两种新型阳离子吲哚啉螺吡喃的合成、表征和光致变色性质的研究

螺吡喃是一类重要的光致变色化合物．螺吡喃的正向光致变色是指在紫外光照下,螺吡喃分子的Ｃ—Ｏ键异裂,由闭环无色体（ＳＰ）可逆地变成开环有色体（ＭＣ）．所形成的有色体可以在暗条件下热致褪色或在可见光照下褪成无色体（示意图１）．它的逆向光致变色是指某一类螺...     

具有双荧光发射的螺吡喃的合成与性质研究

设计合成了未见文献报道的含有双官能团的螺吡喃类化合物1,通过红外光谱、核磁共振氢谱、碳谱和高分辨质谱对其结构进行了确证。紫外可见吸收光谱表明化合物在有机溶剂中的光致变色性良好;化合物的乙醇溶液在365 nm光激发时产生双荧光发射,分别为闭环体和开环体所对应的的荧光峰。本文首次从场效应角度推测了螺吡喃吲哚林N原子上含有极性基团时开环体稳定的原因。     

双吲哚啉螺吡喃化合物的合成及其酸和金属离子致变色性能

设计、合成了一种新型双吲哚啉螺吡喃化合物1,用核磁、红外及质谱等技术手段表征了其结构。 利用紫外可见吸收光谱研究了化合物1的酸致变色和金属离子变色性能。 结果表明,化合物1能够在氢离子或金属离子的作用下发生可逆的开环与闭环反应。 当氢离子或金属离子加入到化合物1的异丙醇溶液中,溶液颜色从无色变为红色,同时产生460 nm新吸收峰。 进一步加入氢氧根离子或EDTA溶液后,溶液颜色变回无色,460 nm处的吸收峰又消失。 该化合物的酸和金属离子致变色性质在分子传感和离子识别等领域有潜在的应用价值。     

羟基螺吡喃探针可视化检测果酸类化妆品的pH值

基于螺吡喃酸致变色性质制备了一种用于可视化检测果酸类化妆品pH值的探针。通常,螺吡喃分子的水溶性较差,未经修饰的螺吡喃难以应用于含水体系的测定。本研究通过在螺吡喃上修饰羟基基团调控探针的pK_a值从而改善其水溶性,拓宽其使用范围,并基于此制备了对H⁺具有识别能力的探针。采用核磁共振氢谱(¹H NMR)、核磁共振碳谱(¹³C NMR)、红外光谱(IR spectra)和高分辨质谱(HRMS)对研制的多羟基螺吡喃(SP-OH)探针进行了表征,考察了探针浓度、含水量及其它阳离子对吸光度的影响。紫外-可见(UV-Vis)吸收光谱显示,H⁺浓度(pH值)与探针在420和560 nm处的吸光度的比值呈线性关系,标准曲线方程为A_{420 nm}/A_{560 nm}=-55.66pH+276.83 (R²=0.996),线性范围为pH 3.0～5.0。通过¹H NMR、分子轨道能级计算验证了探针在酸性溶液下自发地快速...     

基于引达省并二噻吩吡喃的稠环受体材料的设计合成及其在有机太阳能电池中的应用研究

设计合成了一个基于引达省并二噻吩吡喃的稠环有机受体材料.吡喃环的引入提高了分子中间核的给电子能力,使分子的最高占有轨道能级(HOMO)显著提升,进而使分子的吸收光谱红移.通过理论计算,证实了分子的设计思路的可行性.紫外吸收光谱分析发现,该受体材料具有较窄的带隙(1.30 eV),其最大吸收峰在843 nm,吸收截止到956 nm,有利于活性层材料对太阳光的充分吸收利用.将该受体材料与聚合物给体材料PM6共混制备有机太阳能电池器件,获得了0.86 V的开路电压(opencircuit voltage,V_(oc))、20.61 mA cm~(-2)的短路电流密度(short-circuit current density,J_(sc))和10.85%的能量转化效率(power conversion efficiency,PCE).     

烷基化螺吡喃吲哚的合成及光学性质研究

为了增加螺吡喃吲哚与透明聚合物（ＰＭＭＡ）的相溶性,在螺吡喃吲哚分子中引入长烷基链,合成了１′－「十八烷基」－３′,３′－二甲基－６－硝基－８－「二十二酰氧基」－螺「２Ｈ－１－苯并吡喃－２,２′－二氢吲哚」,并用ＮＭＲ确定各中间体和最终产物的结构,ＨＰＬＣ显示产物中烷基化螺吡喃吲哚含量在９７％以上。将烷基化螺吡喃吲哚与ＰＭＭＡ制成厚度为５００ｎｍ左右的膜,研究该膜对紫外光的响应,获得烷基化螺吡喃吲哚开环和紫外吸收的关系,以及Ｊ－耦合构型与陈化的关系。     

酶解小麦蛋白产物-还原糖美拉德反应的光谱研究

采用紫外-可见吸收光谱和荧光光谱研究了酶解小麦蛋白产物与还原糖不同加热条件下的美拉德反应及其产物.美拉德反应在紫外区240和294 nm产生两个特征峰,荧光的最大激发和发射波长为347和450 nm;随反应进行,紫外光吸收和荧光强度迅速增加,表明美拉德反应进入高级阶段,产生的糠醛类、呋喃酮类、吡喃酮类、噻吩类及噻唑类等小分子物质表现较大的积累速率.温度升高,强度增加速率增大.在较高温度时,紫外光吸收出现最大平稳值;荧光强度则到达最大值后降低,表明小分子物质间或与肽聚合生成大分子黑素类物质,小分子物质的积累表现消除速率,反应进入终级阶段.     

新型芳并吡喃类多环化合物的合成与光谱性质研究

本文设计并经由分子内碳-碳偶联反应合成了一系列基于芳并吡喃供电子功能片段的有机功能小分子,包括萘并[2,1-b：6,5-b’]二苯并吡喃4a,萘并[2,1-b：6,5-b’]二萘并吡喃4b,萘并[2,1-b：6,5-b’]二[2-（5-己基噻吩基）]苯并吡喃4c。通过紫外光谱和荧光光谱研究表明,这类化合物在370~400 nm波长范围内具有最大紫外吸收,在417~462 nm波长范围内具有最大荧光发射。说明随着共轭平面的增大或共轭链长度的增加,化合物的吸收和荧光光谱均发生显著的红移,是一类具有丰富光电活性的有机功能分子。     

动态吸收光谱研究6-硝基-1’,3’,3’-三甲基吲哚啉螺苯并吡喃的光致变色性质

利用自行搭建的线阵CCD连续直读紫外-可见吸收光谱仪,研究了合成的螺吡喃类化合物6-硝基-1’,3’,3’-三甲基吲哚啉螺苯并吡喃的光致变色反应。通过研究在光照后闭环体开环与光照后开环体的闭环两个过程的光谱变化,讨论了合成产物的光致变色性质。证明该化合物的开环反应是一个快反应,在光照下的变色过程则是一个振荡平衡过程,而开环体的退色反应是一级动力学过程。     

苯乙烯嘧啶化合物的合成及其作为pH探针的光谱特点

合成并表征了化合物4,6-二[（4′-二乙基胺基）苯乙烯基]嘧啶-2-醇。 通过研究该化合物在不同pH值的磷酸盐缓冲溶液中紫外-可见吸收光谱和荧光光谱的变化,发现λmax约为500 nm的吸收峰在溶液pH=6.78中吸收强度最大。 荧光发射峰随着pH值的升高逐渐减弱,直至淬灭（pH=5.51）。     

Synthesis of macrocyclic,potential protease inhibitors using a generic scaffold

A generic macrocyclic peptide structure 2 was designed as a potential inhibitor of a range of proteinases, by using as a basis for the design the known structures of a series of enzyme-inhibitor complexes. The macrocyclic nature of the target 2 was chosen so as to reduce the entropic advantage in the hydrolytic enzymatic step, and thereby to inhibit the function of the enzyme. The nature of the linking group was identified as a benzoxazole by molecular modeling, so as to preserve the recognized conformation of the peptide chain. The specificity of the potential inhibitor was tuned by variation of the P(1) group (by incorporating phenylalanine, aspartic acid, or lysine), to allow recognition by different enzyme classes. The targets were prepared from the bis-amino acid derivative 5, itself prepared using the Pd-catalyzed coupling of an organozinc reagent with the iodobenzothiazole 7 and subsequent macrocyclization of the open-chain derivatives 22-24 using HATU. None of the macrocylic compounds 25, 28-30, and 32 inhibited their target enzymes. NMR and MS studies on the interaction of macrocycle 29 and chymotrypsin established that compound 29 was in fact a substrate of the enzyme. This result indicated that while the design had been partially successful in identifying a compound that bound, the reduction in entropic advantage due to its macrocyclic nature was not sufficient to allow 29 to act as an inhibitor.     

Syntheses, and optical, fluorescence, and nonlinear optical characterization of phosphine-substituted terthiophenes

Earlier studies of phosphine-substituted terthiophenes have demonstrated that some of these materials exhibit nonlinear absorption at 532 nm. However, this wavelength is significantly removed from the linear absorption maxima of the complexes, suggesting that better nonlinear absorption might be observed at wavelengths closer to the linear absorption maxima. To investigate this possibility, a library of compounds has been prepared either by varying the group attached to the nonbonding pair of electrons on the phosphorus atoms of 5,5'-bis(diphenylphosphino)-2,2':5',2'-terthiophene (PT(3)P), or by introducing additional substituents on the 5'-position of 5-(diphenylphosphino)-2,2':5',2'-terthiophene (PT(3)). All these compounds have been characterized using multinuclear NMR, UV-vis, and fluorescence spectroscopy. The compounds are strongly fluorescent, and both the fluorescence wavelength and the intensity depend upon the thiophene substituents. The nonlinear optical properties have also been evaluated at various wavelengths in the blue region. Each compound exhibits reverse saturable absorption, and the intensity of the reverse saturable absorption at a particular wavelength depends on the chemical structure of the compound.     

芳香寡聚磺酸酯桥联大环化合物的合成及其对Sn2+和Bi3+的识别作用

以4,6-二烷氧基-1,3-苯二磺酰氯和芳香二酚为原料,三乙胺作缚酸剂,二氯甲烷作溶剂,采取一步成环法合成了3种磺酸酯桥联大环化合物。合成产物的结构用IR、¹H NMR、¹³C NMR和MALDI-TOF等技术手段进行了确认。利用紫外光谱分析的方法研究了4,6,16,18-四正戊氧基-11,23-二甲基-1,3,13,15-四磺酸酯间苯芳香大环(5)对Ca²⁺、Pb²⁺及部分过渡金属等20种金属离子的识别。结果发现,其对Sn²⁺显示出一定的选择性,由于Sn²⁺和Bi³⁺协同作用的影响,在化合物5-Sn²⁺的体系中加入Bi³⁺,紫外吸收光谱在325 nm左右的吸收增强了许多,这说明化合物5对Bi³⁺显示出优于Sn²⁺的较好选择性。     

Optical spectra of anionic boron cluster compounds and their utilization for photometric detection

The article presents first collection of UV-vis absorption spectra of purely synthetic boron cluster compounds. Single-cage compounds have at least 11 cluster atoms; cobaltadicarboranes consists of 2 substituted 11-vertex bis(dicarbollide) clusters sandwiching the central cobalt atom. Spectrum of any of 18 investigated compounds has absorption maximum between 200 and 210 nm; its molar extinction coefficient is of the order of 10(3)-10(4)L/molcm. Second maximum exists in a spectrum of a single-cage compound if its exo-skeletal substituent absorbs UV-light above 200 nm. Spectra of cobaltadicarbaboranes both bridged and unbridged have pronounced second maxima between 270 and 300 nm. Their molar extinction coefficients range from 10(4) to 10(5)L/molcm. First light absorption minimum is close to 254 nm in spectra with two and more absorption maxima. Several correlations are derived between structure of investigated compounds and their UV-vis absorption spectra.     

2-糠醛缩N-乙基-3,6-二氨基咔唑双席夫碱的合成及其性能

以咔唑为起始原料经N-取代、硝化和还原反应制备中间体N-乙基-3,6-二氨基咔唑,然后以其与2-糠醛发生缩合反应制得新型双席夫碱化合物N-乙基-3,6-二(2-亚糠基亚氨基)咔唑,产率为72.36%。通过元素分析、FTIR、UV-Vis、1H NMR、溶液及固体荧光光谱、循环伏安(CV)和TG-DTA分析研究了标题化合物的分子结构、光物理特性、电化学特性和热稳定性。结果表明,化合物的DMF稀溶液在200~400 nm波段有较宽较强的紫外吸收;在365nm波长激发下,溶液发射深蓝色荧光,λem为446nm,固体荧光为λem=467nm的蓝色荧光,与溶液荧光相比固体荧光红移了21nm。由循环伏安测试得到产物的Eg=2.19e V,IP=4.99e V以及EA=2.80e V,说明其具有良好的空穴和电子传输材料性能。TG-DTA测试显示目标产物具有良好的热稳定性。该化合物在有机荧光、空穴注入传输材料以及电子传输材料方面具有潜在应用前景。     

新型同分异构芘基查尔酮的理论研究和超快三阶非线性光学响应

合成了3个新型同分异构芘基查尔酮:1-(芘-1-基)-3-(吡啶-2-基)-2-丙烯-1-酮(3a)、1-(芘-1-基)-3-(吡啶-3-基)-2-丙烯-1-酮(3b)和1-(芘-1-基)-3-(吡啶-4-基)-2-丙烯-1-酮(3c)。 通过核磁共振波谱仪(NMR)、傅里叶变换红外光谱仪(FTIR)和液-质联用仪(LC-MS)等技术手段表征3个化合物的结构、热稳定性和线性光学性质和三阶非线性光学吸收性能。 结果表明,在532 nm和180 fs条件下,化合物3a-3c均表现出超快三阶非线性光学响应,化合物3c的非线性吸收系数分别是化合物3b和3a的1.14和2.67倍。 运用密度泛函理论方法计算了化合物3a-3c的非线性光学性质及其电子性质,结果表明,化合物3c分子具有最大的静态第一超极化率(β₀)(2830.9 a.u.),并具有最小的最高占据分子轨道(HOMO)-最低空分子轨道(LUMO)之间的能隙(3.11 eV)和最小的跃迁能(ΔE)(2.67 eV),这与N原子在吡啶环上的位置有关;分子内部均存在电荷转移现象。 3个化合物的紫外-可见光谱在450 nm以上无吸收,有良好的热稳定性,在激光防护方面有应用前景。     

两个二茂铁基查尔酮衍生物的合成及超快三阶非线性光学响应

合成两种新颖的含二茂铁基团的查尔酮衍生物：1-二茂铁基-3-(4-叔丁基苯基)丙烯酮(a)和1-二茂铁基-3-联苯基丙烯酮(b),经₁H NMR、₁₃C NMR、HR-MS对其结构进行了表征;测定了该两化合物的热力学性质;采用量子化学方法计算了它们的分子轨道能量和极化率,给出了轨道电子云图;采用紫外-可见吸收光谱和Z-扫描技术测定了其线性和非线性光学性质。结果表明：与原料相比,化合物a和b的紫外吸收明显增加,且b的吸收波长更长;化合物a和b均存在分子内电荷转移现象,表现出超快三阶非线性光学响应。     

5-甲基-3-硝基-4-异噁唑甲酰腙的晶体结构、电子光谱、抑菌活性及其量化计算

将3-硝基水杨醛和5-甲基-4-异噁唑甲酰肼于中温混合溶剂热体系中合成了标题化合物5-甲基-3-硝基-4-异噁唑甲酰腙(C12H10O4N4,3),并对其进行了单晶结构解析、紫外、荧光和热重分析等表征.结果表明,晶体属正交晶系,Pna21空间群.晶胞参数:a=1.28783(6)nm,b=1.13108(6)nm,c=0.86535(4)nm,V=1.2605nm3,Z=4.标题物3的水溶液在486nm处呈现一强蓝色荧光发射峰,归属于激发态分子内质子转移电荷发光;标题物3对枯草芽孢杆菌、铜绿脓杆菌、大肠杆菌和金黄色葡萄球菌等都有明显的抑菌活性;分子的静电势图(EPM)再现其具有较强的广谱抗菌活性.     

Synthesis and Spectroscopic Study of Coumarin Derivatives

Five new coumarin amide derivatives were synthesized with coupling reagent,the structures of which were characterized by IR,1H NMR,13C NMR,MS and element analysis.Their spectral properties were studied in dichloromethane,in N,N-dimethylformamide(DMF) and in solid state.Solvent polarity has less influence on the UV-Vis maximum absorption at about 430 nm.The maximum emission wavelengths change from 464 nm to 474 nm in dichloromethane,from 476 nm to 482 nm in DMF and from 521 nm to 548 nm in solid state,respec...     

Synthesis and studies of new photochromic spiropyrans containing a formylcoumarin fragment

A computer search for new photoactive compounds among indoline spiropyrans of coumarin series was carried out using DFT B3LYP/6-31G(d,p) method. Based on the data obtained, the spiropyrans containing a formylcoumarin fragment annulated to the 2H-pyran ring and possessing photochromic properties were synthesized. The structure and photochromism of these compounds were studied by ¹H NMR, IR, and UV/Vis spectroscopy. The introduction of a formyl group into the coumarin moiety of spiropyrans led to a bathochromic shift of the long wavelength absorption maxima of merocyanine isomers, as well as to a considerable increase in their lifetime.