The conversion of CF3-alkenes to gem-difluoroalkenes using reductive cross-coupling strategy has received much attention in recent years, however, the use of green and readily available reducing salt to mediate these reactions remains to be explored. In this work a concise construction of gem-difluoroalkenes, which requires neither a catalyst nor a metal reducing agent, was established. Rongalite, a safe and inexpensive industrial product, was employed as both a radical initiator and reductant. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates (>70 examples). The utility of this approach was demonstrated through gram-scale synthesis and efficient late-stage functionalizations of anti-inflammatory drugs.

All-Polymer solar cells (all-PSCs) have attracted considerable attention due to their inherent advantages over other types of organic solar cells, including superior optical and thermal stability, as well as exceptional mechanical durability. Recently, all-PSCs have experi-enced remarkable advancements in device performance thanks to the invention of polymerized small-molecule acceptors (PSMAs) since 2017. Among these PSMAs, PY-IT has garnered immense interest from the scientific community due to its exceptional perfor-mance in all-PSCs. In this review, we presented the design principles of PY-IT and discussed the various strategies employed in device engineering for PY-IT-based all-PSCs. These strategies include additive and interface engineering, layer-by-layer processing methods, meniscus-assisted coating methods, and ternary strategy. Furthermore, this review highlighted several novel polymeric donor materials that are paired with PY-IT to achieve efficient all-PSCs. Lastly, we summarized the inspiring strategies for further advancing all-PSCs based on PY-IT. These strategies aim to enhance the overall performance and stability of all-PSCs by exploring new materials, optimizing device architectures, and improving fabrication techniques. By leveraging these approaches, we anticipate significant progress in the development of all-PSCs and their potential as a viable renewable energy source.

L-Hexoses are key components of many biologically relevant natural products and pharmaceuticals. As rare sugars, L-hexoses are not readily obtained from natural sources. Access to L-hexose building blocks from commercially available and inexpensive D-sugars is highly desirable from the viewpoints of organic synthesis and drug discovery. As demonstrated by the convenient preparation of L-glucosyl, L-galactosyl, and L-mannosyl fluorides from readily available β-D-C-glucosyl, β-D-C-mannosyl, and β-D-C-galactosyl derivatives, we describe a novel and efficient approach to the demanding L-glycosyl fluorides. The transformation features the installation of anomeric hydroxymethyl group under mild conditions and head-to-tail inversion of sugar rings through radical decarboxylative fluorination of uronic acids. The power of this protocol is highlighted by the first assembly of a pentasaccharide repeating unit of Pseudomonas ATCC 31554 extracellular polysaccharide (S-88). This synthesis relies on the efficient extension of sugar chain at the sterically hindered hydroxy group and the facile introduction of L-mannosyl unit using L-mannosyl fluoride as glycosylating agent. The methods developed in this work would provide new tools to the arsenal of synthesis of L-sugar building blocks and of assembly of glycans containing L-sugar moieties.

This review covers the isolation, structural determination, plausible biosynthetic pathways, and biological activities of 166 natural terpenoids including 57 sesquiterpenoids, 65 diterpenoids, 15 sesterterpenoids, and 29 triterpenoids from January 2017 to December 2022.

Carbon dots (CDs) are an emerging class of nanomaterials with intriguing photophysical properties. Recently, achieving room-temperature phosphores-cence (RTP) for CDs have attracted considerable attention for biomedical and information applications. However, the CDs based RTP materials generally require the use of polymeric and inorganic matrix to provide the rigid environments, which remains a great challenge to obtain matrix-free CDs with RTP. Herein, a novel supramolecular strategy based on strong interparticle interactions has been developed to attain this objective, by covalent decoration of ureido-pyrimidinone (UPy, a multiple hydrogen bonding unit) on the surface of CDs. Structural characterizations validated the core-shell structure of the as-prepared CDs (EDTA-CDs) and demonstrated the successful attachment of UPy via post-modification (UPy-CDs). The presence of UPy recognition units render the strong hydrogen bonding between UPy-CDs, which stabilizes the triplet state via rigidifying effect. As a result, UPy-CDs exhibit matrix-free efficient RTP (λem = 534 nm) with high brightness and long lifetime (33.6 ms) in the solid state. Owing to the dual-emission character, we further explored the application potential of UPy-CDs in information encryption and anti-counterfeiting. Overall, this work provides a new and facile strategy for achieving matrix-free phosphorescent CDs with elegant incorporation of supramolecular chemistry.

With rational designability, versatile tunability, and quantum coherence, molecular electron spin qubits could offer new opportunities for quantum information science, enabling simplified implementation of quantum algorithms and chemical-specific quantum sensing. The development of these transformative technologies relies on coherent addressing of single molecular electron spin qubits with high initialization, manipulation, and readout fidelities. This is formidable to conventional electron spin resonance spectroscopy, which is widely used for coherent addressing of ensemble electron spins, due to its low initialization efficiency and readout sensitivity. Taking advantage of single spin detectability of single-molecule spectroscopy, scanning tunneling microscopy, atomic force microscopy, and quantum metrology, several strategies have been developed to empower electron spin resonance spectroscopy with single qubit addressability. In this Emerging Topic, we introduce principles and technical implementation of strategies for coherently addressing single molecular electron spin qubits and point out their challenges in molecular design and/or decoherence suppression. We discuss future directions to overcome these challenges and to improve single qubit addressing technologies, which will facilitate the advancement of molecular quantum information science.

C-Glycosides are critical, naturally occurring products and medicinal candidates, and extensive efforts have been made to explore efficient approaches for creating C-glycosidic bonds. Transition-metal-catalysis, particularly nickel-catalyzed C-glycosylation reactions constitute a promising strategy. However, achieving a stereoselective synthesis of α- and β-C-glycosides has been a long-standing challenge. To address this problem, a variety of nickel-mediated strategies have been developed. This review highlights recent developments in the nickel-catalyzed diastereoselective C-glycosylation reactions and briefly summarizes the mechanistic understandings of these methods.

The kinetic process of a slow oxygen evolution reaction (OER) always constrains the efficiency of overall water electrolysis for H2 production. In particular, nonprecious metal electrodes for the OER have difficulty simultaneously possessing good electrocatalytic activity and long-term stability in pH-universal media. In this work, urea is first used as a pore-forming agent and active C/N source to fabricate a nanoporous NiFeCoCN medium-entropy alloy (MEA) by high-temperature sintering based on the nanoscale Kirkendall effect. The NiFeCoCN MEA achieves an overpotential of 432 mV at a current density of 10 mA cm-2 and a lower Tafel slope of 52.4 mV dec-1 compared to the IrO2/Ti electrode (58.6 mV dec-1) in a 0.5 M H2SO4 solution. In a 1 M KOH solution, the NiFeCoCN MEA obtains an overpotential of 177 mV for 10 mA cm-2 and a Tafel slope of 36.1 mV dec-1, which is better than IrO2/Ni foam. This work proves a novel strategy to design and prepare nanoporous MEA materials with desirable C/N species, which provides promising prospects for the industrial production of H2 energy.

Lobophorins (LOBs) belong to a large family of spirotetronate antibiotics with antibacterial and antitumor activities. In this study, we demonstrated the function of LobP1, a P450 monooxygenase encoded in the LOB biosynthetic gene cluster, by in vivo deletion and in vitro biochemical assays. The disruption of lobP1 led to the isolation of three new LOBs derivatives (3‒5) and three known ones (6‒8) without the hydroxyl group at C-32. LobP1 was shown to have relatively broad substrate scope. Determing the kinetic parameters of LobP1 towards different substrates revealed that LobP1 preferred substrate with a nitrosugar. The major product LOB E (6) from the ∆lobP1 mutant displayed better cytotoxic activities against several cancer cell lines than LOB B, the C-32 hydroxlated counterpart.

Dehydration of serine/threonine residues necessitates the activity of a dehydratase enzyme (domain) during the biosynthesis of ribosomally synthesized and post-translationally modified peptide (RiPP). Recently, it was reported that the dehydration process in thioviridamide relies on a distinct dehydratase complex which showcases the activities of a phosphotransferase TvaC for serine/threonine phosphorylation and a lyase TvaD for subsequent phosphate elimination. Herein, we report that the dehydration process of lantibiotic cacaoidin involves a similar dehydratase complex, CaoK/CaoY. Remarkably, this dehydratase complex exhibits flexible enzymatic activity and tolerates significant variations in its substrate peptide sequence. By binding with the leader peptide (LP) sequence of precursor peptide CaoA, the dehydration reactions proceed directionality from the C-terminus of the core peptide (CP) to its N-terminus, and C-terminally truncated variants of CP are acceptable. We show that fusing CaoK to CaoY in a 1:1 molar ratio enables the resulting enzyme CaoYK to exert enhanced dehydration activity. CaoK binds with the LP to improve its own solubility and to ensure the phosphate transfer activity, while CaoY functions independently of the LP. This work advances our understanding of the dehydration process of cacaoidin, and provides valuable enzymes and methods for the studies of the rapidly emerging RiPPs.

One-dimensional semiconductor-metal heterostructures manifest improved charge separation capability, tunable band gap and increased surface area, and have been regarded as promising photocatalysts for solar-to-fuel conversion through water splitting. We herein review the synthetic strategies for the rational design and preparation of one-dimensional semiconductor-metal heterostructures with precise control in terms of size, shape, composition and function. Approaches that are capable of improving the photocatalytic performance of one-dimensional semiconductor-metal heterostructures have been proposed and analyzed The present work is expected to give the rational design of one-dimensional semiconductor-metal heterostructures and provide insights into accomplishing highly efficient photocatalysis based on such materials

Protein glycosylation is the most complex and diverse form of post-translational modification in human body. Meanwhile, glycosylation of peptides and proteins emerges as a promising strategy to improve the pharmacokinetic profile of peptide- and protein-based therapeutics. Owing to the importance of protein glycosylation, rigorous evaluation of the relationship between the precise structure and biological function of glycoproteins has to be per-formed. Recently, chemical synthesis, chemoenzymatic synthesis and semisynthesis strategy have attracted extensive attentions towards the prepara-tion of structurally defined glycopeptides and glycoproteins; the obtained synthetic glycoforms thus enable the thorough investigation of specific effects of protein glycosylation. This review highlights the recent progress in the development of novel strategies, preparation of homogeneous glycoproteins and exploration of structure-activity relationships. On this basis, the challenges and prospects are discussed.

Radiotherapy is a mainstay treatment for malignant tumors in clinical. However, enhancing radiation damage to tumor cells meanwhile sparing normal tissues is still a great challenge in radiotherapy. Nanomaterials with high atomic number (Z) values are promising radiosensitizers by promoting the radiation energy deposition in irradiated tumor cells, thus enhancing the therapeutic ratio of radiotherapy. In this review, we described the mechanisms of high-Z element radiosensitizers and systematically summarized the recent progress on metal-based nanomaterials, including high-Z metal nanoparticles, metal-organic frameworks (MOFs) and other high-Z-containing nanomaterials. Finally, further potential and challenges in this field were discussed.

Polycyclic N-heterocycles are very important scaffolds in biomedicinal chemistry and materials science. Intramolecular alkyne hy-droamination is a powerful method for the construction of N-heterocycles. In the last two decades, copper-catalyzed domino reac-tions based on intramolecular alkyne hydroamination has emerged as a robust strategy for assembling various polycyclic N-heterocycles. Great progress has been achieved in this area. This short review covers the advances made in copper-catalyzed domino synthesis of polycyclic N-heterocycles based on this strategy from 2008 to 2023, and will hopefully serve as an inspiration towards the exploration of new copper-catalyzed versions of the transformation. The domino transformations are introduced and discussed from five aspects according to the different key processes involved in these reactions.

Fuel-driven dissipative self-assembly, which is a well-established concept in recent years, refers to out-of-equilibrium molecular self-assembly initiated and supported by the addition of active molecules (chemical fuel). It widely exists in nature since many tempo-rary, active micro- or nanostructures in living bodies are generated by the dissipative self-assembly of biomolecules. Therefore, the study on dissipative self-assembly provides a good opportunity to have an insight into the microscopic mechanism of living organisms. In the meantime, dissipative assembly is thought to be a potential pathway to achieve dynamic, temporary supramolecular materials. Recently, a number of temporary materials have been developed with the aid of strategies for realizing dissipative self-assembly. Some of their properties, including solubility, stiffness, turbidity, color, or self-healing ability, change upon the addition of chemical fuel but spontaneously restore with chemical fuel consumption. The dynamic of these materials brings them various unprecedented functions. In this review, the principles of fabricating a fuel-driven temporary material are first reviewed and subsequently, recent examples of fuel-driven temporary materials are emphatically summarized, including gels, self-erased inks, nanoreactors, self-healing materials, and nanochannels. Finally, the challenges of developing fuel-driven temporary materials and some perspectives on the function and application of such kind of materials are discussed.

Herein we report an asymmetric two-component alkenyl Catellani reaction for the construction of C–N axial chirality through a pal-ladium/chiral norbornene cooperative catalysis and an axial-to-axial chirality transfer process. Various partially aromatic iodinated 2-pyridones, quinolones, coumarin and uracil substrates react with 2,6-disubstituted aryl bromides with a tethered amide group, to afford a wide variety of polycyclic C–N atropisomers (38 examples, up to 97% e.e.). The obtained C–N axial chirality is originated from the preformed transient C–C axial chirality with high fidelity. The synthetic utility of this chemistry is demonstrated by facile preparation of complex quinoline and pyridine based C–N atropisomers through a N-deprotection and aromatization sequence. In addition, a remote axial-to-central diastereoinduction process dictated by C–N axial chirality is observed with excellent diastere-ocontrol.

In recent years, flexible photodetectors (FPDs) have received increasing attention due to their applications in electronic eyes, flexible sensing, terminal devices, and wearable devices. In addition, metallic halide perovskite materials are considered as future materials for FPDs due to their compatibility with flexible substrates, low cost, simple synthesis methods, and superior optoelectronic properties. This review provides a comprehensive overview of the relevant cutting-edge research in the field of flexible perovskite photodetectors (FPPDs) from 2020 to 2022. First, the evaluation criteria for FPPDs are discussed and the development of perovskite stability criteria is emphatically described. Afterwards, the synthesis methods and device construction processes of metal halide perovskite materials commonly used by researchers in the past three years were described. These include single crystals and low-dimensional materials. Moreover, we have elaborated on the research of self-powered FPPD and its contributions in wearability, terminals, and portability. Finally, a summary of developments and possibilities in the field of FPPDs from 2020 to 2022 is provided.

The study of luminescence phenomena in non-conjugated systems, namely clusteroluminescence, has gained significant attention for the development of advanced luminescent materials. While conventional strategies to manipulate the luminescent performances are based on complicated chemical reactions. In contrast, nature employs complexation to modulate luminescence, inspiring researchers to adopt an engineering approach for the construction of efficient clusteroluminogens. In this work, we explore the complexation-induced clusteroluminescence of carbonyl-based polymers with nitrogen-containing organic bases, exemplified by polyamide, polyester, polycarbonate, and poly(monothiocarbonate). The results demonstrate an increase in the intrinsic 440 nm emission of carbonyl groups and the emergence of new emission peaks upon complexation. The study proposes a through-space n‧‧‧π complex mechanism, highlighting the potential of complexation as a strategy for modulating the clusteroluminescent properties of non-conjugated systems. Further research is necessary to unravel underlying mechanisms, optimize cluster structures, and explore new materials for complexation, thereby advancing optoelectronics and photonics fields and enabling practical applications of clusteroluminescent materials.