Group 14 metallated 6-amino-1-azafulvene dimers : evidence for a double intramolecular nitrogen-tin interaction

The structures of group 14 C-metalated 6-amino-1-azafulvene dimers have been investigated in solution and in the solid state by NMR spectroscopy. For one of these compounds, 5,10-bis(dimethylamino)-3,8-bis(trimethylstannyl)-5H,10H-dipyrrolo[1,2-a: 1\u27,2\u27-d]-pyrazine (2c), the molecular structure in the solid state has been determined by X-ray diffractometry. The two tin centers have a distorted-trigonal-bipyramidal co-ordination geometry with the more electronegative N ligand at a pseudoaxial position, resulting in one of the longest known Sn - N interactions: 3.101 (5) A°. Moreover, the temperature-dependent 13C CP-MAS NMR spectrum of this compound shows an appreciable narrowing of the Me3Sn signal between 296 and 333 K. By comparison with nonmetalated analogs or with isomer 5c, the nonreactivity of compound 2c toward hydrolytic decomposition into corresponding 5-(trimethylstannyl)-pyrrole-2-carbaldehyde (3c) may be the result of stabilization of the dimeric form 2c by a double Sn - N interaction. In silicon and germanium analogs (2a, 2b) the Si(Ge) - N interaction is weaker

Collected world experience about the performance of the snorkel/chimney endovascular technique in the treatment of complex aortic pathologies: The PERICLES registry

Objectives: We sought to analyze the collected worldwide experience with use of snorkel/chimney endovascular aneurysm repair (EVAR) for complex abdominal aneurysm treatment. Background: EVAR has largely replaced open surgery worldwide for anatomically suitable aortic aneurysms. Lack of availability of fenestrated and branched devices has encouraged an alternative strategy utilizing parallel or snorkel/chimney grafts (ch-EVAR). Methods: Clinical and radiographic information was retrospectively reviewed and analyzed on 517 patients treated by ch-EVAR from 2008 from 2014 by prearranged defined and documented protocols. Results: A total of 119 patients in US centers and 398 in European centers were treated during the study period. US centers preferentially used Zenith stent-grafts (54.2%) and European centers Endurant stent-grafts (62.2%) for the main body component. Overall 898 chimney grafts (49.2% balloon expandable, 39.6% self-expanding covered stents, and 11.2% balloon expandable bare metal stents) were placed in 692 renal arteries, 156 superior mesenteric arteries (SMA), and 50 celiac arteries. At a mean follow-up of 17.1 months (range: 1-70 months), primary patency was 94%, with secondary patency of 95.3%. Overall survival of patients in this high-risk cohort for open repair at latest follow-up was 79%. Conclusions: This global experience represents the largest series in the ch-EVAR literature and demonstrates comparable outcomes to those in published reports of branched/fenestrated devices, suggesting the appropriateness of broader applicability and the need for continued careful surveillance. These results support ch-EVAR as a valid off-the-shelf and immediately available alternative in the treatment of complex abdominal EVAR and provide impetus for the standardization of these techniques in the future

Synthesis and structure of metallated macrocycle-bearing cyclophophazenes. - Part I : The (Li, Mg, Zn)/SPIR0(30203) derivatives

Syntheses and molecular structures of three metallated (Li, Zn, Mg) derivatives of the macrocycle-bearing cyclophosphazene N3P3Cl4 [HN---(CH2)3---O---(CH2)2---O---(CH2)3---NH] (coded as SPIRO 30203, 1) are reported. These three molecular structures reveal three different patterns of metal coordination. In compound 2 one of the two hydrogen atoms in SPIRO 3O2O3 is substituted by lithium generating a dimeric structure with pentacoordinated lithium centers. This structure is further stabilized by N---H hydrogen bonds. In 3 both hydrogen atoms of the macrocyclic loop are replaced by two zinc atoms through a cross-link metallation leading again to a dimeric molecule. In this compound the Zn atom is found to be in a trigonal bipyramidal environment with one very long N---Zn interaction. The origin of the dimerization of the magnesium compound 4 is analogous to 3. Magnesium is in the center of a distorted octahedron, coordinated with the O- and N-donors of the macrocyclic loop and also one nitrogen atom of the N3P3 ring. 4 is the first example of a metallic center coordinated by a neutral phosphazene ligand. Typical metal-N and metal-O distances are (in Å): Li-O, 2.05—2.07; Li-N, 2.07—2.36; Zn-O, 2.08—2.14; Zn---N, 1.94—1.95 (2.49); Mg---O, 2.09—2.14; Mg---N, 2.07—2.31

Synthesis and structure of metallated macrocycle-bearing cyclophophazenes. - Part II : The (Al) /SPIRO (30203) derivatives

Synthesis and molecular structures of two metallated (aluminium) derivatives, [C9H19Cl4AlN5O2P3]· 1.5C7H8 and [C8H16Cl5AiN5O2P3] · 1.5C7H8, of the macrocycle-bearingcyclophosphazene N3P3Cl4 [HN--- (CH2)3---O---(CH2)2---O---(CH2)3-NH] (coded as SPIRO 30203) are reported. These two molecular structures reveal the same pattern of metal coordination where the two hydrogen atoms in SPIRO 30203 are substituted by aluminium generating monomeric structures with pentacoordinated aluminium centres in the inner cavities. In the first compound the exocyclic ligand at aluminium is a methyl group, in the second a chlorine atom. Typical Al---N, Al---O and Al-X distances are (Å):1.84-1.89, 1.97-2.04 and 1.93 in the former, 1.81-1.86, 1.93-2.01 and 2.12 in the latter, respectively

RS12. Sustained Late Branch Patency and Low Incidence of Persistent Type Ia Endoleaks Following Snorkel/chimney EVAR Shown in the Updated PERICLES Registry

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Advances in the Surface Passivation of Silicon Solar Cells

AbstractThe surface passivation properties of aluminium oxide (Al2O3) on crystalline Si are compared with the traditional passivation system of silicon nitride (SiNx). It is shown that Al2O3 has fundamental advantages over SiNx when applied to the rear of p-type silicon solar cells as well as to the p+ emitter of n-type silicon solar cells. Special emphasis is paid to the transfer of Al2O3 into industrial solar cell production. We compare different Al2O3 deposition techniques suitable for mass production such as ultrafast spatial atomic layer deposition, inline plasma-enhanced chemical vapour deposition and reactive sputtering. Finally, we review the most recent cell results with Al2O3 passivation and give a brief outlook on the future prospects of Al2O3 in silicon solar cell production

Surface passivation of silicon solar cells using industrially relevant Al2O3 deposition techniques

The next generation of industrial silicon solar cells aims at efficiencies of 20% and above. To achieve this goal using ever-thinner silicon wafers, a highly effective surface passivation of the cell front and rear is required. In the past, finding a suitable dielectric layer providing a high-quality rear passivation has been a major challenge. Aluminium oxide (Al2O3) grown by atomic layer deposition (ALD) has only recently turned out to be a nearly perfect candidate for such a dielectric. However, conventional ALD is limited to deposition rates well below 2nm/min, which is incompatible with industrial solar cell production. This paper assesses the passivation quality provided by three different industrially relevant techniques for the deposition of Al2O3 layers, namely high-rate spatial ALD, plasma-enhanced chemical vapour deposition (PECVD) and reactive sputtering

Group 14 metallated 6-amino-1-azafulvene dimers : evidence for a double intramolecular nitrogen-tin interaction

The structures of group 14 C-metalated 6-amino-1-azafulvene dimers have been investigated in solution and in the solid state by NMR spectroscopy. For one of these compounds, 5,10-bis(dimethylamino)-3,8-bis(trimethylstannyl)-5H,10H-dipyrrolo[1,2-a: 1',2'-d]-pyrazine (2c), the molecular structure in the solid state has been determined by X-ray diffractometry. The two tin centers have a distorted-trigonal-bipyramidal co-ordination geometry with the more electronegative N ligand at a pseudoaxial position, resulting in one of the longest known Sn - N interactions: 3.101 (5) A°. Moreover, the temperature-dependent 13C CP-MAS NMR spectrum of this compound shows an appreciable narrowing of the Me3Sn signal between 296 and 333 K. By comparison with nonmetalated analogs or with isomer 5c, the nonreactivity of compound 2c toward hydrolytic decomposition into corresponding 5-(trimethylstannyl)-pyrrole-2-carbaldehyde (3c) may be the result of stabilization of the dimeric form 2c by a double Sn - N interaction. In silicon and germanium analogs (2a, 2b) the Si(Ge) - N interaction is weaker