Precise Proton Mapping near Ionic Micellar Membranes with Fluorescent Photoinduced-Electron-Transfer Sensors

One of the challenges for fluorescent sensors is to reduce their target environment size from a micrometer scale, such as biological cells, to a nanometer scale. Proton maps near membranes are of importance in bioenergetics and are the first goal in nanometer-scale analysis with fluorescent sensors. Thirty-three fluorescent photoinduced-electron-transfer pH sensors bearing an environment-sensitive benzofurazan fluorophore and having different hydrophobicity/hydrophilicity and hydrogen-bonding abilities were prepared. These sensors were scattered in nanospaces associated with anionic and cationic micelles as model membranes to indicate proton availability and polarity in local spaces. Gathering the data from the sensors allowed the successful drawing of proton maps near anionic and cationic micelles, in which electrostatic attraction/repulsion of protons by the charged head groups of micelles and dielectric suppression of protons were clearly observed.     

A unique approach to development of near-infrared fluorescent sensors for in vivo imaging

Near-infrared (NIR) fluorescent sensors have emerged as promising molecular tools for imaging biomolecules in living systems. However, NIR fluorescent sensors are very challenging to be developed. Herein, we describe the discovery of a new class of NIR fluorescent dyes represented by 1a/1c/1e, which are superior to the traditional 7-hydroxycoumarin and fluorescein with both absorption and emission in the NIR region while retaining an optically tunable hydroxyl group. Quantum chemical calculations with the B3LYP exchange functional employing 6-31G(d) basis sets provide insights into the optical property distinctions between 1a/1c/1e and their alkoxy derivatives. The unique optical properties of the new type of fluorescent dyes can be exploited as a useful strategy for development of NIR fluorescent sensors. Employing this strategy, two different types of NIR fluorescent sensors, NIR-H(2)O(2) and NIR-thiol, for H(2)O(2) and thiols, respectively, were constructed. These novel sensors respond to H(2)O(2) or thiols with a large turn-on NIR fluorescence signal upon excitation in the NIR region. Furthermore, NIR-H(2)O(2) and NIR-thiol are capable of imaging endogenously produced H(2)O(2) and thiols, respectively, not only in living cells but also in living mice, demonstrating the value of the new NIR fluorescent sensor design strategy. The new type of NIR dyes presented herein may open up new opportunities for the development of NIR fluorescent sensors based on the hydroxyl functionalized reactive sites for biological imaging applications in living animals.     

Design of fluorescent materials for chemical sensing

There is an enormous demand for chemical sensors for many areas and disciplines. High sensitivity and ease of operation are two main issues for sensor development. Fluorescence techniques can easily fulfill these requirements and therefore fluorescent-based sensors appear as one of the most promising candidates for chemical sensing. However, the development of sensors is not trivial; material science, molecular recognition and device implementation are some of the aspects that play a role in the design of sensors. The development of fluorescent sensing materials is increasingly captivating the attention of the scientists because its implementation as a truly sensory system is straightforward. This critical review shows the use of polymers, sol-gels, mesoporous materials, surfactant aggregates, quantum dots, and glass or gold surfaces, combined with different chemical approaches for the development of fluorescent sensing materials. Representative examples have been selected and they are commented here.     

New 3-hydroxyflavone derivatives for probing hydrophobic sites in microheterogeneous systems

Nine new 3-hydroxyflavone derivatives as fluorescent molecular sensors having two well-separated emission bands were synthesized. These sensors can occupy well-determined locations and orientations in macromolecular ensembles, such as micelles due to their finely-tuned designs. These polarity-sensitive dyes can incorporate into the anhydrous hydrophobic core of aqueous micelles.     

手性荧光传感器的研究进展

随着手性化合物在制药、不对称合成、生物科学及临床医学等领域应用的增长,迫切需要发展一种快速、灵敏的对映异构体检测技术。手性荧光传感器引起了人们的高度关注。近年来,发展了很多手性荧光传感器并对手性化合物表现出较高的选择性和灵敏度。该文综述了以1,1'-联-2-萘酚衍生物、杯芳烃衍生物、高分子聚合物、纳米材料、金属有机多孔材料为骨架的手性荧光传感器,总结了其在手性化合物识别中的应用,并展望了手性荧光传感器的发展方向。     

A general approach for rational design of fluorescent DNA aptazyme sensors based on target-induced unfolding of DNA hairpins

DNA aptazymes are allosteric DNAzymes activated by the targets of DNA aptamers. They take the advantages of both aptamers and DNAzymes, which can recognize specific targets with high selectivity and catalyze multiple-turnover reactions for signal amplification, respectively, and have shown their great promise in many analytical applications. So far, however, the available examples of DNA aptazyme sensors are still limited in utilizing only several DNAzymes and DNA aptamers, most likely due to the lack of a general and simple approach for rational design. Herein, we have developed such a general approach for designing fluorescent DNA aptazyme sensors. In this approach, aptamers and DNAzymes are connected at the ends to avoid any change in their original sequences, therefore enabling the general use of different aptamers and DNAzymes in the design. Upon activation of the aptazymes by the targets of interest, the rate of fluorescence enhancement via the cleavage of a dually labeled substrate by the active aptazymes is then monitored for target quantification. Two DNAzymes and two aptamers are used as examples for the design of three fluorescent aptazyme sensors, and they all show high selectivity and sensitivity for the detection of their targets. More DNA aptazyme sensors for a broader range of targets could be developed by this general approach as long as suitable DNAzymes and aptamers are used.     

Simultaneous In Situ Quantification of Two Cellular Lipid Pools Using Orthogonal Fluorescent Sensors

Lipids regulate a wide range of biological activities. Since their local concentrations are tightly controlled in a spatiotemporally specific manner, the simultaneous quantification of multiple lipids is essential for elucidation of the complex mechanisms of biological regulation. Here, we report a new method for the simultaneous in situ quantification of two lipid pools in mammalian cells using orthogonal fluorescent sensors. The sensors were prepared by incorporating two environmentally sensitive fluorophores with minimal spectral overlap separately into engineered lipid‐binding proteins. Dual ratiometric analysis of imaging data allowed accurate, spatiotemporally resolved quantification of two different lipids on the same leaflet of the plasma membrane or a single lipid on two opposite leaflets of the plasma membrane of live mammalian cells. This new imaging technology should serve as a powerful tool for systems‐level investigation of lipid‐mediated cell signaling and regulation.     

硼-二吡咯亚甲基染料类分子荧光传感器

分子荧光传感器以其灵敏度高、使用方便等优点备受人们的关注，近年来得到了迅速的发展。本文介绍了分子荧光传感器的构成、分类、传感机制以及设计原理,重点介绍了基于硼-二吡咯亚甲基(BDP)染料类分子荧光传感器的制备、识别机理和应用展望。     

Building fluorescent sensors by template polymerization: the preparation of a fluorescent sensor for D-fructose

[formula: see text] The application of molecular imprinting in making fluorescent sensors has been hampered by the lack of suitable fluorescent tags, which would respond to the binding event with significant fluorescence intensity changes. We have designed and synthesized a fluorescent monomer which allows for the preparation of fluorescent sensors of cis diols using molecular imprinting methods. This monomer was used for the preparation of sensitive fluorescent sensors for D-fructose.     

香豆素类荧光传感器

荧光传感器能够将分子识别的信息转换成荧光信号,荧光法在灵敏度、选择性和实时原位检测等方面优势突出。实时检测被分析物的水平已引起包括化学家、生物学家、临床生物化学家和环境学家的极大兴趣。以香豆素为基础的荧光传感器近年来已成为一个新兴的研究热点。本文综述了香豆素类荧光传感器在阳离子、阴离子、中性分子识别检测中的分子设计、作用机理和应用效果,展望了该领域的发展方向。     

Recent advances and applications in QDs-based sensors

As a unique nanomaterial, quantum dots (QDs) are not only applied in fluorescent labeling and biological imaging, but are also utilized in novel sensing systems. Because QDs have attractive optoelectronic characteristics, QD-based sensors present high sensitivity in detecting specific analytes in the chemical and biochemical fields. In this review, we describe the basic principles and different conjugation strategies in QD-based sensors. An overview of recent advances and various models of QD-sensing systems is also provided. Furthermore, perspectives for sensors based on QDs are discussed.     

Development of Enantioselective Fluorescent Sensors for Chiral Recognition

Novel chiral compounds have been synthesized for the enantioselective fluorescent recognition of alpha-hydroxycarboxylic acids and amino acids. By introducing dendritic branches to the chiral receptor units, the fluorescence signals of the receptors are significantly amplified because of the light-harvesting effect of the dendritic structure. This has greatly increased the sensitivity of the sensors in the fluorescent recognition. Highly enantioselective fluorescent responses have also been ac…     

Targetable fluorescent sensors for advanced cell function analysis

Chemistry-based bioimaging techniques have contributed to the elucidation of intracellular physiological events. During the last few decades, many fluorescent sensors have been developed and used in live cell experiments. Owing to immense efforts by numerous research groups, several strategies have been developed to design fluorescent sensors based on various components such as small molecules and fluorescent proteins. Recently, site-specific targeting of fluorescent sensors has attracted increasing attention. Strategies for fluorescent sensor targeting were surveyed in this review with the aims to expand current knowledge on chemistry-based bioimaging and aid in the emergence of related innovative technologies. The first discussed strategy is based on the intrinsic properties of small molecules for localization at specific organelles, such as mitochondria, nuclei, and lysosomes. As a further elaboration of the topic, our recent study about in vivo targeting of pH sensors was briefly introduced. The second strategy exploits genetically encoded tags and their specific ligands. Here, fluorescent sensors with commercially available tags and corresponding ligands were mainly reviewed. As the final topic, our original protein labeling technique, which enables fluorogenic labeling as an advanced technology, was introduced.     

Tuning saccharide selectivity in modular fluorescent sensors

Five modular photoinduced electron-transfer (PET) sensors bearing two phenylboronic acid receptors with different fluorophores have been prepared. The sensors’ interaction with saccharides was assessed via fluorescence spectroscopy. It was shown that monosaccharide selectivity is influenced by the choice of fluorescent moiety.     

Fluorescent properties of coumarins with dual functions constructed by two sequential reactions

A series of coumarins with two aryl moieties was constructed from 3-azide-6-bromocoumarin scaffold by means of two sequential reactions, Huisgen 1,3-cycloaddition and Suzuki-Miyaura coupling reactions. Evaluation of their fluorescence properties indicated that the mode of fluorescent change by substituted group on each aryl group would be different. So this structure could be promising candidates as multi-analyte type fluorescent sensors, whose mode of spectroscopic changes, such as fluorescence intensity, and absorption or fluorescence maximum wavelength, are different for each analyte.     

喹啉衍生物锌离子荧光传感器*

本文综述了近年来用于锌离子检测的喹啉衍生物荧光传感器的研究进展,介绍了基于喹啉、8-羟基喹啉和8-氨基喹啉合成的锌离子荧光传感器的结构和设计原理,概述了锌离子对喹啉衍生物荧光传感器光学性能的影响,分析了喹啉衍生物锌离子荧光传感器在检测过程中的优点及其实际应用价值,并展望了这类锌离子荧光传感器的研究和发展方向。     

TPE based aggregation induced emission fluorescent sensors for viscosity of liquid and mechanical properties of hydrogel

Two amphiphilic TPE E/Z isomers with aggregation induced emission(AIE) property have been synthesized and characterized. The logarithmic fluorescent intensity of the two molecules was in positive relationship with logarithmic viscosity of liquid. To note, the Z-TPE isomer exhibited more sensitivity in the viscosity of liquid sensing in comparison with the corresponding E-TPE counterpart(around 1.80 folds).Furthermore, two molecules could be used as fluorescent sensors for mechanical properties(v...     

Fluorescent detection of anions by dibenzophenazine-based sensors

Binding studies of two sulfonamide-functionalized dibenzophenazine-based sensors are reported. Spectroscopic studies showed that both sensors are effective fluorescent turn-on sensors for several anions. Both sensors showed responses to acetate, benzoate, cyanide, and fluoride ions. NMR titrations confirmed the mode of binding of the sensors to be through H-bonding to the sulfonamide groups.     

Squaraine dyes: The hierarchical synthesis and its application in optical detection

Squaraine dyes, a four-membered ring system with structural rigidity, possess unique photoelectrical properties and are marked by their exceptionally sharp and intense absorption associated with a strong fluorescent emission in solution. These favorable characteristics have prompted their exploitation in a number of state of the art applications including photoconductivity, data storage, light-emitting field-effect transistors, solar cells and fluorescent histological probes. In this review, we first summarize the recently proposed novel methods in the synthesis of these versatile derivatives. Subsequently, their extensive applications in the prevalent optical detection of the surrounding medium such as ions, pH, thiol-based compounds, biomolecules and cell over the past decades are covered and discussed. In addition, different categories for the synthesis and sensing mechanisms for various squaric acid-based chemo-/bio- sensors are illustrated. Finally, the challenges and opportunities in the synthesis and application of these derivatives are also briefly discussed.     

Mechanistic studies of fluorescent sensors for the detection of reactive oxygen species

Two new sensors for the detection of reactive oxygen species have been synthesized and characterized; they contain the 4-amino-7-nitrobenzofurazan (ABF) moiety covalently tethered to a phenol. Comparison of sensors ABFhd and dABFhd (the latter containing two ortho-methyl groups) shows that introduction of steric bulk leads to an improvement of fluorescent sensor performance, thus confirming our previous predictions based on computational chemistry. ABFhd and dABFhd are new tools for biological applications involving reactive oxygen species, in particular oxygen-centered radicals.