁染料-蛋白质散射体系的研究与应用

基于蛋白质对花菁染料的共振散射效应,以新型水溶性碳菁染料(1,1′-丙磺酸-3,3,3′,3′-四甲基吲哚三次甲基碳菁-5,5′-二磺酸钾)为探针,建立了一种新的蛋白质共振散射检测体系.在最优条件下,蛋白质对该碳菁染料具有明显的散射增强作用,散射强度与蛋白质浓度成良好的线性关系,牛血清蛋白BSA和人血清蛋白HSA线性响应范围分别为0.20～15.0μg/mL和0.50～10.0μg/mL,检测灵敏度(3σ/K)为0.05、0.10μg/mL.测定了BSA血清合成样品,回收率94.5%～104.0%;测定HSA血清合成样品,回收率95.6%～103.0%,测定相对标准偏差为1.1%～1.9%,测定较为稳定、准确.     

A Novel Ruthenium(III) and Lithium Complex: Synthesis,Crystal Structure,and Magnetic Properties

A novel complex [Li₃{μ‐(H₂O)₆}(H₂O)₆]·[RuCl₆] has been synthesized and was characterized by single‐crystal X‐ray diffraction. The compound crystallizes in rhombohedral space group R3¯c, with the unit cell parameters a = b = 9.948(2)Å, c = 33.376(14)Å, γ = 120°, V = 2860.5(15)ų, Z = 6, D_c = 1.918 Mg m^—3, μ = 1.703 mm^—1, R = 0.0244, wR = 0.0478. The compound consists of a cation, which contains three lithium ions linked by six bridged water molecules, and an anion, which contains a ruthenium(III) ion. The whole complex can be described as a three‐dimensional structure linked by hydrogen bonds between cation and anion. The magnetic properties of the complex have been investigated. The IR, UV‐vis and EPR spectra are studied.     

新型不对称五甲川菁染料的合成及光稳定性能研究

合成并表征了5种不对称五甲川菁染料,染料在甲醇中的最大吸收和荧光光谱在646—666nm之间.光降解实验证明两端取代基结构呈不对称的染料,其光稳定性明显高于两端取代基结构对称的染料.染料荧光光谱和pH值的关系表明,染料中引入苯环取代基可以增强染料在酸性或碱性溶液中的稳定性.     

Synthesis, Crystal Structure and Properties of Complex VO（C12H12N2O2） （C13H10NO2）

IntroductionAsthevanadate dependentenzyme ,ahaloperox idase,andvanadiumnitrogenasehavebeenfoundinsuccession ,somescientistsareinterestedinthecoor dinationchemistryandthebiochemistryofvanadi um[1] .Thereactivecenterofvanadiumbromoperoxi dasecontainstheoxovanadiumVO3+ coordinatedbyoxygenandnitrogenatoms[2 ] .However,thestudiesaboutoxovanadiumVO3+ coordinationcompoundscontainingbioactiveligandsarerarelyfound[3— 8] .Hydroximicacidthatcanbeconsideredtobethederivativeofthecarboxylicacid ,theamide…     

新型水溶性不对称五甲川菁染料的合成、光稳定性及蛋白质的荧光标记

合成并表征了系列水溶性五甲川菁染料, 研究了其在不同溶剂中的光谱性能. 结果表明, 染料在水中的最大吸收和荧光光谱在647~665 nm波长范围内, 荧光量子产率达到0.1左右. 考察了N位取代基对染料水溶液光稳定性的影响, 结果表明, 在N原子上引入带有苯环结构和大体积的磺酸基, 可以提高染料的光稳定性. 高效液相色谱(HPLC)分析结果表明, 染料4a的N-羟基琥珀酰亚胺(NHS)活性酯标记牛血清白蛋白(BSA)的检测限为1.2×10^-8 mol/L, 与紫外检测相比, 检测灵敏度提高了近2个数量级.     

Crystal Structure and Characterization of a Dye with Two-photon Pumoed Frequency-upconverted Lasing Properties

The title compound, trans-4-[ p-( N-ethyl-N-(hydroxyethyl ) amino) styryl ]-N-methylpyridiniumtetraphenylborate (abbreviated as ESMT, C46H49N4OB) crystallizes in a space group P1- with a= 0. 983 23 (15)nm, b=1.410 73(16) nm, c=1.54 21(12) nm, a=95.252(13)°, β=91.959(17)°, γ= 107.421(12)°, Z=2, F(000)=712, μ= 0.1 mm-1 Mo Ka radiation, R=0. 093 8. The result shows that the cation of themolecule almost lies in one plane, the hydroxyethyl group is perpendicular to the plane, the anion takes a slightdistorted tetrahedral geometry. Also the thermal stability, two-photon fluorescence, two-photon pumped lasingproperty for the title compound were studied.     

光谱法研究噻菁染料与血清蛋白的相互作用

本文通过吸收和荧光光谱法研究了一种噻菁染料与人血清蛋白及牛血清蛋白的相互作用。吸收光谱数据表明,与血清蛋白结合后,噻菁染料单体的吸收峰发生红移,同时强度也有很大变化;还通过吸收光谱计算确定了噻菁染料与血清蛋白的结合位点数（ n ）。与人血清蛋白或牛血清蛋白结合后,噻菁染料的荧光量子产率增加。分析噻菁染料的荧光强度随溶液中血清蛋白浓度的变化得到了二者反应的表观结合常数（ K _a）和自由能变化（ ΔG ）。根据表观结合常数（ K _a）可以判断,人血清蛋白比牛血清蛋白与噻菁染料的结合更强。     

Synthesis, Crystal Structure and Properties of Complex VO（C10H9NO3） （C13H10NO2）

Complex VO(C10H9NO3)(C13H10NO2)(C10H9NO2-3=N-salicylidene-L-alaninate, C13H10NO-2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, UV, 1H NMR spectroscopies, cyclic voltammetry and single crystal X-ray diffraction. The complex crystallized in a monoclinic system with space group P21 and crystal cell parameters a=0.9720(1) nm, b=1.8274(2) nm, c=1.2542(1) nm, β=104.868(9)°, V=2.1532(4) nm3, Mr=470.34, Z=2. The two oxygen atoms and the one nitrogen atom of the tridentate Schiff base ligand and the one oxime oxygen atom of the hydroxamate ligand coordinate to the vanadium atom, forming an equatorial plane, the two axial positions are respectively occupied by the oxygen atom of the oxovanadium and the carbonyl oxygen atom of the hydroxamate and the vanadium atom exhibits a distorted octahedral VO(ONO)(OO) coordination sphere. The 1H NMR spectrum suggests that the two isomers, endo and exo in a molar ratio of 1/1.7, coexist in the solution of the title complex in CDCl3. There exists a quasi-reversible one-electron redox reaction corresponding to VⅤ/VⅥ couple in the three non-aqueous solvents, and the redox potential E1/2 of the title complex substantially shifts in the direction of the positive voltage increase in the order: CH2Cl2＜CH3CN＜DMF.     

烷氧基键合的VO3+腙配合物的合成和晶体结构及氧化还原性质研究

合成了配合物VO(L)(CH₃O)(CH₃OH)(H₂L为水杨醛苯甲酰腙),并对其进行了元素分析,IR,UV,¹HNMR,CV和单晶X射线衍射实验。晶体属单斜晶系,P2₁/c空间群,晶胞参数a=0.8161(1)nm,b=1.6946(2)nm,c=1.2232(1)nm,β=104.274(9),V=1.6394(3)nm³,M_r=368.26,Z=4.三齿腙配体中的2个氧原子和1个氮原子均与饥原子配位并形成赤道平面,钒原子具有扭曲的八面体配位构型。电化学研究表明,配合物的氧化还原电位E_1/2按CH₂Cl2相似文献