Iron(III)‐Selective Chelation‐Enhanced Fluorescence Sensing for In Vivo Imaging Applications

A “turn‐on” pattern Fe³⁺‐selective fluorescent sensor was synthesized and characterized that showed high fluorescence discrimination of Fe³⁺ over Fe²⁺ and other tested ions. With a 62‐fold fluorescence enhancement towards Fe³⁺, the probe was employed to detect Fe³⁺ in vivo in HeLa cells and Caenorhabditis elegans, and it was also successfully used to elucidate Fe³⁺ enrichment and exchange infected by innexin3 (Inx3) in hemichannel‐closed Sf9 cells.     

Pt nanohelices with highly ordered horizontal pore channels as enhanced photothermal materials

Recent studies have further demonstrated that the conjugation of noble metal helical nanostructures could alter their optical and catalytic activities. However, the intrinsic isotropic crystal growth of Pt makes the synthesis of high-quality Pt NCs with unique porous or branched nanostructures difficult. In this work, a new, powerful capping agent, N,N-dimethyloctadecylammonium bromide acetate sodium, was synthesized and used to coordinate Pt ions, slowing down the reaction rate. As a result, in aqueous solution, Pt nanohelices with highly ordered horizontal pore channels were successfully fabricated. Importantly, the Pt nanohelices were composed of several sub-2 nm Pt nanowires coiled together around a central point. The as-obtained samples exhibited enhanced photothermal properties compared with the classic Pt nanoparticles.     

Monodispersed AuPd nanoalloy: composition control synthesis and catalytic properties in the oxidative dehydrogenative coupling of aniline

A series of AuPd@C nanoalloy catalysts with tunable compositions were successfully prepared by a co-reduction method. The use of borane-tert-butylamine complex as reductant and oleylamine as both solvent and reductant was very effective for the preparation of the monodispersed nanoalloy. We evaluated the catalytic activity of these AuPd@C nanoalloys for oxidative dehydrogenative coupling of aniline, which showed better catalytic activity than equal amounts of sole Au@C or Pd@C catalyst. The Au₁Pd₃@C catalyst exhibited the best performance, indicating that the conversion and selectivity were improved along with the increase of Pd composition. However if the Pd composition was too high in the AuPd alloy, Au₁Pd₇@C achieved only 81% conversion in this reaction.     

Highly stable and reusable imprinted artificial antibody used for in situ detection and disinfection of pathogens

Sandwich ELISA methods have been widely used for biomarker and pathogen detection because of their high specificity and sensitivity. However, the main drawbacks of this assay are the cost, the time-consuming procedure for the isolation of antibodies and their poor stability. To overcome these restrictions, we herein fabricated artificial antibodies based on imprinting technology and developed a sandwich ELISA for pathogen detection. Both the capture and detection antibodies were obtained via an in situ method, with simplicity, rapidity and low cost. The peroxidase mimics, the CeO₂ nanoparticles, as signal generators were integrated with the detection antibody. The fabricated artificial antibodies exhibited not only natural antibody-like binding affinities and selectivities, but also superior stability and reusability. The detection limit was about 500 CFU mL^–1, which is much lower than that of traditional ELISA methods (10⁴ to 10⁵ CFU mL^–1). Furthermore, the capture antibody can disinfect pathogens in situ.     

Synthesis of open-mouthed,yolk–shell Au@AgPd nanoparticles with access to interior surfaces for enhanced electrocatalysis

We have successfully produced open-mouthed, yolk–shell (OM-YS) Au@AgPd nanoparticles (NPs) via galvanic replacement reaction at room temperature; each NP has a large opening on its AgPd shells. Owing to the openings on the AgPd shells, the inner surfaces of the AgPd shells of as-prepared OM-YS Au@AgPd NPs become accessible to the surrounding media. These new structural characters make the present OM-YS Au@AgPd NPs excellent catalysts for electrochemical oxidation of ethanol in alkaline media. Their electrochemical active surface area is 87.8 m² g^–1 and the mass activity is 1.25 A mg_Pd^–1. Moreover, the openings on the AgPd shells also make the surfaces of the Au cores in OM-YS Au@AgPd NPs accessible to the reaction media, which significantly facilitates the removal of CO and other carbonaceous intermediate species, thus leading to substantially enhanced durability and stability. This superior electrocatalytic performance cannot be implemented by using conventional YS Au@AgPd NPs or commercially available Pd/C catalysts.     

Unstrained C–C bond activation and directed fluorination through photocatalytically-generated radical cations

Expanding the repertoire of controlled radical fluorination techniques, we present a photosensitized unstrained C–C bond activation/directed monofluorination method using Selectfluor and 9-fluorenone. The reaction is amenable to the opening of multiple 1-acetal-2-aryl substituted rings to yield ω-fluoro carboxylic acids, esters, alcohols, and ketones with relative ease. Initial mechanistic insight suggests radical ion intermediates.     

Cytotoxicity of guanine-based degradation products contributes to the antiproliferative activity of guanine-rich oligonucleotides

Guanine-rich oligonucleotides (GROs) have attracted considerable attention as anticancer agents, because they exhibit cancer-selective antiproliferative activity and can form G-quadruplex structures with higher nuclease resistance and cellular uptake. Recently, a GRO, AS1411 has reached phase II clinical trials for acute myeloid leukemia and renal cell carcinoma. The antiproliferative activity of GROs has been associated with various protein targets; however the real mechanisms of action remain unclear. In this study, we showed evidence that antiproliferative activity of GROs (including AS1411) is mainly contributed by the cytotoxicity of their guanine-based degradation products, such as monophosphate deoxyguanosine (dGMP), deoxyguanosine (dG) and guanine. The GROs with lower nuclease resistance exhibited higher antiproliferative activity. Among nucleotides, nucleosides and nucleobases, only guanine-based compounds showed highly concentration-dependent cytotoxicity. Our results suggest that it is necessary to reconsider the cancer-selective antiproliferative activity of GROs. Since guanine-based compounds are endogenous substances in living organisms, systematic studies of the cytotoxicity of these compounds will provide new information for the understanding of certain diseases and offer useful information for drug design.     

Insights into the structure–photoreactivity relationships in well-defined perovskite ferroelectric KNbO3 nanowires

Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this study, the geometric and electronic structure of perovskite ferroelectric KNbO₃ nanowires with respective orthorhombic and monoclinic polymorphs have been systematically addressed. By virtue of aberration-corrected scanning transmission electron microscopy, we directly visualize surface photocatalytic active sites, measure local atomic displacements at an accuracy of several picometers, and quantify ferroelectric polarization combined with first-principles calculations. The photoreactivity of the as-prepared KNbO₃ nanowires is assessed toward aqueous rhodamine B degradation under UV light. A synergy between the ferroelectric polarization and electronic structure in photoreactivity enhancement is uncovered, which accounts for the prominent reactivity order: orthorhombic > monoclinic. Additionally, by identifying new photocatalytic products, rhodamine B degradation pathways involving N-deethylation and conjugated structure cleavage are proposed. Our findings not only provide new insights into the structure–photoreactivity relationships in perovskite ferroelectric photocatalysts, but also have broad implications in perovskite-based water splitting and photovoltaics, among others.