Stimulus‐Responsive Copper Complex Nanoparticles Induce Cuproptosis for Augmented Cancer Immunotherapy

Advanced Science, Journal Year: 2024, Volume and Issue: 11(13)

Published: Jan. 25, 2024

Abstract Cuproptosis, an emerging form of programmed cell death, has received tremendous attention in cancer therapy. However, the efficacy cuproptosis remains limited by poor delivery efficiency copper ion carriers. Herein, complex nanoparticles (denoted as Cu(I) NP) are developed that can efficiently deliver into cells to induce cuproptosis. NP demonstrate stimulus‐responsive release complexes, which results mitochondrial dysfunction and promotes aggregation lipoylated dihydrolipoamide S‐acetyltransferase (DLAT), leading Notably, not only cuproptosis, but also elicit robust immune responses suppress tumor growth. Overall, this study provides a promising strategy for cuproptosis‐based

Language: Английский

---

Carborane-Cluster-Wrapped Copper Cluster with Cyclodextrin-like Cavities for Chiral Recognition

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16729 - 16736

Published: June 5, 2024

Chiral atomically precise metal clusters, known for their remarkable chiroptical properties, hold great potential applications in chirality recognition. However, advancements this field have been constrained by the limited exploration of host–guest chemistry, involving clusters. This study reports synthesis a chiral Cu16(C2B10H10S2)8 (denoted as Cu16@CB8, where C2B10H12S2H2 = 9,12-(HS)2-1,2-closo-carborane) cluster an achiral carboranylthiolate ligand. The R-/S-Cu16@CB8 features cavities reminiscent cyclodextrins, which are surrounded carborane yet they crystallize racemate. These cyclodextrin-like demonstrated specific recognition amino acids, indicated responsive output circular dichroism and circularly polarized luminescence signals Cu16 moieties Cu16@CB8 cluster. Notably, quantitative analysis acids short time concomitant deracemization were achieved. Density functional tight-binding molecular dynamics simulation noncovalent interaction further unraveled importance binding sites Dipeptide, tripeptide, polypeptide containing corresponding (Cys, Arg, or His residues) display same recognition, showing generality approach. synergy dual comprising is first cluster, resulting valuable quantification enantiomeric excess (ee) value acids. work opens new avenue sensors based on clusters with unique properties inspires development chemistry.

Language: Английский

---

Photoinduced Selective B–H Activation of nido-Carboranes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7791 - 7802

Published: March 10, 2024

The development of new synthetic methods for B–H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope clusters. Herein, we present a reaction strategy direct site-selective functionalization nido-carboranes initiated by photoinduced cage via noncovalent cage···π interaction. As result, nido-carborane radical is generated through single electron transfer from 3D 2D photocatalyst upon irradiation with green light. resulting transient could be directly probed advanced time-resolved EPR technique. In air, subsequent transformations active have led efficient and selective B–N, B–S, B–Se couplings presence N-heterocycles, imines, thioethers, thioamides, selenium ethers. This protocol also facilitates both late-stage modification drugs synthesis nido-carborane-based drug candidates neutron capture therapy (BNCT).

Language: Английский

---

Triamine and Tetramine Edge-Length Matching Drives Heteroleptic Triangular and Tetragonal Prism Assembly

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5215 - 5223

Published: Feb. 13, 2024

Heteroleptic metal–organic capsules, which incorporate more than one type of ligand, can provide enclosed, anisotropic interior cavities for binding low-symmetry molecules biological and industrial importance. However, the selective self-assembly a single mixed-ligand architecture, as opposed to numerous other possible outcomes, remains challenge. Here, we develop design strategy subcomponent heteroleptic architectures with internal void spaces. Zn6Tet3Tri2 triangular prismatic Zn8Tet2Tet′4 tetragonal were prepared through careful matching side lengths tritopic (Tri) or tetratopic (Tet, Tet′) panels.

Language: Английский

---

Carborane Meets Metal Nanocluster: New Opportunities in Nanomaterials

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: March 28, 2025

ConspectusMetal nanoclusters, distinguished by their atom-precise structures and quantum size effect, are regarded as a crucial bridge between organometallic complexes plasmonic metal nanoparticles. These nanoclusters primarily composed of metallic core enveloped protective ligands, wherein the ligands play vital role in determining nanoclusters' synthesis, structural integrity, physicochemical properties. Considerable efforts ligand engineering have concentrated on exploring novel coordinating functional groups to advance nanocluster research, particularly precise controlled synthesis superatomic fine-tuning intrinsic properties, subsequent assembly application. However, backbone these seems equally important but attracts less attention. It is reasonable that if utility two moieties (coordinating group backbone) provokes profound synergistic contributions properties resultant extremely inestimable. In this context, carborane, with its spherical shape three-dimensional aromaticity (electronic effect), has emerged promising candidate for design. Over past decades, incorporation carborane into enabled construction various exhibiting distinct architectures, enhanced stability, unique reactivity. Therefore, it present current status challenges associated carboranyl ligand-protected guide future development. This Account provides comprehensive summary recent advances ligand-stabilized primary focus from our laboratory. We begin discussing advantages introducing carborane-based preparation, particular emphasis virtues heterometal-doped isostructural nanoclusters. Subsequently, we summarize strategies modification hierarchical elucidating how facilitates modulation specific promotes supramolecular covalent assembly. Furthermore, discuss cooperativity achieved framework broaden scope applications versatile fields, including hypergolic fuels, previously unexplored area. Finally, facing research nido-carborane or metallocarborane, fundamental understanding structure–property relationships, potential such boron neutron capture therapy radionuclide extraction. aims stimulate interest attributes corresponding among students researchers across diverse disciplines, chemistry, crystal engineering, materials science.

Language: Английский

---

Recent Advances in Carborane-Based Crystalline Porous Materials

Molecules, Journal Year: 2024, Volume and Issue: 29(16), P. 3916 - 3916

Published: Aug. 19, 2024

The field of carborane research has witnessed continuous development, leading to the construction and development a diverse range crystalline porous materials for various applications. Moreover, innovative synthetic approaches are expanding in this field. Since first report carborane-based (CCPMs) 2007, synthesis ligands, particularly through methods, consistently posed significant challenge discovering new structures CCPMs. This paper provides comprehensive summary recent advances CCPMs, along with their applications different domains. primary challenges future opportunities expected stimulate further multidisciplinary

Language: Английский

---

Dative Bonding Activation Enables Precise Functionalization of the Remote B–H Bond of nido-Carborane Clusters

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

The innovation of synthetic strategies for selective B-H functionalization is a pivotal objective in the realm boron cluster chemistry. However, precise, efficient, and rapid bond carboranes that distant from existing functional groups remains intractable owing to limited approaches site-selective control established methods. Herein, we report dative bonding activation strategy nonclassical remote site

Language: Английский

---

Bi-anthracene based ruthenium and iridium metalla-rectangles: Coordination driven self-assembly and anti-cancer activities

Inorganic Chemistry Communications, Journal Year: 2025, Volume and Issue: unknown, P. 113916 - 113916

Published: Jan. 1, 2025

Language: Английский

---

A variable bidentate traceless directing group for nickel-catalyzed regioselective B–H poly-chalcogenation of o-carboranes

Inorganic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A nickel-catalyzed direct cage B–H poly-chalcogenation of icosahedral carborane clusters, enabled by a variable bidentate 8-aminoquinoline traceless directing group, has been developed under oxidant-free and weakly basic conditions.

Language: Английский

---

Palladium-Catalyzed Cross-Coupling Reactions of Carboranes with Alkenes via Selective B–H Bond Activation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

A palladium-catalyzed Heck-type cross-coupling reaction of carboranes with alkenes in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was realized. This shows good B(9) selectivity for m-carboranes and is also suitable o- p-carborane. Meanwhile, a series mono-, di-, trisubstituted were compatible substrates to afford the alkenylated products 16–89% yields. The 1,2-bis(carboranyl)ethylene first synthesized by vinyltrimethylsilane m-carborane. Further transformations C═C bond product examined hydroboration oxidation, hydroboration, bromination generate corresponding B(9)-functionalized m-carboranes.

Language: Английский

---