Jun Yin

Cyanine-Based Fluorescent Probe for Highly Selective Detection of Glutathione in Cell Cultures and Live Mouse Tissues

Glutathione (GSH) plays a crucial role in human pathologies. Near-infrared fluorescence-based sensors capable of detecting intracellular GSH in vivo would be useful tools to understand the mechanisms of diseases. In this work, two cyanine-based fluorescent probes, 1 and 2, containing sulfonamide groups were prepared. Evaluation of the fluorescence changes displayed by probe 1, which contains a 2,4-dinitrobenzenesulfonamide group, shows that it is cell-membrane-permeable and can selectively detect thiols such as GSH, cysteine (Cys), and homocysteine (Hcy) in living cells. The response of 1 to thiols can be reversed by treatment with N-methylmaleimide (NMM). Probe 2, which possesses a 5-(dimethylamino)naphthalenesulfonamide group, displays high selectivity for GSH over Cys and Hcy, and its response can be reversed using NMM. The potential biological utility of 2 was shown by its use in fluorescence imaging of GSH in living cells. Furthermore, probe 2 can determine changes in the intracellular levels of GSH modualated by H2O2. The properties of 2 enable its use in monitoring GSH in vivo in a mouse model. The results showed that intravenous injection of 2 into a mouse generates a dramatic image in which strong fluorescence is emitted from various tissues, including the liver, kidney, lung, and spleen. Importantly, 2 can be utilized to monitor the depletion of GSH in mouse tissue cells promoted by excessive administration of the painkiller acetaminophen. The combined results coming from this effort suggest that the new probe will serve as an efficient tool for detecting cellular GSH in animals.

Anion-activated, thermoreversible gelation system for the capture, release, and visual monitoring of CO2.

Carbon dioxide (CO2) is an important green house gas. This is providing an incentive to develop new strategies to detect and capture CO2. Achieving both functions within a single molecular system represents an unmet challenge in terms of molecular design and could translate into enhanced ease of use. Here, we report an anion-activated chemosensor system, NAP-chol 1, that permits dissolved CO2 to be detected in organic media via simple color changes or through ratiometric differences in fluorescence intensity. NAP-chol 1 also acts as a super gelator for DMSO. The resulting gel is transformed into a homogeneous solution upon exposure to fluoride anions. Bubbling with CO2 regenerates the gel. Subsequent flushing with N2 or heating serves to release the CO2 and reform the sol form. This series of transformations is reversible and can be followed by easy-to-discern color changes. Thus, NAP-chol 1 allows for the capture and release of CO2 gas while acting as a three mode sensing system. In particular, it permits CO2 to be detected through reversible sol-gel transitions, simple changes in color, or ratiometric monitoring of the differences in the fluorescence features.

One-photon and two-photon sensing of biothiols using a bis-pyrene-Cu(II) ensemble and its application to image GSH in the cells and tissues.

Glutathione (GSH), cysteine (Cys), and homocysteine (Hcy) are three major biothiols, which play key roles in various biological systems. Accordingly, the development of imaging probes has been actively studied. We report a new pyrene derivative 1, which showed large fluorescence quenching with Cu(2+) at pH 7.4. The ensemble 1-Cu(2+) was applied to detect biothiols. Among the various amino acids, GSH, Cys, and Hcy induced distinct turn-on fluorescence changes. The 1-Cu(2+) ensemble was further applied for GSH detection in living cells.

Visualization of Endogenous and Exogenous Hydrogen Peroxide Using A Lysosome-Targetable Fluorescent Probe

Reactive oxygen species (ROS) play crucial roles in diverse physiological processes; therefore, the efficient detection of ROS is very crucial. In this study, we report a boronate-based hydrogen peroxide (H2O2) probe having naphthalimide fluorophore. This probe also contained a morpholine moiety as a directing group for lysosome. The recognition property indicated that the probe exhibited high selectivity towards H2O2 not only in the solution but also in the living cells. Furthermore, it was used to monitor the level of endogenous and exogenous H2O2. These results support that the probe can function as an efficient indicator to detect H2O2.

Amide- and urea-functionalized dithienylethene: synthesis, photochromism, and binding with halide anions.

A versatile amide- and urea-functionalized dithienylethene has been successfully synthesized. Upon irradiation with UV or visible light, the compound showed excellent fatigue resistance. As a synthetic receptor, the dithienylethene displayed switchable affinities for Cl(-) and Br(-) anions when the UV/vis light was introduced. The switchable binding ability also had good reversibility.

Aggregation-induced emission-active gold(I) complexes with multi-stimuli luminescence switching

A series of diisocyano-based dinuclear gold(I) complexes have been synthesized, differing only in the bridge linking the two (identical) arms. All of these complexes have been thoroughly characterized by NMR and IR spectroscopy and elemental analysis. The gold(I) complexes 1a, 1b and 1c all exhibit aggregation-induced emission (AIE) characteristics and mechanochromic behavior; their phosphorescence properties show reversible switchable off–on green luminescence in response to grinding. We have investigated the origins of these phenomena by spectroscopy, phosphorescence quantum yields and X-ray powder diffraction. From the experimental data, we conclude that the changing of multiple intermolecular C–H⋯F, C⋯F, weak π–π interactions and the formation of aurophilic interactions are critical elements that determine the AIE-active and switchable mechanochromic luminescence.

Ammonium-bearing dinuclear copper(II) complex: a highly selective and sensitive colorimetric probe for pyrophosphate.

Two dinuclear copper complexes with and without ammonium moieties were synthesized. The complexes exhibited selective binding affinity to pyrophosphate in aqueous solution. The dinuclear copper complex, with ammonium arms, showed a ca. 527-fold enhancement in pyrophosphate binding affinity compared with its analogue without ammonium units.

Preparation of a cyanine-based fluorescent probe for highly selective detection of glutathione and its use in living cells and tissues of mice

Glutathione (GSH) is a major endogenous antioxidant that has a central role in cellular defense against toxins and free radicals. This protocol describes the preparation of CPDSA, a cyanine-based near-infrared (NIR) fluorescent probe for the detection of GSH in cells and in vivo. CPDSA is prepared with high yield through a simple two-step process. The first step is to react commercially available IR-780 iodide with excess anhydrous piperazine in anhydrous N,N-dimethyl formamide at 85 °C to form cyanine-piperazine (CP). The second step is the sulfonylation of CP with dansyl chloride in anhydrous dichloromethane. CPDSA selectively detects GSH in cells, and it has been shown to not react with other biothiols such as cysteine (Cys) and homocysteine (Hcy). This probe can also be used to monitor the GSH level of mouse bone marrow–derived neutrophils (BMDNs). The preparation of probe CPDSA takes 2 d, and experiments in cells and mice take 12–13 d.

Arynes in the synthesis of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons are of great interest as a result of their self-assembly properties and excellent charge-transfer abilities. They are therefore promising candidates for organic semiconducting devices. In order to develop better optoelectronic devices, chemists have made considerable effort to investigate synthetic methods for polycyclic aromatic hydrocarbons. Among many building blocks, arynes are a promising reactive intermediate for the construction of polycyclic aromatic hydrocarbons and so have been studied over many decades. In this review, we will summarize recent progress on the construction of polycyclic aromatic hydrocarbons using arynes as starting materials.

Experimental and Theoretical Studies of Charge Delocalization in Biruthenium–Alkynyl Complexes Bridged by Thiophenes

A series of binuclear ruthenium-alkynyl complexes that are bridged by thiophene groups (thiophene, bithiophene, and terthiophene) have been synthesized. All of these complexes have been well-characterized by NMR spectroscopy, X-ray diffraction, and elemental analysis. The electronic properties of these complexes have been examined by using cyclic voltammetry, UV/Vis/NIR and IR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT) calculations. Electrochemical results showed that the potential difference (ΔE) and comproportionation constant (Kc) decreased with increasing size of the thiophene bridging unit. The UV/Vis/NIR spectra and TDDFT calculations of the monocations indicated that the NIR transitions displayed aromatic bridging character. EPR studies of the mono-oxidized radical species further demonstrated that the unpaired electron/hole was delocalized over both metals and the bridging ligand and established significant participation in the ligand oxidation.