Natural Sunlight Photocatalytic Synthesis of Benzoxazole-Bridged Covalent Organic Framework for Photocatalysis.

Although natural sunlight-mediated photocatalysis is a clean, efficient, and green approach to access organic products, its application in the synthesis of covalent organic frameworks (COFs), however, is still unprecedented. Herein, we first report the sunlight photocatalytic synthesis of COF under ambient conditions. Furthermore, this "window ledge" reaction generated benzoxazole-linked COF is stable and can be applied as a reusable photocatalyst to highly promote visible-light-driven aerobic oxidation of sulfides to sulfoxides. These results not only enrich the COF synthetic methodology but also open a new route to access COFs in a green and sustainable way.

Exploiting the Twisted Intramolecular Charge Transfer Effect to Construct a Wash-Free Solvatochromic Fluorescent Lipid Droplet Probe for Fatty Liver Disease Diagnosis.

The prominent pathological feature of fatty liver disease lesions is excessive fat accumulation in lipid droplets in hepatocytes. Thus, developing fluorescent lipid droplet-specific probes with high permeability and a high imaging contrast provides a robust tool for diagnosing fatty liver diseases. Herein, we rationally developed a novel donor-acceptor lipophilic fluorescent probe ANI with high photostability for wash-free visualization of lipid droplets and fatty liver disease characteristics. ANI showed a typical twisted intramolecular charge transfer effect with very faint fluorescence in high-polar solvents, but dramatically boosted emissions in low-polar environments. The solvatochromic probe can selectively light up lipid droplets with a high contrast in a wash-free manner. Further use of ANI to reveal the excessive accumulation of lipid droplets with a significantly large size in the liver tissues from the fatty liver disease model mice was successfully demonstrated. The remarkable imaging performances rendered ANI an alternative tool for accurately evaluating fatty liver disease in intraoperative diagnosis.

Tandem [2 + 2] Cycloaddition/Rearrangement toward Carbazoles by Visible-Light Photocatalysis.

Reported herein is the first example of the synthesis of carbazoles via oxidative cyclization of 3-alkenylindoles with styrenes under visible light. The irradiation of a catalytic amount of [Ir(dtbbpy)(ppy)2][PF6] as the photocatalyst enables various 3-alkenylindoles and styrenes to undergo tandem [2 + 2] cycloaddition/rearrangement, thereby leading to carbazole derivatives in good to excellent yields under aerobic conditions. Mechanistic studies reveal that photoinduced energy transfer followed by electron transfer is responsible for the tandem reaction.

Fluorescent AIE-Active Materials for Two-Photon Bioimaging Applications.

Fluorescence imaging has been widely used as a powerful tool for in situ and real-time visualization of important analytes and biological events in live samples with remarkably high selectivity, sensitivity, and spatial resolution. Compared with one-photon fluorescence imaging, two-photon fluorescence imaging exhibits predominant advantages of minimal photodamage to samples, deep tissue penetration, and outstanding resolution. Recently, the aggregation-induced emission (AIE) materials have become a preferred choice in two-photon fluorescence biological imaging because of its unique bright fluorescence in solid and aggregate states and strong resistance to photobleaching. In this review, we will exclusively summarize the applications of AIE-active materials in two-photon fluorescence imaging with some representative examples from four aspects: fluorescence detection, in vitro cell imaging, ex vivo tissue imaging, and in vivo vascular imaging. In addition, the current challenges and future development directions of AIE-active materials for two-photon bioimaging are briefly discussed.

Synthesis of fulvene-containing boron complexes with aggregation-induced emission and mechanochromic luminescence.

Two donor-acceptor motif fulvene-containing boron complexes were synthesized with fulvene diketonate boron difluoride (FDB) as the organic acceptor. Both difluoroboron complexes present aggregation-induced emission (AIE) properties and cell tracing function with excellent biocompatibility. And mechanochromic luminescence has been accomplished by the synthesis, isolation and characterization of BL2.

A sustainable synthesis of 2-aryl-3-carboxylate indolines from N-aryl enamines under visible light irradiation.

With visible light irradiation of a catalytic amount of Ir(ppy)3 at room temperature, a number of N-aryl enamines were transformed into their corresponding indoline products in good to excellent yields without requiring any extra additives. This is the first example of the synthesis of indolines via the intramolecular cyclization of enamines under visible light irradiation.

Visible Light Promoted Synthesis of Indoles by Single Photosensitizer under Aerobic Conditions.

The construction of substituted indole skeletons is always an important concern of synthetic chemists because of its prevalent structure found in natural products and biological molecules. Here, we succeeded in preparing indoles and their derivatives from a wide variety of simple enamines via radical cyclization only with catalytic amounts of an iridium(III) photosensitizer (PS) in DMSO solution under air atmosphere. The mechanistic investigation suggests that the reaction involves a radical course to accomplish the conversion of enamines to indoles under visible light irradiation.

Detection of Pb2+ in Aqueous Solution by Using a DNA-modified Microcantilever.

We developed a novel Pb2+-sensor based on a microcantilever that was modified with a specific Pb2+-dependent DNAzyme molecule. This microcantilever sensor could detect Pb2+ sensitively and selectively in an aqueous solution. Upon complexation with Pb2+, the DNAzyme duplex unwinded and formed a G-quadruplex conformation, which led to an increase of repulsion between the DNAzyme molecules and a subsequent bending of the microcantilever. This microcantilever sensor could be regenerated, flowing through a strong Pb2+ chelator, 1,4,7,10-tetraazacyclododecane- 1,4,7,10-tetraacetic acid. The detection limit of the microcantilever sensor for Pb2+ ions is as low as 10-8 M. The microcantilever sensor also exhibited a high selectivity to Pb2+ over other metal ions such as Mg2+, Fe3+, Zn2+, Ca2+, and Cd2+.

Combining visible light catalysis and transfer hydrogenation for in situ efficient and selective semihydrogenation of alkynes under ambient conditions.

By combining visible light catalysis and transfer hydrogenation, we are able to convert a series of alkynes to their corresponding alkenes in high chemical yields. Then the visible light catalytic transfer hydrogenation reaction can couple photoisomerization to produce E-alkenes or Z-alkenes exclusively depending on the aryl or alkyl substituted alkynes.

Cobalt-catalyzed cross-dehydrogenative coupling reaction in water by visible light.

By using catalytic amount of CoCl2 with dmgH (dimethylglyoxime) as ligand to form a photosensitizer in situ, a highly selective, efficient, and environmentally benign visible light mediated cross-dehydrogenative coupling (CDC) reaction has been developed in aqueous medium. The desired cross-coupling C-C bonds that involve Csp3 with Csp, Csp2, and Csp3, respectively, were achieved exclusively in high yields without formation of any other byproduct.

A unique 1,2-acyl migration for the construction of quaternary carbon by visible light irradiation of platinum(II) polypyridyl complex and molecular oxygen.

A unique 1,2-acyl migration for the construction of quaternary carbon in a one-pot reaction under visible light is described. By irradiating a platinum(II) polypyridyl complex with visible light, enamine 1 is able to react with alcohol 2 to yield compound 3 featuring a quaternary carbon via 1,2-acyl migration and concurrent esterification. Studies on the mechanism reveal that the platinum(II) complex is able to generate singlet oxygen ((1)O2) that is responsible for this unprecedented intramolecular 1,2-acyl migration transformation.

Cross-coupling hydrogen evolution reaction in homogeneous solution without noble metals.

A highly efficient noble-metal-free homogeneous system for a cross-coupling hydrogen evolution (CCHE) reaction is developed. With cheap, earth-abundant eosin Y and molecular catalyst Co(dmgH)2Cl2, good to excellent yields for coupling reactions with a variety of isoquinolines and indole substrates and H2 have been achieved without any sacrificial oxidants. Mechanistic insights provide rich information on the effective, clean, and economic CCHE reaction.

Highly sensitive and selective fluoride ion sensors based on microcantilevers modified with hydrogels.

We have developed two microcantilever sensors, one modified with chitosan/gelatin hydrogels doped with CH3(OCH2CH2)3OTBDPS and another modified with chitosan-OTBDPS/gelatin hydrogels, for the sensitive and selective detection of fluoride ions (F-) in aqueous solution. Upon exposure to F-, the microcantilevers underwent bending deflection due to the cleavage of Si-O bond on reacting with F- in the hydrogel. The results show that the maximum bending deflections are proportional to the concentrations of F-, and the limits of detection are 10(-8) M and 10(-9) M for the two microcantilevers, respectively. Other ions, such as Cl-, Br-, NO3-, H2PO4-, HSO4-, and AcO- have little effect on the deflection of the microcantilevers. The results show that the microcantilever may be used for in situ quantitative detection of F- in an aqueous solution and the mechanism of the bending are discussed.