[Minimally Invasive Direct Coronary Artery Bypass in a Patient with Osteopetrosis and Symptomatic Ischemic Heart Disease:Report of a Case].

Osteopetrosis is a heterogeneous group of heritable conditions. It varies greatly in severity, and fracture treatment remains a matter of controversy due to altered responses to fixation and the risk of osteomyelitis. Therefore, sternotomy outcomes in this condition are unclear. We report the case of a patient with osteopetrosis and coronary artery disease (CAD). A 78-year-old man with osteopetrosis presented with frequent chest pain. Coronary angiography revealed two-vessel CAD. Percutaneous coronary intervention was contraindication because of coronary aneurysm in the left main trunk. Considering risks in median sternotomy, we performed minimally invasive cardiac surgery through left minithoracotomy for coronary artery bypass grafting( CABG). But we needed to break the left fourth rib to obtain sufficient surgical views. To the best of our knowledge, this is the first case report on CABG for a patient with osteopetrosis and endoscopic surgery without rib retractor is recommended.

Analysis of the Optimum Tapering Angle in Microanastomosis Using Computational Fluid Dynamics.

Background: In free flap transfer, size discrepancy between the vascular pedicle and recipient vessel can create a problem for microsurgeons and sometimes induces postoperative thrombus formation. When there is a major difference between the diameters of the vascular pedicle and the recipient vessel, the larger vessel is often tapered to perform the anastomosis properly. However, the decision on the tapering angle used depends mostly on the operator's experience. In this study, computational fluid dynamics (CFD) was used to investigate the optimum tapering angle. Methods: Using ANSYS ICEM 16.0 (ANSYS Japan, Tokyo, Japan), simulated vessels of diameters 1.5 mm and 3.0 mm were designed and then used to produce four anastomosis models with the 3.0-mm vessel tapered at angles of 15º, 30º, 60º, and 90º (no tapering). Venous perfusion with a mean value of 13.0 mL/min was simulated, and this was passed through the four anastomosis models in both the forward direction (F), from the smaller to the larger vessel, and the retrograde direction (R), from the larger to the smaller vessel. The velocity, wall shear stress (WSS), and oscillatory shear index (OSI) were measured in these eight patterns and then analyzed using OpenFOAM version 5. Results: The decrease in velocity was limiting. The WSS was greater in the R direction than the F direction at every tapering angle. The OSI also tended to be almost the same in the F direction, and lower at smaller tapering angles in the R direction. And, it was greater in the F direction than in the R direction at every tapering angle. The OSI values for 15º and 30º were almost identical in the R direction. Conclusion: The risk of thrombus formation is thought to be lower when tapering is used for anastomosis if the direction of flow is from the larger to the smaller vessel, rather than vice versa. These results also suggest that the optimum tapering angle is approximately 30º in both directions.

[Intraoperative Aortic Dissection during Mitral Valve Plasty:Report of a Case].

We report the case of a 74-year-old woman who underwent mitral valve plasty for mitral regurgitation. During the surgery, the ascending aorta was dilated and turned dark red after aortic cannulation. Intraoperative transesophageal echocardiography and direct epiaortic echography revealed type A aortic dissection. In addition to mitral valve plasty, replacement of the ascending aorta was performed under hypothermic circulatory arrest. The postoperative course was uneventful. Because intraoperative aortic dissection is a rare complication, its rapid identification and appropriate management is essential.

Low-Temperature H2 Reduction of Copper Oxide Subnanoparticles.

Invited for the cover of this issue is Kimihisa Yamamoto and co-workers at Tokyo Institute of Technology and International Christian University. The image depicts enhanced reactivity of the copper oxide subnanoparticles under low-temperature conditions. Read the full text of the article at 10.1002/chem.202100508.

Low-Temperature H2 Reduction of Copper Oxide Subnanoparticles.

Subnanoparticles (SNPs) with sizes of approximately 1 nm are attractive for enhancing the catalytic performance of transition metals and their oxides. Such SNPs are of particular interest as redox-active catalysts in selective oxidation reactions. However, the electronic states and oxophilicity of copper oxide SNPs are still a subject of debate in terms of their redox properties during oxidation reactions for hydrocarbons. In this work, in situ X-ray absorption fine structure (XAFS) measurements of Cu28 Ox SNPs, which were prepared by using a dendritic phenylazomethine template, during temperature-programmed reduction (TPR) with H2 achieved lowering of the temperature (T50 =138 °C) reported thus far for the CuII →CuI reduction reaction because of Cu-O bond elongation in the ultrasmall copper oxide particles.

Selective Hydroperoxygenation of Olefins Realized by a Coinage Multimetallic 1-Nanometer Catalyst.

The science of particles on a sub-nanometer (ca. 1 nm) scale has attracted worldwide attention. However, it has remained unexplored because of the technical difficulty in the precise synthesis of sub-nanoparticles (SNPs). We recently developed the "atom-hybridization method (AHM)" for the precise synthesis of SNPs by using a suitably designed macromolecule as a template. We have now investigated the chemical reactivity of alloy SNPs obtained by the AHM. Focusing on the coinage metal elements, we systematically evaluated the oxidation reaction of an olefin catalyzed by these SNPs. The SNPs showed high catalytic performance even under milder conditions than those used with conventional catalysts. Additionally, the hybridization of multiple elements enhanced the turnover frequency and the selectivity for the formation of the hydroperoxide derivative. We discuss the unique quantum-sized catalysts providing generally unstable hydroperoxides from the viewpoint of the miniaturization and hybridization of materials.

Enhanced Catalytic Performance of Subnano Copper Oxide Particles.

Subnanoparticles (SNPs) with ultrasmall particle sizes (<1 nm) have potential to provide catalytic activity that is superior to that of nanoparticles. Size-controlled CunOx (n = 12, 28, and 60) materials supported on zirconia, prepared using a dendritic macromolecular reactor, exhibited increased ionicity of the Cu-O bonds with a decrease in size of the particles, which was suggested on the basis of the peak intensity in the Cu 2p3/2 region. The polarization of the Cu-O bonds in the ultrasmall copper oxides provides size-dependent catalytic activity in aerobic oxidation of the CH3 group bonded with aromatic rings. The smallest Cu12Ox materials achieved an excellent large turnover number (TON = 40 206) without any significant deactivation.

A useful preparation of ultrasmall iron oxide particles by using arc plasma deposition.

Ultrasmall particles, different from the larger size nanoparticles, have recently attracted significant attention in the scientific community in nanotechnology for catalytic, electronic and optical applications; however, their magnetic properties remain unexplored due to the difficult structural analysis. A challenging issue is to develop a preparation method for iron oxide particles (IOPs) with fine size control, and to determine the dependence of magnetic properties on the morphology and crystallinity of the magnetic particles. However, synthetic approaches to obtain IOPs, regarded as one of the new fields of magnetic nanoparticles, have been significantly limited. This article reported a developed synthetic method to prepare IOPs on carbon supports using pulsed arc plasma deposition (APD) in flowing oxygen gas, which clarified the finely-controlled formation of IOPs on graphene nanosheets. Structural characterization of the IOPs revealed the formation of crystalline γ-Fe2O3 ultrasmall particles with oxygen deficiency. The pulsed APD method for IOPs is the first simple and convenient technique to not only prevent significant aggregation and contamination by organic compounds and avoid the need for thermal pretreatment, but also provide uniform crystalline nano-order particles.

New Horizon of Nanoparticle and Cluster Catalysis with Dendrimers.

Among various approaches synthesizing metal nanoparticles and tiny clusters, a template method using dendrimers has significant advantages over other chemical approaches with respect to their synthetic precision and the scalability. A dendrimer of polydentate ligands assembles metal ions or salts into the interior allowing production of metal nanoparticles in the dendrimer. The dendrimer-encapsulated nanoparticles (DENs) exhibit unique and remarkable catalytic properties depending on the size and elemental formula. Recent advances in dendrimer chemistry even enabled the atom precise synthesis of subnanometer metal clusters that have been impossible to prepare by wet chemical methods. In addition, not only for the synthesis of metal nanoparticles and clusters, the dendrimer itself can also provide the modulation of activity and selectivity in the catalysis. In this review, we summarized the most relevant research in which the dendrimer was employed as the template, modulator, or stabilizer for nanoparticle synthesis for catalytic applications.

Bimolecular fusion of [Pd3(µ-CN-C6H3Me2-2,6)3(CN-C6H3Me2-2,6)3] induced by Ph2GeH2: formation of the redox-active Pd6Ge2 complex.

The reaction of Ph2GeH2 with a planar tripalladium(0) complex, [Pd3(µ-CN-C6H3Me2-2,6)3(CN-C6H3Me2-2,6)3], selectively afforded a hexagonal bipyramidal Pd6Ge2 complex, [Pd6(µ-GePh2)2(CN-C6H3Me2-2,6)8(µ-CN-C6H3Me2-2,6)2]. The molecule is stabilized by bridging coordination of isonitrile and GePh2 ligands, although all the Pd-Pd bonds are weak, as revealed by DFT calculations. The resulting complex undergoes two successive redox processes at E1/2 = -1.35 and -1.03 V (vs. Fc+/Fc), which correspond to the stepwise oxidation of the Pd(0)6 complex.

Aerobic Toluene Oxidation Catalyzed by Subnano Metal Particles.

Subnanocatalysts (SNCs) containing various noble metals (Cu, Ru, Rh, Pd, or Pt) with sizes of approximately 1 nm were synthesized using dendritic poly(phenylazomethine)s as a macromolecular template. These materials exhibit high catalytic performance during toluene oxidation without the use of harmful solvents or explosive oxidants, resulting in the formation of valuable organic products, including benzoic acid as the major product. In particular, Pt19 SNC with a narrow particle size distribution exhibits extraordinary catalytic activity, with a turnover frequency of 3238 atom-1 h-1 , which is 1700 times greater than that obtained by commercial Pt/C catalysts.

Synthesis of Chiral cis-Cyclopropane Bearing Indole and Chromone as Potential TNFα Inhibitors.

Conformationally restricted analogues of SPD-304, the first small-molecule TNFα inhibitor, in which two heteroaryl groups, indole and chromone, are connected by chiral methyl- or ethyl- cis-cyclopropane, were designed. Synthesis of these molecules was achieved via Suzuki-Miyaura or Stille coupling reactions with chiral bromomethylenecyclopropane or iodovinyl- cis-cyclopropane as the substrate, both of which were prepared from chiral methylenecyclopropane as a common intermediate, constructing the heteroaryl-methyl or -ethyl- cis-cyclopropane structures as key steps. This study presents an efficient synthesis of a series of chiral cis-cyclopropane conjugates with two heteroaryl groups.

Planar PtPd3 Complexes Stabilized by Three Bridging Silylene Ligands.

A heterobimetallic PtPd3 complex supported by three bridging diphenylsilylene ligands, [Pt{Pd(dmpe)}3 (µ3 -SiPh2 )3 ] (1, dmpe=1,2-bis(dimethylphosphino)ethane), has been synthesized from mononuclear Pd and Pt complexes. The hexagonal core composed of Pt, Pd, and Si atoms is slightly larger than that of the tetrapalladium complex, [Pd{Pd(dmpe)}3 (µ3 -SiPh2 )3 ] (2). Reaction of PhSiH3 with complex 1 in the presence and absence of Ph2 SiH2 results in the formation of a tetranuclear complex with silyl and hydride ligands at the Pt center, [PtH(SiPh2 H){Pd(dmpe)}3 (µ3 -SiHPh)3 ] (3), and an octanuclear complex, [{Pt{Pd(dmpe)}3 (µ3 -SiHPh)3 }2 (κ2 -dmpe)] (5), respectively. Both M-Si (M=Pt, Pd) bond lengths and the 29 Si NMR chemical shifts of 1 and 2 are located between those of mononuclear late transition-metal complexes with a silylene ligand and complexes with donor-stabilized silylene ligands. CuI and AgI adducts of 1 and 2, formulated as [M(µ-M'I){Pd(dmpe)}3 (µ3 -SiPh2 )3 ] (M=Pt, Pd; M'=Cu, Ag), undergo elimination of CuI (AgI) and regenerate the tetrametallic complexes upon heating or addition of a chelating diphosphine. Elimination of AgI from 2-AgI occurs more rapidly than elimination of CuI from 2-CuI, as determined from the results of kinetics experiments.

Design and Synthesis of Cyclopropane Congeners of Resolvin E2, an Endogenous Proresolving Lipid Mediator, as Its Stable Equivalents.

Lipid chemical mediator resolvins with highly potent anti-inflammatory activity can be leads to develop novel anti-inflammatory drugs; however, they are unstable in oxygen due to their characteristic polyunsaturated structures. To solve the problem, CP-RvE2 has been designed and synthesized in which the cis-olefin of RvE2 was replaced with a cyclopropane. CP-RvE2s were much more stable than RvE2 against autoxidation and equipotent or more potent than RvE2. CP-RvE2s were successfully identified as stable equivalents of RvE2.

Bond formation and coupling between germyl and bridging germylene ligands in dinuclear palladium(I) complexes.

The dinuclear palladium(I) complexes [L(Ar2 HGe)Pd(µ-GeAr2 )2 Pd(GeHAr2 )L] (Ar=Ph, p-Tol; L=PMe3 , tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge⋅⋅⋅Ge bond lengths of 2.8263(4) Š(L=PMe3 ) and 2.928(1) Š(L=tBuNC), which are close to the longest Ge-Ge bond reported to date [2.714(1) Å]. Significant Ge⋅⋅⋅Ge interactions between the germylene and germyl ligands (PMe3 complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe3 ligands increases the Ge⋅⋅⋅Ge interaction, and simultaneously activates two Pd-Ge bonds. Adding the chelating diphosphine 1,2-bis(diethylphosphino)ethane (depe) to the PMe3 complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane.

A triangular triplatinum(0) complex with bridging germylene ligands: insertion of alkynes into the Pt-Ge bond rather than the Pt-Pt bond.

A new triangular triplatinum(0) complex with bridging diphenylgermylene ligands, [{Pt(PMe3)}3(µ-GePh2)3], undergoes insertion of ZC≡CZ (Z = COOMe) into a Pt-Ge bond. The product contains a µ3-η(2)(∥)-CZ=CZ-GePh2 ligand on the Pt3 plane. Two molecules of HC≡CZ react to afford the Pt3 complex with chelating C, Ge- and Ge, Ge-ligands.

Preparation of chiral bromomethylenecyclopropane and its use in Suzuki-Miyaura coupling: synthesis of the arylmethyl-(Z)-cyclopropane structure core.

A preparative method for an optically active bromomethylenecyclopropane unit and its practical conversion to (Z)-cyclopropane-containing chiral compounds via Suzuki-Miyaura coupling were established.

Reaction of an alkyne with dinickel-diphenylsilyl complexes. An emissive disilane formed via the consecutive Si-C and Si-Si bond-making processes.

[{Ni(dmpe)}(2)(µ-SiHPh(2))(2)] (dmpe = 1,2-bis(dimethylphosphino)ethane) reacted with PhC≡CPh to yield fluorescent 1,2-bis{(E)-1,2-diphenylethenyl}-1,1,2,2-tetraphenyldisilane via addition of the Si-H bond of the ligand to the alkyne and subsequent coupling of the tertiary silyl ligands forming the Si-Si bond.

Tetrapalladium complex with bridging germylene ligands. Structural change of the planar Pd4Ge3 core.

A complex with a planar hexagonal Pd(4)Ge(3) core, [Pd{Pd(dmpe)}(3)(µ(3)-GePh(2))(3)], was synthesized and characterized by X-ray and NMR measurements as well as by DFT calculations. 4-tert-Butylbenzenethiol converted the Pd(4) complex into a hexapalladium complex, [{Pd(3)(µ-GePh(2))(2)(µ-H)(µ(3)-GePh(2)(SC(6)H(4)(t)Bu-4))}(2)(µ-dmpe)], composed of two Pd(3)Ge(3) units bridged by a dmpe ligand. The addition of CuI or AgI to the Pd(4) complex yielded [Pd(µ-MI){Pd(dmpe)}(3)(µ(3)-GePh(2))(3) ] (M = Cu, Ag), in which Cu or Ag bridges a Pd-Pd bond of the Pd(4)Ge(3) core. The CuI adducts in solution undergo a pivot motion of the CuI on the surface of the Pd(4)Ge(3) plane on the NMR time scale.

Cd(II) and Pb(II) complexes of the polyether ionophorous antibiotic salinomycin.

BACKGROUND: The natural polyether ionophorous antibiotics are used for the treatment of coccidiosis in poultry and ruminants. They are effective agents against infections caused by Gram-positive microorganisms. On the other hand, it was found that some of these compounds selectively bind lead(II) ions in in vivo experiments, despite so far no Pb(II)-containing compounds of defined composition have been isolated and characterized. To assess the potential of polyether ionophores as possible antidotes in the agriculture, a detailed study on their in vitro complexation with toxic metal ions is required. In the present paper we report for the first time the preparation and the structure elucidation of salinomycin complexes with ions of cadmium(II) and lead(II). RESULTS: New metal(II) complexes of the polyether ionophorous antibiotic salinomycin with Cd(II) and Pb(II) ions were prepared and structurally characterized by IR, FAB-MS and NMR techniques. The spectroscopic information and elemental analysis data reveal that sodium salinomycin (SalNa) undergoes a reaction with heavy metal(II) ions to form [Cd(Sal)2(H2O)2] (1) and [Pb(Sal)(NO3)] (2), respectively. Abstraction of sodium ions from the cavity of the antibiotic is occurring during the complexation reaction. Salinomycin coordinates with cadmium(II) ions as a bidentate monoanionic ligand through the deprotonated carboxylic moiety and one of the hydroxyl groups to yield 1. Two salinomycin anions occupy the equatorial plane of the Cd(II) center, while two water molecules take the axial positions of the inner coordination sphere of the metal(II) cation. Complex 2 consists of monoanionic salinomycin acting in polydentate coordination mode in a molar ratio of 1: 1 to the metal ion with one nitrate ion for charge compensation. CONCLUSION: The formation of the salinomycin heavy metal(II) complexes indicates a possible antidote activity of the ligand in case of chronic/acute intoxications likely to occur in the stock farming.