含硫甲基的芴-苯结构化合物的合成、结构和性能

通过双Suzuki偶联反应一步合成了2种含硫甲基的芴-苯结构化合物2,7-二(4-硫甲基苯基)-9,9-二己基-芴(a)和2,7-二(2,6-二甲基-4-硫甲基苯基)-9,9-二己基-芴(b).紫外-可见和荧光光谱以及分子轨道理论计算表明,位阻较小的化合物a具有更好的共轭性能,其最大紫外-可见吸收波长达到351nm,比两端苯基含4个邻位取代基的化合物b红移了38nm;化合物a的最大荧光发射波长达到410nm,为典型的蓝光化合物,比化合物b红移了43nm.化合物a和b都具有较高的荧光量子产率,分别为59%和65%,在光电材料方面具有潜在的应用前景.     

新型含吲哚基噻唑烷硫酮化合物的合成及其光学性质

以吲哚-2-甲酸为起始原料,经酰氯化后在三乙胺作用下与2-噻唑硫酮经缩合反应合成了一种新的含吲哚基噻唑烷硫酮化合物(3),其结构和光学性质经UV-Vis, FL, ¹H NMR, IR和X-射线单晶衍射表征。结果表明：3的最大吸收波长位于315 nm;在312 nm波长激发下,3在正己烷中的最大发射波长位于401 nm,荧光量子产率为0.16;在305 nm波长激发下,3的固体荧光最大发射波长位于476 nm。     

一种新型香豆素酮可见光敏化染料的合成及其光引发性质的研究

高效的可见光光敏引发体系是目前光聚合研究中的重要领域.3,3′-二(7-二乙胺基)香豆素酮(R)已被公认为一种高效的可见光聚合敏化染料,并可以与Ar⁺激光488 nm波长匹配.本文新合成了一种染料3-(4-二乙胺基-苯丙烯酰基)-7-二乙胺基香豆素(S).实验发现在普通碘钨灯照射下,S/邻氯六芳基双咪唑(HABI)体系具有比已有高效染料R/HABI体系更快的光漂白速度和更高的引发聚合效率,是一种新型高效的可见光光敏聚合引发体系.而且S在不同溶剂中的最大吸收波长在452～489 nm之间,比R红移16～30 nm,因此该体系可以更好地与Ar⁺ (488 nm)激光器匹配.本文对该染料的光敏化机理进行了探讨.     

1,4-双(4′-N,N-二甲基氨基苯乙烯基)萘的合成及荧光性质

利用Wittig反应合成了一个以萘为π-Center的对称型“D-π-D”有机绿色发光化合物1,4 双(4′-N,N-二甲基氨基苯乙烯基)萘(BDASN),并测试了其在不同环境中的光谱性质.在378nm激发波长的激发下,BDASN显示出很强的荧光发射峰,峰位在521nm(CH₂Cl₂).随着溶剂极性增大,最大发射波长红移且荧光强度降低,与“D-π-A”分子具有相似的分子内电荷转移(TICT)行为.在β-环糊精(β-CD)中BDASN的绿色发光带被猝灭,同时在450nm附近蓝发光带的荧光强度骤增.     

萤火虫氧化荧光素类似物电子光谱的理论研究

对萤火虫氧化荧光素(S)-2-(6-羟基-2-苯并噻唑基)-2-噻唑啉-4-酮(BTZ)中苯并噻唑环的N和S原子进行取代, 形成一系列萤火虫氧化荧光素类似物, 并采用TD B3LYP/6-31+G(d)方法, 通过计算氧化物中性态与羟基去质子化后的负一价态在气相、水溶液和模拟生物环境下的吸收与发射光谱, 讨论环内不同取代原子对光谱的影响. 结果表明, X₁位以O原子取代S原子的化合物的最大吸收值发生蓝移, 以N原子取代S原子的化合物的最大吸收值发生红移. 去质子化可增加苯环上π轨道成份, 降低能隙, 从而有利于提高电子跃迁几率, 使荧光发射波长红移; 通过取代X₁和X₂位杂原子, 可调节发射光谱红移达44 nm, 蓝移达41 nm(在模拟蛋白中). 6种化合物荧光发光范围较宽, 振子强度较大, 可以作为潜在的化学发光材料用于生物成像研究.     

新型水溶性萘啶基荧光材料的制备及性能研究

本文制备得到一种新型萘啶基的水溶性光致发光聚合物:聚丙烯酸(PAA)-2-苄氨基-7-甲基-1,8-萘啶,PAA₅-PAMN₂(PAMN是2-phenmethy-lamino-7-methyl-1,8-naphthyridine的缩写),经光谱分析和密度泛函理论计算,研究了化合物的结构和组成.这种聚合物在酸性和碱性条件下呈现最大的吸收波长分别为364和342 nm.Zn(OAc)₂的加入致使PAA₅-PAMN₂水溶液的荧光猝灭,而当OAc^-改变为NO₃^-时,在荧光强度不断降低的同时,由于NO₃^-离子的配位使最大发射波长从410 nm蓝移到400 nm.Na⁺+离子对其没有明显的荧光猝灭效应.     

新的N-苯并噻唑基香豆素酰胺类化合物的合成及光谱特性

用具有光学活性和生物学活性的2类化合物(取代)香豆素-3-甲酰氯和2-氨基苯并噻唑作用合成了4种新的兼具香豆素骨架和苯并噻唑基的化合物(3a-3d),用HRMS,IR和1H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱与分子结构的关系进行了讨论.研究发现:在紫外光谱中,新化合物(3a-3d)和2种原料化合物相比,因共轭链的增长而使其最大吸收波长(λmax)红移;4种化合物表现出比原料化合物较强的荧光性能,其中3c的荧光强度最大.文中给出了稀溶液中紫外光谱和荧光光谱相关的一些信息.     

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。     

二{2-{2-{9-乙基-6-[2-(8-羟基喹啉-2-基)乙烯基]咔唑-3-基}乙烯}-8-羟基喹啉}锌配合物的合成与荧光光谱特性

合成了新的N-乙基咔唑衍生物: 3,6-二[2-(8-羟基喹啉基)乙烯基]咔唑(4)及其锌配合物(5); 化合物4经质谱、红外光谱、核磁共振氢谱、元素分析表征其结构, 并测定了它的荧光光谱. 结果显示: 化合物4的荧光发射为蓝绿色光(500 nm), 其发射光谱随着溶剂极性的增大荧光光谱向长波方向移动(即发生红移); 同时, 考察了化合物5的荧光性质, 其荧光发光峰值为600 nm, 与2-甲基-8-羟基喹啉锌相比, 发生了明显的红移.     

过氧化氢激活型近红外氟硼二吡咯光敏剂的设计、合成及光动力治疗研究

基于传统的氟硼二吡咯(BODIPY)荧光染料,设计合成了一种过氧化氢(H₂O₂)激活型近红外光敏剂中位-N-(4-硼酸苄基)吡啶鎓盐取代的碘化双苯乙烯基氟硼二吡咯(FP-IBDP). FP-IBDP在乙腈中的吸收和发射波长均达到近红外区,最大吸收和发射波长分别为681 nm和740 nm,对应的荧光量子效率和单线态氧效率分别为0.01和0.09.在被H₂O₂激活后, FP-IBDP转变为IBDP,其在乙腈中的最大吸收和发射波长分别为661 nm和701 nm.与FP-IBDP相比, IBDP的荧光量子效率和单线态氧效率大幅提升,分别达到0.11和0.48.细胞水平的荧光影像实验表明FP-IBDP对癌细胞内的H₂O₂具有灵敏的响应,并能通过明显的荧光增强变化实现癌细胞与正常细胞的有效区分.活性氧检测实验证明FP-IBDP能够被癌细胞内过表达的H₂O₂激活,并能在660nm光照射下在癌细胞内产生单线态氧.噻唑蓝(MT...     

ESIPT inspired fluorescent 2-(4-benzo[d]oxazol-2-yl)naphtho[1,2-d]oxazol-2-yl)phenol: experimental and DFT based approach to photophysical properties

ESIPT inspired fluorescent 2-(4-benzo[d]oxazol-2-yl)naphtho[1,2-d]oxazol-2-yl)phenol was synthesized from 1-amino-3-(1,3-benzoxazol-2-yl)naphthalen-2-ol. Photophysical behavior of the synthesized compound was studied using UV–visible and fluorescence spectroscopy in polar and non-polar solvents. The synthesized naphthoxazolyl benzoxazole is fluorescent and very sensitive to the micro-environment. It shows a single absorption and dual emission in non-polar solvents with large Stokes shift originating from Excited State Intramolecular Proton Transfer while in polar solvents only a single short wavelength emission is observed. Experimental absorption and emission wavelengths are in good agreement with those predicted using the Time-Dependent Density Functional Theory (TD-DFT) [B3LYP/6-31G(d)]. The largest wavelength difference between the experimental and computed absorption maxima was 16 nm (acetonitrile) and 7 nm (ethyl acetate, THF, and 1,4-dioxane) in the short and long wavelength regions, respectively. A largest difference of 25 nm was observed for the short wavelength emission in DMF and 22 nm for the longer wavelength emission in chloroform.     

双枝[1,3,4]-噁二唑衍生物的合成与荧光性质

通过Wittig反应和Heck反应合成了三个双枝噁二唑衍生物: N-{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}二苯胺(BBOD-2), N,N-双{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}苯胺(BBOD-3), N,N,N-三{4-{2-{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}苯基}胺(BBOD-4). 化合物结构经过红外光谱、核磁共振谱、质谱和熔点确证, 测定了它们在不同溶剂中的紫外光谱和单光子荧光光谱. BBOD-1, BBOD-2, BBOD-3, BBOD-4在二氯甲烷中的最大吸收峰分别位于295, 390, 398和408 nm; 最大发射峰分别为360, 486, 483和487 nm. 讨论了Stokes位移与溶剂极性的关系.     

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.     

Two New Zn(Ⅱ)/Cd(Ⅱ) One-dimensional Coordination Polymers Based on Naphthalimide Dicarboxylic Ligand

The assemble reactions of 5-(1,3-dioxo-~1H-benzo[de]isoquinolin-2(3 H)-yl)isophthalic acid(H_2L) and Zn2+/Cd2+ ions led to two compounds: [ZnL(DMSO)2]?3DMSO(1) and [Cd2 L2(DMSO)4]?DMF(2). 1 and 2 feature 1 D coordination chains. Weak ?-? interactions further connect the 1 D chains into 2D supramolecular networks. Upon grinding, 1 and 2 show increase of quantum efficiencies(34.8 and 45.4 times of increase compared with original samples for the two compounds respectively) and red shift of the emission peaks(45 and 41 nm of shift compared with original samples for the two compounds, respectively). Both indicate the compounds are good mechanoluminescence responsive materials.     

Investigating the Red Shift between in vitro and in vivo Urocanic Acid Photoisomerization Action Spectra

Abstract— Trans-urocanic acid (UCA) is found in the upper layer of the skin and UV irradiation induces its photoisomerization to cis -UCA. Cis -UCA mimics some of the immunosuppressive properties of UV exposure. The wavelength dependence for in vitro photoisomerization of trans-UCA (15 μM) over the spectral range 250 nm-340 nm (10 nm intervals) was determined. The action spectrum revealed that maximal cis-UCA production occurred at 280 nm, which is red-shifted by 10-12 nm from its absorption peak at 268 nm and differs markedly from the reported action spectra for cis-UCA production in mouse skin in vivo , which peaks at 300-310 nm. The reasons for the red shift between the in vitro and in vivo action spectra are not clear. There is limited evidence suggesting that the UV absorption maximum of trans- UCA red shifts from 268 nm in vitro to 310 nm on interaction with stratum corneum proteins in vivo. This phenomenon was investigated by applying trans-UCA (2.5 mg/cm²) in an oil emulsion to isolated human stratum corneum. After incubation at 37°C for 1 h, the absorption spectra of stratum corneum with UCA and with oil only were compared using a Xe arc source and a spectrora-diometer. A moderate red shift in trans-UCA absorption from ∼268 nm to 280 nm was observed. In summary, we suggest that the 10-12 nm red shift between the UCA absorption spectrum peak and the action spectrum peak in vitro may be accounted for by the wavelength dependence of quantum yields reported over the 254-313 nm range. The red shift between the in vitro and in vivo photoisomerization action spectra may result from the 10 to 12 nm red shift in the absorption of UCA in association with stratum corneum proteins, combined with increasing quantum yields over the 254-313 nm range.     

5,9,14,18,23,27,32,36-八烷氧基2,3-萘酞菁镍(Ⅱ)的结构与光谱性质关系的研究

测定了一组八烷氧基萘酞菁镍（Ⅱ）配合物Ni（Ⅱ）（RO）8NPC（R＝C4H9，C8H17，C12H25，NPC＝C48H16N8）在5种有机溶剂（Py、DMSO、DMF、CH2Cl2、C6H12）中的电子吸收光谱和荧光光谱，研究了这些配合物的结构与光谱的关系。结果表明该系列RO取代萘酞菁镍（Ⅱ）配合物的Q带吸收光谱比无取代的红移75nm左右，荧光光谱屯相应红移50～80nm，而溶剂对其影响不大。     

N,N′-二-(2-吡啶基)苝四羧酸二酰亚胺的合成及性能研究

合成了N,N′ 二 (2 吡啶基)四羧酸二酰亚胺,并纯化、调晶.对产物进行了元素分析和IR光谱研究(环状二酰亚胺的CO以双峰1708.8cm-1、1664 5cm-1).α晶型产物溶液的紫外可见光谱(最大吸收波长为526.00nm)和荧光光谱(最大发射波长为538.0nm)存在很好的镜像对称关系.薄膜紫外可见光谱图在450—570nm范围内,α晶型比β晶型有较强的吸收峰.X粉末衍射也反映出α晶型在2θ为25.5°、26.3°上的衍射峰强度分别为1954、2603.α、β晶型分别作为电荷产生材料制得的功能分离型有机光导体,在光源波长λ=532nm曝光下,测得含α的感光体达到饱和电位的时间45s、半衰曝光量5.7μJ/cm2、残余电位22V等数据.测得含β的感光体达到饱和电位的时间49s、半衰曝光量9.9μJ/cm2、残余电位22V等性能数值.     

可溶性镍酞菁的光谱特性研究

利用UV-Vis吸收光谱、荧光光谱及半经验ZINDO/S方法,研究了4种可溶性镍酞菁(FPcNi、MePcNi、iBPcNi、iPPcNi)的电子吸收光谱和荧光光谱.研究结果表明:随着取代基的供电子能力增加,酞菁的最大吸收波长(λ_max)和发射波长(λ_em)发生红移,摩尔消光系数变小;随着溶液浓度增大,酞菁聚集体浓度增大,λ_max发生蓝移,但浓度对λ_em影响较小,同时荧光相对强度随浓度增大,出现最大值;随着溶剂配合能力的增加,λ_max、λ_em都发生红移.     

Enhanced π-conjugation and emission via icosahedral carboranes: synthetic and spectroscopic investigation

The ability of ortho-, meta- and para-carboranes to enhance the emission intensity has been compared. For this purpose a series of carborane-appended 1,3,5-triphenylbenzene (TB) and 1,3,5- tris(biphenyl-4-yl)benzene (TBB) containing three ortho-, meta- and para-carborane clusters directly attached to the conjugated cores have been synthesized employing Suzuki, Heck, and trimerization reactions. The incorporation of the icosahedral carboranes was associated with a red shift in the UV absorption spectrum of up to 13 nm as well as enhancements of the emission intensities of up to 154%. The presence of ortho-carboranes showed the maximum red shift in the UV spectrum whereas the maximum enhancement of the emission intensity was observed in the presence of meta-carborane clusters. The order of π-conjugation extension is found to be ortho > meta ≈ para. A comparative thermal analysis indicated o-carborane-appended trimers to be the most thermally stable in the series. Proton NMR spectra of reported carborane-appended trimers indicated that ortho- and meta-carborane cages have benzenelike characteristics.     

酵母核糖核酸的UV-Vis光谱探针反应的机理研究

采用UV－Vis分光光度法，研究在pH7－8的缓冲溶液中，酵母核糖核酸（RNA）与3－氨基－6－二甲氨基－2－甲基吩嗪盐酸盐（ZR）相互作用；反应生成红色配合物，该配合物的最大吸收波长为540nm；反应前后的吸收光谱变化明显，配合物的吸收峰与试剂本身比较红移90nm；研究了体系的酸度、温度、时间等基本反应条件以及不同类型的离子对体系的影响，发现离子强度的改变对体系的吸光度有明显的影响。