Gold Complexes in Anticancer Therapy: From New Design Principles to Particle‐Based Delivery Systems

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(22)

Опубликована: Фев. 27, 2023

Abstract The discovery of the medicinal properties gold complexes has fuelled design and synthesis new anticancer metallodrugs, which have received special attention due to their unique modes action. Current research in development compounds with therapeutic is predominantly focused on molecular drug leads superior pharmacological activities, e.g., by introducing targeting features. Moreover, intensive aims at improving physicochemical compounds, such as chemical stability solubility physiological environment. In this regard, encapsulation nanocarriers or grafting onto targeted delivery vectors could lead nanomedicines that eventually reach clinical applications. Herein, we provide an overview state‐of‐the‐art progress andmore importantly thoroughly revise nanoparticle‐based systems for chemotherapeutics.

Язык: Английский

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Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Chiral (P,N)-Ligands

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(16), С. 7089 - 7095

Опубликована: Апрель 18, 2022

Presented herein is the first report of enantioselective Au(I)/Au(III) redox catalysis, enabled by a newly designed hemilabile chiral (P,N)-ligand (ChetPhos). The potential this concept has been demonstrated development 1,2-oxyarylation and 1,2-aminoarylation alkenes which provided direct access to medicinally relevant 3-oxy- 3-aminochromans (up 88% yield 99% ee). DFT studies were carried out unravel enantiodetermining step, revealed that stronger trans influence phosphorus allows selective positioning substrate in C2-symmetric environment present around nitrogen, imparting high level enantioselectivity.

Язык: Английский

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Arylgold nanoclusters: Phenyl-stabilized Au ₄₄ with thermal-controlled NIR single/dual-channel phosphorescence

Science Advances, Год журнала: 2024, Номер 10(7)

Опубликована: Фев. 14, 2024

Arylation of gold holds paramount importance in the domain organometallic chemistry; however, exploration arylgold nanoclusters remains its infancy primarily due to synthetic challenge. Here, we present a facile and effective arylation strategy directly synthesize two (

Язык: Английский

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Au⋅⋅⋅H−C Interactions Support a Robust Thermally Activated Delayed Fluorescence (TADF) Gold(I) Complex for OLEDs with Little Efficiency Roll‐Off and Good Stability

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(40)

Опубликована: Авг. 6, 2022

Abstract The practical use of luminescent mononuclear gold(I) complexes as optoelectronic materials has been limited by their inferior stability. Herein we demonstrate a strategy to improve the stability which display thermally activated delayed fluorescence (TADF). A highly rigid and groove‐like σ‐donating aryl ligand used form dual Au⋅⋅⋅H−C hydrogen bonds. secondary metal‐ligand interactions have authenticated single‐crystal structure, NMR spectroscopy theoretical simulations. TADF Au I complex exhibits appealing emission properties (photoluminescence quantum yield=76 %; lifetime=1.2 μs) much improved thermal photo‐stability. Vacuum‐deposited organic light‐emitting diodes (OLEDs) show promising electroluminescence with maximum external efficiency (EQE) over 23 % negligible roll‐off even at 10 000 cd m −2 . An estimated LT 50 longer than 77 h initial luminance 100 reveals good operational This work suggests way for design stable complexes.

Язык: Английский

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L‐Shaped Heterobidentate Imidazo[1,5‐a]pyridin‐3‐ylidene (N,C)‐Ligands for Oxidant‐Free Au^I/Au^III Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(12)

Опубликована: Янв. 25, 2023

In the last decade, major advances have been made in homogeneous gold catalysis. However, Au

Язык: Английский

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Gold(I)-Organic Frameworks as Catalysts for Carboxylation of Alkynes with CO₂

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(41), С. 22720 - 22727

Опубликована: Окт. 4, 2023

Construction of gold-based metal-organic frameworks (Au-MOFs) would bring the merits gold chemistry into MOFs. However, it still remains challenging because cations are easily reduced to metallic under solvothermal conditions. Herein, we present first example Au-MOFs prepared from networking cyclic trinuclear gold(I) complexes by formal transimination reaction in a rapid (<15 min) and scalable (up 1 g) fashion ambient condition. The feature uniform porosity, high crystallinity, superior chemical stability toward base (i.e., 20 M NaOH). With open Au(I) sites skeleton, as heterogeneous catalysts delivered good performance substrate tolerance for carboxylation reactions alkynes with CO2. This work demonstrates facile approach reticularly synthesize combining coordination dynamic covalent chemistry.

Язык: Английский

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Hexafluoroisopropanol (HFIP) as a Multifunctional Agent in Gold-Catalyzed Cycloisomerizations and Sequential Transformations

ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8845 - 8860

Опубликована: Июнь 20, 2023

Despite the unique position of gold catalysis in contemporary organic synthesis, this area research is notorious for requiring activators and/or additives that enable by generating cationic forms catalysts. Cycloisomerization reactions occupy a significant portion gold-catalyzed reaction space, while they represent diverse family are frequently utilized synthesis. Herein, hexafluoroisopropanol (HFIP) shown to be uniquely simple tool cycloisomerizations, rendering use external obsolete and leading highly active catalytic systems with ppm levels catalyst loading certain cases. HFIP assumes dual role as solvent an activator, operating via dynamic activation Au–Cl bond through hydrogen bonding, which initiates cycle. This special mode can efficient scalable cyclization propargylamides ynoic acids [AuCl(L)] complexes. A thorough screening ancillary ligands counter anions has been performed, establishing methodology alternative elaborate ligand/catalyst design activators. Additionally, concept applied C–C bond-forming cycloisomerization 2H-chromenes sequential or one-pot transformations activated ketoesters, functionalized N-heterocyclic carbene (NHC) precursor salt, compound bearing bioactive indole core, among others. Importantly, mechanistic investigations, including "snapshot" species interest solid state, we were able unambiguously detect key H-bonding interaction between catalyst, shedding light on intermolecular enables catalysis. In cases examined herein, not only excellent but also potent activator valuable synthetic handle when incorporated into functional groups products.

Язык: Английский

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Asymmetric gold catalysis enabled by specially designed ligands

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(6), С. 1858 - 1895

Опубликована: Янв. 1, 2024

This review is planned to provide a comprehensive overview of the progress made in design and development chiral ligands for asymmetric gold catalysis.

Язык: Английский

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Aurophilic interaction-based aggregation of gem-digold(I) aryls towards high spin-orbit coupling and strong phosphorescence

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 6, 2025

Luminescent gold(I) compounds have attracted intensive attention due to anticipated strong spin-orbit coupling (SOC) resulting from heavy atom effect of gold atoms. However, some mononuclear are barely satisfactory. Here, we unveil that low participation in transition-related orbitals, caused by 6s-π symmetry mismatch, is the cause SOCs monogold(I) compounds. To address this issue, developed a series acceptor-donor organogold(I) luminescent incorporating gem-digold moiety with various aryl donors. These demonstrate wide-range tunable emission colors and impressive photoluminescence quantum yields up 78%, among highest reported for polynuclear We further reveal integration allows better interaction 6s orbitals π facilitates aryl-to-gold electron transfer, reduces Pauli repulsion between digold units, finally engendering formation aurophilic interaction-based aggregates. Moreover, strength such intermolecular can be systematically regulated donor nature ligands. The those aggregates significantly enhances SOC <10 239 cm−1 mainly accounts high-efficiency phosphorescent solid state. Some unexpectedly weak coupling, thus limiting their phosphorescence efficiency. authors develop organodigold(I) investigate relationship structures, interaction, coupling.

Язык: Английский

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Enantioselective Au(I)-Catalyzed Multicomponent Annulations via Tethered Counterion-Directed Catalysis

ACS Catalysis, Год журнала: 2022, Номер 12(7), С. 4046 - 4053

Опубликована: Март 16, 2022

Gold(I) complexes of a chiral phosphoric acid-functionalized phosphine the CPA-Phos series enable enantioselective multicomponent reactions between aldehydes, hydroxylamines and cyclic yne-enones, leading to 3,4-dihydro-1H-furo[3,4-d][1,2]oxazines. This represents rare example highly reaction in gold(I) catalysis. The proceed at low catalyst loading provide high yields, total diastereoselectivity, enantiomeric excesses up 99%. Silver-free conditions can be applied. method has very broad scope as it applies both aliphatic aromatic aldehydes hydroxylamines, variety yne-enone-derived oximes. DFT calculations complement this study enlighten reactivity issues mechanistic pathways.

Язык: Английский

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