Li-Zhu Wu

BODIPY-Based Ratiometric Fluorescent Sensor for Highly Selective Detection of Glutathione over Cysteine and Homocysteine

We report a ratiometric fluorescent sensor based on monochlorinated BODIPY for highly selective detection of glutathione (GSH) over cysteine (Cys)/homocysteine (Hcy). The chlorine of the monochlorinated BODIPY can be rapidly replaced by thiolates of biothiols through thiol-halogen nucleophilic substitution. The amino groups of Cys/Hcy but not GSH further replace the thiolate to form amino-substituted BODIPY. The significantly different photophysical properties of sulfur- and amino-substituted BODIPY enable the discrimination of GSH over Cys and Hcy. The sensor was applied for detection of GSH in living cells.

Graphene‐Supported Ultrafine Metal Nanoparticles Encapsulated by Mesoporous Silica: Robust Catalysts for Oxidation and Reduction Reactions

Graphene nanosheet-supported ultrafine metal nanoparticles encapsulated by thin mesoporous SiO2 layers were prepared and used as robust catalysts with high catalytic activity and excellent high-temperature stability. The catalysts can be recycled and reused in many gas- and solution-phase reactions, and their high catalytic activity can be fully recovered by high-temperature regeneration, should they be deactivated by feedstock poisoning. In addition to the large surface area provided by the graphene support, the enhanced catalytic performance is also attributed to the mesoporous SiO2 layers, which not only stabilize the ultrafine metal nanoparticles, but also prevent the aggregation of the graphene nanosheets. The synthetic strategy can be extended to other metals, such as Pd and Ru, for preparing robust catalysts for various reactions.

Carbon quantum dots/TiO2 composites for efficient photocatalytic hydrogen evolution

Carbon quantum dots modified P25 TiO2 composites (CQDs/P25) with a “dyade”-like structure were prepared via a facile one-step hydrothermal reaction. CQDs/P25 exhibited improved photocatalytic H2 evolution under UV-Vis and visible light (λ > 450 nm) irradiation without loading any noble metal cocatalyst, compared to pure P25. A possible mechanism of the photocatalytic H2 production activity over CQDs/P25 was proposed based on detailed measurements of the transient photocurrent response, surface photovoltage and hydroxyl radicals. CQDs play dual roles on the improved photocatalytic activity of CQDs/P25. Under UV-Vis light irradiation CQDs act as an electron reservoir to improve the efficient separation of the photoinduced electron–hole pairs of P25. However, under visible light irradiation CQDs act as a photosensitizer to sensitize P25 into a visible light response “dyade” structure for H2 evolution.

Well‐Dispersed ZIF‐Derived Co,N‐Co‐doped Carbon Nanoframes through Mesoporous‐Silica‐Protected Calcination as Efficient Oxygen Reduction Electrocatalysts

A well-dispersed Co,N co-doped carbon nanoframework (Co,N-CNF) with hierarchically porous structure is successfully synthesized from zeolitic imidazolate framework (ZIF) precursors via a mesoporous-silica-protected calcination strategy. By preventing the irreversible fusion and aggregation during the high-temperature pyrolysis step with this protection strategy, the Co,N-CNF exhibits comparable oxygen reduction reaction (ORR) catalytic activity to that of commercial Pt catalysts with the same loading.

Nitrogen-Doped Porous Carbon Nanosheets Templated from g-C3N4 as Metal-Free Electrocatalysts for Efficient Oxygen Reduction Reaction

Nitrogen-doped porous carbon nanosheets (N-CNS) are synthesized by hydrothermal carbon coating of g-C3 N4 nanosheets followed by high-temperature treatment in N2 . g-C3 N4 serves as a template, nitrogen source, and porogen in the synthesis. This approach yields N-CNS with a high nitrogen content and comparable oxygen reduction reaction catalytic activities to commercial Pt/C catalysts in alkaline media.

Reactivity and Mechanistic Insight into Visible-Light-Induced Aerobic Cross-Dehydrogenative Coupling Reaction by Organophotocatalysts

With visible-light irradiation, a mild, simple, and efficient metal-free photocatalytic system for the facile construction of sp(3)-sp(3) C-C bonds between tertiary amines and activated C-H bonds has been achieved. Spectroscopic study and product analysis demonstrate for the first time that photoinduced electron transfer from N-aryl tetrahydroisoquinolines to eosin Y bis(tetrabutylammonium salt) (TBA-eosin Y) takes place to generate TBA-eosin Y radical anion, which can subsequently react with nucleophiles and molecular oxygen. More strikingly, electron spin resonance (ESR) measurements provide direct evidence for the formation of superoxide radical anions (O(2)(-.)) rather than singlet oxygen ((1)O(2)) during visible-light irradiation. This active species is therefore believed to be responsible for the large rate of acceleration of the aerobic photocatalytic reactions.

Alkali-Assisted Synthesis of Nitrogen Deficient Graphitic Carbon Nitride with Tunable Band Structures for Efficient Visible-Light-Driven Hydrogen Evolution

A facile synthetic strategy for nitrogen-deficient graphitic carbon nitride (g-C3 Nx ) is established, involving a simple alkali-assisted thermal polymerization of urea, melamine, or thiourea. In situ introduced nitrogen vacancies significantly redshift the absorption edge of g-C3 Nx , with the defect concentration depending on the alkali to nitrogen precursor ratio. The g-C3 Nx products show superior visible-light photocatalytic performance compared to pristine g-C3 N4 .

Dynamic Covalent Bond Based on Reversible Photo [4 + 4] Cycloaddition of Anthracene for Construction of Double-Dynamic Polymers

Dynamic covalent bonds supplied by reversible anthracene dimerization were combined with pillar[5]arene/imidazole host-guest interactions to construct double-dynamic polymers. Heating such polymers (in solution or as a gel) led to depolymerization by dissociation of either the host-guest complexes alone or the complexes and the anthracene dimers, depending on the extent of heating. The polymers reformed readily upon cooling or irradiation.

Smart Utilization of Carbon Dots in Semiconductor Photocatalysis

Efficient capture of solar energy will be critical to meeting the energy needs of the future. Semiconductor photocatalysis is expected to make an important contribution in this regard, delivering both energy carriers (especially H2 ) and valuable chemical feedstocks under direct sunlight. Over the past few years, carbon dots (CDs) have emerged as a promising new class of metal-free photocatalyst, displaying semiconductor-like photoelectric properties and showing excellent performance in a wide variety of photoelectrochemical and photocatalytic applications owing to their ease of synthesis, unique structure, adjustable composition, ease of surface functionalization, outstanding electron-transfer efficiency and tunable light-harvesting range (from deep UV to the near-infrared). Here, recent advances in the rational design of CDs-based photocatalysts are highlighted and their applications in photocatalytic environmental remediation, water splitting into hydrogen, CO2 reduction, and organic synthesis are discussed.

A turn-on fluorescent sensor for the discrimination of cystein from homocystein and glutathione

We report a turn-on fluorescent sensor based on nitrothiophenolate boron dipyrromethene (BODIPY) derivatives for the discrimination of cystein (Cys) from homocystein (Hcy) and glutathione (GSH). The sensor was applied for detection of Cys in living cells.