Enantioselective Glutamic Acid Discrimination and Nanobiological Imaging by Chiral Fluorescent Silicon Nanoparticles.

Enantioselective discrimination of chiral molecules is essential in chemistry, biology, and medical science due to the configuration-dependent activities of enantiomers. Therefore, identifying a specific amino acid and distinguishing it from its enantiomer by using nanomaterials with outstanding performance are of great significance. Herein, blue- and green-emitting chiral silicon nanoparticles named bSiNPs and gSiNPs, respectively, with excellent water solubility, salt resistance, pH stability, photobleaching resistance, biocompatibility, and ability to promote soybean germination, were fabricated in a facile one-step method. Especially, chiral gSiNPs presented excellent fluorescence recognition ability for glutamic acid enantiomers within 1 min, and the enantiomeric recognition difference factor was as high as 9.0. The mechanism for enantiomeric fluorescence recognition was systematically explored by combining the fluorescence spectra with density functional theory (DFT) calculation. Presumably, the different Gibbs free energy and hydrogen-bonding interaction of the chiral recognition module with glutamic acid enantiomers mainly contributed to the difference in the fluorescence signals. Most noteworthy was the fact that the chiral gSiNPs can showcase not only the ability to recognize l- and d-glutamic acids in living cells but also the test strips fabricated by soaking gSiNPs can be applied for d-glutamic acid visual detection. As a result, this study provided insights into the design of multifunctional chiral sensing nanoplatforms for enantiomeric detection and other applications.

Crystalline Dual-Porous Covalent Triazine Frameworks as a New Platform for Efficient Electrocatalysis.

Crystalline covalent triazine frameworks (CTFs) have gained considerable interest in energy and catalysis owing to their well-defined nitrogen-rich π-conjugated porosity and superior physicochemical properties, however, suffer from very limited molecular structures. Herein we report a novel solvent-free FeCl3 -catalyzed polymerization of 2, 6-pyridinedicarbonitrile (DCP) to achieve the first synthesis of crystalline, dual-porous, pyridine-based CTF (Fe-CTF). The FeCl3 could not only act as a highly active Lewis acid catalyst for promoting the two-dimensional ordered polymerization of DCP monomers, but also in situ coordinate with the tridentate chelators generated between pyridine and triazine groups to yield unique Fe-N3 single-atom active sites in Fe-CTF. Abundant few-layer crystalline nanosheets (Fe-CTF NSs) could be prepared through simple ball-milling exfoliation of the bulk layered Fe-CTF and exhibited remarkable electrocatalytic performance for oxygen reduction reaction (ORR) with a half-wave potential and onset potential up to 0.902 and 1.02 V respectively, and extraordinary Zn-air battery performance with an ultrahigh specific capacity and power density of 811 mAh g-1 and 230 mW cm-2 respectively. By combining operando X-ray absorption spectroscopy with density functional theory calculations, we revealed a dynamic and reversible evolution of Fe-N3 to Fe-N2 during the electrocatalytic process, which could further accelerate the electrocatalytic reaction.

Dual-Function Precious-Metal-Free Metal-Organic Framework for Photocatalytic Conversion and Chemical Fixation of Carbon Dioxide.

Highly efficient transformation of carbon dioxide (CO2) into value-added chemicals is considered a promising route for clean production and future energy sustainability, which is crucial for realizing a carbon-neutral economy. It remains a great challenge to develop highly stable and active catalysts with low-cost, environmentally friendly, and nontoxic materials for catalytic conversion of CO2. Herein, a precious-metal-free and heterogeneous MOF (LTG-FeZr) catalyst, composed of bis(terpyridine)iron(II) complexes and zirconium(IV) ions, was designed and prepared via a metalloligand approach. LTG-FeZr, with a robust framework and regular 1D channels not only can achieve the photocatalytic reduction of CO2 to HCOOH with a high conversion rate (up to 265 µmol·g-1·h-1) under visible-light irradiation but also exhibits exceptional catalytic activities toward the synthesis of cyclic carbonates via cycloaddition reactions of various epoxides and CO2 in the absence of light. Possible mechanisms for two different conversion processes of CO2 catalyzed by LTG-FeZr have been proposed. LTG-FeZr represents an ideal dual-function MOF platform for the catalytic conversion and utilization of CO2 in all weather conditions.

A novel Gd3+ DTPA-bisamide complex with high relaxivity as an MRI contrast agent.

A novel Gd(III) complex-based magnetic resonance imaging (MRI) contrast agent GdL has been designed and synthesized, which exhibited a much higher relaxivity (7.8 mM-1 s-1) than the commercially used Magnevist® (3.5 mM-1 s-1), good water solubility (>100 mg mL-1), excellent thermodynamic stability (log KGdL = 17.21 ± 0.27), high biosafety and biocompatibility. In particular, the relaxivity of GdL increased to 26.7 mM-1 s-1 in a 4.5% bovine serum albumin (BSA) solution at 1.5 T, which was not significant in other commercial MRI contrast agents. The interaction sites and interaction types of GdL and BSA were further demonstrated by molecular docking simulations. Furthermore, the in vivo MRI behaviour was evaluated by using a 4T1 tumour-bearing mouse model. These results suggested that GdL is an excellent T1-weighted MRI contrast agent and has the potential to be applied in clinical diagnosis.

Dual-Fluorophore and Dual-Site Multifunctional Fluorescence Sensor for Visualizing the Metabolic Process of GHS to SO2 and the SO2 Toxicological Mechanism by Two-Photon Imaging.

As a momentous gas signal molecule, sulfur dioxide (SO2) participates in diverse physiological activities. Excess SO2 will cause an apparent decrease in the level of intracellular glutathione (GSH), thereby damaging the body's antioxidant defense system. In addition, endogenous SO2 can be generated from GSH by reacting with thiosulfate (S2O32-) and enzymatically reduced to cysteine (Cys), a synthetic precursor of GSH. In view of their close correlation, a two-photon (TP) mitochondria-targeted multifunctional fluorescence sensor Mito-Na-BP was rationally designed and synthesized for detecting SO2 and GSH simultaneously. Under single-wavelength excitation, the sensor responded to GSH-SO2 and SO2-GSH continuously with blue-shifted and green fluorescence-enhanced signal modes, respectively, not just to GSH (enhanced) and SO2 (quenched) at 638 nm with a completely converse response tendency. Given its favorable spectral performance (high sensitivity, superior selectivity, and fast response rate) at physiological pH, Mito-Na-BP has been successfully applied in monitoring the level fluctuation of GSH affected from high-dose SO2 and visualizing in real time the metabolic process of GSH to SO2 by TP imaging. It is expected that this research will provide a convenient and efficient tool for elucidating intricate relationships of GSH and SO2 and facilitate further exploration of their functions in biomedicine.

Dual-Site Fluorescent Sensor as a Multiple Logic System for Studying the Dichotomous Function of Sulfur Dioxide under Oxidative Stress Induced by Peroxynitrite.

Intracellular reactive oxygen species and reactive sulfur play a vital role in regulating redox homeostasis and maintaining cell functions. Sulfur dioxide (SO2) has emerged as an important gas signal molecule recently, which is not only a potential reducing agent but also a potential inductor of oxidative stress in organisms. Due to high reactivity, peroxynitrite (ONOO-) could act on many biomolecules, such as proteins, lipids, and nucleic acids, and cause irreversible damage, eventually leading to cell apoptosis or necrosis. In order to further illuminate the dichotomous role of SO2 under oxidative stress induced by ONOO-, we designed the first dual-site fluorescent sensor (NIR-GYf) for separate or continuous detection of SO2 and ONOO-. NIR-GYf was successfully used for cell imaging of endogenous SO2 and ONOO-. In addition, western blotting analysis was used to verify the oxidation and antioxidation of SO2 and its dichotomous biological influence. Finally, NIR-GYf was integrated with multiple Boolean logic operations to construct an advanced analysis device, thereby realizing the direct analysis of SO2 and ONOO- levels.