Accurate Control of VS2 Nanosheets for Coexisting High Photoluminescence and Photothermal Conversion Efficiency

In two‐dimensional (2D) amorphous nanosheets, the electron–phonon coupling triggered by localization of the electronic state as well as multiple‐scattering feature make it exhibit excellent performance in optical science. VS₂ nanosheets, especially single‐layer nanosheets with controllable electronic structure and intrinsic optical properties, have rarely been reported owing to the limited preparation methods. Now, a controllable and feasible switching method is used to fabricate 2D amorphous VS₂ and partial crystallized 2D VO₂(D) nanosheets by altering the pressure and temperature of supercritical CO₂ precisely. Thanks to the strong carrier localization and the quantum confinement, the unique 2D amorphous structures exhibit full band absorption, strong photoluminescence, and outstanding photothermal conversion efficiency.     

Visible‐Light Photocatalysis of Asymmetric [2+2] Cycloaddition in Cage‐Confined Nanospace Merging Chirality with Triplet‐State Photosensitization

Although the photodimerization of acenaphthylene (ACE) has been known for 100 years, the asymmetric cycloaddition of its 1‐substituted derivatives is unknown. Herein, we report a supramolecular photochirogenic approach in which a homochiral and photoactive Δ/Λ‐[Pd₆(RuL₃)₈]²⁸⁺ metal–organic cage (Δ/Λ‐MOC‐16) is used as a supramolecular reactor for the enantioselective exited‐state photocatalysis of 1‐Br‐ACE. Owing to preorganization of the substrates by the supramolecular cage, stereochemical control of the triplet state, and nanospace transfer of energy and chirality, the cycloaddition of ACE proceeded with high selectivity for the formation of anti over syn stereoisomers, whereas the regio‐, stereo‐, and enantioselective cycloaddition of unsymmetrical 1‐Br‐ACE showed effective enantiodifferentiation of a pair of anti head‐to‐head stereoisomers. The enzyme‐mimicking photocatalysis was verified by catalytic turnover, rate enhancement, and competing‐guest inhibition experiments.     

Controllable Si−C Bond Activation Enables Stereocontrol in the Palladium‐Catalyzed [4+2] Annulation of Cyclopropenes with Benzosilacyclobutanes

A novel and unusual palladium‐catalyzed [4+2] annulation of cyclopropenes with benzosilacyclobutanes is reported. This reaction occurred through chemoselective Si?C(sp²) bond activation in synergy with ring expansion/insertion of cyclopropenes to form new C(sp²)?C(sp³) and Si?C(sp³) bonds. An array of previously elusive bicyclic skeleton with high strain, silabicyclo[4.1.0]heptanes, were formed in good yields with excellent diastereoselectivity under mild conditions. An asymmetric version of the reaction with a chiral phosphoramidite ligand furnished a variety of chiral bicyclic silaheterocycle derivatives with good enantioselectivity (up to 95.5:4.5 er). Owing to the mild reaction conditions, the good stereoselectivity profile, and the ready availability of the functionalized precursors, this process constitutes a useful and straightforward strategy for the synthesis of densely functionalized silacycles.     

In situ Growth of a Cobalt‐based Metal‐organic Framework on Multi‐walled Carbon Nanotubes for Simultaneously Detection of Hydroquinone and Catechol.

In the present study, we report a facile method for preparing a porous MWCNTs/ZIF‐67 nanocomposite with the help of a morphology‐maintained ZIF‐67 in situ growth on multi‐walled carbon nanotubes. Interesting, the MWCNTs/ZIF‐67 nanocomposite demonstrated excellent electrochemical activity for hydroquinone (HQ) and catechol (CC) attribute to the effective interconnections ZIF‐67 crystals and MWCNTs. The analytical curves for HQ and CC obtained by differential pulse voltammetry (DPV) were linear in the range from 0.5 to 100 μM. Benefitting from the excellent conductivity of MWCNTs as well as the high surface area and porosity of ZIF‐67, the advanced nanocomposite displayed good reproducibility, high selectivity and excellent stability, and was successfully employed to assay the content of dihydroxybenzene isomers in the lake water samples.     

Chemical modification of carbon fiber with diethylenetriaminepentaacetic acid/halloysite nanotube as a multifunctional interfacial reinforcement for silicone resin composites

In the present research, a multifunctional hierarchical reinforcement was prepared by chemical modification of carbon fibers (CFs) with halloysite nanotubes (HNTs) by the bridging diethylenetriaminepentaacetic acid (DTPA) for improving interfacial microstructures and properties of composites. Surface structures and groups of modified HNTs and CFs were characterized systematically. The uniform distributions of the introduced DTPA and HNTs helped to increase fiber polarity, surface energy, and wettability. As a consequence, significant enhancements of interfacial properties and hydrothermal aging resistance of composites were achieved, and interfacial reinforcing mechanisms have also been studied. Moreover, the storage modulus showed a 17.95% improvement, and the glass transition temperature was enhanced by 17°C by dynamic mechanical analysis testing.     

Metal–Organic Frameworks as Metal Ion Precursors for the Synthesis of Nanocomposites for Lithium‐Ion Batteries

Metal–organic frameworks (MOFs) are promising materials with fascinating properties. Their widespread applications are sometimes hindered by the intrinsic instability of frameworks. However, this instability of MOFs can also be exploited for useful purposes. Herein, we report the use of MOFs as metal ion precursors for constructing functional nanocomposites by utilizing the instability of MOFs. The heterogeneous growth process of nanostructures on substrates involves the release of metal ions, nucleation on substrates, and formation of a covering structure. Specifically, the synthesized CoS with carbon nanotubes as substrates display enhanced performance in a lithium‐ion battery. Such strategy not only presents a new way for exploiting the instability of MOFs but also supplies a prospect for designing versatile functional nanocomposites.     

Photocatalytic Conversion of Waste Plastics into C2 Fuels under Simulated Natural Environment Conditions

Reported here is the first highly selective conversion of various waste plastics into C₂ fuels under simulated natural environment conditions by a sequential photoinduced C?C cleavage and coupling pathway, where single‐use bags, disposable food containers, food wrap films, and their main components of polyethylene, polypropylene, and polyvinyl chloride can be photocatalytically transformed into CH₃COOH without using sacrificial agents. As an example, polyethylene is photodegraded 100 % into CO₂ within 40 h by single‐unit‐cell thick Nb₂O₅ layers, while the produced CO₂ is further photoreduced to CH₃COOH. Various methods and experiments disclose that O₂ and ^.OH radicals trigger the oxidative C?C cleavage of polyethylene to form CO₂, while other investigations show that the yielded CH₃COOH stems from CO₂ photoreduction by C?C coupling of ^.COOH intermediates. This two‐step plastic‐to‐fuel conversion may help to simultaneously address the white pollution crisis and harvest highly valuable multicarbon fuels in natural environments.     

Equipping Natural Killer Cells with Specific Targeting and Checkpoint Blocking Aptamers for Enhanced Adoptive Immunotherapy in Solid Tumors

Herein, we propose an aptamer‐equipping strategy to generate specific, universal and permeable (SUPER) NK cells for enhanced immunotherapy in solid tumors. NK cells were chemically equipped with TLS11a aptamer targeting HepG2 cells and PDL1‐specific aptamer without genetic alteration. The dual aptamer‐equipped NK cells exhibited high specificity to tumor cells, resulting in higher cytokine secretion and apoptosis/necrosis compared to parental or single aptamer‐equipped NK cells. Interestingly, dual aptamer‐equipped NK cells induced remarkable upregulation of PDL1 expression in HepG2 cells, enhancing checkpoint blockade. Furthermore, in vivo intravital imaging demonstrated high infiltration of aptamer‐equipped NK cells into deep tumor region, leading to enhanced therapeutic efficacy in solid tumors. This work offers a straightforward chemical strategy to equip NK cells with aptamers, holding considerable potential for enhanced adoptive immunotherapy in solid tumors.     

A Pressure‐Induced Inverse Order–Disorder Transition in Double Perovskites

Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure‐induced disordering could require recognition of an order–disorder transition in solid‐state physics/chemistry and geophysics. Double perovskites Y₂CoIrO₆ and Y₂CoRuO₆ polymorphs synthesized at 0, 6, and 15 GPa show B‐site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long‐range ferrimagnetic ordering in the B‐site ordered samples are gradually overwhelmed by B‐site disorder. Theoretical calculations suggest that unusual unit‐cell compressions under external pressures unexpectedly stabilize the disordered phases of Y₂CoIrO₆ and Y₂CoRuO₆.     

Iridium‐Catalyzed Selective Cross‐Coupling of Ethylene Glycol and Methanol to Lactic Acid

An atom‐economic approach that has an unprecedented high selectivity for the synthesis of lactic acid (LA) based on a catalytic dehydrogenative cross‐coupling by using inexpensive bulk ethylene glycol and methanol is described. This method relies on the synthesis and utilization of a novel iridium catalyst bearing three N‐heterocyclic carbenes derived from 1,3‐dimethylbenzimidazolium salts, and exhibits outstanding activity in the production of LA [turnover frequency (TOF) up to 3660 h^?1] owing to an elegant metal–ligand cooperation.