Octahedral {Ta6I12} Clusters.

Ta powder reacts with I2 at 650 °C with the formation of Ta6I14, which belongs to the family of {M6(µ-X)12} clusters. It undergoes aquation with the formation of the intensely colored [Ta6I12(H2O)6]2+. The crystal structure was determined for [Ta6I12(H2O)6](BPh4)2·xH2O (Ta-Ta 2.9322(6) Å, Ta-I 2.8104(7) Å, Ta-O 2.3430(5) Å). With DMF, [Ta6I12(DMF)6]I2·xDMF was isolated (Ta-Ta 2.9500(2) Å, Ta-I 2.8310(4) Å, Ta-O 2.2880(7) Å). Cyclic voltammetry of [Ta6I12(H2O)6]2+ shows two consecutive quasi-reversible one-electron oxidations (E1/2 0.61 and 0.92 V vs Ag/AgCl). Reaction of Ta6I14 with Bu4NCN yields (Bu4N)4[Ta6I12(CN)6]·xCH3CN (Ta-Ta 2.9777(4) Å, Ta-I 2.8165(6) Å, Ta-C 2.2730(7) Å). Quantum chemical calculations reproduce well the experimental geometry of the aqua complex and show the essentially Ta-centered nature of both the HOMO and LUMO. The long-term stability of [Ta6I12(H2O)6]2+ solutions can be greatly enhanced in the presence of polystyrenesulfonate (PSS), which forms nanoparticle associates with the aqua complex in water (ca. 1 cluster per 3 PSS monomeric units).

Effect of transcatheter aortic valve implantation on health-related quality of life in older adults with multimorbidity.

PURPOSE: The purpose of this study was to determine the effect of transcatheter aortic valve implantation on health-related quality of life in older adults with multimorbidity and to evaluate the predictive factors for postoperative quality of life impairment in such patients. MATERIAL AND METHOD: This study included 141 older adults with severe aortic stenosis scheduled for elective transcatheter aortic valve implantation. Quality of life was examined in all patients using the Short-Form 36 Health Survey Questionnaire, before and 2 years after surgery. Comorbidity was assessed using the Charlson Comorbidity Index. RESULTS: In older adult patients with aortic stenosis and multimorbidity, transcatheter aortic valve implantation significantly improved both physical and mental components of quality of life 2 years after surgery. A Charlson Comorbidity Index ≥5 points was independently associated with the absence of positive dynamics in Physical Health score [odds ratio (OR) 0.38 (0.20-0.75), p = 0.007]. Charlson Comorbidity Index ≥5 points [OR 0.31 (0.19-0.58), p = 0.026] and new-onset arrhythmia [OR 0.54 (0.38-0.78), p = 0.017] were independent predictors of the absence of positive dynamics in Mental Health score after transcatheter aortic valve implantation. CONCLUSIONS: High-level comorbidity (Charlson Comorbidity Index ≥5 points) predicts both Physical and Mental Health scores for quality of life impairment following transcatheter aortic valve implantation in older adults, and new-onset arrhythmia predicts the Mental Health score for quality of life impairment following transcatheter aortic valve implantation in these patients.

A randomized trial of bifurcation stenting technique in chronic total occlusions percutaneous coronary intervention.

BACKGROUND: The optimal strategy to treat bifurcation lesions (BFLs) in a percutaneous coronary intervention (PCI) for chronic total occlusions (CTOs) remains unknown. AIMS: We sought to assess whether T-provisional or mini-crush is appropriate for BFLs within CTO vessels. PATIENTS AND METHODS: From January 2011 to December 2013, patients who underwent successful CTO guidewire crossing and with a BFL within the CTO target vessel were enrolled prospectively and assigned randomly to either T-provisional stenting or the mini-crush technique for BFL treatment. One-year clinical follow-up was performed. Major adverse cardiac and cerebrovascular events (MACCE) were defined as the composite of cardiovascular death, myocardial infarction, target vessel revascularization, and stroke. RESULTS: The prevalence of BFLs was 54.3%. A total of 146 patients with BFLs within CTO vessel were enrolled prospectively and assigned randomly to either T-provisional stenting (N=73) or the mini-crush technique (N=73). Angiographic and clinical success rates were similar in the two groups: 91.8 versus 97.2% (P=0.27) and 91.8 versus 94.5% (P=0.67), respectively.Although T-provisional stenting was associated with a nonsignificantly lower incidence of MACCE in case of BFLs located far from the CTO (9.3 vs. 22.2%; P=0.426), the mini-crush technique resulted in higher MACCE-free survival at 1 year in the presence of BFLs within the CTO body or close to the proximal or the distal cap (89.1 vs. 64.9%; P=0.007). CONCLUSION: The mini-crush technique appeared to be associated with improved 1-year clinical and angiographic outcomes, particularly when used to treat BFLs located within the CTO body or close to the proximal or the distal cap.

Singlet Oxygen Production and Biological Activity of Hexanuclear Chalcocyanide Rhenium Cluster Complexes [{Re6Q8}(CN)6]4- (Q = S, Se, Te).

Octahedral rhenium cluster complexes have recently emerged as relevant building blocks for the design of singlet oxygen photosensitizing materials toward biological applications such as blue-light photodynamic therapy. However, their singlet oxygen generation ability as well as biological properties have been studied only superficially. Herein we investigate in detail the singlet oxygen photogeneration, dark and photoinduced cytotoxicity, cellular uptake kinetics, cellular localization and in vitro photoinduced oxidative stress, and photodynamic cytotoxicity of the series of octahedral rhenium cluster complexes [{Re6Q8}(CN)6]4-, where Q = S, Se, Te. Our results demonstrate that the selenium-containing complex possesses optimal properties in terms of absorption and singlet oxygen productivity. These features coupled with the cellular internalization and low dark toxicity lead to the first photoinduced cytotoxic effect observed for a molecular [{M6Q8}L6] complex, making it a promising object for further study in terms of blue-light PDT.

A comparative study of optical properties and X-ray induced luminescence of octahedral molybdenum and tungsten cluster complexes.

Octahedral metal cluster complexes have high potential for biomedical applications. In order to evaluate the benefits of these moieties for combined CT/X-ray luminescence computed tomography, this paper compares photoluminescence, radiodensity and X-ray induced luminescence properties of eight related octahedral molybdenum and tungsten cluster complexes [{M6I8}L6]n (where M is Mo or W and L is I-, NO3-, OTs- or OH-/H2O). This article demonstrates that despite the fact that molybdenum cluster complexes are better photoluminescence emitters, tungsten cluster complexes, in particular (Bu4N)2[{W6I8}I6], demonstrate significantly higher X-ray induced luminescence due to a combination of relatively good photoluminescence properties and high X-ray attenuation. Additionally, photo-degradation of [{M6I8}(NO3)6]2- was evaluated.

Mid-term outcome of biolimus-eluting stents with biodegradable polymer: results from a multinational prospective 'all-comers' registry.

BACKGROUND: The Nobori biolimus-eluting stent (BES) is a biodegradable polymer drug-eluting stent (DES). Several studies have shown its noninferiority in comparison with durable polymer DES. AIM: We sought to investigate the efficacy and the safety of Nobori BES in an all-comer population undergoing a percutaneous coronary intervention. PATIENTS AND METHODS: A total of 12 912 patients with 19 947 coronary lesions, undergoing percutaneous coronary intervention with Nobori BES implantation at 200 centres around the world between August 2010 and December 2015, were included in this prospective registry. Patients were stratified into four groups according to the total stent length, with cutoffs at 18, 24 and 28 mm. The primary endpoint was the occurrence of major adverse cardiac events defined as the composite of cardiac death, target vessel myocardial infarction and clinically driven target lesion revascularization at 1 year. RESULTS: At 1 year, the major adverse cardiac events rate was the highest (4.6%) in the fourth quartile of stent length (>28 mm), whereas the overall rate of the primary endpoint in the all cohort was 3.5%. Both target lesion revascularization and target vessel revascularization rates were significantly higher in patients with longer stent length was implanted (all P<0.05). The incidence of definite and probable stent thrombosis at 1 year was 0.5% in all cohort and similar across the four groups (varying from 0.4 to 0.7%, all P=NS). CONCLUSION: Our data confirmed the efficacy and the safety of the Nobori BES in routine clinical practice. Longer stent length is associated with a higher risk of adverse cardiac events, and yet, this risk is comparable with that of other DES.

Comprehensive study of hexarhenium cluster complex Na4[{Re6Te8}(CN)6] - In terms of a new promising luminescent and X-ray contrast agent.

Octahedral rhenium cluster complexes may have considerable potential as therapeutic and diagnostic drugs due to their luminescent and X-ray contrast properties, as well as their ability to generate singlet oxygen upon photoirradiation. However, their potential biological effects and toxicity in vitro and in vivo are rather far from being understood. Thus, the aim of our research was to study cytotoxicity, intracellular localization and cellular uptake/elimination kinetics in vitro, biodistribution and acute intravenous toxicity in vivo of a complex Na4[{Re6Te8}(CN)6] as the promising compound for biomedical application. The results have demonstrated that the complex penetrates through cell membranes with the maximum accumulation in cells in 24h of incubation and have low toxic effects in vitro and in vivo. The median lethal dose (LD50) of intravenously administrated Na4[{Re6Te8}(CN)6] is equal to 1082±83mg/kg. These findings will be useful for future development of cluster-based agents for different biomedical applications.