Photo-control of kinesin-microtubule motility using caged peptides derived from the kinesin C-terminus domain

To design a nanoscale biodevice that can be controlled by an external stimulus, we have introduced photochemical switching peptides derived from the kinesin C-terminus domain into the kinesin-microtubule in vitro motility system.     

Asymptotic analysis for an extended discrete Lotka–Volterra system related to matrix eigenvalues

The integrable discrete hungry Lotka–Volterra (dhLV) system is easily transformed to the qd-type dhLV system, which resembles the recursion formula of the qd algorithm for computing matrix eigenvalues. Some of the qd-type dhLV variables play a role for assisting the time evolution of the others. This property does not appear in the original dhLV system. In this article, we first show the existence of a centre manifold for the qd-type dhLV system. With the help of the centre manifold theory, we next investigate the local convergence of the qd-type dhLV system, and then clarify the monotonicity related to the qd-type dhLV variables at the final phase of the convergence.     

Front shock behavior of stable curved detonation waves in rectangular-cross-section curved channels

The propagation of curved detonation waves of gaseous explosives stabilized in rectangular-cross-section curved channels is investigated. Three types of stoichiometric test gases, C₂H₄ + 3O₂, 2H₂ + O₂, and 2C₂H₂ + 5O₂ + 7Ar, are evaluated. The ratio of the inner radius of the curved channel (r_i) to the normal detonation cell width (λ) is an important factor in stabilizing curved detonation waves. The lower boundary of stabilization is around r_i/λ = 23, regardless of the test gas. The stabilized curved detonation waves eventually attain a specific curved shape as they propagate through the curved channels. The specific curved shapes of stabilized curved detonation waves are approximately formulated, and the normal detonation velocity (D_n)?curvature (κ) relations are evaluated. The D_n nondimensionalized by the Chapman–Jouguet (CJ) detonation velocity (D_CJ) is a function of the κ nondimensionalized by λ. The D_n/D_CJ?λκ relation does not depend on the type of test gas. The propagation behavior of the stabilized curved detonation waves is controlled by the D_n/D_CJ?λκ relation. Due to this propagation characteristic, the fully-developed, stabilized curved detonation waves propagate through the curved channels while maintaining a specific curved shape with a constant angular velocity. Self-similarity is seen in the front shock shapes of the stabilized curved detonation waves with the same r_i/λ, regardless of the curved channel and test gas.     

Shimalactone Biosynthesis Involves Spontaneous Double Bicyclo-Ring Formation with 8π-6π Electrocyclization

Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark.     

A novel mediator-polymer-modified anode for microbial fuel cells

A high-performance anode system based on a combination of mediator-polymer-modified graphite felt and bacteria capable of reducing extracellular materials shows significant potential for practical use in microbial fuel cells (MFCs).     

Syntheses of novel di- and trinucleating ligands having a triethylbenzene core with N,N-bidentate tethers: their complexation toward Pd and Rh organometallic fragments

A series of di- and trinucleating ligands with a 1,3,5-triethylbenzene core connected to N,N-bidentate tethers was synthesized. The ligands readily reacted with monuclear Rh and Pd precursors to give the corresponding di- and trinuclear complexes, which were characterized by using NMR and ESI mass spectroscopy. In the solid state, the trinuclear complexes with ligands having pyridylpyrazolyl tethers adopt the most stable ababab configuration, in which the organometallic fragments are on the same side of the benzene plane. On the other hand, in solution, the linker moieties between the benzene core and the metals are flexible enough to interconvert between other configurations, that is, they exhibit dynamic behavior, and the rotational barrier was dependent on the length of the linkers. From variable temperature (VT) 1H NMR measurements, the rotational barrier for a trinuclear Rh-CO complex with a ligand having methylene linkers was estimated to be approximately 12.6 kcal mol(-1). However, no spectral changes were observed for the ethylene derivative in the temperature range of -60 degrees C to 50 degrees C, indicating that the rotation was not frozen out on the 1H NMR timescale, even at -60 degrees C.     

Copper-catalyzed intramolecular hydroamination of allenylamines to 3-pyrrolines or 2-alkenylpyrrolidines

Copper salts, such as CuCl, CuI, CuCl₂ and Cu(OTf)₂, were used to catalyze the intramolecular hydroamination of allenylamines to provide the corresponding 3-pyrrolines or 2-alkenylpyrrolidines.     

Optimized conditions for high-performance liquid chromatography analysis of oligosaccharides using 7-amino-4-methylcoumarin as a reductive amination reagent

Reductive amination reaction using 7-amino-4-methylcoumarin (AMC) as a fluorescent probe enabled analyses of glycoproteins' monosaccharides and N-linked oligosaccharides. Reductive amination of N-acetylhexosamines and AMC using sodium cyanoborohydride or dimethylamine-borane complex indicated slight recovery of derivatives, but pyridine-borane achieved better recoveries. Reversed-phase high-performance liquid chromatography (HPLC) analyses of monosaccharides constituting glycoprotein glycans using fluorimetric detection revealed linearity for 0.2fmol to 1pmol, with less than 5% RSD quantitation reproducibility. Reversed-phase HPLC analyses of glycoprotein glycans, combined with negative-ion electrospray ionization mass spectrometry (LC-ESI-MS), enabled their structural determination. Using this highly hydrophobic reagent, AMC-labeled oligosaccharides displayed one-order to two-order higher ESI-MS intensity than derivatives labeled using other reagents.     

Reduced hydrophobic interaction of polystyrene surfaces by spontaneous segregation of block copolymers with oligo (ethylene glycol) methyl ether methacrylate blocks: force measurements in water using atomic force microscope with hydrophobic probes

Reduction of hydrophobic interaction in water is important in biological interfaces. In our previous work, we have found that poly(styrene- b-triethylene glycol methyl ether methacrylate) (PS-PME3MA) segregates the PME3MA block to the surface in hydrophobic environment, such as in air or in a vacuum, and shows remarkable resistance against adsorption or adhesion of proteins, platelets, and cells in water. In this paper, we report that atomic force microscopy (AFM) with hydrophobic probes can directly monitor the reduced hydrophobic interaction of the PS surfaces modified by poly(styrene- b-origoethylene glycol methyl ether methacrylate) (PS-PME NMA), where N is the number of ethylene glycol units. The pull-off forces between the hydrophobic probes that are coated with octyltrichlorosilane (OLTS) and the PS-PME NMA modified polystyrene (PS) surfaces in water were measured. The absolute spring constants and tip-curvatures of the AFM cantilevers were measured to compute the work of adhesion by the Johnson, Kendall, and Roberts (JKR) theory, which relates the pull-off force at which the separation occurs between a hemisphere and a plane to the work of adhesion. The hydrophobic interactions between the hydrophobic tip and polymer surfaces in water were greatly reduced with the segregated PME NMA blocks. The hydrophobic interactions decrease with increasing N of the series of PS-PME NMA and show a correlation with the amount of protein adsorbed.     

Module assembly for protein-surface recognition: geranylgeranyltransferase I bivalent inhibitors for simultaneous targeting of interior and exterior protein surfaces

Synthetic chemical probes designed to simultaneously targeting multiple sites of protein surfaces are of interest owing to their potential application as site specific modulators of protein-protein interactions. A new approach toward bivalent inhibitors of mammalian type I geranylgeranyltransferase (GGTase I) based on module assembly for simultaneous recognition of both interior and exterior protein surfaces is reported. The inhibitors synthesized in this study consist of two modules linked by an alkyl spacer; one is the tetrapeptide CVIL module for binding to the interior protein surface (active pocket) and the other is a 3,4,5-alkoxy substituted benzoyl motif that contains three aminoalkyl groups designed to bind to the negatively charged protein exterior surface near the active site. The compounds were screened by two distinct enzyme inhibition assays based on fluorescence spectroscopy and incorporation of a [(3)H]-labeled prenyl group onto a protein substrate. The bivalent inhibitors block GGTase I enzymatic activity with K(i) values in the submicromolar range and are approximately one order of magnitude and more than 150 times more effective than the tetrapeptide CVIL and the methyl benzoate derivatives, respectively. The bivalent compounds 6 and 8 were shown to be competitive inhibitors, suggesting that the CVIL module anchors the whole molecule to the GGTase I active site and delivers the other module to the targeting protein surface. Thus, our module-assembly approach resulted in simultaneous multiple-site recognition, and as a consequence, synergetic inhibition of GGTase I activity, thereby providing a new approach in designing protein-surface-directed inhibitors for targeting protein-protein interactions.