Effect of structural change in viologen acceptors on the rate of single electron transfer from tributylphosphine

The "flexible" 3 and "rigid" cyclic viologens 4, diquarternary salts of 2,2'-bipyridine and 1,10-phenanthroline, respectively, were treated with tributylphosphine (1) in acetonitrile containing a large amount of methanol under an argon atmosphere. A single electron transfer (SET) easily occurred from the latter to the former, the SET to 4 being 10(5)-10(6) times faster than the SET to 3. The reorganization energy lambda for the latter SET is thought to be larger than that for the former SET, because 3 undergoes a structural change upon the one-electron reduction to its radical cation, whereas the one-electron reduction of 4 takes place without a structural change. Taking into account the difference in lambda, and also taking into account the bond formation energy brought about by the follow-up reaction of the phosphine radical cation 1*(+) with methanol, the observed kinetics were well interpreted in terms of the Marcus theory.     

Rate enhancement of Diels-Alder reactions in aqueous perfluorinated emulsions

A marked acceleration property for the Diels-Alder reaction was observed in an aqueous micellar system composed of perfluorohexane and lithium perfluorooctanesulfonate. The reaction rate increased with the concentration of the equimolar mixture of PFH and LiFOS, and the rate in 500 mM PFH and 500 mM LiFOS was about 100-fold greater than that in water without the fluorous field. After completion of the reaction, the products were simply extracted from the aqueous reaction mixture using n-hexane. [reaction: see text].     

Disulfide‐Unit Conjugation Enables Ultrafast Cytosolic Internalization of Antisense DNA and siRNA

Development of intracellular delivery methods for antisense DNA and siRNA is important. Previously reported methods using liposomes or receptor‐ligands take several hours or more to deliver oligonucleotides to the cytoplasm due to their retention in endosomes. Oligonucleotides modified with low molecular weight disulfide units at a terminus reach the cytoplasm 10 minutes after administration to cultured cells. This rapid cytoplasmic internalization of disulfide‐modified oligonucleotides suggests the existence of an uptake pathway other than endocytosis. Mechanistic analysis revealed that the modified oligonucleotides are efficiently internalized into the cytoplasm through disulfide exchange reactions with the thiol groups on the cellular surface. This approach solves several critical problems with the currently available methods for enhancing cellular uptake of oligonucleotides and may be an effective approach in the medicinal application of antisense DNA and siRNA.     

Synthesis of A Pincer‐IrV Complex with A Base‐Free Alumanyl Ligand and Its Application toward the Dehydrogenation of Alkanes

A pincer‐iridium complex bearing a Lewis‐base‐free X‐type alumanyl ligand has been synthesized. X‐ray diffraction, NMR and IR spectroscopy, as well as XANES analysis confirmed its tetrahydrido‐Ir^V structure and Lewis acidity at the Al center as supported by DFT calculations. The resulting complex was applied as a catalyst for the transfer dehydrogenation of cyclooctane.     

Ultrathin Silicon Oxide Film-Induced Enhancement of Charge Separation and Transport of Nanostructured Titanium(IV) Oxide Photoelectrode

The development of nanostructured semiconductor electrodes represented by a mesoporous TiO₂ nanocrystalline (mp-TiO₂) film is currently bringing great progresses in photoelectrochemical (PEC) devices for solar-to-electricity and solar-to-chemical conversion. Two serious losses can occur in PEC devices: 1) recombination between the conduction band (CB) electrons and valence band (VB) holes in the bulk and at the surface and 2) back reaction or electron trapping by oxidant in the electrolyte solution during transport to the electron-collecting electrode. Thus, the major challenge in common with the nanostructured semiconductor photoanodes is to achieve efficient charge separation and electron transport. In this study, an ultrathin SiO_x layer was formed on both the external and the internal surface of mp-TiO₂ using an original chemisorption-calcination technique employing 1,3,5,7-tetramethyltetrasiloxane as a starting material. The SiO_x surface modification of the mp-TiO₂ photoanode drastically prolongs the mean lifetime of CB-electrons in TiO₂ because of enhanced charge separation and electron transport by the negative charge applied in aqueous electrolyte solution. We have demonstrated that the performance of a one-compartment H₂O₂-photofuel cell using mp-TiO₂ as the photoanode is greatly boosted by the surface modification with the SiO_x layer. We anticipate that this methodology is widely applicable to nanostructured metal oxide semiconductor electrodes, contributing to the improvement in the performance of PEC devices.     

Chalcogenation reactions of a stable ferrocenyldiphosphene: Formation of thia‐, selena‐, and telluradiphosphiranes

The reactions of TbtPPTbt (Tbt = 2,4,6‐tris[bis(trimethylsilyl)methyl]phenyl) with elemental sulfur and selenium in the presence of triethylamine resulted in the formation of the corresponding thia‐ and selenadiphosphiranes in 71% and 65%, respectively, whereas the tellurization reaction was unsuccessful probably due to the steric reason. On the other hand, treatment of TbtPPFc (Fc = ferrocenyl) with elemental sulfur, selenium, and tributylphosphine telluride afforded the corresponding thia‐, selena‐, and telluradiphosphiranes in 84%, 88%, and 66% yields, respectively. The molecular structures of these three‐membered heterocyclic compounds were confirmed by spectroscopic analysis. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:443–449, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20449     

Molecular chaperone-like properties of sodium caseinate to suppress the pressure-induced aggregation of β-lactoglobulin

ABSTRACT

The objective of this study was to determine whether sodium caseinate can inhibit the aggregation of whey protein induced by pressure treatment. Solutions of β-lactoglobulin (β-Lg, 0.2%, w/v) and mixtures containing 0.2% (w/v) β-Lg and 0–0.5% (w/v) sodium caseinate (NaCas) were pressurized at 400–800?MPa. NaCas suppressed the aggregation of β-Lg induced by pressure treatment, and this function was dependent on the concentration of NaCas. Furthermore, NaCas altered the aggregation process of β-Lg by suppressing the transition of the aggregate from the soluble phase to the insoluble phase and, as a result, the fraction of insoluble aggregates was decreased. During this process, NaCas formed stable complexes with the denatured β-Lg, and the formation of complexes prevented further aggregation of β-Lg. These results indicate that NaCas exhibits a chaperone-like activity under high pressure.