Surface bonding of MN4 macrocyclic metal complexes with pyridine-functionalized multi-walled carbon nanotubes for non-aqueous Li-O2 batteries.

It is essential to develop bifunctional catalysts with high activity and stability for reversible oxygen reduction reactions (ORRs) and oxygen evolution reactions (OERs) in lithium-oxygen (Li-O2) batteries. In this work, pyridine (Py) functionalized multi-walled carbon nanotubes (MWCNTs) were prepared to immobilize various solid MN4 macrocyclic metal complexes (MN4-MC) as cathode electrocatalysts for Li-O2 batteries. Three types of MN4-MC molecules, including iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc) and iron protoporphyrin IX (Heme) were examined to evaluate the influence of central metal atoms and ligand substituents found in MN4-MC molecules on the electrocatalytic performance of the study samples. The order of the ORR/OER catalytic activity of the bifunctional catalysts is FePc > Heme > CoPc. The central metal atom in FePc molecule has the highest occupied molecular orbital (HOMO) energy than the corresponding metal atoms in CoPc and Heme molecules. This made the molecule to have better dioxygen-binding ability and higher catalytic activity in the ORR process; it also made it to easily lose electrons that were oxidized in the OER process. This study proposed a simplified scheme of the electrode surface route to assist in understanding the diverse ORR/OER performances of MN4-MC. It is discovered that the positive core of the MN5 coordination sphere in MN4-MC/Py/MWCNTs composite is the primary active site that can influence the formation of MN5···O2* and MN5-LOOLi cluster in the ORR process. The interfacial electron could be easily delivered between MWCNTs and MN5 active site through the Py bridge. This facilitated the formation and decomposition of MN5-LOOLi species during the ORRs/OERs, leading to the enhancement of its catalytic performance. This work provides a new insight into the effects of the molecular structure and organization of MN4-MC on the catalytic activity of O2 electrodes in Li-O2 batteries.

May-Thurner syndrome: correlation between digital subtraction and computed tomography venography.

BACKGROUND/PURPOSE: Digital subtraction venography (DSV) and computed tomography venography (CTV) are both recommended for diagnosing May-Thurner syndrome. The literature contains little information on the correlation between these imaging tools. We performed a retrospective case-series study to investigate this correlation. METHODS: From August 2009 to August 2010, 42 patients with May-Thurner syndrome (34 women, 8 men; mean age: 52.8 ± 13.5 years) received DSV followed by CTV. The DSV was used to evaluate the degree of venous reflux, reflux start-up time, and flow time. By CTV, the ratio of cross-sectional area and the ratio of diameter between the narrowest region to that of the caudal part of the left common iliac vein were calculated. The correlation between these variables for DSV versus CTV was calculated using Spearman's rank correlation coefficients. RESULTS: In DSV evaluation of the extent of reflux, 19.0% of cases were classified as Grade 0, 11.9% as Grade I, 28.6% as Grade II, and 40.5% as Grade III. The mean ± standard deviation flow times for these groups were 2.00 ± 0.38 seconds, 1.75 ± 0.29 seconds, 1.67 ± 0.72 seconds, and 1.81 ± 0.68 seconds, the mean time for total patients was 1.76 ± 0.78 seconds. The reflux start-up times for Grades I-III were 2.00 ± 1.00 seconds, 1.80 ± 1.23 seconds, and 1.40 ± 0.49 seconds, and the mean time was 1.6 ± 0.8 seconds. In CTV, the mean area ratio and diameter ratio were 0.78 ± 0.22 (range, 0.22-1.27) and 0.75 ± 0.24 (range, 0.33-1.25). The reflux start-up time showed a positive correlation with the cross-sectional area ratio (r = 0.518; p = 0.002) and diameter ratio (r = 0.413; p = 0.019). CONCLUSION: The cross-sectional area ratio and diameter ratio in CTV correlate with the reflux start-up time in DSV. For May-Thurner syndrome, both CTV and DSV provide essential information for diagnosis and evaluation of the disease. The positive correlation between anatomical and hemodynamic properties corresponds with the underlying pathophysiology.

Highly Regio- and Stereoselective Cocyclotrimerization and Linear Cotrimerization of alpha,beta-Unsaturated Carbonyl Compounds with Alkynes Catalyzed by Nickel Complexes.

Cyclic enones 2-cyclohexen-1-one (1a), 4,4-dimethyl-2-cyclohexen-1-one (1b), 2-cyclopenten-1-one (1c), and 2-cyclohepten-1-one (1d) react with octa-1,7-diyne (2) in THF in the presence of Ni(PPh(3))(2)I(2), ZnI(2), and Zn powder at 62 degrees C to give [2 + 2 + 2] cycloaddition-dehydrogenation products 3a-d in 32-80% yields. alpha,beta-Unsaturated lactone 5a (5,6-dihydro-2H-pyran-2-one) undergoes [2 + 2 + 2] cycloaddition with 2 to give both the corresponding cyclohexadiene product 6 (29%) and dehydrogenation product 7 (39%). Under similar reaction conditions, 3-buten-2-one reacts with 2 and various substituted hepta-1,6-diynes 9a-c to give [2 + 2 + 2] cycloaddition-dehydrogenation products 11a-d in 68-80% yields. Diphenylacetylene also reacts with 1a-d, 5a, and 2(5H)-furanone (5b) to afford the corresponding [2 + 2 + 2] cocyclotrimerization products 13a-d and 14a-b. No dehydrogenation of products 13 and 14 was observed under the reaction and workup conditions. The reactions of acrylates with alkynes catalyzed by nickel complexes give products that depend greatly on the reaction conditions. Treating ethyl acrylate (15a) with 1-phenyl-1-propyne (16) in the presence of Ni(PPh(3))(2)Cl(2) and Zn at 90 degrees C in toluene affords cocyclotrimerization product 19aas the major product (54% yield). However, treatment of CH(2)CHCOOR (R = Et and t-Bu) with mono alkynes 16 and 12 in the presence of Ni(PPh(3))(2)X(2) (X = Cl and I) and Zn powder in toluene at 60 degrees C affords the corresponding conjugated trienes 17a-c in 82-92% yields. The MS data of 17firmly support an adduct of two molecules of alkyne and a molecule of acrylate. Similarly, the reaction of 15a with octa-1,7-diyne in the presence of Ni(PPh(3))(2)I(2), ZnI(2), and zinc gives triene derivative 21 in 68% yield. NOE and X-ray results indicate that in these trienes the substituents from each alkyne and alkene moiety are cis to each other. The unique stereoselectivity can be attributed to the exclusive formation of seven-membered nickelacycloheptadiene intermediate 25during the catalytic reaction.