Orbital Coupling of PbO7 Node in Single-Crystal Metal-Organic Framework Enhances Li-O2 Battery Electrocatalysis.

Optimizing the local coordination environment of metal centers in metal-organic frameworks (MOFs) is crucial yet challenging for regulating the overpotential of lithium-oxygen (Li-O2) batteries. Herein, we report the synthesis of a class of PbO7 nodes in a single crystal MOF (naphthalene-lead-MOF, known as Na-Pb-MOF) to significantly enhance the kinetics of both discharge and charge processes. Compared to the PbO6 node in the single-crystal tetramethoxy-lead-MOF (4OMe-Pb-MOF), the bond length between Pb and O in the PbO7 node of Na-Pb-MOF increases, resulting in weaker Pb 5d-O 2p orbital coupling, which optimizes the adsorption interaction toward intermediates, and thereby promotes the rate-determining steps of both the reduction of LiO2 to Li2O2 and the oxidation of LiO2 to O2 for reducing the activation energy of the overall reaction. Consequently, Li-O2 batteries based on Na-Pb-MOF electrocatalysts exhibit a low total charge-discharge overpotential of 0.52 V and an excellent cycle life of 140 cycles.

Fluorescent Biomass-Based Platform for Detection of ClO- in Cells and Water-Soluble Systems.

The generation and presence of excessive hypochlorous acid derivative ionic form (ClO-) could cause various diseases, such as arteriosclerosis, DNA damage, and cardiovascular illness. It is a critical need to develop a highly sensitive sensor for reliable detection of ClO- in cells and water-soluble systems. In this work, a hydroxyl group has been introduced into the compound 2-amino-3-(((E)-4-(2-(2-(2-hydroxyethoxy)ethyl)-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)benzylidene)amino)maleonitrile (NDC) to increase its solubility in water, at the same time, the hydrazone unit was designed as a specific recognition group for the "off-on" fluorescence probe of ClO-. The probe NDC presents high selectivity, sensitivity, anti-interference, and low detection limit (67 nM) for ClO-. The recognition mechanism that ClO- breaks the C=N bond and forms the fluorescent compound 4-(2-(2-(2-hydroxyethoxy)ethyl)-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)benzaldehyde (ND-3) has been confirmed by time-of-flight mass spectrometry. The probe NDC presents a good performance in the actual test of water samples and can be designed as the test papers for the quick and convenient detection of ClO- range from 0 to 1 µM. Moreover, the practical application was demonstrated by the successful imaging of endogenous and exogenous ClO- in HeLa cells. Our fluorescent biomass-based platform opens vast possibilities for repeatability, sensitivity, and selectivity detection of ClO- in cells and water-soluble systems.

From salt water to bioceramics: Mimic nature through pressure-controlled hydration and crystallization.

Modern synthetic technology generally invokes high temperatures to control the hydration level of ceramics, but even the state-of-the-art technology can still only control the overall hydration content. Magically, natural organisms can produce bioceramics with tailorable hydration profiles and crystallization traits solely from amorphous precursors under physiological conditions. To mimic the biomineralization tactic, here, we report pressure-controlled hydration and crystallization in fabricated ceramics, solely from the amorphous precursors of purely inorganic gels (PIGs) synthesized from biocompatible aqueous solutions with most common ions in organisms (Ca2+, Mg2+, CO32-, and PO43-). Transparent ceramic tablets are directly produced by compressing the PIGs under mild pressure, while the pressure regulates the hydration characteristics and the subsequent crystallization behaviors of the synthesized ceramics. Among the various hydration species, the moderately bound and ordered water appears to be a key in regulating the crystallization rate. This nature-inspired study offers deeper insights into the magic behind biomineralization.

Hydrogen-bond activated ESIPT in naphthalimide-based fluorescent probe for sensing volatile amines.

Amines levels present important indicative value in food safety and human health. Although they are involved in some normal physiological responses of the organism, their overproduction or intake may cause pathological responses. Herein, we report a recyclable visual packaging bag for volatile amines detections based on the naphthylamide derivative N-S and its positive PL characteristics. Specifically, handmade test strips based on compound N-S have been applied to fish freshness labeling, and the cyclic fumigation experiment shows its restorable PL effect and efficiency. The possible PL transfer mechanism of naphthylamide derivative N-S is uncovered by the density functional theory (DFT) calculation and titration mass spectrometer and 1H NMR. This work expands a conjugation in a molecule by hydrogen-bond activated ESIPT (H-ESIPT) and provides a portable detection method for volatile amines detection.

An o-hydroxyl aldehyde structure based naphthalimide derivative: Reversible photochromic properties and its application in ClO- detection in living cells.

A bifunctional organic compound 2-butyl-6-hydroxy-1,3-dioxo-2,3-dihydro-1H-benzo[de] isoquinoline-5-carbaldehyde (BHC) with photochromic properties in solid state and probe detection for ClO- in complete water solution was synthesized and fully characterized. A 'white-yellow-white' reversible photochromic behavior could be observed when alternating UV/vis light irradiation on the solid BHC powder. Good fatigue resistance and adjustable bleaching rate were shown when heating conditions changes. In addition, BHC displayed a high selectivity and low detection limit (1.16 × 10-8 M) for ClO-. The photoluminescent fluorescence "on-off" recognition result can be easily identified and BHC has been tested for safely imaging living cells and detecting hypochlorite anion in vitro and vivo. A better water solubility of BHC effectively reduces damage caused by organic solvent in cell imaging progress.

Synthesis, crystal structure and aggregation-induced emission of a new pyrene-based compound, 3,3-diphenyl-2-[4-(pyren-1-yl)phen-yl]acrylo-nitrile.

The title organic compound, C37H23N, crystallizing in the triclinic space group P [Formula: see text], has been designed, synthesized and characterized by single-crystal X-ray diffaction, MS, NMR and elemental analysis. There are alternating relatively strong and weak intermolecular π-π interactions between adjacent pyrene ring systems, forming a one-dimensional supramolecular structure. The compound is weakly fluorescent in THF solution, but it is highly emissive in the condensed phase, revealing distinct aggregation-induced emission (AIE) characteristics.

A series of 4,5,9,10-tetrahydropyrene-based tetraarylethenes: synthesis, structures and solid-state emission behavior.

By controlling the number of 4,5,9,10-tetrahydropyrene segments around the tetraarylethene core, a series of 4,5,9,10-tetrahydropyrene-based tetraarylethenes were synthesized and structurally characterized. An aggregation-induced emission (AIE) study indicated that all the compounds are AIE active: they are weak emitters in good solvents but highly emissive in the condensed phase, and hence are potential solid-state emitters. Their optical properties, electrochemical properties and theoretical calculations were investigated, and the results prove that the π-conjugation degree of these compounds increases with the increasing number of 4,5,9,10-tetrahydropyrene units. However, the fluorescence quantum yield in the solid state doesn't increase with increasing π-conjugation. We studied the reason for this by analyzing the crystal structures of some compounds, and proposed that the close degree of molecular packing in the solid state may be responsible for it. Loose packing of tetraarylethenes in the solid state can restrict the rotation of the aromatic rings but cannot constrain other non-radiative pathways efficiently, such as vibration, which leads to the unpredictable emission of the compounds.