Graphene news, publications and commentary from the two-dimensional community.

Autophagy could play suppressing role in cancer therapy by facilitating release of tumor antigens from dying cells and inducing immunogenic cell death (ICD). Therefore, discovery and rational design of more effective inducers of cytotoxic autophagy is expected to develop new strategies for finding innovative drugs for precise and successful cancer treatment. Herein, we develop MoO3-x nanowires (MoO3-x NWs) with high oxygen vacancy and strong photothermal responsivity to ablate tumors through hyperthermia, thus promote the induction of cytotoxic autophagy and severe ICD. As expected, the combination of MoO3-x NWs and photothermal therapy (PTT) effectively induces autophagy to promote the release of tumor antigens from the ablated cells, and induces the maturation and antigen presentation of dendritic cells (DCs), subsequently activates cytotoxic T lymphocytes (CTLs)-mediated adaptive immunity. Furthermore, the combination treatment of MoO3-x NWs with immune checkpoint blockade of PD-1 could promote the tumor-associated macrophages (TAMs) polarization into tumor-killing M1 macrophages, inhibit infiltration of Treg cells at tumor sites, and alleviate immunosuppression in the tumor microenvironment, finally intensify the anti-tumor activity in vivo. This study provides a strategy and preliminary elucidation of the mechanism of using MoO3-x nanowires with high oxygen vacancy to induce autophagy and thus enhance photothermal immunotherapy.

Published in: "Angewandte Chemie International Edition".

Consecutive photoinduced electron transfer (ConPET) is a powerful and atom-economical protocol to overcome the limitations of the intrinsic redox potential of visible light-absorbing photosensitizers, thereby considerably improving the substrate and reaction types. Likely because such an exothermic single-electron transfer (SET) process usually does not require the aid of chiral catalysts, resulting in an inevitable racemic background reaction, notably, no enantioselective manifolds have been reported. Herein, we report on the viability of cooperative ConPET and chiral hydrogen-bonding catalysis for the [3 + 2] photocycloaddition of cyclopropyl ketones with vinylazaarenes. In addition to enabling the first use of olefins that preferentially interact with chiral catalysts, this catalysis platform paves the way for the efficient synthesis of pharmaceutically and synthetically important cyclopentyl ketones functionalized by azaarenes with high yields, ees and dr. The robust capacity of the method can be further highlighted by the low loading of the chiral catalyst (1.0 mol%), the good compatibility of both 2-azaarene and 3-pyridine-based olefins, and the successful concurrent construction of three stereocenters on cyclpentane rings involving an elusive but important all-carbon quaternary.

Published in: "Angewandte Chemie International Edition".

Although many approaches have been proposed to recycling waste epoxy resin (EP), the separation of mixed degraded products remains a challenge due to their similar structures. To address this, we present a catalytic oxidation strategy that enables mild degradation of EP and in-situ separation of degraded products through supramolecular interactions. The oxidative degradation relies on FeIV=O radicals with strong oxidizing properties, which are generated from the electron transfer of FeCl2 with reaction reagents. As the FeIV=O radicals attacked the C-N bonds of EP, EP was broken into fragments rich in active functional groups. Meanwhile, the FeIV=O radicals were reduced to iron ions that can coordinate with the carboxyl groups on the fragments. As a result, the degraded products with different carboxyl content can be effortlessly separated into liquid and solid phase by coordinating with the catalyst. The success of this work lays the foundation for high-value application of degraded products and provides new design ideas for recycling waste plastics with complex compositions.

Published in: "Angewandte Chemie International Edition".

Widespread use of plant protection agents in agriculture is a major cause of pollution. Apart from active ingredients, the environmental impact of auxiliary synthetic polymers should be minimized if they are highly persistent. An alternative to synthetic polymers is the use of natural polysaccharides, which are abundant and biodegradable. In this study, we explore pectin microgels functionalized with anchor peptides (P-MAPs) to be used as an alternative biobased pesticide delivery system. Using complexed Cu2+ as the active ingredient, P-MAPs effectively prevented infection of grapevine plants with downy mildew under semi-field conditions on par with commercial copper pesticides. By using anchor peptides, the microgels tightly bind to the leaf surface, exhibiting excellent rain fastness and prolonged fungicidal activity. Finally, P-MAPs are shown to be easily degradable by enzymes found in nature, demonstrating their negligible long-term impact on the environment.

Published in: "Angewandte Chemie International Edition".

Glass metal-organic framework (MOF) films can be fabricated from their crystalline counterparts through a melt-quenching process and are prospective candidates for gas separation because of the elimination of the grain boundaries in crystalline MOF films. However, current techniques are limited to producing glass MOF films with a thickness of tens of micrometers, which leads to ultralow gas permeances. Here, we report a novel cathodic deposition-assisted synthesis of glass ZIF-62 films with a thickness as low as ~1 μm. Electrochemical analyses and deposition experiments suggest that the cathodic deposition can lead to pure crystalline ZIF-62 films with a controllable thickness of ~2 μm to ~15 μm. Accordingly, glass ZIF-62 films with a thickness of ~1 μm to ~10 μm can be obtained after a thermal treatment. The fabricated defect-free glass ZIF-62 film measuring 2 μm in thickness shows a remarkable CO2/N2 and CO2/CH4 selectivity of 31.4 and 33.4, respectively, with a CO2 permeance which is over 30 times higher than the best-performing glass ZIF-62 films in literature.

Published in: "Angewandte Chemie International Edition".

In aqueous aluminum-ion batteries(AAIBs), the insertion/extraction chemistry of Al3+ often leads to poor kinetics, whereas the rapid diffusion kinetics of hydrated hydrogen ions (H3O+) may offer the solution. However, the presence of considerable Al3+ in the electrolyte hinders the insertion reaction of H3O+. Herein, we report how oxygen-deficient α-MoO3 nanosheets unlock selective H3O+ insertion in a mild aluminum-ion electrolyte. The abundant oxygen defects impede the insertion of Al3+ due to excessively strong adsorption, while allowing H3O+ to be inserted/diffused through the Grotthuss proton conduction mechanism. This research advances our understanding of the mechanism behind selective H3O+ insertion in mild electrolytes.

Published in: "Angewandte Chemie International Edition".

Alkyl borane compounds-mediated polymerizations have expanded to Lewis pair polymerization, free radical polymerization, ionic ring-opening polymerization, and polyhomologation. The bifunctional organoborane catalysts that contain the Lewis acid and ammonium or phosphonium salt in one molecule have demonstrated superior catalytic performance for ring-opening polymerization of epoxides and ring-opening copolymerization of epoxides and CO2 than their two-component analogues, i.e., the blend of organoborane and ammonium or phosphonium salt. To explore the origin of the differences of the one-component and two-component organoborane catalysts, here we conducted a systematic investigation on the catalytic performances of these two kinds of organoborane catalysts via terpolymerization of epoxide, carbon dioxide and anhydride. The resultant terpolymers produced independently by bifunctional and binary organoborane catalyst exhibited distinct microstructures, where a series of gradient polyester-polycarbonate terpolymers with varying polyester content were afforded using the bifunctional catalyst, while tapering diblock terpolymers were obtained using the binary system. The bifunctional catalyst enhances the competitiveness of CO2 insertion than anhydride, which leads to the premature incorporation of CO2 into the polymer chains and ultimately results in the formation of gradient terpolymers. DFT calculations revealed the role of electrostatic interaction and charge distribution caused by intramolecular synergistic effect for bifunctional organoborane catalyst.

Published in: "Angewandte Chemie International Edition".

Poly(ethylene oxide) (PEO)-based composite solid electrolytes (CSEs) are promising to accelerate commercialization of solid-state lithium metal batteries (SSLMBs). Nonetheless, this is hindered by the CSEs’ limited ion conductivity at room temperature. Here, we propose design, synthesis, and application of the bioinspired neuron-like nanofillers for PEO-based CSEs. The neuron-like superhydrophobic nanofillers are synthesized by controllably grafting silicone nanofilaments onto montmorillonite nanosheets. Compared to various reported fillers, the nanofillers can greatly improve ionic conductivity (4.9 × 10−4 S cm−1, 30 °C), Li+ transference number (0.63), oxidation stability (5.3 V) and mechanical properties of the PEO-based CSEs because of the following facts. The distinctive neuron-like structure and the resulting synaptic-like connections establish numerous long-distance continuous channels over various directions in the PEO-based CSEs for fast and uniform Li+ transport. Consequently, the assembled SSLMBs with the CSEs and LiFePO4 or NCM811 cathodes display superior cycling stability over a wide temperature range of 50 °C to 0 °C. Surprisingly, the pouch batteries with the large-scale prepared CSEs kept working after being repeatedly bent, folded, cut or even punched in air. We believe that design of neuron-like nanofillers is a viable approach to produce CSEs with high room temperature ionic conductivity for SSLMBs.

Published in: "Angewandte Chemie International Edition".

The dynamic nature of calamitic liquid crystals is exploited to perform isothermal phase transitions driven by dynamic covalent chemistry. For this purpose, nematic (N) arrays based on aldehyde 1 were treated with different amines (A-E) in an on-surface process, which resulted in different isothermal phase transitions. These phase transformations were caused by in-situ imination reactions and are dependent on the nature of the added amine. Transitions from the N to crystal (1A, 1E), isotropic (1B), and smectic (Sm) (1C, 1D) phases were achieved, while the resulting materials feature thermotropic liquid crystal behavior. A sequential transformation from the N 1 to the Sm 1C and then to the N 1B was achieved by coupling an imination to a transimination processes and adjusting the temperature. All of these processes were well characterized by microscopic, spectroscopic, and X-ray techniques, unlocking not only the constitutional but also the structural aspects of the phase transitions. This work provides new insights into designing constitutionally and structurally adaptable liquid crystal systems, paving the way toward the conception of programable evolutive pathways and adaptive materials.

Published in: "Angewandte Chemie International Edition".

α-Olefins are valued and abundant building blocks from fossil resources. They are widely used to provide small-molecule or polymeric products. Despite numerous advantages of radical polymerization, it has been well-documented as textbook knowledge that α-olefins and their functionalized derivatives cannot be radically homopolymerized because of the degradative chain transfer side reactions. Herein, we report our studies on the homopolymerization of thiocyanate functionalized α-olefins enabled by 1,4-cyano group migration under radical conditions. By this approach, a library of ABC sequence-controlled polymers with high molecular weights can be prepared. We can also extend this strategy to the homopolymerization of α-substituted styrenic and acylate monomers which are known to be challenging to achieve. Overall, the demonstrated functional group migration radical polymerization could provide new possibilities to synthesize polymers with unprecedented main chain sequences and structures. These polymers are promising candidates for novel polymeric materials.

Published in: "Angewandte Chemie International Edition".

The chlorine radical is a strong HAT (Hydrogen Atom Transfer) agent that is very useful for the functionalization of C(sp3)–H bonds. Albeit highly attractive, its generation from the poorly oxidizable chloride ion mediated by an excited photoredox catalyst is a difficult task. We now report that 8Rf8-4CzIPN, an electron-deficient fluorous derivative of the benchmark 4CzIPN photoredox catalyst belonging to the donor-acceptor carbazole-cyanoarene family, is not only a better photooxidant than 4CzIPN, but also becomes an excellent host for the chloride ion. Combining these two properties ultimately makes the self-assembled 8Rf8-4CzIPN•Cl– dual catalyst highly reactive in redox-neutral Giese-type C(sp3)-H bond alkylation reactions promoted by the chlorine radical. Additionally, because of its fluorous character, the efficient separation/recovery of 8Rf8-4CzIPN could be envisioned.

Published in: "Angewandte Chemie International Edition".