Chemical Science, Год журнала: 2024, Номер unknown
Опубликована: Дек. 11, 2024
The design of a carboxylate–pyridine–triazole integrated ligand, coupled with strategy “rivet” substitution and “hinge” linkage, facilitates the construction largest [Zn 54 ] cluster in hierarchical supramolecular framework.
Язык: Английский
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)
Опубликована: Фев. 8, 2024
Abstract Albeit sonodynamic therapy (SDT) has achieved encouraging progress in microbial sterilization, the scarcity of guidelines for designing highly effective sonosensitizers and intricate biofilm microenvironment (BME), substantially hamper therapeutic efficacy against infections. To address bottlenecks, we innovatively design a Ru(II) metallacycle‐based sonosensitizer/sonocatalyst (named Ru‐A3‐TTD ) to enhance potency sonotherapy by employing molecular engineering strategies tailored BME. Our approach involves augmenting ’s production ultrasonic‐triggered reactive oxygen species (ROS), surpassing performance commercial sonosensitizers, through straightforward but potent π‐expansion approach. Within BME, synergistically amplifies sonotherapeutic via triple‐modulated approaches: (i) alleviation hypoxia, leading increased ROS generation, (ii) disruption antioxidant defense system, which shields from glutathione consumption, (iii) enhanced penetration, enabling deep sites. Notably, sono‐catalytically oxidizes NADPH, critical coenzyme involved defenses. Consequently, demonstrates superior eradication multidrug‐resistant Escherichia coli compared conventional clinical antibiotics, both vitro vivo. our knowledge, this study represents pioneering instance supramolecular sonosensitizer/sonocatalyst. It provides valuable insights into structure‐activity relationship paves promising pathway treatment
Язык: Английский
Процитировано
34
Journal of the American Chemical Society, Год журнала: 2023, Номер 145(36), С. 19440 - 19457
Опубликована: Авг. 29, 2023
The utilization of carboranes in supramolecular chemistry has attracted considerable attention. unique spatial configuration and weak interaction forces can help to explore the properties complexes, particularly via host–guest chemistry. Additionally, certain difficulties encountered carborane development─such as controlled B–H bond activation─can be overcome by judiciously selecting metal centers their adjacent ligands. However, few studies are being conducted this nascent research area. With advances field, novel carborane-based complexes will likely prepared, structurally characterized, intrinsically investigated. To expedite these efforts, we present major findings from recent studies, including π–π interactions, associations, steric effects, which have been leveraged implement a regioselective process for activating B(2,9)–, B(2,8)–, B(2,7)–H bonds para-carboranes B(4,7)–H ortho-carboranes. Future should clarify interactions potential enhancing utility complexes. Although exhibit several (such dihydrogen-bond [Bδ+–Hδ−···Hδ+–Cδ−], Bδ+–Hδ−···M+, Bδ+–Hδ−···π interactions), manner they utilized remains unclear. Supramolecular those based on chemistry, platform demonstrating applications interactions. Owing importance alkane separation, related recognition separation isomers primarily summarized. Advances certainly lead more possibilities
Язык: Английский
Процитировано
28
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Янв. 14, 2025
Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of carborane cage, they have low nucleophilicity and reluctant alkylate. Moreover, asymmetric synthesis chiral carboranes is still in its infancy. Herein we achieved first catalytic N-alkylation o-carboranyl amine, providing general access diverse secondary with high efficiency enantioselectivity under mild conditions. For time, organocatalysis was introduced chemistry. Key success use situ generated (naphtho-)quinone methides as alkylating reagents suitable acid catalysts. This protocol also applicable S-alkylation 1-SH-o-C2B10H11. Control experiments kinetic studies provided important insights into reaction mechanism, which likely involves rate-determining generation quinone methide followed by fast enantio-determining nucleophilic addition.
Язык: Английский
Процитировано
2
Inorganic Chemistry Frontiers, Год журнала: 2025, Номер unknown
Опубликована: Янв. 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.
Язык: Английский
Процитировано
1
Science China Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Янв. 24, 2025
Язык: Английский
Процитировано
1
Inorganic Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Май 8, 2025
The self-assembly of metallo-supramolecules has attracted considerable attention in recent decades. These discrete architectures are primarily driven by coordination interactions, typically involving M-N/O (Werner-type) or M-C (organometallic) bonding. However, the use M-π interactions for constructing these multinuclear complexes remains largely unexplored. In this work, we report trinuclear and tetranuclear copper(I) a combination interactions. Cu(I)-NHC were synthesized from nido-carborane-supported N-heterocyclic carbene (NHC) precursors Cu(I) ions. solution, dynamic equilibrium between species was observed, as confirmed variable-temperature NMR spectrum. Van't Hoff analysis revealed that is endothermic (ΔHeq = 53.6 kJ mol-1) entropically (ΔSeq 158 J mol-1 K-1). solid-state structures both forms elucidated through single-crystal XRD analysis. Density functional theory calculations showed Cu-CNHC bonds relatively weak (∼100 mol-1, approximately one-third strength typical bonds). This attributed to strong Coulombic attraction positively charged negatively nido-carborane ligands (M-π interactions), which significantly reduces bond neutral NHC moieties (M-C bonding).
Язык: Английский
Процитировано
1
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5215 - 5223
Опубликована: Фев. 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.
Язык: Английский
Процитировано
9
Angewandte Chemie, Год журнала: 2024, Номер 136(15)
Опубликована: Фев. 8, 2024
Abstract Albeit sonodynamic therapy (SDT) has achieved encouraging progress in microbial sterilization, the scarcity of guidelines for designing highly effective sonosensitizers and intricate biofilm microenvironment (BME), substantially hamper therapeutic efficacy against infections. To address bottlenecks, we innovatively design a Ru(II) metallacycle‐based sonosensitizer/sonocatalyst (named Ru‐A3‐TTD ) to enhance potency sonotherapy by employing molecular engineering strategies tailored BME. Our approach involves augmenting ’s production ultrasonic‐triggered reactive oxygen species (ROS), surpassing performance commercial sonosensitizers, through straightforward but potent π‐expansion approach. Within BME, synergistically amplifies sonotherapeutic via triple‐modulated approaches: (i) alleviation hypoxia, leading increased ROS generation, (ii) disruption antioxidant defense system, which shields from glutathione consumption, (iii) enhanced penetration, enabling deep sites. Notably, sono‐catalytically oxidizes NADPH, critical coenzyme involved defenses. Consequently, demonstrates superior eradication multidrug‐resistant Escherichia coli compared conventional clinical antibiotics, both vitro vivo. our knowledge, this study represents pioneering instance supramolecular sonosensitizer/sonocatalyst. It provides valuable insights into structure‐activity relationship paves promising pathway treatment
Язык: Английский
Процитировано
8
Molecules, Год журнала: 2024, Номер 29(16), С. 3916 - 3916
Опубликована: Авг. 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
Язык: Английский
Процитировано
8
Journal of the American Chemical Society, Год журнала: 2024, Номер unknown
Опубликована: Сен. 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
Язык: Английский
Процитировано
8