The structure of a biosynthetic intermediate of pyrroloquinoline quinone (PQQ) and elucidation of the final step of PQQ biosynthesis

Pyrroloquinoline quinone (PQQ) is a tricyclic o-quinone, which serves as a cofactor in several enzyme-catalyzed redox reactions in certain bacteria. PQQ is also important for human health, and its role as a vitamin in mammals has recently been suggested. Although much is known about the function of enzymes that use PQQ as cofactor, relatively little is known about the biosynthesis of this coenzyme. Six gene products in Klebsiella pneumoniae (PqqA-F) are involved in PQQ biosynthesis, and PqqC has been shown to catalyze the last step in the pathway. The chemical structure of the substrate for PqqC has remained elusive and has hampered our understanding of the nature of this reaction. In this report we describe the purification and structure of the substrate as deduced by a number of spectroscopic and chemical methods. The substrate is 3a-(2-amino-2-carboxyethyl)-4,5-dioxo-4,5,6,7,8,9-hexahydroquinoline-7,9-dicarboxylic acid-a fully reduced derivative of PQQ, which has not undergone ring cyclization. These results show that PqqC catalyzes a novel reaction, which involves ring closure and an amazing eight-electron oxidation of the substrate.     

Preparation of novel hydrophobic fluorine-substituted-alkyl sulfate ionic liquids and application as an efficient reaction medium for lipase-catalyzed reaction

Various types of differently fluorinated-alkyl sulfate ionic liquids have been prepared; the hydrophobicity was dependent on the content ratio of the fluorine on the alkyl sulfate anion and 2,2,3,3,4,4,5,5-octafluoropentyl sulfate salts showed hydrophobic properties. Melting point and viscosity were also dependent on the fluorine contents of the anionic part, while conductivity was determined by the cationic part and not influenced by the fluorine contents. Efficient lipase-catalyzed transesterification was demonstrated using hydrophobic 1-butyl-3-methylimidazolim 2,2,3,3,4,4,5,5-octafluoropentyl sulfate ([bmim][C5F8]) as solvent.     

Activation of C–H and H–H bonds by dinuclear iridium complexes. Oxidative addition to highly active unsaturated 32e− diiridium species

Reactions of [(Cp¹Ir)₂(μ-dmpm)(μ-H)₂][OTf]₂ (1) with NaO^tBu in aromatic solvent at room temperature give [(Cp¹Ir)(H)(μ-dmpm)(μ-H)(Cp¹Ir)(Ar)][OTf] [Ar = Ph (3), p-Tol (4a), m-Tol (4b), 2-furyl (5a), 3-furyl (5b)] via intermolecular aromatic C–H activation. Treatment of [(Cp¹Ir)₂(μ-dppm)(μ-H)₂][OTf]₂ (2) with weak base (Et₂NH) results in intramolecular C–H activation of a phenyl group in the dppm ligand to give [(Cp¹Ir)(H){μ-PPh(C₆H₄)CH₂PPh₂}(μ-H)(Cp¹Ir)][OTf] (6). Reaction of 1 with NaO^tBu in tetrahydrofuran under H₂ (1 atm) results in activation of the H–H bond to give [{(Cp¹Ir)(H)}₂(μ-dmpm)(μ-H)][OTf] (7). Reaction of 1 with NaO^tBu in dichloromethane under carbon monoxide (1 atm) gives a carbonyl-bridged Ir^II–Ir^II complex, [(Cp¹Ir)₂(μ-dmpm)(μ-H)(μ-CO)][OTf] (8-OTf). These results strongly suggest that the active species in C–H and H–H bond activation starting with 1 and 2 would be unsaturated 32e^? diiridium species. The structures of 3, 5a, 6, 7, and 8-BPh₄ have been determined by X-ray diffraction methods.     

An intermediate temperature solid oxide fuel cell utilizing superior oxide ion conducting electrolyte, doubly doped LaGaO3 perovskite

LaGaO₃-based perovskite oxide doped with Sr and Mg exhibits high ionic conduction over a wide oxygen partial pressure. In this study, the stability of the LaGaO₃ based oxide was investigated. It became clear that LaGaO₃ based oxide is very stable for reduction and oxidation. SOFCs utilizing LaGaO₃-based perovskite type oxide for electrolyte were further studied for the decreased temperature solid oxide fuel cells. The power generation characteristics of cells were strongly affected by the electrode, both anode and cathode. It became clear that Ni and LnCoO₃ (Ln: rare earth) are suitable for anode and cathode, respectively. Rare earth cations in the Ln-site of Co-based perovskite cathode also have a great effect on the power generation characteristics. In particular, high power density could be attained in the temperature range from 973 to 1273 K by using doped SmCoO₃ for the cathode. The electrical conductivity of SmCoO₃ increases with increasing Sr amount doped for the Sm site and attained the maximum at Sm_0.5Sr_0.5CoO₃. The cathodic overpotential and the internal cell resistance exhibit almost opposite dependence on the amount of doped Sr. Consequently, the power density of the cell reaches a maximum when Sm_0.5Sr_0.5CoO₃ is used for cathode. On this cell, the maximum power density is as high as 0.58 W/cm² at 1073 K, although a 0.5 mm thick electrolyte is used. Therefore, this study reveals that the LaGaO₃ based oxide for electrolyte and the SmCoO₃ based oxide for cathode are promising for solid oxide fuel cells at intermediate temperature. Paper presented at the 97th Xiangshan Science Conference on New Solid State Fuel Cells, Xiangshan, Beijing, China, June, 14–17, 1998.     

Biogenous iron oxide-immobilized palladium catalyst for the solvent-free Suzuki–Miyaura coupling reaction

Iron oxide produced by iron-oxidizing bacteria, Leptothrix ochracea, (biogenous iron oxide: BIO) was used as a support for immobilized palladium catalysts with organic cross-linkers. Palladium immobilized on BIO bearing imidazolium chloride delivered the desired biaryl products in sufficient yields in the Suzuki–Miyaura coupling reactions under solvent-free conditions and could be reused several times without significant loss of catalytic activity. It is shown that BIO can be exploited as a useful support for immobilization of palladium and the BIO-immobilized palladium catalyst effectively promotes the solvent-free Suzuki–Miyaura coupling reactions.     

Complete classification of pseudo <Emphasis Type="Italic">H</Emphasis>-type Lie algebras: I

Let \({\mathscr {N}}\) be a 2-step nilpotent Lie algebra endowed with a non-degenerate scalar product \(\langle .\,,.\rangle \), and let \({\mathscr {N}}=V\oplus _{\perp }Z\), where Z is the centre of the Lie algebra and V its orthogonal complement. We study classification of the Lie algebras for which the space V arises as a representation space of the Clifford algebra \({{\mathrm{{\mathrm{Cl}}}}}({\mathbb {R}}^{r,s})\), and the representation map \(J:{{\mathrm{{\mathrm{Cl}}}}}({\mathbb {R}}^{r,s})\rightarrow {{\mathrm{End}}}(V)\) is related to the Lie algebra structure by \(\langle J_zv,w\rangle =\langle z,[v,w]\rangle \) for all \(z\in {\mathbb {R}}^{r,s}\) and \(v,w\in V\). The classification depends on parameters r and s and is completed for the Clifford modules V having minimal possible dimension, that are not necessary irreducible. We find necessary conditions for the existence of a Lie algebra isomorphism according to the range of the integer parameters \(0\le r,s<\infty \). We present a constructive proof for the isomorphism maps for isomorphic Lie algebras and determine the class of non-isomorphic Lie algebras.     

Fundamental solution of a higher step Grushin type operator

We examine a class of Grushin type operators _Pk$P_k$ where k∈_N0$k\in {\mathbb{N}}_0$ defined in (1.1). The operators _Pk$P_k$ are non-elliptic and degenerate on a sub-manifold of R^N+?${\mathbb{R}}^{N+?}$. Geometrically they arise via a submersion from a sub-Laplace operator on a nilpotent Lie group of step k+1$k+1$. We explain the geometric framework and prove some analytic properties such as essential self-adjointness. The main purpose of the paper is to give an explicit expression of the fundamental solution of _Pk$P_k$. Our methods rely on an appropriate change of coordinates and involve the theory of Bessel and modified Bessel functions together with Weber's second exponential integral.