Strong Inhibition of Ice Growth by Biomimetic Crowding Coacervates

The freezing of biological fluids is intensively studied but remains elusive as it is affected not only by the various components but also by the crowding nature of the biological fluids. Herein, we constructed spherical crowders, fibrous crowders, and coacervates by various components ranging from surfactants to polymers and proteins, to mimic three typical crowders in biological fluids, i.e., globular proteins, fibrous networks, and condensates of biomolecules. It is elucidated that the three crowders exhibit low, moderate, and strong ice growth inhibition activity, respectively, resulting from their different abilities in slowing down water dynamics. Intriguingly, the coacervate consisting of molecules without obvious ice growth inhibition activity strongly inhibits ice growth, which is firstly employed as a highly-potent cryoprotectant. This work provides new insights into the survival of freezing-tolerant organisms and opens an avenue for the design of ice-controlling materials.     

Self-Assembled Monolayers of Bi-Functionalized Porphyrins: A Novel Class of Hole-Layer-Coordinating Perovskites and Indium Tin Oxide in Inverted Solar Cells

Self-assembled monolayers (SAMs) offer the advantage of facile interfacial modification, leading to significant improvements in device performance. In this study, we report the design and synthesis of a new series of carboxylic acid-functionalized porphyrin derivatives, namely AC-1, AC-3, and AC-5, and present, for the first time, a strategy to exploit the large π-moiety of porphyrins as a backbone for interfacing the indium tin oxide (ITO) electrode and perovskite active layer in an inverted perovskite solar cell (PSC) configuration. The electron-rich nature of porphyrins facilitates hole transfer and the formation of SAMs, resulting in a dense surface that minimizes defects. Comprehensive spectroscopic and dynamic studies demonstrate that the double-anchored AC-3 and AC-5 enhance SAMs on ITO, passivate the perovskite layer, and function as conduits to facilitate hole transfer, thus significantly boosting the performance of PSCs. The champion inverted PSC employing AC-5 SAM achieves an impressive solar efficiency of 23.19 % with a high fill factor of 84.05 %. This work presents a novel molecular engineering strategy for functionalizing SAMs to tune the energy levels, molecular dipoles, packing orientations to achieve stable and efficient solar performance. Importantly, our comprehensive investigation has unraveled the associated mechanisms, offering valuable insights for future advancements in PSCs.     

Engineered Bacteria Labeled with Iridium(III) Photosensitizers for Enhanced Photodynamic Immunotherapy of Solid Tumors

Despite metal-based photosensitizers showing great potential in photodynamic therapy for tumor treatment, the application of the photosensitizers is intrinsically limited by their poor cancer-targeting properties. Herein, we reported a metal-based photosensitizer-bacteria hybrid, Ir-HEcN , via covalent labeling of an iridium(III) photosensitizer to the surface of genetically engineered bacteria. Due to its intrinsic self-propelled motility and hypoxia tropism, Ir-HEcN selectively targets and penetrates deeply into tumor tissues. Importantly, Ir-HEcN is capable of inducing pyroptosis and immunogenic cell death of tumor cells under irradiation, thereby remarkably evoking anti-tumor innate and adaptive immune responses in vivo and leading to the regression of solid tumors via combinational photodynamic therapy and immunotherapy. To the best of our knowledge, Ir-HEcN is the first metal complex decorated bacteria for enhanced photodynamic immunotherapy.     

Thermally-Induced Isomerization of Prenucleation Clusters During the Prenucleation Stage of CdTe Quantum Dots

The evolution of prenucleation clusters in the prenucleation stage of colloidal semiconductor quantum dots (QDs) has remained unexplored. With CdTe as a model system, we show that substances form and isomerize prior to the nucleation and growth of QDs. Called precursor compounds (PCs), the prenucleation clusters are relatively optically transparent and can transform to absorbing magic-size clusters (MSCs). When a prenucleation-stage sample at 25, 45, or 80 °C is dispersed in a mixture of cyclohexane (CH) and octylamine (OTA) at room temperature, either MSC-371, MSC-417, or MSC-448 evolves with absorption peaking at 371, 417, or 448 nm, respectively. We propose that PC-371 forms at 25 °C, and isomerizes to PC-417 at 45 °C and to PC-448 at 80 °C. The PCs and MSCs are quasi isomers. Relatively large and small amounts of OTA favor PC-371 and PC-448 in dispersion, respectively. The present findings suggest the existence of PC-to-PC isomerization in the QD prenucleation stage.     

Self-Polarization Triggered Multiple Polar Units Toward Electrochemical Reduction of CO2 to Ethanol with High Selectivity

Electrochemical conversion of CO₂ to highly valuable ethanol has been considered a intriguring strategy for carbon neutruality. However, the slow kinetics of coupling carbon-carbon (C−C) bonds, especially the low selectivity ethanol than ethylene in neutral conditions, is a significant challenge. Herein, the asymmetrical refinement structure with enhanced charge polarization is built in the vertically oriented bimetallic organic frameworks (NiCu-MOF) nanorod array with encapsulated Cu₂O (Cu₂O@MOF/CF), which can induce an intensive internal electric field to increase the C−C coupling for producing ethanol in neutral electrolyte. Particularly, when directly employed Cu₂O@MOF/CF as the self-supporting electrode, the ethanol faradaic efficiency (FE_ethanol) could reach maximum 44.3 % with an energy efficiency of 27 % at a low working-potential of −0.615 V versus the reversible hydrogen electrode (vs. RHE) using CO₂-saturated 0.5 M KHCO₃ as the electrolyte. Experimental and theoretical studies suggest that the polarization of atomically localized electric fields derived from the asymmetric electron distribution can tune the moderate adsorption of *CO to assist the C−C coupling and reduce the formation energy of H₂CCHO*-to-*OCHCH₃ for the generation of ethanol. Our research offers a reference for the design of highly active and selective electrocatalysts for reducing CO₂ to multicarbon chemicals.     

Balancing the Crystallinity and Film Formation of Metal–Organic Framework Membranes through In Situ Modulation for Efficient Gas Separation

Polycrystalline metal–organic framework (MOF) layers hold great promise as molecular sieve membranes for efficient gas separation. Nevertheless, the high crystallinity tends to cause inter-crystalline defects/cracks in the nearby crystals, which makes crystalline porous materials face a great challenge in the fabrication of defect-free membranes. Herein, for the first time, we demonstrate the balance between crystallinity and film formation of MOF membrane through a facile in situ modulation strategy. Monocarboxylic acid was introduced as a modulator to regulate the crystallinity via competitive complexation and thus concomitantly control the film-forming state during membrane growth. Through adjusting the ratio of modulator acid/linker acid, an appropriate balance between this structural “trade-off” was achieved. The resulting MOF membrane with moderate crystallinity and coherent morphology exhibits molecular sieving for H₂/CO₂ separation with selectivity up to 82.5.     

Electroreduction Enables Regioselective 1,2-Diarylation of Alkenes with Two Electrophiles

Precisely introducing two similar functional groups into bulk chemical alkenes represents a formidable route to complex molecules. Especially, the selective activation of two electrophiles is in crucial demand, yet challenging for cross-electrophile-coupling. Herein, we demonstrate a redox-mediated electrolysis, in which aryl nitriles are both aryl radical precursors and redox-mediators, enables an intermolecular alkene 1,2-diarylation with a remarkable regioselectivity, thereby avoiding the involvement of transition-metal catalysts. This transformation utilizes cyanoarene radical anions for activating various aryl halides (including iodides, bromides, and even chlorides) and affords 1,2-diarylation adducts in up to 83 % yield and >20 : 1 regioselectivity with more than 80 examples, providing a feasible approach to complex bibenzyl derivatives.     

Electrocatalytic Synthesis of Essential Amino Acids from Nitric Oxide Using Atomically Dispersed Fe on N-doped Carbon

How to transfer industrial exhaust gases of nitrogen oxides into high-values product is significantly important and challenging. Herein, we demonstrate an innovative method for artificial synthesis of essential α-amino acids from nitric oxide (NO) by reacting with α-keto acids through electrocatalytic process with atomically dispersed Fe supported on N-doped carbon matrix (AD-Fe/NC) as the catalyst. A yield of valine with 32.1 μmol mg_cat⁻¹ is delivered at −0.6 V vs. reversible hydrogen electrode, corresponding a selectivity of 11.3 %. In situ X-ray absorption fine structure and synchrotron radiation infrared spectroscopy analyses show that NO as nitrogen source converted to hydroxylamine that promptly nucleophilic attacked on the electrophilic carbon center of α-keto acid to form oxime and subsequent reductive hydrogenation occurred on the way to amino acid. Over 6 kinds of α-amino acids have been successfully synthesized and gaseous nitrogen source can be also replaced by liquid nitrogen source (NO₃⁻). Our findings not only provide a creative method for converting nitrogen oxides into high-valued products, which is of epoch-making significance towards artificial synthesis of amino acids, but also benefit in deploying near-zero-emission technologies for global environmental and economic development.     

Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero-Dimensional [(C6H5)4P]2SbCl5 Enabled by Pressure-Induced Lone Pair-π Interaction

Low-dimensional (low-D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low-D OMHHs, especially the zero-D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near-unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C₆H₅)₄P]₂SbCl₅. In situ experimental characterizations and theoretical simulations reveal that the pressure-induced electronic coupling between the lone-pair electrons of Sb³⁺ and the π electrons of benzene ring (lp-π interaction) serves as an unexpected “bridge” for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp-π interactions in organic–inorganic hybrid systems.     

Stereoselective Synthesis of the O-antigen of A. baumannii ATCC 17961 Using Long-Range Levulinoyl Group Participation

Herein, we described the first synthesis of the pentasaccharide and decasaccharide of the A. baumannii ATCC 17961 O-antigen for developing a synthetic carbohydrate-based vaccine against A. baumannii infection. The efficient synthesis of the rare sugar 2,3-diacetamido-glucuronate was achieved using our recently introduced organocatalytic glycosylation method. We found, for the first time, that long-range levulinoyl group participation via a hydrogen bond can result in a significantly improved β-selectivity in glycosylations. This solves the stereoselectivity problem of highly branched galactose acceptors. The proposed mechanism was supported by control experiments and DFT computations. Benefiting from the long-range levulinoyl group participation strategy, the pentasaccharide donor and acceptor were obtained via an efficient [2+1+2] one-pot glycosylation method and were used for the target decasaccharide synthesis.