一种新型喹啉衍生物的合成及其对Hg2+的检测

以吡喃并喹啉为荧光团,吡咯啶二硫代甲酸铵为识别基团,合成了一种新的荧光探针分子,7-苯基-6H-吡喃[4,3-b]喹啉-2-吡咯啶二硫代乙酰胺.采用红外光谱、核磁共振谱和质谱对其结构进行了表征,并对其荧光性质进行了研究.结果表明,该化合物可以作为检测Hg2+的比率荧光探针,对于Hg2+有着很好的选择性及很高的灵敏度,在...     

2,5-二氰基-1,4-二（3′,4′,5′-三甲氧基苯乙烯基）苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(3′,4′,5′-三甲氧基苯乙烯基)苯(TMOS)的合成和非线性光学性质。用核磁、红外和元素分析进行了表征。测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面。在800 nm的飞秒脉冲激光激发下,目标化合物发出很强的黄绿色上转换荧光。TMOS的最大吸收波长、单光子荧光波长、双光子荧光波长、荧光量子产率、双光子吸收系数、最大双光子吸收截面及双光子荧光寿命分别是395 nm、523 nm5、26 nm、0.26、1.2 cm.GW-14、05 GM、230 ps。这些数据表明对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,TMOS是细胞中DNA双光子荧光显微与成像应用的良好候选材料。     

2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯(DCHO)的合成。用核磁、红外和元素分析进行了表征。测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面。在800 nm的飞秒脉冲激光激发下,标题化合物发出很强的绿色上转换荧光。化合物2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的最大吸收波长、单光子发射波长、最大双光子荧光波长、荧光量子产率、双光子吸收系数及双光子吸收截面分别是393 nm、470 nm、475 nm、0.12、0.8 cm/GW、270 GM。这些数据表明,对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,DCHO是双光子荧光显微与成像应用的一个良好的候选材料。     

2,5-二氰基-1,4-二(3'',4'',5''-三甲氧基苯乙烯基)苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(3′,4′,5′-三甲氧基苯乙烯基)苯(TMOS)的合成和非线性光学性质.用核磁、红外和元素分析进行了表征.测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面.在800 nm的飞秒脉冲激光激发下,目标化合物发出很强的黄绿色上转换荧光.TMOS的最大吸收波长、单光子荧光波长、双光子荧光波长、荧光量子产率、双光子吸收系数、最大双光子吸收截面及双光子荧光寿命分别是395 nm、523 nm、526 nm、0.26、1.2 cm·GW-1、405 GM、230 ps.这些数据表明对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,TMOS是细胞中DNA双光子荧光显微与成像应用的良好候选材料.     

2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯(DCHO)的合成.用核磁、红外和元素分析进行了表征.测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面.在800 nm的飞秒脉冲激光激发下,标题化合物发出很强的绿色上转换荧光.化合物2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的最大吸收波长、单光子发射波长、最大双光子荧光波长、荧光量子产率、双光子吸收系数及双光子吸收截面分别是393 nm、470 nm、475 nm、0.12、0.8 cm/GW、270 GM.这些数据表明,对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,DCHO是双光子荧光显微与成像应用的一个良好的候选材料.     

新型喹啉类Zn2+探针的合成及细胞成像研究

以2-甲酰基-8-羟基喹啉为原料,与苯肼进行缩合反应合成了荧光分子探针HSZn,采用FTIR、NMR、HRMS对其结构进行了表征。紫外可见光谱和荧光光谱分析结果表明:该探针在水相中对Zn~(2+)具有较好的荧光增强效应,而其他金属离子对其干扰较小;HSZn的荧光强度与Zn~(2+)浓度(1.0×10–5~1.0×10–4 mol/L)具有良好的线性关系,检测限低至4.0×10–8 mol/L;Job’s曲线和LC-MS分析表明:Zn~(2+)与HSZn的络合比为1∶2,且探针在pH=5~13内对Zn~(2+)都有较灵敏的荧光响应。细胞成像实验表明:该探针可在Hela活细胞中实现对Zn~(2+)的荧光成像。     

一个衍生于苯并15-冠-5的双光子荧光钠离子探针

钠离子在人体生理与病理上起着关键性的作用,特别是在神经传导、肌肉与心脏收缩、电解质平衡、阳离子运输和细胞容积等方面都发挥着至关重要的功能。因此,开发用于细胞中钠离子三维动态成像的双光子荧光探针显得尤为重要。以苯并15-冠-5和双氰基二苯代乙烯分别作为钠离子受体与双光子荧光团开发出探针DNa,对DNa的结构进行了表征鉴定。探针DNa具有诸如小的分子尺寸、大的双光子吸收截面（δTPA, 1054 GM）、极好的光稳定性、适宜的水溶性和优良的细胞渗透性等优点. DNa对Na 显示了优良的专一选择性,不受其它离子的干扰,对Na 的解离常数Kd ＝ 23 ? 2 mmol?L-1。DNa能用于细胞中Na 的三维成像,是一个性能优良的双光子荧光探针。     

柱[5]芳烃对偶氮二异丁腈分子识别的研究及应用

以三氟化硼乙醚为催化剂、1,4-对甲氧基苯和多聚甲醛为原料合成具有高亲和性的全甲氧基柱[5]芳烃,通过核磁共振氢谱、紫外可见光谱、荧光光谱等检测手段研究了全甲氧基柱[5]芳烃对偶氮二异丁腈的分子识别能力。结果表明,全甲氧基柱[5]芳烃和偶氮二异丁腈可在氯仿中形成1∶1的主客体络合物,同时,全甲氧基柱[5]芳烃对偶氮二异丁腈具有刺激响应性,可作为荧光分子探针检测偶氮二异丁腈。     

色满酮类化合物的合成及其抗炎活性研究

设计合成了4种色满酮类化合物,并利用熔点、红外光谱、核磁共振氢谱等手段确定了其结构。采用二甲苯致小鼠耳肿胀法,测定了该化合物的抗炎活性,实验结果表明在200mg／kg剂量下所合成的3个目标化合物6-[2-（4-吗啉基）乙氧基]色满酮、6-[（喹啉-2-基）甲氧基]色满酮、7-[2-（4-吗啉基）乙氧基]色满酮对二甲苯所致小鼠耳肿胀具有显著的抑制作用。     

基于喹啉Zn~(2+)荧光探针的合成及其性能

以邻氨基苯甲酸和咔唑等为原料,经Skraup、Vilsmeier-Haack和Knoevenagel等反应合成了3-{2-[8-(1H-苯并咪唑-2-基)喹啉-2-基]乙烯基}-9-苯甲基-9H-咔唑(探针L),并通过1HNMR、13CNMR、MS对其结构进行了表征。荧光光谱测试结果表明,探针L对Zn~(2+)的选择性好,抗干扰能力较强,50 s内响应,在pH=5~9内对pH不敏感。加入Zn~(2+)后,探针L的荧光强度与Zn~(2+)浓度(0~60μmol/L)呈现良好的线性关系,相关系数R2=0.998 6,检测限为2.003 1×10-8mol/L。Job's曲线、荧光滴定实验和ESI-MS谱分析表明,探针L与Zn~(2+)的络合比为1∶1。     

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

We report here the synthesis and structural characterization of novel cationic (phenothiazinyl)vinyl-pyridinium (PVP) dyes, together with optical (absorption/emission) properties and their potential applicability as fluorescent labels. Convective heating, ultrasound irradiation and mechanochemical synthesis were considered as alternative synthetic methodologies proficient for overcoming drawbacks such as long reaction time, nonsatisfactory yields or solvent requirements in the synthesis of novel dye (E)-1-(3-chloropropyl)-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium bromide 3d and its N-alkyl-2-methylpyridinium precursor 1c. The trans geometry of the newly synthesized (E)-4-(2-(7-bromo-10-ethyl-10H-phenothiazin-3-yl)vinyl)-1-methylpyridin-1-ium iodide 3b and (E)-1-methyl-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium tetrafluoroborate 3a′ was confirmed by single crystal X-ray diffraction. A negative solvatochromism of the dyes in polar solvents was highlighted by UV-Vis spectroscopy and explanatory insights were supported by molecular modeling which suggested a better stabilization of the lowest unoccupied molecular orbitals (LUMO). The photostability of the dye 3b was investigated by irradiation at 365 nm in different solvents, while the steady-state and time-resolved fluorescence properties of dye 3b and 3a′ in solid state were evaluated under one-photon excitation at 485 nm. The in vitro cytotoxicity of the new PVP dyes on B16-F10 melanoma cells was evaluated by WST-1 assay, while their intracellular localization was assessed by epi-fluorescence conventional microscopy imaging as well as one- and two-photon excited confocal fluorescence lifetime imaging microscopy (FLIM). PVP dyes displayed low cytotoxicity, good internalization inside melanoma cells and intense fluorescence emission inside the B16-F10 murine melanoma cells, making them suitable staining agents for imaging applications.     

The synthesis and two-photon excited fluorescence properties of novel branched fluorene derivatives

Two novel, V-shaped fluorene derivatives branched from triphenylamine and their linear analogue were synthesized via Cu-mediated Ullmann condensation and subsequent Pd-catalyzed Heck coupling reaction. Their two-photon excited fluorescence properties as well as their linear absorption and single-photon excited fluorescence properties were examined. When excited at 730 nm by a Ti:sapphire femtosecond laser, the compounds exhibited strong two-photon excited blue fluorescence. The two-photon excited fluorescence cross-sections of V-shaped derivatives in toluene at 730 nm were ∼506 GM in the case of N, N-bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-aniline) and 397 GM for N, N-Bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-4-acetyl-aniline), respectively.     

新型近红外咔唑吲哚类硼酸酯荧光探针的合成与表征

以咔唑为起始原料,经过与亲电取代反应、Vilsmeier反应、溴化反应以及与双联频哪醇硼酸酯的偶联反应,合成了N-乙基咔唑-3-甲醛-6-苯硼酸酯,以合成的N-乙基咔唑-3-甲醛-6-苯硼酸酯,以合成的乙基取代咔唑硼酸,以合成的乙基取代咔唑硼酸酯醛与1,2,3,3-四甲基-3H-吲哚碘化物缩合,合成了一种新型近红外咔唑吲哚啉类硼酸酯荧光探针,其结构经过1H NMR,IR进行了表征。     

5-硝基苯并三唑-1-乙酸镝与1,10-邻菲啰啉配合物的合成和性质研究

采用溶液合成法,合成了标题化合物,通过元素分析、摩尔电导率、紫外光谱、红外光谱和热分析法确定配合物的组成为Dy(L)3phen.1.5H2O(HL=5-硝基苯并三唑-1-乙酸;phen=1,10-邻菲啰啉)。荧光光谱表明:镝配合物的荧光强度较强,说明配体5-硝基苯并三唑-1-乙酸和1,10-邻菲啰啉是很好的敏化剂。     

The synthesis and two-photon excited fluorescence properties of novel branched fluorene derivatives

Two novel, V-shaped fluorene derivatives branched from triphenylamine and their linear analogue were synthesized via Cu-mediated Ullmann condensation and subsequent Pd-catalyzed Heck coupling reaction. Their two-photon excited fluorescence properties as well as their linear absorption and single-photon excited fluorescence properties were examined. When excited at 730 nm by a Ti:sapphire femtosecond laser, the compounds exhibited strong two-photon excited blue fluorescence. The two-photon excited fluorescence cross-sections of V-shaped derivatives in toluene at 730 nm were 506 GM in the case of N, N-bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-aniline) and 397 GM for N, N-Bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-4-acetyl-aniline), respectively.     

A two-photon fluorescent probe for lipid raft imaging: C-laurdan

The lipid-rafts hypothesis proposes that naturally occurring lipid aggregates exist in the plane of membrane that are involved in signal transduction, protein sorting, and membrane transport. To understand their roles in cell biology, a direct visualization of such domains in living cells is essential. For this purpose, 6-dodecanoyl-2-(dimethylamino)naphthalene (laurdan), a membrane probe that is sensitive to the polarity of the membrane, has often been used. We have synthesized and characterized 6-dodecanoyl-2-[N-methyl-N-(carboxymethyl)amino]naphthalene (C-laurdan), which has the advantages of greater sensitivity to the membrane polarity, a brighter two-photon fluorescence image, and reflecting the cell environment more accurately than laurdan. Lipid rafts can be visualized by two-photon microscopy by using C-laurdan as a probe. Our results show that the lipid rafts cover 38 % of the cell surface.     

N-Positive ion activated rapid addition and mitochondrial targeting ratiometric fluorescent probes for in vivo cell H2S imaging

Heterocyclic compound quinoline and its derivatives exist in natural compounds and have a broad spectrum of biological activity.They play an important role in the design of new structural entities for medical applications.Similarly,indoles and their derivatives are found widely in nature.Amino acids,alkaloids and auxin are all derivatives of indoles,as are dyes,and their condensation with aldehydes makes it easy to construct reaction sites for nucleophilic addition agents.In this work,we combine these two groups organically to construct a rapid response site(within 30 s)for H₂S,and at the same time,a ratiometric fluorescence response is presented throughout the process of H₂S detection.As such,the lower detection limit can reach 55.7 nmol/L for H₂S.In addition,cell imaging shows that this probe can be used for the mitochondrial targeted detection of endogenous and exogenous H₂S.Finally,this probe application was verified by imaging H₂S in nude mice.     

水杨醛缩对氯苯胺Co(Ⅱ)配合物的合成、表征及其荧光性质研究

以水杨醛和对氯苯胺为原料合成了水杨醛缩对氯苯胺(HL),将其作为主要配体与1,4-对苯二酚以及氯化钴(CoCl2·6H2O)反应生成了Co(Ⅱ)的配合物[Co(C6H4O2)(L)2]n,用元素分析、红外吸收光谱、紫外可见吸收光谱对其结构进行了表征,并通过荧光光谱对配体、配合物荧光发光性质进行了研究。结果表明,配体水杨...     

The facile synthesis of novel phenothiazine derivatives for blue,yellow-green,and red light emission

Two blue emitters, 3,7-bis(5′-(trifluoromethyl)-1′H-pyrazole-3′-yl)10-ethylphenothiazine and 3,7-bis(5′-(phenyl)-1′H-pyrazole-3′-yl)10-ethyl-phenothiazine and one red, bis-dioxaborine emitter, each based on two, yellow-green emitting, bis-β-diketonate, phenothiazine derivatives, were obtained in high yield and characterized. Systematic investigation of the two-photon absorption characteristics was carried out using one-photon absorption, one-photon excited fluorescence as well as two-photon excited fluorescence spectra. TDDFT computational studies were undertaken to secure an insight into the nature of the compounds' electrochemical and photophysical properties. Low-energy absorption transmissions resemble those observed for the experimental one-photon absorption spectra.