Improvement of Ni/SDC anode by alkaline earth metal oxide addition for direct methane–solid oxide fuel cells

The anodic performances of Ni/CeO₂–Sm₂O₃(Ni/SDC) modified by the addition of alkaline earth metal oxides (MgO, CaO, and SrO) were investigated for direct oxidation of CH₄ in solid oxide fuel cells (SOFCs). Although the initial power density of cell with Ni/SDC anode modified by the addition of CaO was slightly lower than that of cell with Ni/SDC, the former anode exhibited an excellent stability compared to the latter one. Such a high stability of Ni–CaO/SDC anode may come from the inhibition of carbon deposition in addition to the retained ionic conductivity of anode.     

Study of the acute cardiovascular effects of several antihypertensive agents with the measurement of plasma catecholamines in mice

A highly sensitive determination method was established for catecholamines (norepinephrine (NE), epinephrine, and dopamine) with high-performance liquid chromatography-peroxyoxalate chemiluminescence reaction detection. In this study, the method was applied to mouse plasma, and it was determined that only 10 μl of mouse plasma was necessary for the selective and reproducible determination of catecholamines. Studies were then conducted in acute cardiovascular effects of sodium nitroprusside, nicardipine, captopril (angiotensin-converting enzyme (ACE) inhibitor), candesartan, and olmesartan (type 1 angiotensin receptor antagonists (AT₁ antagonists)) by this method. Sodium nitroprusside and nicardipine elevated plasma NE concentrations significantly, whereas the ACE inhibitor and the AT₁ antagonists did not change plasma NE concentrations in anesthetized mice. These results suggested that angiotensin II-induced augmentation may be mainly carried through the central baroreflex pathway.     

Two-dimensional structure control by molecular width variation with metal coordination

The self-assembled monolayer of bipyridine derivative 1, which has two alkyl chains on each end, at the HOPG/1-phenyloctane interface was studied by in situ scanning tunneling microscopy (STM). The detailed mechanism of a spontaneous change in the monolayer packing pattern by Pd coordination was studied. Uncomplexed 1 existed in a bent form in the monolayer, and the alkyl chains were interdigitated, whereas Pd-complexed 1 was in a straight form and the alkyl chains were not interdigitated. An intermediate state of 1 was successfully observed during metal coordination. The structure was the bent form with noninterdigitated alkyl chains. Equilibrium intermolecular distances reported from ab initio calculations indicate that the molecular width of the central aromatic part of uncomplexed 1 (7.5 A) is substantially smaller than that of the peripheral alkyl chain part (9.2 A). The bent form was suitable for covering up the surface to maximize the packing density. However, the molecular width of the aromatic unit of Pd-complexed 1 (9.1 A) was almost identical to that of the alkyl chain unit (9.2 A). Therefore, Pd-complexed 1 took the straight form in the monolayer. The observation of surface coverage by STM suggests that the bent form increases the packing density by as much as 16% compared with that of the straight form. These results indicate that the control of molecular width can be used to design molecular templates for nanostructure formation.     

Photosensitized reduction of water to hydrogen using human serum albumin complexed with zinc-protoporphyrin IX

We present the photophysical properties of complexes of recombinant human serum albumin (rHSA) with Zn(II)-protoporphyrin IX (ZnPP) and their activities in the photosensitized reduction of water to hydrogen (H2) using methyl viologen (MV2+) as an electron relay. The ZnPP is bound in subdomain IB of wild-type rHSA [rHSA(wt] by an axial coordination of Tyr-161 and, in the rHSA(I142H/Y161L) mutant [rHSA(His], by a His-142 coordination. Both the rHSA(wt)-ZnPP and rHSA(His)-ZnPP complexes showed a long-lived photoexcited triplet state with lifetimes (tauT) of 11 and 2.5 ms, respectively. The accommodation of ZnPP into the protein matrix efficiently eliminated the collisional triplet self-quenching process. The addition of a water-soluble electron acceptor, MV2+, resulted in a significant decrease in the triplet lifetime. The transition absorption spectrum revealed the oxidative quenching of rHSA-3ZnPP* by MV2+. The quenching rate constant (kq) and backward electron transfer rate constant (kb) were determined to be 1.4 x 10(7) and 4.7 x 10(8) M(-1) s(-1) for rHSA(wt)-ZnPP. In the presence of the colloidal PVA-Pt as a catalyst and triethanolamine (TEOA) as a sacrificial electron donor, the photosensitized reduction of water to H2 takes place. The efficiency of the photoproduction of H2 was greater than that of the system using the well-known organic chromophore, tetrakis(1-methylpyridinium-4-yl)porphinatozinc(II) (ZnTMPyP4+), under the same conditions.     

Selective synthesis of 2-pyridones and pyrimidine-2,4-diones by neutral rhodium(I) complex-catalyzed cyclocotrimerization of alkynes and isocyanates

A neutral rhodium(I) complex, ‘RhCl(PPh₃)₂’ generated by the combination of [RhCl(C₂H₄)₂]₂ with a fourfold amount of PPh₃, effectively catalyzed the cyclocotrimerization of alkynes (1) and isocyanates (2) to give 2-pyridones (3) and/or pyrimidine-2,4-diones (4), selectively, by controlling the molar ratio of alkynes (1) and isocyanates (2).     

Efficient construction of biaryls and macrocyclic cyclophanes via electron-transfer oxidation of Lipshutz cuprates

An efficient method for the homocoupling of aryl halides by electron-transfer oxidation of Lipshutz cuprates (Ar2Cu(CN)Li2) with organic electron acceptors is disclosed. Thus, various types of Lipshutz cuprates are prepared by successive treatment of aryl or heteroaryl bromides with tert-butyllithium and CuCN. The electron-transfer oxidation of Lipshutz cuprates with p-benzoquinones proceeds smoothly to afford the corresponding homocoupling products in moderate to good yields. Furthermore, it can be applied to the construction of either thiophene- or benzene-fused 10-membered ring cyclophanes. For the synthesis of 10-membered cyclophanes, the linear C-Cu-C structure of Lipshutz cuprates should be maintained in the dimetallacyclic intermediates, producing the large ring cyclophanes efficiently. The X-ray analysis of the cyclophanes reveals that the difference in the bridging atoms results in the different conformations of the macrocyclic rings. Thus, the silicon-bridged cyclophane 5a adopts a D2-symmetric structure with a twisted rhombic arrangement of four thiophene rings, whereas the methylene- and oxygen-bridged cyclophanes 5b and 5c possess C2h- and C2-symmetric structures with chair- and boatlike conformations, respectively. The 1H NMR spectrum of C2-symmetric 5c is temperature-dependent, and the activation energy (DeltaG) for the conformational change is 10.1 kcal/mol.     

Cooperative catalytic reactions using distinct transition-metal catalysts: ruthenium- and copper-catalyzed enantioselective propargylic alkylation

The enantioselective propargylic alkylation of propargylic alcohols with β-ketoesters in the presence of a thiolate-bridged diruthenium complex and a copper complex as co-catalyst affords the corresponding propargylic alkylated products in excellent yields as a mixture of two diastereoisomers with high enantioselectivity (up to 95% enantiomeric excess (ee)). The findings reported herein not only open up a new type of enantioselective propargylic substitution reaction, but also a new aspect of cooperative catalytic reactions using distinct transition metals to realize a useful transformation that cannot be achieved by a single catalyst.     

Theoretical and experimental investigation on the electronic properties of the shuttlecock shaped and the double-decker structured metal phthalocyanines, MPc and M(Pc)2 (M = Sn and Pb)

The molecular geometries, electronic structures, and excitation energies of tin and lead phthalocyanine compounds, SnPc, PbPc, Sn(Pc)(2), and Pb(Pc)(2), were investigated using the B3LYP method within a framework of density functional theory (DFT). The geometries of SnPc, PbPc, Sn(Pc)(2), and Pb(Pc)(2) were optimized under C(4v), C(4v), D(4d), and D(4d) molecular symmetries, respectively. The excitation energies of these molecules were computed by the time-dependent DFT (TD-DFT) method. The calculated results for the excited states of three compounds other than the unknown Pb(Pc)(2) corresponded well with the experimental results of electronic absorption spectroscopy. The non-planar C(4v) molecular structure of SnPc and PbPc influences especially on the orbital energy of the HOMO-1 through mixing of the s-type atomic orbital of the central metal atom to the π system of the Pc ring in an anti-bonding way; however, the HOMO and the LUMO have little effect of the deviation from the planar structure because they have no contribution from the atomic orbital of the central metal. This orbital mixing pushes up the orbital energy of the HOMO-1, and reduces the energy of the metal-to-ligand charge transfer band of SnPc and PbPc. The calculated results also reproduced well the excitation profile of Sn(Pc)(2), which was quite different from that of SnPc. The strong interactions between the π-type orbitals of two Pc moieties altered the electronic structure resulting in the characteristic excitation profile of Sn(Pc)(2). In addition, this caused a reduction of about 0.8 eV in the ionization potential as compared to usual MPcs including SnPc, which was consistent with the experimental results.     

Nuclear Spin Alignment of 12,13B Produced in Heavy Ion Collisions

The nuclear spin alignments of the β-emitting fragments ¹²B(I ^π=1⁺, T _1/2=20.2 ms) and ¹³B(I ^π=3/2⁻, T _1/2=17.4 ms) produced in the 100A-MeV ¹³C, ¹⁵N + ⁹Be collisions respectively have been observed for the first time detecting asymmetric β-ray emission from these nuclei. By means of the spin manipulation technique based on the hyperfine interaction of B isotopes in TiO₂, both the polarization P and the alignment A were determined reliably. The obtained P and A were significantly smaller than the expectation from the kinematical model. From the fact that the quenching factors for P and A are almost the same, there may be some depolarization mechanism in the collision process itself. This revised version was published online in September 2006 with corrections to the Cover Date.     

Preparation of 1,3‐diphosphabuta‐1,3‐dienes from sterically encumbered phosphaalkyne and phosphaethenyllithium

Kinetically stabilized 2‐lithio‐1‐(2,4,6‐tri‐t‐butylphenyl)‐1‐phosphapropene was allowed to react with a bulky phosphaalkyne Mes*CP (Mes* = 2,4,6‐t‐Bu₃C₆H₂) followed by quenching with iodomethane or benzyl bromide to give the corresponding 1,3‐diphosphabuta‐1,3‐dienes. The presence of the bulky Mes* group on the 1‐phosphorus atom prevents intramolecular [2+2] cyclization and gave the PC PC skeleton, whereas Mes*CP reacted with half an equivalent of nucleophile to afford the PCPC four‐membered ring compounds. X‐ray crystallography of 4‐benzyl‐1,3‐diphosphabuta‐1,3‐diene confirmed the molecular structure showing conjugation on the 1,3‐diphosphabuta‐1,3‐diene moiety. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:357–360, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20104