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1.
ACS Omega ; 9(23): 24654-24664, 2024 Jun 11.
Artículo en Inglés | MEDLINE | ID: mdl-38882114

RESUMEN

The synthesis of metal macrocycle complexes holds paramount importance in coordination and supramolecular chemistry. Toward this end, we report a new, mild, and efficient protocol for the synthesis of cyclometalated macrocycle Ir(III) complexes: [Ir(L1)](PF6) (1), [Ir(L2)](PF6) (2), and [Ir(L3)](PF6) (3), where L1 presents 10,17-dioxa-3,6-diaza-2(2,8),7(8,2)-diquinolina-1,8(1,4)-dibenzenacyclooctadecaphane, L2 is 10,13,16,19,22,25-hexaoxa-3,6-diaza-2(2,8),7(8,2)-diquinolina-1,8(1,4)-dibenzenacyclohexacosaphane, and L3 is 4-methyl-10,13,16,19,22,25-hexaoxa-3,6-diaza-2(2,8),7(8,2)-diquinolina-1,8(1,4)-dibenzenacyclohexacosaphane. This synthesis involves the preassembly of two symmetric 2-phenylquinoline arms into C-shape complexes, followed by cyclization with diamine via in situ interligand C-N cross-coupling, employing a metal ion as a template. Moreover, the synthetic yield of these cyclometalated Ir(III) complexes, tethered by an 18-crown-6 ether-like chain, is significantly enhanced in the presence of K+ ion as a template. The resultant cyclometalated macrocycle Ir(III) complexes exhibit high stability, efficient singlet oxygen generation, and superior catalytic activity for the aerobic selective oxidation of sulfides into sulfoxides under visible light irradiation in aqueous media at room temperature. The photocatalyst 2 demonstrates recyclability and can be reused at least 10 times without a significant loss of catalytic activity. These results unveil a new and complementary approach to the design and in situ synthesis of cyclometalated macrocycle Ir(III) complexes via a mild interligand-coupling strategy.

2.
Inorg Chem ; 61(51): 20834-20847, 2022 Dec 26.
Artículo en Inglés | MEDLINE | ID: mdl-36520143

RESUMEN

The selective photoreactions under mild conditions play an important role in synthetic chemistry. Herein, efficient and mild protocols for switching the photoreactions of Ir(III)-diamine complexes between the interligand C-N coupling and dehydrogenation are developed in the presence of O2 in EtOH solution. The photoreactions of achiral diamine complexes rac-[Ir(L)2(dm)](PF6) (L is 2-phenylquinoline or 2-(2,4-difluorophenyl)quinoline, dm is 1,2-ethylenediamine, 1,2-diaminopropane, 2-methyl-1,2-diamino-propane, or N,N'-dimethyl-1,2-ethylenediamine) are competitive in the oxidative C-N coupling and dehydrogenation at room temperature, which can be switched into the interligand C-N coupling reaction at 60 °C, affording hexadentate complexes in good to excellent yields, or the dehydrogenative reaction in the presence of a catalytic amount of TEMPO as an additive, affording imine complexes. Mechanism studies reveal that 1O2 is the major reactive oxygen species, and metal aminyl is the key intermediate in the formation of the oxidative C-N coupling and imine products in the photoreaction processes. These will provide a new and practical protocol for the synthesis of multidentate and imine ligands in situ via the postcoordinated strategy under mild conditions.

3.
BMC Nephrol ; 23(1): 185, 2022 05 14.
Artículo en Inglés | MEDLINE | ID: mdl-35568810

RESUMEN

OBJECTIVE: To explore the technical specifications and clinical outcomes of thrombosed aneurysmal haemodialysis arteriovenous fistula (AVF) treated with ultrasound-guided percutaneous transluminal angioplasty combined with minimal aneurysmotomy. METHODS: This case series study included 11 patients who had thrombosed aneurysmal AVF and underwent salvage procedures over a 13-month period. All procedures were performed under duplex guidance. Minimal aneurysmotomy was performed, along with manual thrombectomy and thrombolytic agent infusion, followed by angioplasty to macerate the thrombus and sufficiently dilate potential stenoses. A successful procedure was defined as immediate restoration of flow through the AVF. RESULTS: The 11 patients (four males and seven females) had a mean age of 49.6 years ± 11.9 years. Six patients (54.5%) had two or more aneurysms. The mean aneurysm maximal diameter was 21.5 mm (standard deviation: ± 5.0 mm), and the mean thrombus length was 12.9 cm (8-22 cm). Ten (83.3%) of the 12 procedures were technically successful. The mean duration of operation was 150.9 minutes (standard deviation: ± 34.2 minutes), and mean postoperative AVF blood flow was 728.6 ml/min (standard deviation: ± 53.7 mi/min). The resumption of hemodialysis was successful in all 11 cases, with a clinical success rate of 100%. The primary patency rates were 90.0% and 75.0% at three and four months over a mean follow-up time of 6.3 months (3-12 months). The secondary patency rates were 90.4% at three and four months. CONCLUSION: A hybrid approach combining ultrasound-guided percutaneous transluminal angioplasty and minimal aneurysmotomy might be a safe and effective method for thrombosed aneurysmal AVF salvage.


Asunto(s)
Aneurisma , Fístula Arteriovenosa , Derivación Arteriovenosa Quirúrgica , Trombosis , Aneurisma/complicaciones , Aneurisma/diagnóstico por imagen , Aneurisma/cirugía , Derivación Arteriovenosa Quirúrgica/efectos adversos , Femenino , Humanos , Masculino , Persona de Mediana Edad , Diálisis Renal , Estudios Retrospectivos , Trombosis/diagnóstico por imagen , Trombosis/etiología , Trombosis/cirugía , Resultado del Tratamiento , Grado de Desobstrucción Vascular
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