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

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.

Besides serving as therapeutic agents and building blocks for glycoprotein synthesis, homogeneous synthetic glycopeptides also benefit understanding function of specific glycoform. However, the selectivity coupling of oligosaccharides to a given peptide remains challenging despite the fact that the synthesis of structure-defined complex oligosaccharides has been greatly facilitated by chemoenzymatic based approaches. Herein, a Ca2+-promoted glycosylation approach was developed to exclusively modify phenolic peptide using a panel of biologically important glycans.

This review presents a comprehensive examination of fully conjugated covalent organic frameworks (COFs), which constitute an emerging class of porous materials with immense potential for diverse applications. This article focuses on diversified fully conju-gated COFs, including sp2 carbon-carbon linkages, pyrazine linkages, benzobisoxazole linkages, dioxin linkages, β-aminoalkenone linkages, etc. The synthesis techniques and structural attributes of these COFs are expounded upon in great detail, along with their potential applications in various fields. The review thus provides a valuable resource for researchers keen on delving into the synthe-sis and applications of fully conjugated COFs, thereby highlighting their potential for developing novel functional materials with dis-tinctive properties.

A photo-triggered cascade cyclization of silyl enolate to prepare angularly fused tricyclic scaffold is developed. The reaction demonstrates good substrate scope and stereo-selectivity. The excellent stereo- and regio-selectivity for this cascade reaction is elucidated via conformational analysis and DFT calculation, respectively.

A transition-metal-free one-pot direct synthesis of tetrathiophosphates (R1S)2P(S)SR2 from white phosphorus (P4), through inter-mediate S-sodium S,S-dialkylphosphorotetrathioates (R1S)2P(S)SNa, is presented. In the presence of NaSH, various disulfides such as diaryl disulfides and dialkyl disulfides are easily coupled with P4 to give S-sodium S,S-dialkylphosphorotetrathioates (R1S)2P(S)SNa in almost quantitative yield, which react with alkyl halides in one pot to generate (R1S)2P(S)SR2. Furthermore, S-(2-cyanoethyl)-substituted tetrathiophosphates (R1S)2P(S)SCH2CH2CN are successfully designed as a kind of tetrathiophosphorylation reagents to react with diaryl iodonium salts involving deprotection-dealkylation process.

Nickel(II) complexes with pyrazole-based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel-Crafts alkylation of toluene. We have prepared ten new nickel(II) dibromide complexes with various substituted bis(azolyl)methanes. They have been characterized using 1H NMR, IR, high resolution mass spectrometry and elemental analysis. The structures of three complexes have been unambiguously established using X-ray diffraction. It was found that these complexes in the presence of Et2AlCl or Et3Al2Cl3 are active both in ethylene oligomerization and Friedel-Crafts alkylation processes (activity up to 3720 kgoligomer·mol[Ni]−1·h−1). The use of Et3Al2Cl3 results in the higher share of alkylated products (up to 60%). Moreover, catalytic systems activated with Et3Al2Cl3 produced small amounts of odd carbon number olefins (up to 0.8%). The Friedel-Crafts alkylation was used as a trap for previously undetected short-chain odd carbon number olefins (C3 and C5).

A new electrophilic monofluoromethylthiolating reagent N-fluoromethylthiophthalimide PhthSCH2F 1 was developed. Reagent 1 could be readily synthesized from easily available starting materials benzyl mercaptan and CH2FCl in three steps. N-fluoromethylthiophthalimide 1 is a powerful electrophilic monofluoromethylthiolating reagent that allows the monofluorome-thylthiolation of a wide range of nucleophiles including alkynes, aryl/vinyl boronic acids, electron-rich heteroarenes,-ketoesters and oxindoles, as well as thiols under mild conditions.

Traditional molecular biology tools have elucidated the identities and functions of RNA molecules, which are essential to the understanding of gene transcription and protein translation. Deepening this research field would further require the direct visualization of RNA dynamics such as the DNA-RNA interactions and RNA-protein interactions. Towards this goal, the rise of RNA imaging tools over the past 15 years has reformed how we looked at these processes. In this emerging topic, we first highlighted recent advances on three main RNA imaging tools based on the species of interacting molecules: RNA-RNA pairing, RNA-protein binding, and small molecule-RNA complex. We introduced the advantages of these tools from a technical viewpoint, including binding affinity, fluorescent turn-on ratio, stability, and impacts on targeted RNA. Next, we discussed new rising opportunities and future directions, echoing the state-of-the-art imaging tools in the fields of fluorescent proteins and small fluorescent molecules. Together, we believe this emerging field will bring new insights on how we study RNA biology in living systems.

We herein report a simple ether-directed iridium-catalyzed site- and enantioselective C(sp2)-H borylation of benzhydryl ethers for the first time. Various chiral benzhydryl ethers were obtained with high enantioselectivities in the presence of a tailor-made chiral bi-dentate boryl ligand. We found that the kinetic resolution relay significantly amplified the enantioselectivity. The synthetic utility of the current method was demonstrated by gram-scale C-H borylation and C-B bond transformations.

Ultra-narrow bandgap (ultra-NBG) small molecule acceptors (SMAs) show great potential in organic solar cells (OSCs) due to the extend-ed near-infrared (NIR) absorption. In this work, a synergetic alkoxy side-chain and chlorine-contained end group strategy is employed to achieve A-DA’D-A type ultra-NBG SMAs by introducing alkoxy chains with oxygen atom at the second position into the thiophene β posi-tion as well as replacing the F atoms with Cl atoms in the end group. As a result, the heptacyclic BZO-4F shows a redshifted absorption onset (960 nm) than Y11 (932 nm) without oxygen atoms in the side chains. Then, the fluorinated end groups are substituted with the chlorinated ones to synthesize BZO-4Cl. The absorption onset of BZO-4Cl is further redshifted to 990 nm, corresponding to an optical ultra-NBG of 1.25 eV. When blending with the polymer donor PBDB-T, the binary devices based on PBDB-T: BZO-4F and PBDB-T: BZO-4Cl delivers power conversion efficiencies (PCEs) over 12%. Furthermore, ternary devices with the addition of BZ4F-O-1 into PBDB-T: BZO-4Cl system achieve the optimal PCE of 15.51%. This work proposes a synergetic alkoxy side-chain and chlorine-contained end group strategy to achieve A-DA’D-A type ultra-NBG SMAs, which is important for future molecular design.

The stereoselective preparation of fullerene bis-adducts through nontethered methods remains difficult due to the significant amount of regioisomers produced. The trans-4 aziridino[60]fullerenes, C60(NC6H4R)n (n = 1 or 2, R = OMe, OEt, OBu), were selectively synthesized even without a catalyst by reacting octabromofullerene with the corresponding aniline. Nuclear magnetic resonance spectroscopy, UV-vis spectroscopy, and X-ray structural analysis provided convincing characterization of the compounds. A possible reaction process was proposed to clarify the synthesis of highly regioselective trans-4-bisaziridino[60]fullerenes. The possible use of these aziridino[60]fullerene derivatives as propellant stabilizers was also explored.

Chemically, N1 nitrogen of piperazic acid is more nucleophilic than N2 nitrogen, but amide bonds predominantly formed at N2 nitrogen are prevalent in piperazic acid-containing natural products, with only one exception of sanglifehrin. Thus two orthogonal protecting groups of nitrogen are often employed to realize selective coupling of N2 nitrogen, resulting in increased synthetic steps and low synthetic efficiency. However, we developed selective deprotection of N2-Cbz from the N1,N2-diCbz piperazic acid-containing peptide to form the N2 amide exclusively, avoiding the tedious orthogonal protection strategy commonly applied to the easily-accessible N1,N2-diCbz piperazic acid as the building block. We employ this method to achieve an efficient synthesis of piperazic acid-containing cyclodepsipeptide core of verucopeptin with an overall yield of 21%. The key steps include late stage coupling of piperazic acid with 3-hydroxyleucine derivatives, and HATU-mediated macrolactamization of 19-membered macrocycle at N9 and C10. The selective deprotection of N2-Cbz from the N1,N2-diCbz-piperazic acid at late-stage would greatly facilitate the total syntheses of piperazic acid-containing cyclodepsipeptides of biological interest.

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.

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.

Organic luminogens with persistent room temperature phosphorescence (RTP) have drawn tremendous attentions due to their prom-ising potentials in optoelectronic devices, information storage, biological imaging, and anti-counterfeiting. In this work, six triazatrux-ene-based lumiogens with different peripheral substituents and configurations are synthesized and systematically studied. The results show that their fluorescence quantum yields in solid states range from 15.73% to 37.58%. Dispersing the luminogens as guest into the host (PPh3) could turn on the persistent RTP, where PPh3 acts as not only a rigid matrix to suppress the non-radiative transitions of the guest, but also provides energy transfer channels to the guest. The maximum phosphorescence efficiency and the longest lifetime could reach 29.35% and 0.99 s in co-crystal films of 6-TAT-CN/PPh3 and 5-TAT-H/PPh3, respectively. Moreover, these host-guest co-crystalline films exhibit great potentials in advanced dynamic data encryption and anti-counterfeiting. This work deepens the insight for low cost, halogen-free, and facile fabrication of all-organic persistent RTP materials.

Isochromanone is the core structure of many bioactive compounds. Direct oxidation of isochromans is one of leading methods for the construction of isochromanones, while most established processes remain suffering from the use of environmental unfriendly metal oxidants, harsh reaction conditions, and the difficulty in catalyst recycling and production separation. Herein, we report a convenient, cost-effective, and green method for the synthesis of high-value added isochromanones via isochroman oxidations with O2 by a novel heterogeneous vanadium cluster catalyst (Cat.1) under mild conditions. This reaction protocol demonstrates high catalytic activity with good catalyst recyclability and reusability for a wide scope of substrates.

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.