具有双光子荧光的新型香豆素类衍生物的合成及其光学性能

以7-碘代香豆素-3-甲酸乙酯为原料通过Sonogashira偶联、酯水解和酰胺化反应合成了新型香豆素类衍生物--7-（4-甲氧基苯乙炔基）香豆素-3-N-炔丙基甲酰胺（4）,其结构经¹H NMR, ¹³C NMR, HR-MS(ESI)和元素分析表征。并对其紫外-可见吸收光谱、荧光发射光谱及双光子荧光光谱进行了研究。结果表明：溶剂极性对4的光学性质影响显著,4具有明显的溶致变色效应。此外,4具有较大的有效双光子吸收截面（在乙酸乙酯、甲苯和氯仿中分别为222.57、 168.98 和211.77 GM）,并可发射较强的双光子诱导荧光。     

苯并香豆素羧酸衍生物的合成及荧光性能研究（英文）

合成了具有较高荧光性能的香豆素衍生物:7-羟基-6-氧代-6H-苯并香豆素-8-羧酸(3a)及2,3-苯并-7-羟基-6-氧代-6H-苯并香豆素-8-羧酸(3b),通过单晶X射线衍射对化合物结构进行了表征.3a和3b在乙醇溶液、晶体结构下具有较高的荧光量子产率(Ф_F).3a晶体结构存在羧酸二聚体,较强的分子间作用力使其荧光量子效率可达0.32,组成二聚体单元的所有原子处在同一平面内,3a的分子刚性较强.二聚体单元间则通过C—H…O分子间氢键以边对面的堆积方式相连.     

一种电荷转移型咔唑苯腙衍生物的合成及其发光行为

合成了具有强电子给体和拉电子能力基团的新化合物:9-乙基-3.-咔唑亚甲基-(2,4-二硝基)苯腙,研究了其光谱性质和光物理行为.结果表明,化合物在溶液中,随着溶剂极性的增大,发生了分子内电子转移,激发态和基态的偶极矩差值(μE-μG)为4.530 D,并在强极性溶剂中出现了有趣的双荧光发射.随着其浓度增大,会形成二聚或多聚体,荧光发射发生红移.     

酸性离子交换树脂催化合成二氢香豆素类化合物

以强酸性离子交换树脂为催化剂,由间苯三酚与丙烯酸或取代丙烯酸反应合成了3个二氢香豆素和1个四氢苯并二吡喃酮类化合物,其中5-羟基-3,4,6,7-四氢苯并[1,2-b;5,4-b']二吡喃-2,8-二酮(2a)和3-甲基-5,7-二二羟基-3,4-二氢香豆素(1b)还未见文献报道.取代丙烯酸的反应活性低于丙烯酸,使用甲苯-四氢呋喃混合溶剂代替甲苯单一溶剂可使2a的产率由20%提高到66%.     

KF/Al2O3催化下2-氨基-4-芳基-4H-吡喃并[3,2-c]香豆素衍生物的一步合成

以芳醛、4-羟基香豆素和丙二腈或氰乙酸酯为原料,在KF/Al2O3催化下以乙醇为溶剂,在80℃合成了一系列2-氨基-4-芳基-4H-吡喃并[3,2-c]香豆素衍生物,并通过IR,1H NMR和元素分析确证产物的结构.     

基于三苯胺的双氰基二苯代乙烯型双光子荧光溶剂生色探针

以双氰基二苯代乙烯为双光子荧光母体,借助电子供体-π-电子受体(D-π-A)构-效关系,以二苯氨基作电子供体,氰基作电子受体,开发了一个新型的双光子荧光溶剂生色探针(SP1),并对其结构进行了表征.性能测试结果表明,SP1在环己烷和二甲亚砜(DMSO)中的最大发射波长分别为452和604 nm,显示出很宽的溶剂生色范围(152 nm),可用于溶剂极性与黏度的检测,亦能根据最大发射波长识别溶剂种类.SP1拥有较大的双光子吸收截面,在环己烷和DMSO中的最大双光子吸收截面分别为6670和2040 GM,并具有较大的斯托克斯位移(194 nm),其光稳定性、水溶性和细胞渗透性均比较优良.该探针可用于细胞中黏度的检测与成像.     

高效液相色谱-荧光光度测定及质谱鉴定酒中脂肪醛

合成了一种新的荧光试剂[1,2-苯并-3,4-二氢咔唑-9-乙基肼基甲酸酯(以下简写作BCEC)]并在酒中脂肪醛高效液相色谱(HPLC)分离及测定中作为柱前衍生试剂.衍生反应在乙腈溶剂中,用三氯乙酸作催化剂并在60 ℃条件下进行,并能在10 min后获得稳定的荧光产物.用Zorbax Eclipse XDB C8(4.6 mm×150 mm,5 μm)作色谱柱,并以不同浓度的乙腈-水溶液作流动相进行梯度淋洗.采用荧光检测,检测的激发波长为333 nm,发射波长为390 nm.采用在线质谱检测对10种脂肪醛进行定性鉴定,醛的物质的量在0.166 5～83.3 fmol之间与其色谱峰面积呈线性关系,相关系数均优于0.999 9 ,被测各醛的检出限(S/N=3)在3.75～16.65 fmol之间.     

芳杂环推拉型大分子的多光子上转换荧光性质

用Wittig反应和Heck反应制备了2个新的芳杂环推-拉型荧光大分子聚[(2,5-二苯撑-1,3,4-噁二唑)-4,4'-乙烯撑-交替-N,N'-二(4-苯乙烯撑)]苯胺(P1)和聚[(2,5-二苯撑-1,3,4-噁二唑)-4,4'-乙烯撑-交替-N-乙基-3,6-咔唑乙烯撑](P2). P1和P2的分解温度分别为373和412 ℃, 热稳定性良好. 电化学性能用循环伏安法测定. P1和P2的最高占有分子轨道(HOMO)能级分别为-5.39和-5.81 eV, 最低未占有分子轨道(LUMO)能级分别为-2.81和-3.09 eV. 用飞秒Ti:Sapphire激光器测定了P1和P2的三光子和双光子上转换荧光光谱. 在1250 nm波长激发下, 在四氢呋喃溶液中P1和P2的三光子荧光发射峰分别位于510和491 nm. 在800 nm波长激发下, 在四氢呋喃溶液中P1和P2的双光子荧光发射峰分别位于511和495 nm. 在四氢呋喃溶液中大分子P1和P2单光子荧光发射峰分别位于503 和475 nm, P1和P2的荧光量子产率分别为0.80和0.31. 研究了多光子荧光发射过程的溶剂效应. 结果表明, 溶剂极性增大, P1和P2的多光子荧光发射波长明显红移.     

基于香豆素荧光团的新型极性检测荧光探针的开发及其成像应用

极性是生物微环境的重要参数之一, 在很大程度上, 生物体内许多生命活动都受到极性变化的影响, 本工作通过改变香豆素母体上的推-拉电子基团, 设计并合成了一种具有较大斯托克斯位移的新型极性荧光探针COM-PO, 该探针的荧光强度和波长会随着测试体系的极性变化而发生改变. 当极性增加时, COM-PO的激发态能量会通过偶极-偶极的相互作用散失在溶剂中, 荧光发射强度降低, 而在低极性溶剂中荧光发射强度增强, 利用这种特性实现了对极性的检测. 本工作通过荧光光谱、荧光成像实验表明COM-PO能够在样品中实现极性检测, 该探针有望实现与极性相关的疾病的早期诊断.     

可见光响应的荧光增白剂基多功能光引发体系

将4,4'-双(苯并噁唑-2-基)二苯乙烯(BBS)、 7-二乙氨基-4-甲基香豆素(C 1)、 双-(三嗪基氨基)-二苯乙烯二磺酸(CBUS 450)、 4,4'-双(2-磺酸苯乙烯基钠)联苯(CBS X)和1,4-双(2-苯并噁唑基)萘(OB 7)等5种含有不同荧光发射基团的商用荧光增白剂分别与二苯基碘鎓六氟磷酸盐(IOD)组成二元光引发体系, 再与N-乙烯基咔唑(或叔胺)组成三元光引发体系, 在可见光发光二极管(LED)光源辐照下, 通过自由基聚合反应制备丙烯酸酯树脂, 同时通过阳离子/自由基同步聚合反应制备互穿网络聚合物. 利用紫外-可见分光计荧光分光计、 电子自旋共振波谱仪、 傅里叶变换红外光谱仪、 扫描电子显微镜和原子力显微镜对荧光增白剂和互穿网络聚合物进行了表征. 研究结果表明, 荧光增白剂在可见光LED的照射下可作为具有高效能的多功能光引发剂. 其中苯并噁唑-萘衍生物(OB 7)、 三嗪茋衍生物(CBUS 450)、 二苯乙烯-联苯衍生物(CBS X)和香豆素衍生物(C 1)基二元光引发体系和三元光引发体系即使在空气中也表现出了优异的光引发能力.     

Influence of polarity of solvents on the spectral properties of bichromophoric coumarins

Absorption and fluorescence spectra of bichromophoric coumarins were investigated in different solvents and in polymer matrices. These bichromophoric coumarins were composed of a coumarin dimethylamino-substituted at position 7 or unsubstituted coumarin and phthalimide or a 1,8-naphthylimide linked with an iminomethyl bridge to the position 3 or 8 of the coumarin ring. Absorption spectra of 7-dimethylamino derivatives in position 3 of coumarin were quite similar, exhibiting broad bands around 430-440 nm like the parent compound 7-dimethylaminocoumarin-3-carbaldehyde. For coumarin derivatives substituted in position 8, the absorption maximum was shifted to shorter wavelength as for derivatives without position 7 dimethylamino substitution. The most intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin in polar solvent, while intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)iminomethyl]-coumarin in non polar solvent (chloroform), comparable with the fluorescence of 7-amino-4-methylcoumarin. Spectral measurements of bichromophoric coumarins in polymer matrices revealed that the maxima lies in between those for chloroform and methanol yielding more intense fluorescence then in solutions. Completely different solvent effects were observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)imino-methyl]coumarin and 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin. With addition of polar methanol the intensity of fluorescence decreases, yielding a Stern-Volmer-like constant of 0.54 dm3 mol?1 for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxo-benz[de]isoquinolinyl)iminomethyl]coumarin and an even higher one of 1.08 dm3·mol?1 for 7-dimethylaminocoumarin-3-carbaldehyde compared to the rather low one of 0.024 dm3 mol?1 for 7-amino-4-methylcoumarin. Contrary to this, addition of methanol under identical conditions brings about an increase in fluorescence intensity of 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin (about 60-fold). The reasons for these different solvent effects are discussed.     

Sesquiterpenoid derivatives from Ferula ferulaeoides [correction of ferulioides]. V

Nine novel prenyl-dihydrofurocoumarin-type sesquiterpenoid derivatives, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadien-6-onyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-2-[4-methyl-5- (4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2R*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadien-6-onyl]-furo-[3,2-c]coumarin, and 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, were isolated from the roots of Ferula ferulaeoides [corrected]. The structures were established by comprehensive spectral analysis. The biosynthetic pathway leading to these prenyl-furocoumarin-type sesquiterpenoids is proposed based on their structures.     

Sesquiterpenoid derivatives from Ferula ferulaeoides [correction of ferulioides]. IV

Four novel prenyl-furocoumarin type sesquiterpenoid derivatives, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-3-[4,8-dimethyl-3(E),7-nonadie nyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-3-[4,8-dimethyl-3(E),7-nonadie nyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-3-[4-methyl-5-(4-methyl-2-furyl)- 3(E)-pentenyl]-furo[3,2-c]coumarin, and 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-3-[4,8-dimethyl-3(E),7-nonadie nyl]-furo]3,2-c]coumarin were isolated from the roots of Ferula ferulaeoides [corrected]. Their structures were established by detailed spectral analysis and the biosynthetic pathway leading to these prenyl-furocoumarin type sesquiterpenoids is proposed based on these structures.     

Chromenone 12-crown-4 substituted zinc phthalocyanine complexes: investigation of spectral, photophysical and photochemical properties

The synthesis of novel 6,7-[(12-crown-4)-3-[p-(3,4-dicyanophenoxy)phenyl]coumarin (1), 6,7-[(12-crown-4)-3-[p-(2,3-dicyanophenoxy)phenyl]coumarin (2), and their corresponding tetra-(chromenone 12-crown-4)-substituted zinc (II) phthalocyanine complexes (3 and 4) have been prepared. These new compounds have been characterized by elementel analysis, (1)H NMR (1 and 2), MALDI-TOF, IR and UV-Vis spectral data. The fluorescence intensity changes for 1 and 2 by addition of Na(+) or K(+) ions have been determined at 25°C in THF. Intensity of the binding Na(+)- and K(+)-complexes (1 and 2) have decreased. The effects of the chromenone crown ether on the phthalocyanine molecule concerning photophysical and photochemical properties are also investigated. Photodegredation, singlet oxygen, fluorescence quantum yields, and fluorescence lifetimes of zinc phthalocyanine complexes (3 and 4) are also examined in DMSO.     

Ion-induced FRET on-off in fluorescent calix[4]arene

A novel calix[4]arene bearing one 2,3-naphthocrown-6 and two coumarin amide units at the lower rim in partial-cone conformation was synthesized as a colorimetric and FRET-based fluorometric sensor for F(-) and Cs(+) ions. Intramolecular FRET from the naphthalene emission to the coumarin absorption affords high fluorescence selectivity toward F(-) and Cs(+) ions.     

Systematic study of the fluorescence decays of amino‐coumarin dyes in polymer matrices

We measured the fluorescence decays of seven different amino‐coumarin dyes in polymer films of poly(methyl methacrylate) (PMMA), poly(styrene) (PS), and ethylene‐butene rubber (EBR); as well as in the small molecule analogs ethyl acetate and toluene. Many of the dye‐solvent and dye‐polymer combinations exhibited single exponential decays with lifetimes ranging from 2.3 to 3.9 ns. Small deviations from single exponential behavior occurred for most of the dyes in EBR. Significant deviations from single exponential behavior occurred for 7‐(diethylamino)‐2‐oxo‐2H‐1‐benzopyran‐3‐carboxylic acid (coumarin‐3) in ethyl acetate and in all polymer matrices and 2,3,6,7‐tetrahydro‐11‐oxo‐1H,5H,11H‐[1]benzopyrano[6,7,8‐ij]quinolizin‐10‐carboxylic acid (coumarin‐343) in all of the polymer matrices. Time‐resolved fluorescence spectra indicated the presence of two different excited states for coumarin‐3 and coumarin‐343 in PMMA; these spectra were qualitatively different from the time‐resolved spectra of coumarin‐3 in ethyl acetate. We rationalize these results in terms of the chemical functionalities of the various dyes. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2333–2343, 2007     

Synthesis and Cytotoxic Activity of Coumarin Derivatives Containing Benzotriazole Moieties

Three coumarin derivatives containing benzotriazole moieties, 3-(1-benzotriazolyl)-4-methyl-coumarin (BMC), 3-(1-benzotriazolyl)-4-methyl-benzo[7,8]coumarin (BMBC), and 3-(4-methyl-1-benzotriazolyl)-4-methyl-benzo[7,8]coumarin (MBMBC), were synthesized. Among them, 3-(4-methyl-1-benzotriazolyl)-4-methyl-benzo[7,8]coumarin has been structurally characterized by X-ray crystallography. The cytotoxic effect by Sulforhodamine B (SRB) assay with these compounds against the human hepatocellular carcinoma cell lines (HepG-2) was carried out in vitro. The preliminary results showed that all compounds inhibit HepG-2 growth effectively.     

Synthesis,characterization and fluorescence behavior of new fluorescent probe phthalocyanines bearing coumarin substituents

In this study, we report a new ligand, 6-hexyloxy-3-[p-(3′,4′-dicyanophenoxy)phenyl]coumarin, and its fluorescent tetrasubstituted phthalocyanines {M[Pc(OBzCou)₄], M = 2H, Zn(II), Co(II); Bz: Benzene}. The effect of the coumarin derivative on the intensity of the fluorescence spectra of the metal-free (H₂Pc) and zinc phthalocyanine (ZnPc) derivatives was investigated. The change of the emission properties of both the coumarin moieties and the phthalocyanine core in the presence of the metal ion and the ring-opening reaction of the coumarin were studied by means of steady-state fluorescence spectroscopy. The radiative decay of the Pcs and the treated coumarin substituents bound to the Pcs was examined. The novel chromogenic compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, Maldi-TOF, IR and UV–Vis spectral data. The photophysical properties of the Pcs are extensively affected by their state of aggregation: in particular, dimerization and aggregation result in a remarkable modification of the absorption and emission bands and may induce significant quenching of the usually strong Pc fluorescence. The electronic spectra exhibit a band of coumarin identity together with characteristic Q and B bands of the phthalocyanine core.     

香豆素-咪唑类荧光染料的设计与研究

合成了不同给电子取代基(羟基、丁氧基、二乙基氨基等)的菲并[9,10-d]咪唑(CA1~CA6)或4,5-二苯基咪唑(CB1~CB6)修饰的香豆素衍生物,初步考察了它们的溶液发光和固体发光现象.研究表明,当香豆素取代基为氨基时,化合物在二氯甲烷中的荧光较强,而羟基取代、丁氧基取代或者无取代的衍生物在二氯甲烷中的荧光都很弱,而菲并[9,10-d]咪唑修饰的衍生物CA1~CA5的溶液荧光要比4,5-二苯基取代咪唑修饰的衍生物CB1~CB5的溶液强.另外,染料分子的分子内氢键强度及咪唑基-香豆素环间二面角大小都会对染料分子的发光性能产生影响.     

Regioselective Synthesis of 2H - Pyrano [3, 2-c] Benzopyran-5H-One and 3H-Pyrano [2, 3-c] Benzopyran-5H-ONE

The hitherto unreported title compounds were obtained in good yields by [3, 3] sigmatropic rearrangement of 4 - [2-propynyloxy] coumarin and 3 - [2-propyny-loxy] coumarin respectively.