可聚合萘酰亚胺类衍生物的合成及光谱研究

以4-溴-1,8-萘酐和4-硝基-1,8-萘酐为原料制备了分别含碳-碳双键和硅氧烷结构的可聚合萘酰亚胺衍生物4-二甲胺基-1,8-萘酐、4-二甲胺基-N-烯丙基-1,8-萘酰亚胺、4-硝基-N-烯丙基-1,8-萘酰亚胺和4-硝基-N-[(3-三甲氧基硅基)丙基] -1,8-萘酰亚胺. 通过¹H、¹³C及多种二维核磁共振（NMR）技术表征了其分子结构,完成了氢和碳的谱峰归属. 利用紫外吸收光谱与荧光发射光谱研究了这些化合物的光学性质,并讨论了取代基对这些化合物荧光性质的影响.      

磺化金属萘酞菁聚集倾向的光谱研究

在磺化金属萘酞菁的荧光光谱和电子吸收光谱的Q谱带上观察到激基缔合物的荧光光谱峰和基态聚集物的吸收光谱峰。荧光光谱和吸收光谱实验说明 ,溶液中聚体分子和单体分子同时存在 ;聚体放出或吸收光子后都解离为单体 ;在荧光光谱中金属萘酞菁的激基缔合物荧光峰相对于单体荧光峰发生红移 ,在吸收光谱中金属萘酞菁基态聚集体的吸收峰相对于单体吸收峰发生蓝移 ,聚集体的荧光光谱和吸收光谱有镜像对称关系。磺化萘酞菁钴浓度较大时 ,其荧光光谱的猝灭较大。     

新型荧光功能单体2,4-二甲基-7-丙烯酰胺基-1,8-萘啶的合成及其光谱特性

设计合成了可与DNA碱基通过氢键选择性结合的新型荧光功能单体2,4-二甲基-7-丙烯酰胺基-1,8-萘啶(DMAAN)。其反应原理是,2,6-二胺基吡啶与乙酰丙酮在磷酸介质中反应生成中间产物2,4-二甲基-7-胺基-1,8-萘啶(DMAN)。 DMAN与丙烯酰氯在三乙胺存在下,于氯仿溶剂中反应即可得到熔点为239～241 ℃的产物。采用1H核磁共振波谱、质谱、紫外-可见光谱对中间产物DMAN和目标化合物DMAAN进行了光谱表征,并进一步研究了其荧光光谱特性。     

萘酰亚胺铁离子荧光探针的合成及识别性能

以1,8-萘酐、N,N-二甲基乙醇胺、三乙烯四胺为原料,通过酰亚胺化、缩合等反应,合成一种萘酰亚胺荧光探针,并通过核磁氢谱、红外光谱结构表征,测定了探针在乙醇与水的混合溶液中的荧光光谱。考察了金属离子浓度等因素的影响,对其配位机理进行了研究。结果显示,目标产物在乙醇-水溶液中对Fe~(3+)表现出了专属选择性识别性能,在(1.87~6.53)×10~(-6)g/m L的Fe~(3+)浓度范围内,探针荧光强度与Fe~(3+)浓度有很好的线性关系,线性相关系数R=0.995 3,检出限为405.1 ng/mL。     

4-苯乙炔-1, 8-萘酰亚胺荧光化合物的合成及电致发光性能

采用Pd(PPh₃)₂Cl₂-CuI为催化剂,Ph₃P为配体,4-溴-1,8-萘二酸酐为原料,在乙醇溶液中高收率地合成了4-苯乙炔-1,8-萘酰亚胺和4-对甲基苯乙炔-1,8-萘酰亚胺荧光新化合物。光谱研究表明,它们的最大紫外吸收波长(λ_UV,max)分别为374,380 nm,最大荧光发射波长(λ_FL,max)分别为446,462 nm,且有较高的荧光量子效率。电致发光性能测试表明,器件的最大发光亮度达到2250 cd/m²,是一类有潜在应用价值的小分子发光材料。     

2,6-二氨基吡啶衍生物作为过渡金属离子荧光探针的研究

2,6-二氨基吡啶(DAPD)衍生物都有较强的荧光。除DMHND(2,4-二甲基-7-羟基-1,8-萘啶)外,2,4-二甲基-7-胺基-1,8-萘啶(DMAND)和2,4-二甲基-7-丙烯酰胺基-1,8-萘啶(DMAAN)在加入过渡金属离子后,荧光强度增强,发射光谱红移,可以作为过渡金属离子的荧光探针。根据Irving-Williams顺序,以过渡金属中络合能力较强的Cu2+为代表,求算了DMAND和DMAAN与Cu2+的结合比,通过非线性拟合计算了结合常数,比较了它们与金属离子结合的强弱,DMAND较DMAAN为更灵敏的过渡金属离子荧光探针。     

胭脂红和苋菜红分子结构与光谱性质的对比研究

应用英国Edinburgh FLS920P稳态-瞬态荧光光谱仪,对互为同分异构体的胭脂红、苋菜红分子的吸收光谱和荧光光谱实验检测,得到二者的光谱特性参数,并进行对比。分别采用密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）对这两种分子的基态和激发态结构进行优化,将所得基态分子构型进行频率计算,结果显示均无虚频存在,进而比较两分子构型在不同能态下的差异。在此基础上,应用TD-DFT并结合极化连续介质模型（PCM）在6-311++G(d, p)水平上分别计算二者的吸收光谱和荧光光谱,对两种分子的发光机制、荧光光谱特性差异与分子结构的关系进行了分析。结果表明,两种分子的基态结构均为非平面,它们中的两个萘环不共面,存在一定的夹角;苋菜红含有分子内氢键,且氢键所在萘环的平面性要优于胭脂红分子对应的萘环部分;激发态时二者各自的两个萘环均共平面。量子化学计算得到的光谱理论值与实验结果较为吻合,说明优化所得胭脂红与苋菜红的分子构型基本合理。与苋菜红相比,胭脂红右侧萘环结构的平面性稍差,分子从激发态跃迁回到基态经历了更多的振动和转动,损耗了更多的能量,导致用来产生荧光光子的能量减少,因此,胭脂红的荧光发射波长更长。本文首次得到胭脂红、苋菜红分子基态与激发态下的分子结构信息,并找出二者光谱特性差异的原因,结果可为研究同分异构体分子的光谱特性与分子结构的关系提供参考。     

苋菜红分子基态和激发态结构与光谱性质的量子化学研究

应用英国Edinburgh FLS920P光谱仪对苋菜红的吸收光谱和荧光光谱进行了实验检测.同时,分别采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)对苋菜红分子的基态和激发态构型进行优化,经振动分析合理后,比较这两种能态下分子结构的差异,并对其前线分子轨道和发光机制进行了分析.在此基础上,选用6种泛函并结合溶剂化模型(PCM)在6-311++G(d,p)水平上分别计算苋菜红的吸收光谱和荧光光谱.计算结果表明:苋菜红含有分子内氢键,基态结构非平面,两个萘环所在平面有一定的夹角,激发态时两个萘环共平面;CAM-B3LYP泛函得到光谱的理论值与实验结果基本吻合;421 nm处的荧光峰值波长对应的轨道跃迁为LUMO→HOMO-1.     

萘酰亚胺衍生物的合成及对铁离子（Ⅲ）的识别

以4-溴-1,8-萘酐为原料合成了新型萘酰亚胺衍生物N-正己基-4-苄胺基-1,8-萘酰亚胺（HBN）,通过NMR和 MS 表征了其结构。利用荧光光谱研究它对铁离子（Ⅲ）的识别作用。实验显示,在 C2 H5 OH／H2O （φ：1／1）体系中,当Fe3+浓度为4×10－7～1×10－2 mol·L－1时,HBN荧光强度随Fe3+浓度增加大幅度下降。线性回归方程为：F0／F＝623．2532cFe3++0．9642（R2＝0．9963）。常见金属离子,如Ca2+,Na+, Cu2+,Zn2+,Pb2+,Co2+,Ni2+,Mn2+及Fe2+等,均不干扰HBN对Fe3+的识别。结果表明,HBN对Fe3+具有较好的选择性和灵敏度。     

萘酰亚胺接枝壳聚糖Al3+荧光探针的合成及光谱性能研究

以1,8-萘酰亚胺、壳聚糖、盐酸吗啉胍为原料,通过酰亚胺化、席夫碱等反应,设计合成了一种萘酰亚胺接枝壳聚糖类增强型荧光探针（NCFP）。采用红外、核磁共振等技术对其结构进行表征,利用荧光光谱研究了其光谱性能及对金属离子的识别作用。研究结果表明,合成的荧光探针对Al³⁺具有较高的选择识别性能,且受常见离子的干扰较小。探针的荧光强度与Al³⁺浓度（29.90~253.41 μmol/L）有良好的线性关系,线性相关系数R²=0.997 9,Al³⁺的最低检出限达4.279 μmol/L,Job's曲线表明,荧光探针与Al³⁺的络合比为1：1。     

荧光波长对共焦显微镜成像特性的影响

导出了共焦显微镜中不同荧光波长情况下的荧光功率传输函数、三维脉冲响应函数（3D－PSF）和三维光学传递函数（3D－OTF）。结果表明，不同的荧光波长对共焦显微镜的空间截止频率、分辨率、光学传递函数存在明显的影响。当激发波长与荧光波长的比值下降到一定程度时，可以看到明显的失锥现象。     

TDDFT study on the excited‐state hydrogen bonding of N‐(2‐hydroxyethyl)‐1,8‐naphthalimide and N‐(3‐hydroxyethyl)‐1,8‐naphthalimide in methanol solution

The time‐dependent density functional theory method was performed to investigate the excited‐state hydrogen‐bonding dynamics of N‐(2‐hydroxyethyl)‐1,8‐naphthalimide (2a) and N‐(3‐hydroxyethyl)‐1,8‐naphthalimide (3a) in methanol (meoh) solution. The ground and excited‐state geometry optimizations, electronic excitation energies, and corresponding oscillation strengths of the low‐lying electronically excited states for the complexes 2a + 2meoh and 3a + 2meoh as well as their monomers 2a and 3a were calculated by density functional theory and time‐dependent density functional theory methods, respectively. We demonstrated that the three intermolecular hydrogen bonds of 2a + 2meoh and 3a + 2meoh are strengthened after excitation to the S₁ state, and thus induce electronic spectral redshift. Moreover, the electronic excitation energies of the hydrogen‐bonded complexes in S₁ state are correspondingly decreased compared with those of their corresponding monomer 2a and 3a. In addition, the intramolecular charge transfer of the S₁ state for complexes 2a + 2meoh and 3a + 2meoh were theoretically investigated by analysis of molecular orbital. Copyright © 2014 John Wiley & Sons, Ltd.     

Naphthalene-based fluorophores: Synthesis characterization, and photophysical properties

U-type, 1,8-diarylnaphthalenes and 1,8-diarylethynylnaphthalenes were synthesized and their structures were characterized by spectroscopic methods. Emission performance of these compounds with donor and acceptor was largely depended upon the solvent polarity and environmental acidity, which implied that they might be used as solvent polarity sensors or pH sensors as well. Moreover, some 1,8-diarylnaphthalenes exhibited aggregation-induced emission enhancement (AIEE) based on their photophysical investigation and might be used as light emitting materials for optoelectronic applications.     

Detecting H_2S Gas Concentration by 1,8-Naphthalimides Fluorescent Probe

针对传统硫化氢检测方法灵敏度低的问题,以1,8-萘酰亚胺为荧光基团,基于H₂S的还原性,通过在荧光分子结构上引入具有氧化性的硝基,合成一种可与硫化氢气体发生氧化还原反应生成有荧光响应的小分子荧光探针。该探针本身荧光十分微弱,且荧光峰值在λ=467 nm和λ=522 nm处。与H₂S反应之后,522 nm处的荧光效应消失,467 nm处的荧光效应显著增强。测定小分子荧光探针在通入H₂S气体前后的荧光光谱,分析467 nm处的荧光强度与气体浓度关系。结果表明：荧光光谱法检测出的H₂S气体浓度与荧光强度之间存在很强的线性关系,相关系数为0.979 3,最低可检测极限可达0.88×10-6 mol·L-1量级。表明基于1,8-萘酰亚胺衍生物的荧光光谱检测法可为油气田H₂S气体浓度的的快速测定提供参考。     

含稳定氮氧自由基聚磷酸酯的合成及其弛豫性能研究

通过二氮磷酸-O-(1-氧-2,2,6,6,-四甲基-4-哌啶醇)酯分别与四甘醇、三甘醇、二甘醇、1,6-己二醇、1,8-辛二醇、N-乙基二乙酰胺、N-正丁基二乙酰胺缩聚,制得七个含稳定氮氧自由基(TEMPO)的聚磷酸酯.对这些新的聚磷酸酯进行了结构表征,并测试了部分聚合物的纵向弛豫性能.     

Use of the red-edge excitation effect for investigation of dielectric interactions in biomembranes

Dipole moments of the fluorescent probes 1-phenylnaphthylamine (1-AN) and 1-anilinonaphthalene-8-sulfonate (1,8-ANS) are measured using electro-optical absorption and emission methods. Dipole moments in the ground and excited states were measured in cyclohexane and dioxane. It is shown that the charge distributions in the 1-AN and 1,8-ANS molecules differ substantially. The spectral dependence of the electro-optical coefficients suggests that the absorption spectrum of 1,8-ANS is due to a superposition of (at least two) electronic transitions. It is found that spectra of 1-AN in erythocyte ghosts are inhomogeneously broadened. The above effect makes it possible to selectively excite probe molecules localized at different sites of a membrane. Dielectric interactions (described by the local dielectric constant) are investigated in human erythrocyte membranes. It is found that the dielectric constant of erythrocyte membranes varies from 6.79 ±0.8 to 17.6±3.5 depending on the excitation frequency and, therefore, on the localization of the probe. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 387–393, May–June, 1999.     

吡唑林荧光化合物的合成与红外光谱研究

由苯并噻唑基及苯并咪唑基取代的吡唑林类化合物是一类新型荧光化合物。此类荧光化合物可用于多种领域,但一直发展较缓慢。依据Schellhammer经验中化学结构与荧光性关系,在吡唑林的1-位引入了苯并噻唑基或苯并咪唑基,3-位引入苯基衍生物,使其具有荧光性,5-位引入苯基作为助色团,可使荧光谱红移,增加荧光性。作者设计出新型荧光化合物的结构式,新合成了两种苯并咪唑及苯并噻唑吡唑林荧光化合物,用元素分析确定其结构。两种化合物具有较好的荧光性,荧光发射波长处在蓝绿光的范围内。经红外光谱分析,找出由苯并噻唑基或苯并咪唑基取代的吡唑林类化合物具有的典型特征吸收峰,可由此作为基准,推断化合物的结构。两种化合物的合成与光谱分析研究可为吡唑林类荧光化合物的研究开拓新途径。     

A Highly Selective Fluorescent Probe for the Detection of Nitroreductase Based on a Naphthalimide Scaffold

The development of fluorescent probes for nitroreductase (NTR) has received intense attention because of its biological significance and wide application. In this work, a novel fluorescent probe for the detection of NTR in aqueous solution was designed and synthesized on a 1,8-naphthalimide scaffold. In the presence of NTR and nicotinamide adenine dinucleotide (NADH) under physiological conditions, the probe was converted into a 4-hydroxy-1,8-naphthalimide derivative and exhibited a sharp fluorescence enhancement at 550 nm, with a high selectivity for NTR over various analytes. The detection limit for NTR was determined to be 9.8 ng/ml by this probe. Due to its low signal background, this probe showed?>?70-fold fluorescence enhancement. Theoretical calculations revealed that the reason for the fluorescence quenching of this probe is the photoinduced electron transfer (PET) from both the nitrobenzene and morpholine groups to the naphthalimide fluorophore.

     

Synthesis and Characterization of a Fluorescent Water-Borne Polyurethane Based on a Novel Naphthalimide Dye

A waterborne-polyurethane (WPU) dye, based on the fluorescent dye 4-diamino propane-N-allyl-1,8- naphthalimide (WPU-DAN), was synthesized by attaching 4-diamino propane-N-allyl-1,8- naphthalimide (DAN) onto both ends of the polyurethane (PU) chains according to a prepolymer?ionomer process. The synthetic process was confirmed by Fourier transform infrared spectroscopy (FTIR) and UV-visible absorption. The glass transition temperature, molecular weight and average particle sizes were measured. The glass transition temperatures of WPU and WPU-DAN were 46.6 and 49.8°C, respectively. In addition, the particle size distributions of WPU-DAN and WPU were 140 and 134 nm, respectively. The thermal behaviour of WPU-DAN showed improvement compared to WPU. The fluorescence intensity of WPU-DAN was enhanced more than DAN due to the naphthalimide groups attached to the chains, and the fluorescence intensity of WPU-DAN and DAN were increased by increasing temperature. Moreover, the fluorescence intensity of WPU-DAN emulsion was stable during 30 days and no loss of fluorescence intensity occurred for these days.