Vegawillard1075

The reaction of a silyl dienolate, a Cu(II) salt and TBAT yielding the corresponding copper dienolate is addressed. A combined NMR and cyclic voltammetry analysis first highlight the role of TBAT in the Cu(II) to Cu(I) reduction and the structure of the precatalytic species. From these first results a second set of NMR and theoretical studies enable the determination of the structure and the mechanism of formation of the copper dienolate catalytic species. Finally, we showed that that the copper catalyst promote the E/Z s-cis/s-trans equilibration of the silyl dienolate precursor through a copper dienolate intermediate. All of these results unveil some peculiarities of the catalytic and asymmetric vinylogous Mukaiyama reaction.Manganese oxides have attracted great interest in electrochemical energy storage due to high theoretical specific capacitance and abundant valence states. The multiple valence states in the redox reactions are beneficial for enhancing the electrochemical properties. Herein, three manganese microspheres were prepared by a one-pot hydrothermal method and subsequent calcination at different temperatures using carbon spheres as templates. The trivalent manganese of Mn2 O3 exhibited multiple redox transitions of Mn3+ /Mn2+ and Mn4+ /Mn3+ during the intercalation/deintercalation of electrolyte ions. The possible redox reactions of Mn2 O3 were proposed based on the cyclic voltammetry and differential pulse voltammogram results. Mn2 O3 microsphere integrated the advantages of multiple redox couples and unique structure, demonstrating a high specific capacitance and long cycling stability. The symmetric Mn2 O3 //Mn2 O3 device yielded a maximum energy density of 29.3 Wh kg-1 at 250 W kg-1 .As promising photoresponsive materials and potential smart materials, hybrid photochromic materials (HPMs), especially for crystalline HPMs (CHPMs), have been broadly explored for their potential in inheriting the merits of each constituents, and intriguing photomodulated functionality. Hitherto, the photoresponsive functionality in explored CHPMs mainly concentrate on dyad combination. By contrast, triple or quadruple photoresponsive properties are very rare because of the limited compatibility of multiple photoresponsive functionality in a single system. In this work, the electron-transfer (ET) and crystal engineering strategies were utilized to predesign CHPMs with multiple photoresponsive properties via the collaboration of paramagnetic metal ion (Dy3+ ), electron-donor (ED) ligand (benzene-1,2,3-tricarboxylic acid, H3 BTA) and electron-acceptor (EA) ligand (1,10-phenanthroline, phen). The resulting complex [Dy(BTA)(phen)2 ]⋅2H2 O (1) shows hybrid chain with the intrachain Dy3+ ions bridged and chelated by tricarboxylate and phen ligands, respectively. After photostimuli, the ET between tricarboxylate and phen results in photogenerated radicals and the resultant quadruple photoresponsive properties. Considering the abundant resources of paramagnetic metal ions, ED- and EA-ligands, this work provides a general method to construct CHPMs with multiple photoresponsive performances via the collaboration of each unit under the guidance of ET and crystal engineering strategies.A field-induced chiral YbIII Single-Molecule Magnet (SMM) displayed an unprecedented near-infrared circularly polarized luminescence (NIR-CPL) in the solid-state. The bridging bis(1,10-phenantro[5,6b])tetrathiafulvalene triad (L) allowed an efficient sensitization of the NIR 2 F5/2 →2 F7/2 emission while the NIR-CPL is associated to the f-f transitions of the YbIII ion bearing chiral β-diketonate derived-camphorate ancillary ligands.The selectivity patterns of iron catalysts of the Fe(PDP) family in aliphatic C-H oxidation with H2 O2 have been studied (PDP=N,N'-bis(pyridine-2-ylmethyl)-2,2'-bipyrrolidine). Cyclohexane, adamantane, 1-bromo-3,7-dimethyloctane, 3,7-dimethyloctyl acetate, (-)-acetoxy-p-menthane, and cis-1,2-dimethylcyclohexane were used as substrates. The studied catalyst systems generate low-spin (S=1/2) oxoiron(V) intermediates or high-spin (S=3/2) oxoiron(V) intermediates, depending on the electron-donating ability of remote substituents at the pyridine rings. https://www.selleckchem.com/products/fdi-6.html The low-spin perferryl intermediates demonstrate lower stability and higher reactivity toward aliphatic C-H groups of cyclohexane than their high-spin congeners, according to the measured self-decay and second-order rate constants k1 and k2 . Unexpectedly, there appears to be no uniform correlation between the spin state of the oxoiron(V) intermediates, and the chemo- and regioselectivity of the corresponding catalyst systems in the oxidation of the considered substrates. This contrasts with the asymmetric epoxidations by the same catalyst systems, in which case the epoxidation enantioselectivity increases when passing from the systems featuring the more reactive low-spin perferryl intermediates to those with their less reactive high-spin congeners.

Myocutaneous pedicled flaps are the method of choice for sternal reconstruction after deep sternal wound infection (DSWI) following cardiac surgery. We set out to investigate whether free flaps provide a superior alternative for particularly extended sternal defects.

Between October 2008 and February 2020, 86 patients with DSWI underwent sternal reconstruction with myocutaneous flaps at our institution. Patients were retrospectively grouped into pedicled (A; n = 42) and free flaps (B, n = 44). The objective was to compare operative details, outcome variables, surgical as well as medical complication rates between both groups, retrospectively. Binary logistic regression analysis was applied to determine the effect of increasing defect size on flap necrosis.

Rates of partial flap necrosis (>5% of the skin island) were significant higher in pedicled flaps (n = 14), when compared to free flaps (n = 4) (OR 5.0; 33 vs. 9%; p = .008). Increasing defect size was a significant risk factor for the incidence of partial flap necrosis of pedicled flaps (p = .012), resulting in a significant higher rate of additional surgeries (p = .036). Binary regression model revealed that the relative likelihood of pedicled flap necrosis increased by 2.7% with every extra square-centimeter of defect size.

To avoid an increased risk of partial flap necrosis, free flaps expand the limits of extensive sternal defect reconstruction with encouragingly low complication rates and proved to be a superior alternative to pedicled flaps in selected patients.

To avoid an increased risk of partial flap necrosis, free flaps expand the limits of extensive sternal defect reconstruction with encouragingly low complication rates and proved to be a superior alternative to pedicled flaps in selected patients.