Aggregated structure analysis of polymer-protected platinum/ruthenium colloidal dispersions using EXAFS, HRTEM, and electron diffraction measurements

Polymer-protected platinum/ruthenium colloidal dispersions were prepared by refluxing mixed solutions of hexachloroplatinic(IV) acid and ruthenium(III) chloride in a mixture of ethanol/water (1/1 v/v) in the presence of poly(N-vinyl-2-pyrrolidone). The electronic spectra and transmission electron micrographs suggested that the colloidal dispersions are almost composed of the mixture of the small monometallic Pt and Ru clusters over all the ratio of Pt/Ru compositions. Extended X-ray absorption fine structure analyses and high resolution electron microprobe analyses indicated that no Pt/Ru alloy clusters exist in the dispersions, and the aggregation occurs between small monometallic Pt clusters (diameter ca. 15 A) and partially oxidized Ru microclusters (diameter less than 10 A). Electron diffraction measurements also suggested that the diffraction pattern of aggregated Pt/Ru cluster particles prepared by the simultaneous reduction of Pt and Ru ions is the same as that of the physical mixture of the small monometallic Pt and Ru clusters separately prepared. Therefore, it can be concluded that the aggregated Pt/Ru cluster particles, with 10 to 60 A in diameter, are built up by small monometallic Pt clusters and partially oxidized Ru microclusters, and that Pt/Ru alloy clusters are not formed.     

Chimeric (alpha/beta + alpha)-peptide ligands for the BH3-recognition cleft of Bcl-XL: critical role of the molecular scaffold in protein surface recognition

Molecules that bind to specific surface sites on proteins are of great interest from both fundamental and practical perspectives. We are exploring a ligand development strategy that is based on oligomers with discrete folding propensities ("foldamers"); we target a specific cleft on the cancer-associated protein Bcl-xL because this system is well characterized structurally. In vivo, this cleft binds to alpha-helical segments (BH3 domains) of other proteins. We evaluated several types of helical foldamer, built entirely from beta-amino acid residues or from mixtures of alpha- and beta-amino acid residues, and ultimately identified foldamers in the latter class that bind very tightly to Bcl-xL. Our results suggest that combining different types of foldamer backbones will be an effective and general strategy for creating high-affinity and specific ligands for protein surface sites.     

Lewis Acid-Catalyzed Hydrostannation of Acetylenes. Regio- and Stereoselective Trans-Addition of Tributyltin Hydride and Dibutyltin Dihydride

Lewis acids such as ZrCl(4) or HfCl(4) catalyze the hydrostannation of acetylenes 1 by tributyltin hydride to produce the cis vinylstannanes 2 by regio- and stereoselective anti-hydrostannation. The hydrostannation of acetylenes using dibutyltin dihydride was also catalyzed by ZrCl(4) to give the stereodefined Z-Z divinyltin derivatives 4 by an anti-hydrostannation pathway. The use of nonpolar solvents such as toluene or hexane was essential for obtaining high stereoselectivity and chemical yield. Since ZrCl(4) and HfCl(4) are not soluble in such solvents, the hydrostannations were carried out in a heterogeneous system. The reactions of internal acetylenes with Bu(3)SnH proceeded smoothly, although the use of stoichiometric amounts of ZrCl(4) gave better results. The ZrCl(4)-catalyzed hydrostannation at 0 degrees C gave better yields and stereoselectivities than the reaction at room temperature. To help clalify the reason, the reaction of Bu(3)SnH with ZrCl(4) was monitored by (1)H and (119)Sn NMR spectroscopy, and it was found that Bu(3)SnH reacted with ZrCl(4) at room temperature to afford a mixture of tributyltin hydride, dibutyltin dihydride, and tetrabutyltin.     

Domino allylation and cyclization of ortho-alkynylbenzaldehydes with allyltrimethylsilane catalyzed by Pd(II)-Cu(II) bimetallic systems

The reaction of ortho-alkynylated benzaldehydes 1 with allyltrimethylsilane under the Pd(OAc)₂-CuCl₂ catalyst system gave the isochromene derivatives 2 together with the chlorinated products 3. When the reaction was conducted in the presence of half equiv of H₂O, the formation of 3 was suppressed and 2 was obtained in good to high yields. When the reaction of 1a was carried out with trimethylsilylcyanide instead of allylsilane, the cyano group-substituted isochromene 9 was obtained in 94% yield.     

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.     

Electroreductive intramolecular coupling of aliphatic cyclic imides with ketones and O-methyloximes

The electroreductive intramolecular coupling of aliphatic cyclic imides with ketones in isopropanol gave five- and six-membered cyclized products. Similarly, the electroreductive intramolecular coupling of aliphatic cyclic imides with O-methyloximes afforded five-, six-, and seven-membered cyclized products. These reactions provide a useful method to synthesize azabicyclo[n.m.0] compounds. The bicyclic products were stereoselectively transformed to the corresponding deoxylated compounds by reduction with NaB(CN)H₃ or Et₃SiH/BF₃·Et₂O.     

Halorhodopsin from natronomonas pharaonis forms a trimer even in the presence of a detergent, dodecyl-beta-D-maltoside

Halorhodopsin (HR) is a transmembrane seven-helix retinal protein, and acts as an inward light-driven Cl⁻ pump. HR from Natronomonas pharaonis (NpHR) can be expressed in Escherichia coli inner membrane in large quantities. Here, we showed that NpHR forms the trimer structure even in the presence of 0.1% (2 m m ) to 1% (20 m m ) dodecyl-β- d -maltoside (DDM), whose concentrations are much higher than the critical micelle concentration (0.17 m m ). This conclusion was drawn from the following observations. (1) NpHR in the DDM solution showed an exciton-coupling circular dichroism (CD) spectrum. (2) From the elution volume of gel filtration, the molecular mass of the NpHR–DDM complex was estimated. After evaluation of the mass of the bound DDM molecules, the mass of NpHR calculated was approximately equal to that of the trimer. (3) The cross-linked NpHR by glutaraldehyde gave the SDS-PAGE corresponding to the trimer. Mass spectra of these samples also support the notion of the trimer. Using the membrane fractions expressing NpHR ( Escherichia coli and Halobacterium salinarum ), CD spectra showed exciton-coupling, which suggests strongly the trimer structure in the cell membrane.     

Synthesis, structure and thermal stability of fully hydrophobic porphyrin-DNA conjugates

The DNAs modified with tetraphenyl porphyrin at the center of 13mer oligonucleotide were synthesized using phosphoramidite chemistry and automated DNA synthesis. When the porphyrin modified oligonucleotide was annealed with its complementary strand, they formed a standard B-form duplex. The porphyrin moiety intercalated in the duplex, and moderately lowered the thermal stability.