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Two‐dimensional metal–organic frameworks (2D MOFs) can be used as the cathodes for high‐performance zinc‐ion battery due to their large one‐dimensional channels. However, the conventionally poor electrical conductivity and low structural stability hinder their advances. Herein, we report an alternately stacked MOF/MX heterostructure, exhibiting the 2D sandwich‐like structure with abundant active sites, improved electrical conductivity and exceptional structural stability. Ex situ characterizations and theoretical calculations reveal a reversible intercalation mechanism of zinc ions and high electrical conductivity in the 2D heterostructure. Electrochemical tests confirm excellent Zn2+ migration kinetics and ideal pseudocapacitive behaviors. As a consequence, Cu‐HHTP/MX shows a superior rate performance (260.1 mAh g−1 at 0.1 A g−1 and 173.1 mAh g−1 at 4 A g−1) and long‐term cycling stability of 92.5 % capacity retention over 1000 cycles at 4 A g−1. [ABSTRACT FROM AUTHOR]

A convenient and rapid detection method for methanol in ethanol remains a major challenge due to their indistinguishable physical properties. Herein, a novel fluorescence probe based on perovskite was successfully designed to overcome this bottleneck. We report a new zero‐dimensional (0D) hybrid perovskite of [MP]2InxSb1−xCl7 ⋅ 6 H2O (MP=2‐methylpiperazine) displaying an unusual green light emission with near‐unity photoluminescence quantum yield. Remarkably, this 0D perovskite exhibits reversible methanol‐response luminescence switching between green and yellow color but fail in any other organic vapors. Even for blended alcohol solutions, the luminescent probe exhibits excellent sensing performance with multiple superiorities of rapid response time (30 s) and ultra‐low detection limit (40 ppm), etc. Therefore, this 0D perovskite can be utilized as a perfect fluorescence probe to detect traces of methanol from ethanol with ultrahigh sensitivity, selectivity and repeatability. To the best of our knowledge, this work represents the first perovskite as fluorescence probe for methanol with wide potential in environmental monitoring and methanol detection, etc. [ABSTRACT FROM AUTHOR]

Light‐driven hydrogen production from biomass derivatives offers a path towards carbon neutrality. It is often however operated with the limitations of sluggish kinetics and severe coking. Herein, a disruptive air‐promoted strategy is explored for efficient and durable light‐driven hydrogen production from ethanol over a core/shell Cr2O3@GaN nanoarchitecture. The correlative computational and experimental investigations show ethanol is energetically favorable to be adsorbed on the Cr2O3@GaN interface, followed by dehydrogenation toward acetaldehyde and protons by photoexcited holes. The released protons are then consumed for H2 evolution by photogenerated electrons. Afterward, O2 can be evolved into active oxygen species and promote the deprotonation and C−C cleavage of the key C2 intermediate, thus significantly lowering the reaction energy barrier of hydrogen evolution and removing the carbon residual with inhibited overoxidation. Consequently, hydrogen is produced at a high rate of 76.9 mole H2 per gram Cr2O3@GaN per hour by only feeding ethanol, air, and light, leading to the achievement of a turnover number of 266,943,000 mole H2 per mole Cr2O3 over a long‐term operation of 180 hours. Notably, an unprecedented light‐to‐hydrogen efficiency of 17.6 % is achieved under concentrated light illumination. The simultaneous generation of aldehyde from ethanol dehydrogenation enables the process more economically promising. [ABSTRACT FROM AUTHOR]

Herein, we report an unprecedented skeletal rearrangement reaction of tetrahydro‐β‐carbolines enabled by copper‐catalyzed single‐electron oxidative oxygenation, in which H2O and O2 act as oxygen sources to generate a unique 2‐hydroxyl‐3‐peroxide indoline intermediate. The synthetic reactivity of 2‐hydroxyl‐3‐peroxide indoline species was demonstrated by a unique multi‐step bond cleavage and formation cascade. Using a readily available copper catalyst under open‐air conditions, highly important yet synthetically difficult spiro[pyrrolidone‐(3,1‐benzoxazine)] products were obtained in a single operation. The synthetic utility of this methodology is demonstrated by the efficient synthesis of the natural products donaxanine and chimonamidine, as well as the 3‐hydroxyl‐pyrroloindoline scaffold, in just one or two steps. [ABSTRACT FROM AUTHOR]

The application of Suzuki–Miyaura coupling reaction to forge the atropisomeric biaryls has seen remarkable progress but exploration of this chemistry to directly forge chiral C(aryl)‐C(alkene) axis is underdeveloped. The replacement of arene substrates by alkenes intensifies the challenges in terms of reactivity, configurational atropostability of product and selectivity control. By meticulous ligand design and fine‐tuning of reaction parameters, we identified a highly active 3,3′‐triphenylsilyl‐substituted phosphite ligand to realize arene‐alkene Suzuki–Miyaura coupling of hindered aryl halides and vinyl boronates under very mild conditions. The axially chiral acyclic aryl‐alkenes were generated in commendable efficiency, enantioselectivity and E/Z selectivity. [ABSTRACT FROM AUTHOR]

Probing pro‐metastatic biomarkers is of significant importance to evaluate the risk of tumor metastasis, but spatially selective imaging of such targets in extracellular microenvironment is particularly challenging. By introducing the bilinguality of PNA/peptide hybrid that can speak both peptide substrate and nucleobase‐pairing languages to combine with aptamer technology, we designed a smart DNA nanodevice programmed to respond sequentially to dual pro‐metastatic targets, MMP2/9 and ATP, in extracellular tumor microenvironment (TME). The DNA nanodevice is established based on the combination of an ATP‐responsive aptamer sensor and a MMP2/9‐hydrolyzable PNA/peptide copolymer with a cell membrane‐anchoring aptamer module. Taking 4T1 xenograft as a highly aggressive tumor model, the robustness of the DNA nanodevice in spatioselective imaging of MMP2/9 and ATP in TME is demonstrated. We envision that this design will enable the simultaneous visualization of multiple pro‐metastatic biomarkers, which allows to gain insights into their pathological roles in tumor metastasis. [ABSTRACT FROM AUTHOR]

Frontispiz: A Multivariate-Gated DNA Nanodevice for Spatioselective Imaging of Pro-metastatic Targets in Extracellular Microenvironment Aptamers, DNA nanodevices, pro-metastatic biomarkers, spatioselective imaging, tumor microenvironment Keywords: aptamers; DNA nanodevices; pro-metastatic biomarkers; spatioselective imaging; tumor microenvironment EN aptamers DNA nanodevices pro-metastatic biomarkers spatioselective imaging tumor microenvironment 1 1 1 01/18/22 20220121 NES 220121 B DNA-Nanofunktionseinheiten b In ihrer Zuschrift (e202111836) berichten Jun Song, Lele Li et al. über eine multivariate DNA-Nanofunktionseinheit für die räumlich-selektive Bildgebung von prometastatischen Targets in der extrazellulären Mikroumgebung. [Extracted from the article]