Freeze–Thaw-Promoted Fabrication of Clean and Hierarchically Structured Noble-Metal Aerogels for Electrocatalysis and Photoelectrocatalysis

Noble-metal aerogels (NMAs) have drawn increasing attention because of their self-supported conductive networks, high surface areas, and numerous optically/catalytically active sites, enabling their impressive performance in diverse fields. However, the fabrication methods suffer from tedious procedures, long preparation times, unavoidable impurities, and uncontrolled multiscale structures, discouraging their developments. By utilizing the self-healing properties of noble-metal aggregates, the freezing-promoted salting-out behavior, and the ice-templating effect, a freeze–thaw method is crafted that is capable of preparing various hierarchically structured noble-metal gels within one day without extra additives. In light of their cleanliness, the multi-scale structures, and combined catalytic/optical properties, the electrocatalytic and photoelectrocatalytic performance of NMAs are demonstrated, which surpasses that of commercial noble-metal catalysts.     

Two-Photon Absorption Enhancement by the Inclusion of a Tropone Ring in Distorted Nanographene Ribbons

A new family of distorted ribbon-shaped nanographenes was designed, synthesized, and their optical and electrochemical properties were evaluated, pointing out an unprecedented correlation between their structural characteristics and the two-photon absorption (TPA) responses and electrochemical band gaps. Three nanographene ribbons have been prepared: a seven-membered-ring-containing nanographene presenting a tropone moiety at the edge, its full-carbon analogue, and a purely hexagonal one. We have found that the TPA cross-sections and the electrochemical band gaps of the seven-membered-ring-containing compounds are higher and lower, respectively, than those of the fully hexagonal polycyclic aromatic hydrocarbon (PAH). Interestingly, the inclusion of additional curvature has a positive effect in terms of non-linear optical properties of those ribbons.     

Redox-Active Two-Dimensional Covalent Organic Frameworks (COFs) for Selective Reductive Separation of Valence-Variable,Redox-Sensitive and Long-Lived Radionuclides

We report the first example of 2D covalent organic framework nanosheets (Redox-COF1) for the selective reduction and in situ loading of valence-variable, redox-sensitive and long-lived radionuclides (abbreviated as VRL nuclides). Compared with sorbents based on chemical adsorption and physical adsorption, the redox adsorption mechanism of Redox-COF1 can effectively reduce the impact of functional group protonation under the usual high-acidity conditions in chemisorption, and raise the adsorption efficiency from the monotonous capture by pores in physisorption. The adsorption selectivity for UO₂²⁺ reaches up to unprecedented ca. 97 % at pH 3, more than for any analogous adsorbing material.     

In Situ Electropolymerization Enables Ultrafast Long Cycle Life and High-Voltage Organic Cathodes for Lithium Batteries

Organic cathode materials have attracted extensive attention because of their diverse structures, facile synthesis, and environmental friendliness. However, they often suffer from insufficient cycling stability caused by the dissolution problem, poor rate performance, and low voltages. An in situ electropolymerization method was developed to stabilize and enhance organic cathodes for lithium batteries. 4,4′,4′′-Tris(carbazol-9-yl)-triphenylamine (TCTA) was employed because carbazole groups can be polymerized under an electric field and they may serve as high-voltage redox-active centers. The electropolymerized TCTA electrodes demonstrated excellent electrochemical performance with a high discharge voltage of 3.95 V, ultrafast rate capability of 20 A g⁻¹, and a long cycle life of 5000 cycles. Our findings provide a new strategy to address the dissolution issue and they explore the molecular design of organic electrode materials for use in rechargeable batteries.     

Introducing tox-Profiles of Chemical Reactions

In this Essay, we present a critical analysis of two common practices in modern chemistry—that is, of using speculations about the “greenness” and “nontoxicity” of developed synthesis procedures and of a priori labelling various compounds derived from natural sources as being environmentally safe. We note that every organic molecule that contains functional groups should be biologically active. Thus, analysis of the particular greenness and the potential environmental impact of a given chemical process should account for the biological activity of all its components in a measureable (rather than empirical) way. We highlight the necessity of clarifying discussions on biological activity and toxicity and propose possible ways of introducing tox-Profiles as a reliable overview of the overall toxicity of chemical reactions.     

Structural-Deformation-Energy-Modulation Strategy in a Soft Porous Coordination Polymer with an Interpenetrated Framework

To achieve unique molecular-recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (E_def) of soft PCPs and the guest interaction is key for selective a guest-triggered structural-transformation behavior. Therefore, it is vital to investigate and control E_def to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an E_def-modulation strategy via encoding inter-framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced E_def of PCP enables a selective gate-opening behavior toward CHCl₃ over CH₂Cl₂ by changing the adsorption-energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials.     

Hypoxia-Induced Pro-Protein Therapy Assisted by a Self-Catalyzed Nanozymogen

The success of intracellular protein therapy demands efficient delivery and selective protein activity in diseased cells. Therefore, a cascaded nanozymogen consisting of a hypoxia-activatable pro-protein, a hypoxia-inducing protein, and a hypoxia-strengthened intracellular protein delivery nanovehicle was developed. RPAB, an enzymatically inactive pro-protein of RNase, reversibly caged with hypoxia-cleavable azobenzene, was delivered with glucose oxidase (GOx) using hypoxia-responsive nanocomplexes (NCs) consisting of azobenzene-cross-linked oligoethylenimine (AOEI) and hyaluronic acid (HA). Upon NC-mediated delivery into cancer cells, GOx catalyzed glucose decomposition and aggravated tumoral hypoxia, which drove the recovery of RPAB back to the hydrolytically active RNase and expedited the degradation of AOEI to release more protein cargoes. Thus, the catalytic reaction of the nanozymogen was self-accelerated and self-cycled, ultimately leading to a cooperative anti-cancer effect between GOx-mediated starvation therapy and RNase-mediated pro-apoptotic therapy.