活性炭分离-桑色素荧光法测定天然水中痕量铍

在溴化十四烷基吡啶存在下,铬天菁S与铍生成三元胶束络合物。在pH10.0氨～氯化铵缓冲介质中,活性炭定量吸附此络合物,用热盐酸洗脱铍,可与其他干扰离子分离,用桑色素荧光法进行测定。该法用于测定美国EPA标准水样和天然水中的痕量铍,结果令人满意。     

A Picosecond Time-Resolved Spectroscopic Investigation of the Effect of pH on Morin Fluorescence

In this work, we investigated for the first time morin in MeOH at different pH values by picosecond time-resolved fluorescence. We identified the two species responsible for the fluorescence at low and high pH. The solvated morin-solvent hydrogen-bonded complex has been experimentally observed for the first time. We give also the typical fluorescence spectra as well as the fluorescence lifetimes of the probable emitting species. In this work we put forward new insights concerning the contribution of free morin to the fluorescence. We hope that these new data improve the accuracy of the interpretation of the cation:morin complexes titration using fluorescence signal.     

Theoretical Investigations on the Sensing Mechanism of Phenanthroimidazole Fluorescent Probes for the Detection of Selenocysteine

The level of selenocysteine (Sec) in the human body is closely related to a variety of pathophysiological states, so it is important to study its fluorescence sensing mechanism for designing efficient fluorescent probes. Herein, we used time-dependent density functional theory to investigate the fluorescence sensing mechanism of phenanthroimidazole derivates A4 and B4 for the detection of Sec, which are proposed to be designed based on excited state intramolecular proton transfer (ESIPT) and intramolecular charge transfer (ICT) mechanisms. The calculation results show that the fluorescence quenching mechanism of A4 and B4 is due to the photo-induced electron transfer (PET) process with the sulfonate group acts as the electron acceptor. Subsequently, A4 and B4 react with Sec, the sulfonate group is substituted by hydroxyl groups, PET is turned off, and significant fluorescence enhancement of the formed A3 and B3 is observed. The theoretical results suggest that the fluorescence enhancement mechanism of B3 is not based on ICT mechanism, and the charge transfer phenomenon was not observed by calculating the frontier molecular orbitals, and proved to be a local excitation mode. The reason for the fluorescence enhancement of A3 based on ESIPT is also explained by the calculated potential energy curves.     

桑色素金属(Ⅱ)固体配合物的抗氧性研究（英文）

本文报道了五种金属(Ⅱ)桑色素固体配合物的合成.通过元素分析、溶解尔电导、红外光谱、热重差热、核磁共振氢谱和荧光分析测定了配合物的组成和性质，结果表明配合物组成为ML2*nH2O[M=Mn(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cu（Ⅱ)、Zn(Ⅱ)；L=Morin(失去2`-OH中质子）；n=2或3].并对配体、配合物进行了脂质过氧化物生成的抑制和清除O-2。自由基的对比研究。     

Fluorimetric Determination of Aluminium Traces (ppb) in Hemodialysis Solutions Using Morin and Pontachrome Blue Black

Abstract

Two simple procedures for spectrofluorimetric microdosage of Al in dialysis fluids using Morin and Pontachrome Blue Black (PBB) dyestuffs are described. The optimum experimental conditions for both the fluorimetric reagents and for the particular kind of matrix are reported. Linearity between emission intensity and Al concentration was observed in the range 5–50 ppb for PBB and 2–30 pbb for Morin respectively. The Al amount was determined by applying the standard addition method. Both the spectrofluorimetric reagents proved to be suitable for sensitivity and accuracy to Al determination in dialysis fluids.     

一种新型吡唑啉类染料荧光性质的研究

本文利用紫外吸收、荧光光谱、偏振荧光和时间分辨瞬态光技术,研究了1-对氨硫酰苯基-3-对氯苯基吡唑(SCPL)在不同溶剂     

桑色素荧光光度法测定二氯化双(丁氧羰乙基)锡

在ｐＨ３．０的ＨＡｃ－ＮａＡｃ缓冲溶液中和有Ｔｒｉｔｏｎ Ｘ－１００存在下,二氯化双（丁氧羰乙基）锡（简写为Ｒ２ＳｎＣｌ２）与桑色素形成１：１的荧光络合物。络合物的激发波长和发射波长分别为４４３．２ｎｍ和５１４。４ｎｍ。Ｒ２ＳｎＣｌ２中的Ｓｎ浓度在０￣３．０ｍｇ／Ｌ范围内,与络合物荧光强度呈线性关系。方法检出限为７．８１μｇ／Ｌ Ｓｎ,用于ＰＶＣ中间产品和污水中Ｒ２ＳｎＣｌ２的测定,结果满意,相对     

Triton X-100增敏桑色素荧光法测定痕量三苯基锡

pH4～5的介质中，三苯基锡（TPhT）与过量的桑色素（Morin）迅速形成络合物，此络合物能发较强的荧光，在适量的TritonX－100存在下，由于TritonX－100的增敏作用荧光大大增强。λex／λem＝415／525nm，三苯基锡在0．05×10－6～1．4×10－6mol／L范围内与荧光强度呈良好的线性关系，检出限1．2×10－9mol／L，用于实际水样测定，结果令人满意。     

4-羟基香豆素衍生物的荧光性能

4-羟基香豆素衍生物的荧光性能;水杨酸; 羟基香豆素衍生物; 荧光     

含钕聚合物的制备及荧光性质

用复分解的方法制备了辛酸钕[Nd(OCA)_3]和甲基丙烯酸钕[Nd(MAA)_3];将它们分别加入甲基丙烯酸甲酯和甲基丙烯酸的混合体系,聚合后得到交联的[含Nd(MAA)_3]和非交联的[含有Nd(OCA)_3]二种聚合物。研究了上述钕的有机酸盐和二种含钕聚合物的荧光性质。     

Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept,Examples and Applications

Dual-state emissive (DSE) fluorophores are organic dyes displaying fluorescence emission both in dilute and concentrated solution and in the solid-state, as amorphous, single crystal, polycrystalline samples or thin films. This comes in contrast to the vast majority of organic fluorescent dyes which typically show intense fluorescence in solution but are quenched in concentrated media and in the solid-state owing to π-stacking interactions; a well-known phenomenon called aggregation-caused quenching (ACQ). On the contrary, molecular rotors with a significant number of free rotations have been engineered to show quenched emission in solution but strong fluorescence in the aggregated-state thanks to restriction of the intramolecular motions. This is the concept of aggregation-induced emission (AIE). DSE fluorophores have been far less explored despite the fact that they are at the crossroad of ACQ and AIE phenomena and allow targeting applications both in solution (bio-conjugation, sensing, imaging) and solid-state (organic electronics, data encryption, lasing, luminescent displays). Excited-State Intramolecular Proton Transfer (ESIPT) fluorescence is particularly suitable to engineer DSE dyes. Indeed, ESIPT fluorescence, which relies on a phototautomerism between normal and tautomeric species, is characterized by a strong emission in the solid-state along with a large Stokes’ shift, an enhanced photostability and a strong sensitivity to the close environment, a feature prone to be used in bio-sensing. A drawback that needs to be overcome is their weak emission intensity in solution, owing to detrimental molecular motions in the excited-state. Several strategies have been proposed in that regard. In the past few years, a growing number of examples of DSE-ESIPT dyes have indeed emerged in the literature, enriching the database of such attractive dyes. This review aims at a brief but concise overview on the exploitation of ESIPT luminescence for the optimization of DSE dyes properties. In that perspective, a synergistic approach between organic synthesis, fluorescence spectroscopy and ab initio calculations has proven to be an efficient tool for the construction and optimization of DSE-ESIPT fluorophores.     

磁性荧光纳米材料的制备与性能

采用表面活性剂3-氨丙基三乙氧基硅烷(APTES)修饰Fe₃O₄磁性纳米粒子, 经质子化后, Fe₃O₄磁性纳米粒子表面披覆大量的正电荷, 与表面带负电荷的巯基丙酸(MPA)修饰的核壳CdSe/CdS/ZnS量子点(QDs)通过强烈的静电作用而发生组装, 得到兼具磁性和荧光性能的磁性荧光纳米材料. 利用透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)、荧光分光光度计和振动样品磁强计(VSM)等测试手段对磁性荧光纳米材料进行表征. 研究表明, 由两种粒子组装的核壳结构复合粒子拥有良好的磁性能和荧光性能.     

三核欠完整立方烷金属原子簇二阶非线性光学性质的理论研究

研究了具有欠完整立方烷构型的过渡金属原子簇分子的二阶非线性光学性质。利用TDDFT方法计算了选取的簇分子及相应模拟构造分子的静态和动态的一阶非线性光学超级化率(ijk);并计算了不同金属、桥原子和配体以及簇芯对该类化合物一阶超级化率的影响。选取其中的一个簇分子为基本模型,分析了该分子的电子结构和分子轨道,在微观水平上阐述了其非线性光学性质的可能起源。认为由过渡金属和硫原子组成的簇芯和与桥原子相连的配体对该类簇合物的二阶非线性光学性质的起决定性的作用。     

Theoretical Studies on the Electronic Structures and Optical Properties of Tri-aryl End-capped Terthiophene Derivatives

The relationships between electronic structures and spectra properties are investigated by DFT/TDDFT for terthiophene derivatives, BMA‐3T (tri‐aryl amine end‐capped terthiophene), BBA‐3T (tri‐aryl amine and tri‐aryl boron end‐capped terthiophene) and BPB‐3T (tri‐aryl boron end‐capped terthiophene). The calculated results show that BMA‐3T, BBA‐3T and BPB‐3T have higher HOMO energy level and lower ionization potentials (IPs) than 3T. BMA‐3T has good hole injection ability and hole‐transport property as reported in experiment. The designed molecule of BBA‐3T and BPB‐3T own lower LUMO level and higher electron affinities (EAs) than BMA‐3T, which facilitate electron injection and improve their electron‐transport properties. Surprisingly, BPB‐3T has preferable charge equilibrium property since its hole reorganization energy (λ_h) is close to electron reorganization energy (λ_e). The ΔE (HOMO−LUMO) and E_g of these three derivatives are narrower compared to 3T, and the absorption as well as emission spectrum exhibited red‐shifts.     

环二肽的自组装及其荧光性能

环二肽由两个氨基酸通过肽键环合形成,在氢键相互作用驱动下具有较强的自组装倾向.本工作研究了c-SF,c-SY,c-SH及c-DF等四种环二肽的自组装行为和组装体的荧光特性.实验结果表明,c-SH为无规卷曲而其他三种环二肽均采取β-sheet二级结构,且除c-SH未形成明显组装体外,其他三种环二肽均形成不同尺寸的纳米纤维.荧光光谱检测发现环二肽在不同波长的激发下存在多个不同的荧光发射峰;对于c-SH,侧链咪唑基官能团与Zn（II）配位可以增大荧光发射的强度;对于c-SY,侧链酚羟基的氧化也可以增强荧光强度.推测在氢键作用的驱动下环二肽分子可以逐个堆叠形成纳米纤维,自组装导致的分子聚集和分子的侧链结构均可使环二肽具有可调变的荧光性能.     

水热法新型水溶性荧光碳点的制备及其性能研究

以阿拉伯糖和磷酸酪蛋白肽进行水热反应,制备水溶性多色荧光碳点,利用透射电子显微镜(TEM)、紫外吸收光谱(UV)、荧光光谱(FL)、红外光谱(FTIR)和X射线衍射(XRD)等对所制备碳点的粒径大小、吸收光谱、发光性质、表面基团等进行表征,并考察了其性能和对不同金属离子的识别作用。结果表明:制备的荧光碳点平均粒径为4.62 nm,其紫外最大吸收波长为281 nm,XRD峰值约为21°,可在紫外灯下发出明亮的荧光,最大发射波长为414 nm,且呈荧光多元发射。红外光谱分析表明存在—COOH,—NH2和—OH基团。该荧光碳点具有良好的性能,且对Cu2+和Fe3+有较强的选择性识别作用,其原因可能是荧光碳点的聚合导致粒径增大从而使荧光强度减弱。该碳点有望作为荧光探针用于检测分析和生物成像等领域。     

Theoretical investigation on dual fluorescence and intramolecular charge transfer of 5-phenyl-5H-phenanthridin-6-one

Quantum-chemical calculations with the time-dependent density function theory (TDDFT) have been carried out for 5-phenyl-5H-phenanthridin-6-one (PP). For this molecule, dual fluorescence and in- tramolecular charge transfer (ICT) were experimentally observed. The B3LYP functional with 6-311 G (2d, p) basis set has been used for the theoretical calculations. The solvent effects have been described within the polarizable continuum model (PCM). Ground-state geometry optimization reveals that the phenyl/phenanthridinone dihedral angle equals 90.0°, a nearly perpendicular structure. Vertical ab- sorption energy calculations characterize the lower singlet excited states both in gas phase and in solvents. It can be found that the lower excited states have locally excitation (LE) feature. Through constructing the potential energy curves of both isolated and solvated systems describing the LE→ICT reaction and fluorescence emission, we obtain the enthalpy difference ΔH between the LE and ICT states, energy barrier Ea, and energy difference δEFC, indicating the structural changes taking place during the ICT reaction. Potential curve and calculated emission energies for both isolated and sol- vated systems show a dual fluorescence phenomenon, consisting of a LE emission band and a red-shifted ICT band. Our calculations including the solvent effects indicate that the dual fluorescence is brought about by the change in molecular structure connected with the planarization of the twisted N-phenylphenanthridinone during the ICT reaction.     

Combined Experimental and Theoretical Investigation into the Photophysical Properties of Halogenated Coelenteramide Analogs

Marine Coelenterazine is one of the most well-known chemi-/bioluminescent systems, and in which reaction the chemi-/bioluminophore (Coelenteramide) is generated and chemiexcited to singlet excited states (leading to light emission). Recent studies have shown that the bromination of compounds associated with the marine Coelenterazine system can provide them with new properties, such as anticancer activity and enhanced emission. Given this, our objective is to characterize the photophysical properties of a previously reported brominated Coelenteramide analog, by employing a combined experimental and theoretical approach. To better analyze the potential halogen effect, we have also synthesized and characterized, for the first time, two new fluorinated and chlorinated Coelenteramide analogs. These compounds show similar emission spectra in aqueous solution, but with different fluorescence quantum yields, in a trend that can be correlated with the heavy-atom effect (F > Cl > Br). A blue shift in emission in other solvents is also verified with the F–Cl–Br trend. More relevantly, the fluorescence quantum yield of the brominated analog is particularly sensitive to changes in solvent, which indicates that this compound has potential use as a microenvironment fluorescence probe. Theoretical calculations indicate that the observed excited state transitions result from local excitations involving the pyrazine ring. The obtained information should be useful for the further exploration of halogenated Coelenteramides and their luminescent properties.     

荧光性自组装双层膜的制备及其性能研究

借助Au-S化学键的作用,在金基底上组装DL-半胱氨酸,利用DL-半胱氨酸与1-萘胺乙酸(NAA)的静电吸引作用在金表面间接组装荧光试剂NAA,从而构建了双层自组装膜NAA/Cys/Au.该自组装膜有较强的荧光信号,能被Cu²⁺猝灭,并具有较好的可逆再生性能,可用于超痕量铜离子的界面荧光测定,对Cu²⁺的检出下限为7.87×10^-11mol/L.同时采用电化学、荧光光谱及电子能谱等方法表征自组装膜的结构,并采用电化学阻抗谱技术和循环伏安法研究自组装膜在K₃[Fe(CN)₆]/K₄[Fe(CN)₆]溶液中的电化学行为研究.结果表明,金表面组装的单层膜具有良好的“针孔”效应,组装上荧光试剂之后形成的无“针孔”缺陷的自组装双层膜对溶液与基底间的界面电子转移有强烈的阻碍作用.     

Azetidines-Containing Fluorescent Purine Analogs: Synthesis and Photophysical Properties

Analogues of N,N-dimethyladenine exploiting both thieno-and isothiazolo-pyrimidine cores were modified with 3-subsituted azetidines to yield visibly emissive and responsive fluorophores. The emission quantum yields, among the highest seen for purine analogues (0.64 and 0.77 in water and dioxane respectively), correlated with the Hammett inductive constants of the substituents on the azetidine ring. Ribosylation of the difluoroazetidino-modified nucleobase yielded an emissive nucleoside that displayed a substantially lower emission quantum yield in water, compared to the precursor nucleobase. Importantly, high emission quantum yield was restored in deuterium oxide, which highlights the potential impact of the sugar moiety on the photophysical features of fluorescent nucleosides, a functionality usually considered non-chromophoric and photophysically benign.