超分子光化学的前景

近二十年来光化学研究取得了巨大进展.其基本状况可归纳为下列几个方面:一是大量的有机分子、配位化合物、金属有机化合物的光化学和光物理行为已被了解,并得到理论上的阐明,许多重要激发态在结构上、能量上以及动态学方面的研究也已相当深入和完善;另一方面,人们对自然界存在的某些重要的光生物过程也有了相当的认识,包括如光合作用,视觉过程等,但尚未完全弄清.     

检测硫酸氢根离子光化学探针分子研究进展

酸氢根离子(HSO4)在生命、环境科学中发挥着非常重要的作用,进入环境后会污染环境,对人体造成危害.因此,选择性和高灵敏识别检测生物与环境样品中HSO4具有非常重要的意义.在众多的分析检测手段中,基于分子识别理念发展起来的光化学传感分子(探针)具有独特的优势.阴离子光化学传感体系以其选择性好、灵敏度高、易于实现在线分析,特别是可通过目视比色识别和原位检测等特点成为目前研究的热点.本文根据探针分子与HSO4之间的作用机理, 对近年来HSO4的光化学探针分子进行分类和总结,综述了HSO4光化学探针的研究进展,并对其应用前景与发展趋势进行了展望.     

萘酰亚胺类荧光分子探针的研究进展

荧光分子探针作为一种有效的金属离子检测手段,不仅使用方便,而且具有高灵敏度,高选择性等突出的优点.作者综述了萘酰亚胺类荧光分子探针的最新研究进展;指出萘酰亚胺化合物具有独特的荧光化学性质(如荧光量子产率高、荧光发射波长适中、斯托克斯位移大、光稳定性好、结构易于修饰等),因此被广泛应用于荧光探针研究领域,并且在合成、离子识别、检测及细胞成像等方面不断取得新的应用.     

基于联合荧光机制的激发态分子内质子转移荧光探针研究进展

荧光探针能够实现对分析物的快速检测,并因其优异的选择性、高灵敏度和操作简便等优点成为近年的研究热点.激发态分子内质子转移(ESIPT)是最基础的荧光设计策略之一,基于ESIPT原理设计的荧光探针具有发光强度高、Stokes位移大以及反应过程可逆等优点,但也存在对环境敏感、发射波段较短等不足.近年来,将ESIPT与其它荧...     

细胞器靶向型气体信号分子荧光探针的研究进展

NO、CO和H2S是细胞内重要的内源性气体信号分子,他们不仅在血管舒张、神经传递和免疫应答等生理过程中发挥重要作用,还与肿瘤、高血压、糖尿病和阿尔茨海默症等多种疾病密切相关.基于有机小分子荧光探针的荧光成像分析法具有灵敏度高、选择性好、操作简便、时空分辨率强和原位实时等特点,是细胞内气体信号分子检测的重要方法,而细胞器...     

基于大环分子的主客体超分子荧光探针

针对环境污染源的早期检测和疾病的预防与治疗已经研究开发出许多检测技术手段,其中,荧光探针作为一种方便、灵敏、可视化的检测技术得到了广泛关注与认可。大环分子荧光探针作为一类重要的荧光探针逐渐引起了研究者的关注。大环分子具有特定尺寸、可特异性配合某些基团的空腔。因此,在设计这类荧光探针时可以充分利用大环分子的空腔优势。此外,大环分子容易通过化学修饰制备多种功能化衍生物,这也为设计大环荧光探针提供了更多选择。本文回顾了大环分子荧光探针的设计策略,主要从探针的化学组成以及相互作用机理来阐述,为大环分子荧光探针的设计提供了系统的理论指导。     

应用光化学探针研究环氧丙烯酸酯的固化

光响应高聚物作为功能材料的组成部分已受到极大的关注。近年来利用光化学探针研究高聚物的结构、形态和分子运动不断有所报导。方法的特点是利用反应体系环境的变化引起探针分子光物理性质的响应,从而达到监测的目的。本文报导以N,N-二甲胺基苄叉丙二腈(DMABM)作探针分子研究酚醛环氧丙烯酸酯的光固化过程。     

激发态分子内质子转移型离子探针的研究进展

激发态分子内的质子转移(ESIPT),是特殊的激发态光物理过程,此过程中的一个重要特征就是给质子基团通常会发生互变异构现象,如烯醇在激发态时发生烯醇式向酮式的转变,导致这类化合物具有很大的斯托克斯位移(Stokes shift),是良好的荧光探针或光致变色材料。本文结合国内外最新研究工作,综述了基于ESIPT机理在阴、阳离子荧光探针的研究进展;并对ESIPT分子结构的特点、工作原理、存在的问题及其应用前景作了评述。     

现场光化学荧光探针法测定DNA──以9，10－蒽醌－2－磺酸钠为光化学荧光探针

现场光化学荧光探针法测定ＤＮＡ──以９，１０－蒽醌－２－磺酸钠为光化学荧光探针李文友，许金钩，郭祥群，朱庆枝，赵一兵（材料和生命过程分析科学开放研究实验室，厦门大学化学系，厦门，３６１００５）关键词ＤＮＡ，光化学荧光探针，９，１０－蒽醌－２－磺酸钠光...     

Molecular logic circuits and a security keypad lock based on a novel colorimetric azo receptor with dual detection ability for copper(II) and fluoride ions

A novel azoimine dye-based colorimetric chemosensor (1) has been designed and synthesised for dual recognition of copper(II) and fluoride ions in aqueous media. Significantly, the outstanding dual-ion recognition properties along with the excellent reversibility prompted us to consider 1 as an ideal candidate for fabrication of multiple logic circuits. According to the response profile of 1 towards Cu²⁺ and F^? inputs, we developed a unique tunable system integrated with one INHIBIT logic gate as well as one OR gate. Also, 1 behaved as a molecular keypad lock with sequential addition of Cu²⁺ and F^? inputs. In accession, a reversible ‘Write–Read–Erase–Read’ function with complementary ‘IMP/INH’ logic gate has been demonstrated through a feedback loop using F^? and trifluoroacetic acid as two chemical inputs. To the best of our knowledge, this is the first report where the symmetrical bis azo-azomethine dye has been exploited as a molecular keypad lock.     

基于C=N双键异构化传感机制的荧光探针

多种传感机制已经被用于荧光探针分子的设计中,其中,基于C=N双键异构化传感机制的荧光探针的研究近年来引起了较大关注。本文归纳总结了过去10年基于C=N双键异构化传感机制的阳离子、阴离子和中性分子探针的发展情况。文章最后对其应用前景及发展趋势进行了展望。     

Recent advances in molecular fluorescent probes for organic phosphate biomolecules recognition

This review provided a systematic overview of the recent researches on the small-molecule fluorescent probes for recognition various organic phosphate biomolecules (OPBs) including nucleotides, NAD(P)H, FAD/FMN and PS. The general strategies and the recognition mechanisms for these OPBs probe designs were described and emphasized to inspire the better design for fluorescent probes in the future.     

Recent advances in molecular fluorescent probes for organic phosphate biomolecules recognition

Organic phosphate biomolecules (OPBs) are indispensable components of eukaryotes and prokaryotes, such as acting as the fundamental components of cell membranes and important substrates for nucleic acids. They play pivotal roles in various biological processes, such as energy conservation, metabolism, and signal modulation. Due to the difficulty of detection caused by variety OPBs, investigation of their respective physiological effects in organisms has been restrained by the lack of efficient tools. Many small fluorescent probes have been employed for selective detection and monitoring of OPBs in vitro or in vivo due to the advantages of tailored properties, biodegradability and in situ high temporal and spatial resolution imaging. In this review, we summarize the recent advances in fluorescent probes for OPBs, such as nucleotides, NAD(P)H, FAD/FMN and PS. Importantly, we describe their identification mechanisms in detail and discuss the general strategies for these OPBs probe designs, which provide new insights and ideas for the future probe designs.     

Design and synthesis of squaraine based near infrared fluorescent probes

A novel class of dialkylanthracene containing squaraine dyes (Sq1-3) possessing intense absorption and emission in the NIR region has been synthesized. Structural and electronic features investigated using DFT methods suggest that the significant bathochromic shifts observed on replacing dialkylaniline by dialkylanthracene in this class of molecules can be attributed to a reduction in the HOMO-LUMO gap mainly due to enhanced hydrogen bonding between the carbonyl group of the cyclobutane ring and the neighboring aromatic hydrogen in the dyes containing the anthracene moiety. The absence of fluorescence in aqueous media and high fluorescence when encapsulated into hydrophobic domains make this class of dyes especially useful as probes for mapping such domains in biological systems.     

Fluorescent probes for detection of biothiols based on “aromatic nucleophilic substitution-rearrangement” mechanism

“Aromatic nucleophilic substitution-rearrangement (SNAr-rearrangement)” mechanism provided a powerful tool to design fluorescent probes for the discrimination between biothiols.     

Sustainable alternative in environmental monitoring using carbon nanoparticles as optical probes

Environmental monitoring is getting more important nowadays due to the greater stress faced by the natural environment in the era of urbanisation and industrialisation. To accomplish the task, rapid and reliable analytical probes are essentially needed to perform the monitoring at real time basis with high sensitivity and accuracy. In view of this, analytical probes developed using carbon nanoparticles are one of the latest alternatives that are proven with capability to detect various analytes of the environment. Carbon nanoparticles portray good fluorescence property that enables the integration onto optical sensing transducers. Further engineering via surface functionalization can be performed in the interest to improve the selectivity and sensitivity of the probes. There are several advantages of using carbon nanoparticles and the most significant benefit is the sustainability prospect as compared to other groups of fluorophores. Carbon nanoparticles can be synthesised with greener approach via simple pyrolysis or hydrolysis processes that involve minimum use of toxic or harmful starting precursors, besides able to tap on using renewable resources such as carbon rich agricultural wastes. The synthesis is often performed under mild condition and produces less or no side chemical products. Carbon nanoparticles by nature show low toxicity effect to the environment. This review focuses specifically of the sustainable significances, advantages and achievements in adopting carbon nanoparticles as an alternative for environmental monitoring.     

Synthesis and spectroscopic characterization of red-shifted spironaphthoxazine based optical switch probes

Spironaphthoxazine (NISO) is an efficient optical switch probe that has applications in high contrast detection of Förster resonance energy transfer (FRET) using optical lock-in detection (OLID). NISO exists in two distinct states, spiro (SP) and merocyanine (MC), that can be independently controlled by using alternate irradiation with near ultraviolet and visible light. Unfortunately, the SP-state of NISO has an absorption centered at 350 nm, which may lead to phototoxic effects when manipulating the probe within a living cell. To overcome this problem we introduce new, red-shifted amino-substituted NISO probes compared to NISO that undergo an efficient SP to MC transition in response to irradiation by using 405-nm light, which is less damaging to living cells. This study details the synthesis of amino-substituted NISO and their N-hydroxysuccinimide ester and maleimide derivatives and their use in generating covalent attached protein conjugates. This study also presents a characterization of the spectroscopic and optical switching properties of these red-shifted NISO probe in solution.     

Elongation of the molecular probe DDNP with phenylethynylidene or phenyldiazenylidene spacers

In this work, we report the synthesis, X-ray structures, and optical properties of two DDNP analogs containing an unsaturated spacer inserted between the donor N,N-dimethylamino group and the naphthalene ring. The new compounds have longer distances between the donor and acceptor groups and are intended to serve as molecular probes for the assessment of spatial and polarity requirements for binding to protein aggregates found in the central nervous system (CNS) of patients with neurodegenerative diseases.     

Synthesis of isoprenoid chain-contained chemical probes for an investigation of molecular interactions by using quartz crystal microbalance

Five probes including four that contained isoprenoid chain were synthesized. These probes were assembled onto the gold-coated quartz crystal chips for analysis of their interactions with four yeast proteins by using the quartz crystal microbalance technology. Results showed that 3-phosphoglycerate phosphokinase and triosephosphate isomerase had clear interactions with certain probes, while glutathione reductase and phosphoglucose isomerase gave much lower interaction signals. It also suggested that 3-phosphoglycerate phosphokinase had two sites interacting with the probe attached with a geranyl moiety. Further molecule simulation experiments provided supportive information on these intermolecular interactions. Together, our data suggested that there are hydrophobic interactions, with relatively good selectivity, between isoprenoid chain and proteins.