The development of efficient and highly selective catalysts for the electrochemical CO2 reduction reaction (CO2RR) is crucial for achieving carbon neutrality and sustainable energy cycles. In this study, the stable structure of the MoS3 monolayer was determined using the crystal structure prediction software CBD-GM. Owing to its distinct sulfur coordination environments and large dipole moment, MoS3 serves as an ideal support for single-atom catalysts. By doping transition metals at specific sulfur sites (S1-S3), we systematically screened a series of single-atom configurations for CO2 activation. The results demonstrate that CO2 molecules are effectively activated when Sc, Mn, Fe, Co, and Ni single atoms are doped at the S2 site. Remarkably, CoS2@MoS3 and NiS2@MoS3 are demonstrated as highly effective catalysts for selective CO2-to-CH4 conversion, with low limiting potentials of -0.17 and -0.49 V, respectively. This study provides theoretical insights into the rational design of MoS3-based single-atom systems for efficient and selective CO2 electroreduction.

The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering. Nevertheless, substantial challenges remain in constructing nanoscale supramolecular architectures with precisely controlled giant dimensions. Herein, we report a precision-guided synthetic strategy for constructing giant 2D and 3D supramolecular architectures with rhomboidal motifs, which was achieved through a dovetail joint strategy. Initial assembly of bis-mortise ligand L1 with dovetail tenon ligand L2 in the presence of Cd2+ ions yielded the fundamental bis-rhombic supramolecule R1 . Subsequent structural elaboration of the dovetail tenon motif enabled the development of multitopic ligands L3 and L4 , which facilitated the construction of expanded architectures of the giant bis-propeller supramolecule R2 and tris-propeller supramolecule R3 . The synthesized supramolecules R1-R3 were fully characterized multidimensional NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), traveling wave ion mobility mass spectrometry (TWIM-MS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). This work develops an innovative dovetail-joint assembly strategy for constructing rigid giant supramolecular architectures, establishing a new paradigm for precision engineering of complex 3D molecular systems. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Chinese of Medical Sciences.

Multisegment Ser/Thr ligation (STL) is an important technique for the chemical synthesis of proteins. The Fmoc group is currently widely used in multisegment STL to temporarily protect the reactive Ser or Thr residue at the N-terminus of the salicylaldehyde ester segment(s). However, the alkaline conditions required for Fmoc removal are incompatible with base-sensitive post-translational modifications and can readily induce aspartimide formation. Here, we report the Mmoc group-based multisegment STL. The Mmoc protection group can be rapidly removed under trifluoroacetic acid (TFA) and NH4I conditions, and this new strategy has been proven to efficiently synthesize proteins containing O-acetylation as well as Asp-Gly sequences.

Controllable modifications on dimensionalities and topologies of supramolecules are crucial for tuning their properties. Here, we report a robust component-controlled topological transformation, initiating with a two-dimensional (2D) layered coordination network S2 formed by the self-assembly of a metallo-organic ligand (MOL) LA with Zn(II). The strategic introduction of a V-shaped modulator LB with peripheral arms into the S2 system triggered a remarkable topological transformation, thus affording a discrete zero-dimensional (0D) hexagon-framed Star of David S1. This unprecedented 2D to 0D control facilitates direct comparison of their intrinsic properties, with structures unequivocally confirmed by nuclear magnetic resonance (NMR) spectroscopy, high-resolution electrospray ionization mass spectrometry (ESI-MS), traveling-wave ion mobility mass spectrometry (TWIM-MS), and microscopy. In the aerobic sulfide oxidation, the extended 2D network S2 exhibited significantly improved photocatalytic performance over S1. This enhanced efficiency was attributed to S2's pseudo-heterogeneous nature, which maximizes active site exposure and overcomes typical limitations of heterogeneous catalysts. This work not only establishes a novel strategy for controlling supramolecular architecture but also compellingly demonstrates that for catalytic applications, ensuring active site accessibility through judicious structural design can be a more potent strategy than pursuing isolated structural complexity.

Metallo-cages with distinctive cavities and intricate molecular frameworks have found extensive applications in diverse fields. However, it is still challenging to construct larger frameworks with high rigidity and complexity via facile methods and simple ligands, which is crucial for further applications of these alluring architectures. Herein, we propose a cage-on-cage assembly based on the development of a judiciously designed dendritic ligand that enables the bottom-up growth of a series of C2v-symmetric multitopic ligands (LA, LB, and LC). Through systematic increase of branches on the ligand, the assemblies were precisely controlled, yielding a series of supramolecular architectures with hierarchically increased complexity from a C2h-symmetric chairlike [Zn2LA2], to a C3v-symmetric bowl-shaped [Zn6LB3], and ultimately into a Td-symmetric giant tetrahedral cage [Zn36LC12]. Remarkably, the [Zn36LC12] metallo-cage achieved an unprecedented molecular weight of 51 kDa and an outer ball diameter of 6.7 nm, representing the largest single-component ligand-based molecular tetrahedron reported to date in terms of both molecular weight and physical dimensions. Owing to the high rigidity of the single-component framework, the [Zn36LC12] exhibited a superior fluorescence quantum yield of 60.3%. This research introduces an innovative hierarchical strategy for the architecture of single-component metallo-organic cages, which provides a promising candidate for the development of luminescent materials in advanced optoelectronics.

Fe(II)-based supramolecules have attracted considerable interest in catalysis, environmental science, and biomedicine due to their low toxicity, low cost, and versatile oxidation states. However, the strong coordination affinity of Fe(II) often compromises the reversibility of self-assembly, and conventional one-pot synthesis─hindered by intricate ligand design and kinetic traps─hampers the direct formation of desired Fe(II)-based topological architectures. To overcome these limitations, a postsynthetic transmetalation strategy was employed: a Zn(II)-based hexagon-fused wheel was first assembled from a Ru(II)-centered metallo-ligand LA and a multitopic terpyridine ligand LB, followed by complete Zn(II)-to-Fe(II) exchange to afford the target discrete Fe(II) complex (diameter 14.2 nm, molecular weight ∼ 47,690 Da). This work demonstrates a supramolecule-to-supramolecule metal exchange within a large discrete architecture. The structure was characterized by UV-vis spectroscopy, NMR, and mass spectrometry. Therefore, this transmetalation strategy presents an alternative platform that overcomes the reversibility constraint in Fe(II) coordination. It facilitates the creation of novel functional complexes beyond the scope of direct synthesis, promoting the development of structurally sophisticated and functional Fe-based supramolecules.

Although the structural framework for constructing regular polyhedral supramolecular cages from symmetric ligands is relatively well established, assembling distorted polyhedra using ligands of lower symmetry remains a considerable challenge. Herein, we report two distorted octahedral supramolecular cages, S1 and S2, based on a spirobiindane-derived rigid core with varying π-conjugation lengths and heteroatoms. The nearly perpendicular spirobiindane unit provides a rigid structural platform and promotes the formation of distorted cage-like structures. Octahedron S1 exhibited a high fluorescence quantum yield (ΦF) of up to 72.87% in pure DMF, and the ΦF increased to 96.24% in a DMF/H2O mixed solvent with 20% water content, surpassing that of most reported metal-organic cages. In contrast, the π-extended and heteroatom system S2 shows progressively red-shifted and aggregation-induced emission enhancement; however, the strong electron-withdrawing effect of the phenazine unit and the enlarged cavity size likely result in a significantly lower ΦF for S2 compared to S1. By reporting the synthesis of luminescent supramolecular cages with novel structures, this work further reveals how π-conjugation extension and heteroatoms modulate the emission behavior of supramolecular assemblies, thereby offering a new perspective for the rational design and construction of tunable luminescent supramolecular systems.

H2 relaxin is an important member of the insulin superfamily, but little is known about how H2-relaxin activates the RXFP1 receptor. Affinity-tag containing peptide probes could separate receptor from cell/tissue lysate through pull-down methods, and the probe-receptor complex could be applied in the structure resolution to understand the receptors activate mechanism. The affinity-tag modified H2 relaxin probe has about 70-residue, it was very difficult to obtain through our previous diaminodiacid (DADA) based single-shot solid-phase synthesis strategy. Here we report a click chemistry-assisted single-shot solid-phase synthesis strategy for the synthesis of H2 relaxin probe bearing affinity-purified tags. This study highlights the utility of modern chemical protein synthesis in obtaining custom designed tools for biological studies.

In this study,we present the fabrication of vertical SnO/β-Ga2O3 heterojunction diode(HJD)via radio frequency(RF)reactive magnetron sputtering.The valence and conduction band offsets between β-Ga2O3 and SnO are determined to be 2.65 and 0.75 eV,respectively,through X-ray photoelectron spectroscopy,showing a type-Ⅱ band alignment.Compared to its Schot-tky barrier diode(SBD)counterpart,the HJD presents a comparable specific ON-resistances(Ron,sp)of 2.8 mΩ·cm² and lower reverse leakage current(IR),leading to an enhanced reverse blocking characteristics with breakdown voltage(BV)of 1675 V and power figure of merit(PFOM)of 1.0 GW/cm².This demonstrates the high quality of the SnO/β-Ga2O3 heterojunction inter-face.Silvaco TCAD simulation further reveals that electric field crowding at the edge of anode for the SBD was greatly depressed by the introduction of SnO film,revealing the potential application of SnO/β-Ga2O3 heterojunction in the future β-Ga2O3-based power devices.

Owing to its less oxygen-dependent mechanism, type I photodynamic therapy (PDT) has exhibited significant superiority over the more common type II PDT in the treatment of hypoxic tumors. Supramolecular coordination complexes (SCCs) have shown great potential in photodynamic cancer therapy; however, SCC-based photosensitizers which can achieve type I PDT have rarely been reported. Herein, we present the design and synthesis of a novel heteroleptic/trimetallic OsII-RuII-ZnII Sierpiński triangle ST-2 via coordination-driven self-assembly. The distinctive SCC ST-2 displayed high generation ability of reactive oxygen species (ROS) and boosted the production of O2-• involved in the type I mechanism. Detailed in vitro investigations demonstrated ST-2 exhibited excellent PDT efficacy against all tested cancer cell lines with low IC50 values in the subnanomolar range and high phototoxicity indexes (PI) up to 750 even under hypoxic conditions and induced cancer cell death mainly through type I PDT. The anticancer mechanism could be ascribed to the mitochondrial and lysosomal damages as well as cell apoptosis and cell cycle arrest. Further studies confirmed that ST-2 disintegrated 3D multicellular tumor spheroids and effectively inhibited the growth of solid hypoxic tumors in mice with minimal side effects. This work not only provides an alternative strategy for the development of highly efficient type I photosensitizers but also opens new possibilities for Sierpiński triangles in biomedicine.

Porous organic polymers (POPs) serve a key function as transition metal carriers and have attracted widespread attention in the catalysis field. However, a preferred and universal transition metal carrier remains elusive. In this study, we designed and synthesized a preferred 2,2':6',2''-terpyridine-containing building motif and prepared a POP (POP-Tpy-1) via the Buchwald-Hartwig coupling reaction of a diamino-linker and trisbromo-node. Taking full advantage of the strong bonding ability of the terpyridine moiety and the availability of binding room, coupled with the high stability of the POP itself, POP-Tpy-1 displayed universal coordination binding and a high load capacity for many common transition metals (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Ru3+, Pd2+, Fe2+, and Cu+). The corresponding metal-loaded porous organic polymers (POP-Tpy-1-M) can serve as transition metal heterogeneous catalysts, and these were conceptually verified by typical synthesis reactions, including cross-dehydrogenative coupling, click reactions, and Suzuki-Miyaura coupling reactions.

In the realm of photocatalytic production, discrete metallo-organic cages have emerged as promising photocatalysts. However, their performance is often constrained by limited substrate accessibility and sluggish oxygen reduction reaction (ORR) kinetics. Herein, we designed and synthesized two novel nonnoble metallo-cages, S1 and S2 , and evaluated their photocatalytic activities. Benefit from the high structural stability, low exciton binding energy (52.9 meV), ultrafast intramolecular electron transfer (49.50 ps), and prolonged excited-state lifetime (1, 970 ps), S2 exhibits efficient charge carrier separation. In addition, a bottom-up approach was employed to disperse S2 into ultrasmall nanoscale particles, which significantly enhanced substrate accessibility and the reaction kinetics. Furthermore, the addition of sodium oxalate not only optimizes charge carrier separation and utilization but also provides a kinetically favorable pathway for superoxide radical anion (·O 2 − ) generation, overcoming ORR kinetic bottlenecks. These synergistic effects culminate in a record production rate of 77, 401 µmol g −1 h −1 and a solar-to-chemical conversion efficiency of 0.97%, outperforming most reported organic photocatalytic systems.

AlGaN ternary alloy is a potential candidate for visible blind or even solar blind photodetection application in extreme environmental conditions due to its excellent thermal stability and radiation hardness. However, the screw dislocations formed during the heteroepitaxial growth have proved to be responsible for high dark current, which is unfavorable to ultraviolet (UV) detection. In this study, KOH wet etching was adopted to eliminate the surface states of Ga-polar AlGaN epilayer and reconstruct the surface oxides. The dark current of the KOH-etched AlGaN epilayer was lowered by three orders of magnitude, leading to a high photo-to-dark current ratio (PDCR) of 870. X-ray photoelectron spectroscopy (XPS) indicated the upward surface band bending after etching and the increase of surface barrier height by 0.4 eV. UVB/UVA rejection ratio ( ${R}_{{300}}/{R}_{{365}}{)}$ of the device was calculated to be 353, exhibiting the potential application in sensitive UVB photodetection. The study provides a facile way for enhanced UVB photodetection of AlGaN epilayer. The simple device structure, along with the easy manufacturing process, may facilitate the integration with other components on optoelectronic circuits.

Cell-penetrating peptides (CPP) enable to deliver large biomolecules (proteins, peptides, oligonucleotides, etc.) into cells. An important step for the conjugation of CPPs to target proteins is the acquisition of activated CPPs, however, it requires a multi-step isolation and purification process. Here, we report a facile strategy for the synthesis of activated cell-penetrating peptides via a one-step solid-phase synthesis through the reaction of 5,5 ' dithiobis(2-nitrobenzoic acid) (DTNB) with CPP on resins, which can then be treated with a TFA cocktails to directly obtain activated CPP (TNB-CPP). Using this strategy, we successfully obtained activated cyclic cellpenetrating deca-arginine peptide (TNB-cR10) and activated Tat (TNB-Tat) and efficient cytosolic delivery of ubiquitin (Ub) can be achieved by linking it to these CPPs.

We report a new serine/threonine ligation (STL)-assisted diaminodiacid (DADA) strategy for the flexible construction of disulfide surrogates by the option of more abundant -Aa-Ser/Thr- ligation sites. The practicality of this strategy was evidenced by the synthesis of the intrachain disulfide surrogate of C-type natriuretic peptide and the interchain disulfide surrogate of insulin.

In this letter, we reported a self-powered periodic inverse micropyramid (PIMP)-Si/graphene photodiode with high responsivity, specific detectivity and fast response speed of 0.78 A $\text{W}^{-{1}}$ , ${3}.{83}\times {10} ^{{14}}$ Jones and 226/ $364~\mu \text{s}$ for rise/fall time at zero bias upon 880 nm illumination, respectively. It was found that the introduction of ultrathin interfacial oxide layer can passivate surface states and thereby lead to an excellent current stability, which enables high-quality Fourier single-pixel imaging (FSI). A ${256} \times {256}$ -pixel image achieved at 7.79% sampling rate showed the peak-signal-to-noise ratio (PSNR) of 28.3 dB and structural similarity index measure (SSIM) of 0.50, revealing the high-quality single-pixel imaging (SPI).

Supramolecular architectures with multiple emissive units are especially appealing due to their desired properties, such as artificial light harvesting and white-light emission. But fully achieving multi-wavelength photoluminescence in a single supramolecular architecture remains a challenge. In this paper, functionalized supramolecular architectures containing twelve metal centers and six pyrene moieties were nearly quantitatively synthesized by multi-component self-assembly and fully characterized by 1D and 2D nuclear magnetic resonance, dynamic light scattering, electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy. Moreover, the hierarchical nano-assemblies were prepared by introducing anionic dyes to the positively charged self-assembled framework, which contained three luminescence centers, namely, pyrene, tpy-Cd coordination parts, and Sulforhodamine B anions. Such a hierarchically assembled system displayed tunable emission by taking full advantage of aggregation-induced emission enhancement, aggregation-caused quenching, and fluorescence resonance energy transfer effects and showed the diverse emission colors. This research provides a new insight for constructing multiple emissive metallo-supramolecular assemblies.

Fractal structures with self-similarity are of fundamental importance in the fields of aesthetic, chemistry and mathematics. Here, by taking advantage of constructs the rational geometry-directed precursor design, we report the construction of two fascinating Platonic solids, the Sierpiński tetrahedron ST-T and the Sierpiński octahedron ST-O, in which each possesses a fractal Sierpiński triangle on their independent faces. These two discrete complexes are formed in near-quantitative yield from the multi-component self-assembly of truncated Sierpiński triangular kernel L1 with tribenzotriquinacene-based hexatopic and anthracene-based tetratopic terpyridine ligands (L3 and L4 ) in the presence of metal ions, respectively. The enhanced stabilities of the 3D discrete structures were investigated by gradient tandem mass spectrometry (gMS2 ). This work provides new constructs for the imitation of complex virus assemblies and for the molecular encapsulation of giant guest molecules.

Histone post-translational modifications play critical roles in dynamic regulation of chromatin structure. For instance, histone iodination has been confirmed to directly influence the stability of the histone core. However, it remains difficult for the construction of atom-customized iodinated histones for biochemical and biophysical studies. Here we report a practical strategy for the total chemical synthesis of homogenous histone H2B-Y81-iodination through the sequential ligation of four segments based on peptide hydrazides. The synthesized Y81-iodinatied H2B can be used for the construction of iodinated nucleosomes. Our results showed that iodinated histones synthesized by utilizing this strategy can provide multi-milligram-scale protein for biochemical studies.

Nanosized cage-within-cage compounds represent a synergistic molecular self-assembling form of three-dimensional architecture that has received particular research focus. Building multilayered ultralarge cages to simulate complicated virus capsids is believed to be a tough synthetic challenge. Here, we synthesize two large double-shell supramolecular cages by facile self-assembly of presynthesized metal-organic hexatopic terpyridine ligands with metal ions. Differing from the mixture of prisms formed from the inner tritopic ligand, the redesigned metal-organic hexatopic ligands bearing high geometric constraints that led to the exclusive formation of discrete double-shell structures. These two unique nested cages are composed of inner cubes (5.1 nm) and outer huge truncated cubes (12.0 and 13.2 nm) with six large bowl-shape subcages distributed on six faces. The results with molecular weights of 75 232 and 77 667 Da were among the largest synthetic cage-in-cage supramolecules reported to date. The composition, size and shape were unambiguously characterized by a combination of 1H NMR, DOSY, ESI-MS, TWIM-MS, TEM, AFM, and SAXS. This work provides an interesting model for functional recognition, delivery, and detection of various guest molecules in the field of supramolecular materials.