Latest ArticlesReductive amination between glycolaldehyde derivatives and lysine residues is a widely used strategy for constructing neoglycoproteins in biomedical applications. Here, α- and β-glycolaldehyde glycosides of five biologically relevant monosaccharides (Glc, Gal, Man, GlcNAc, GalNAc) were synthesized and conjugated to protein at a fixed sugar-to-protein ratio. Continuous kinetic monitoring revealed that anomeric configuration markedly influences both reaction rates and final sugar loading: α-Man > β-Man; β-Gal/GalNAc > their α-counterparts; Glc and GlcNAc showed no significant anomeric preferences. NMR analysis identified cyclic intermediates that reduce the effective concentration of reactive aldehyde, while DFT calculations provided complementary insight into anomer-specific electrophilic character. These findings offer a mechanistic rationale for selecting anomeric configuration in glycoconjugate design.
Precise control over the dimensionality and morphology of supramolecular assemblies remains a key challenge in hybrid material design. Here we report a directional assembly strategy that exploits synergistic portal-specific hydrogen bonding and ion–dipole interactions between cucurbit[5]uril (CB[5]) and an Anderson-type polyoxometalate (POM) functionalized with terminal protonated amines. This tailored interaction drives the formation of elongated two-dimensional hybrid sheets with spatial confinement and anisotropic growth. The resulting CB[5]-NH2POM hybrids exhibit high thermal stability and surface-accessible CB[5] units, enabling hierarchical integration with gold nanorods (AuNRs). These AuNRs@CB[5]-NH2POM hybrids demonstrate efficient photothermal conversion (37.8%) and enable near-quantitative catalytic conversion (>99%) in NIR-triggered sulfide oxidation. Comparative controls confirm the critical role of CB[5]-mediated portal interactions in both structural definition and functional performance. This study highlights a transferable supramolecular design principle for dimensional control and modular interface engineering, offering a promising platform for developing adaptive hybrid materials in photothermal catalysis and related applications.
Site-selective deuterated reduction of quinoline to deuterium-labelled 1,2,3,4-tetrahydroquinoline scaffold can offer a powerful strategy for drug development, mechanistic studies, and synthesis of isotopically labeled standards. Existing deuterated reduction methods predominantly produce fully deuterated piperidines, lacking control over regioselectivity and deuterium stoichiometry. Herein, we report a Ni-catalyzed sequential deuteration protocol that enables regio- and multiplicity-controlled synthesis of mono-, di-, and tri-deuterated tetrahydroquinolines with simple deuterating reagents. Nucleophilic and electrophilic deuterating sources were combined to achieve site-selective reductive deuteration at 2-, 3- and 4-positions of quinolines. The method features broad functional group compatibility and delivers D-labeled tetrahydroquinolines in high yields with excellent positional deuterium incorporation. The protocol was further extended to the double-deuteration of different classes of olefins, quinoxalines and acridines, thus providing a unified platform for efficient synthesis of selectively D-labeled N-containing heterocycles and alkenes derivatives.
Nitrogen-doped carbon dots (N-CDs) were synthesized via a hydrothermal method, utilizing citric acid and urea as precursor materials. Through a systematic characterization and evaluation process, the N-CDs variant with the highest amino group density was identified as an outstanding metal-free photocatalyst. Under ambient conditions, this photocatalyst exhibited remarkable catalytic performance in promoting visible-light-driven cross-dehydrogenative coupling (CDC) reactions between heteroaryl substrates and a wide range of H-phosphine oxide derivatives. This methodology presents several noteworthy advantages, such as operational stability and recyclability of the photocatalyst system, compatibility with various functional groups, mild reaction parameters, scalability for practical applications, and eco-friendly implementation using a mixed solvent system composed of 2-methyl tetrahydrofuran (2-Me THF) and water as the solvent medium. The developed protocol demonstrates enhanced process sustainability through its combination of environmental benignity and technical practicality.
The development of recyclable materials has been the key to designing sustainable materials. Dynamic supramolecular polymers, taking advantages of the reversibility of noncovalent and dynamic covalent bonds, offer many opportunities for constructing responsive and recyclable material. Here, we report dynamic supramolecular network polymers based on the cooperation between hydrogen bond and the pillar[5]arene-based host–guest interaction. The backbones of the polymer network are constructed by poly(disulfides) and the side chains are cross-linked by hydrogen bond and the pillar[5]arene-based host–guest interaction. The introduction of host-guest interaction renders the resulting network with enhanced mechanical performances. The dynamic performance of poly(disulfides) backbones and the noncovalent side chain endow the polymer materials with depolymerization ability into monomer in a closed-loop manner. We foresee this dynamic supramolecular polymer system will show widespread potential toward developing sustainable materials.
Lactic acid plays a crucial role in tumor growth, maintenance, and metastasis. Given its significant impact on tumorigenesis, modulating lactic acid levels within the tumor microenvironment (TME) presents new opportunities for cancer therapy. Herein we developed a supramolecularly engineered bacterial reactor using a strong host-guest interaction between cucurbit[7]uril (CB[7])-modified attenuated Salmonella typhimurium VNP20009 (VNP) and adamantane (ADA)-functionalized lactate oxidase (LOX)-loaded liposomes. The VNP-mediated tumor colonization of these reactors facilitated LOX-driven lactic acid depletion in the hypoxic TME, simultaneously producing hydrogen peroxide (H2O2). The presence of H2O2 triggered the expression of catalase in VNP, which, in turn, catalyzed the conversion of H2O2 to oxygen (O2). This cyclic cascade reactor thus provided a continuous and stable oxygen source, promoting sustained lactic acid consumption for metabolic treatment, ultimately leading to tumor growth suppression and an enhanced anticancer effect.
The interfacial electronic interaction between the support and catalyst has been demonstrated to play a significant role in regulating the d-band structure of metal centers. Still, it requires dedicated control over the interaction in a reasonable manner. Herein, we developed a heterostructured support by covalently linking carbon nitride quantum dots (CNQDs) on TiO2, to anchor electroactive CoP clusters (TiO2–CNQD/CoP) for hydrogen evolution reaction (HER). The interfacial electronic interaction between the heterostructured support (TiO2–CNQD) and CoP can be controlled by varying the size of CNQDs, owing to the number of conjugated N-heterocycles in CNQDs induces tunable π-electron delocalization. As a result, a volcano-shaped correlation between the shift of the Co d-band center (Δd) and the HER performance was established, suggesting that TiO2–CNQD/CoP-C2 with a moderate size of CNQD is the optimal HER catalyst. This study highlights the critical role of interfacial interaction in supported catalysts, providing a predictive descriptor focusing on the support design of advanced HER catalysts.
Bifunctional molecules incorporating both germyl and boryl groups represent a significant class of compounds that have attracted considerable attention in organic synthesis due to their unique reactivity and versatility in diverse chemical trans-formations. Here, we present a highly efficient, one-step synthesis of such molecules through the catalytic C–H borylation of parent organogermanes, utilizing germanium as a directing atom. The process employs an iridium catalyst in conjunction with a ligand and acetate base, facilitating the formation of a germylametallacycle intermediate within the catalytic cycle. This methodology demonstrates broad substrate scope, successfully accommodating three distinct classes of organogermanes: benzylhydrogermanes, biaryl-type hydrogermanes, and triarylhydrogermanes, encompassing both sp2 and sp3 C–H activation. The versatile reactivity of the products, derived from both boron and germanium chemistry, highlights their potential utility in various applications.
Metal-catalyzed alkylarylation of two carbon−carbon (C-C) bonds across vicinal C(sp2) sites in olefins can provide access to diverse combinatorial chemical space. Pre-activated arenes are often used as aryl sources, but the direct utilization of Csp2−H bond instead of pre-activated arenes remains underdeveloped. Herein, ruthenium-catalyzed alkylarylation of alkenes via para-selective C-H functionalization of unprotected aniline has been reported. It bears good functional group tolerance and enables late functionalization of complex natural products. Evaluation of cone angle and minimum percent buried volume help to determine the optimal ligand. The mechanism studies reveal the dissociation of p-cymene during the catalytic cycle which triggers the redox processes for radical generation.
The radical-mediated 1,2-difunctionalization of alkenes or alkynes has emerged as an efficient strategy for augmenting molecular diversity and complexity. Nevertheless, developing remote 1,4-difunctionalization reactions through radical cascade additions involving two intermolecular unsaturated bonds confronts complex chemo-, regio-, and stereoselectivity challenges. Here, we report a photocatalytic strategy that enables the first radical 1,4-difunctionalization across simple alkenes and arylacetylenes, leveraging the distinct reactivity between alkyl phosphites and different carbon radicals, by employing 1 mol% fac-Ir(ppy)3 as the photocatalyst and quinuclidine as the base. Mechanistic studies reveal that the photoexcited Ir(Ⅲ)* synergistically governs two processes: (1) Single-electron transfer (SET) activation of Rf-X to generate fluoroalkyl radicals, and (2) triplet energy transfer (TEnT)-mediated stereo-control of the constructed alkenyl phosphonates to achieve high Z/E selectivity. This method enables the efficient synthesis of various δ-fluoroalkyl-substituted alkenyl phosphonates with high Z/E selectivity under mild conditions. Furthermore, some products exhibit a synergistic inhibitory effect on porcine epidemic diarrhea virus (PEDV), effectively blocking viral adsorption and replication while preventing PEDV-induced cell apoptosis in vitro.
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