Catalytic enantioselective Michael addition of 1,3-dicarbonyl compounds to nitroalkenes catalyzed by well-defined chiral ru amido complexes

Well-defined chiral Ru amido complexes promoted asymmetric Michael addition of 1,3-dicarbonyl compounds including malonates, beta-keto esters, and 1,3-diketones to nitroalkenes to give the corresponding adducts with excellent ees and in excellent yields.     

Dynamic coordination polymers with 4,4'-oxybis(benzoate): reversible transformations of nano- and nonporous coordination frameworks responding to present solvents

Reversible construction of a nanoporous framework from a nonporous framework has been found in the zinc(II) coordination polymer with 4,4'-oxybis(benzoate) (oba). [Zn(2)(oba)(2)(dmf)(2)].2DMF (1), which has 1 nm scale channels, transforms to the nonporous coordination polymer [Zn(oba)(H(2)O)] (2) with the loss of the open framework. Compound 2 on treatment with DMF reversibly yields nanoporous compound 1.     

Discrete palladium clusters that consist of two mutually bisecting perpendicular planes

The construction of novel molecules with unprecedented alignments of the constituent elements has revolutionized the field of functional materials. The arrangement of two or more planar subunits in a mutually perpendicular fashion is a frequently encountered approach to produce novel functional materials. Previous examples of such materials can be categorized into two well-investigated families: spiro-conjugated and dumbbell-shaped structures, wherein the two planes are aligned orthogonally via a single atom or an axis, respectively. This article describes a third family: reaction of [Pd(CN^tBu)₂]₃ with Sn₃Me₈ or Ge₆Me₁₂ afforded a Pd₇Sn₄ cluster and a Pd₈Ge₆ cluster that consist of two mutually bisecting perpendicular planes. In the Pd₇Sn₄ cluster, the two equivalent Pd₅Sn₂ planes share three palladium atoms that include a dihedral angle of 85.6°.

The construction of Pd₇Sn₄ and Pd₈Ge₆ clusters that consist of two mutually bisecting perpendicular planes was accomplished by the reaction of [Pd(CN^tBu)₂]₃ with Me₃Sn–SnMe₂–SnMe₃ or Ge₆Me₁₂.     

Single-component nanodiscs via the thermal folding of amphiphilic graft copolymers with the adjusted flexibility of the main chain

Nanodiscs have attracted considerable attention as structural scaffolds for membrane-protein research and as biomaterials in e.g. drug-delivery systems. However, conventional disc-fabrication methods are usually laborious, and disc fabrication via the self-assembly of amphiphiles is difficult. Herein, we report the formation of polymer nanodiscs based on the self-assembly of amphiphilic graft copolymers by adjusting the persistence length of the main chain. Amphiphilic graft copolymers with a series of different main-chain persistence lengths were prepared and these formed, depending on the persistence length, either rods, discs, or vesicles. Notably, polymer nanodiscs were formed upon heating a chilled polymer solution without the need for any additives, and the thus obtained nanodiscs were used to solubilize a membrane protein during cell-free protein synthesis. Given the simplicity of this disc-fabrication method and the ability of these discs to solubilize membrane proteins, this study considerably expands the fundamental and practical scope of graft-copolymer nanodiscs and demonstrates their utility as tools for studying the structure and function of membrane proteins.

A strategy for the fabrication of nanodiscs via the self-assembly of thermoresponsive amphiphilic graft copolymers is demonstrated.     

Birth–death process of local structures in defect turbulence described by the one-dimensional complex Ginzburg–Landau equation

Defect turbulence described by the one-dimensional complex Ginzburg–Landau equation is investigated and analyzed via a birth–death process of the local structures composed of defects, holes, and modulated amplitude waves (MAWs). All the number statistics of each local structure, in its stationary state, are subjected to Poisson statistics. In addition, the probability density functions of interarrival times of defects, lifetimes of holes, and MAWs show the existence of long-memory and some characteristic time scales caused by zigzag motions of oscillating traveling holes. The corresponding stochastic process for these observations is fully described by a non-Markovian master equation.     

Structural confirmation of oligosaccharides newly isolated from sugar beet molasses

ABSTRACT: BACKGROUND: Sugar beet molasses is a viscous by-product of the processing of sugar beets into sugar. The molasses is known to contain sucrose and raffinose, a typical trisaccharide, with a well-established structure. Although sugar beet molasses contains various other oligosaccharides as well, the structures of those oligosaccharides have not been examined in detail. The purpose of this study was isolation and structural confirmation of these other oligosaccharides found in sugar beet molasses. RESULTS: Four oligosaccharides were newly isolated from sugar beet molasses using high-performance liquid chromatography (HPLC) and carbon-Celite column chromatography. Structural confirmation of the saccharides was provided by methylation analysis, matrix-assisted laser desorption/ionaization time of flight mass spectrometry (MALDI-TOF-MS), and nuclear magnetic resonance (NMR) measurements. CONCLUSION: The following oligosaccharides were identified in sugar beet molasses: beta-D-galactopyranosyl-(1- > 6)-beta-D-fructofuranosyl-(2 <-> 1)-alpha-D-glucopyranoside (named beta-planteose), alpha-D-galactopyranosyl-(1- > 1)-beta-D-fructofuranosyl-(2 <-> 1)-alpha-D-glucopyranoside (named1-planteose), alpha-D-glucopyranosyl-(1- > 6)-alpha-D-glucopyranosyl-(1 <-> 2)-beta-D-fructofuranoside (theanderose), and beta-D-glucopyranosyl-(1- > 3)-alpha-D-glucopyranosyl-(1 <-> 2)-beta-D-fructofuranoside (laminaribiofructose). 1-planteose and laminaribiofructose were isolated from natural sources for the first time.     

Engineering Plant Alternative Oxidase Function in Mammalian Cells: Substitution of the Motif-like Sequence ENV for QDT Diminishes Catalytic Activity of Arum concinnatum AOX1a Expressed in HeLa Cells

Alternative oxidase (AOX) is a nonproton motive quinol–oxygen oxidoreductase which is a component of the mitochondrial respiratory chain in higher plants. In this study, we have characterized the catalytic activity and regulatory behaviors of Arum concinnatum AOX isoforms, namely AcoAOX1a and AcoAOX1b, and their artificial mutants in HeLa cells. We demonstrated that substitution of the motif-like sequence ENV on the C-terminal half of AcoAOX1a for QDT diminishes its activity and proposed that the innate inactivity of AcoAOX1b in HeLa cells is, at least in part, attributable to its QDT motif. Furthermore, we show that introduction of F130L in the hydrophilic N-terminal extension of AcoAOX1a resulted in greater activity in the presence of pyruvate. This result indicates that functional significance of the N-terminal extension is not particular to the conventional regulatory cysteine. On the basis of these findings, we discuss new insights into the structural integrity of AOX in HeLa cells and the applicability of mammalian cells for functional analysis of this enzyme.     

Physical and Chemical Properties of Four-Membered Bis(triphenylphosphane)platinum(II) Sulfenato Thiolato Complexes

The reaction of isolable dithiirane 1-oxides with (Ph 3 P) 2 Pt( m 2 -C 2 H 4 ) provided the title complexes in high yields. 31 P NMR spectroscopy of the phosphine ligands of the complexes and x-ray crystallographic analysis of a complex were reported.     

1,4‐Bis[2‐(4‐ferrocenylphenyl)ethynyl]anthraquinone from synchrotron X‐ray powder diffraction

The title compound, [Fe₂(C₅H₅)₂(C₄₀H₂₂O₂)] or 1,4‐(FcPh)₂Aq [where FcPh is 2‐(4‐ferrocenylphenyl)ethynyl and Aq is anthraquinone], was synthesized in an attempt to obtain a new solvent‐incorporating porous material with a large void space. Thermodynamic data for 1,4‐(FcPh)₂Aq show a phase transition at approximately 430 K. The crystal structure of solvent‐free 1,4‐(FcPh)₂Aq was determined at temperatures of 90, 300 and 500 K using synchrotron powder diffraction data. A direct‐space method using a genetic algorithm was employed for structure solution. Charge densities calculated from observed structure factors by the maximum entropy method were employed for model improvement. The final models were obtained through multistage Rietveld refinements. In both phases, the structures of which differ only subtly, the planar Aq fragments are stacked alternately in opposite orientations, forming a one‐dimensional column. The FcPh arms lie between the stacks and fill the remaining space, leaving no voids. C—H...π interactions between the Ph and Fc fragments mediate crystal packing and stabilization.