Nickel-catalyzed reductive cleavage of aryl alkyl ethers to arenes in absence of external reductant

The reductive cleavage of the C–O bonds of aryl ethers has great potential in organic synthesis. Although several catalysts that can promote the reductive cleavage of aryl ethers have been reported, all such systems require the use of an external reductant, e.g., hydrosilane or hydrogen. Here, we report the development of a new nickel-based catalytic system that can cleave the C–O bonds of ethers in the absence of an external reductant. The hydrogen atom required in this new reductive cleavage reaction is provided by the alkoxy group of the substrate, which serves as an internal reductant. The absence of an external reductant enables the unique chemoselectivity, i.e., the selective reduction of an alkoxy group over alkenes and ketones.     

Total Synthesis of cis‐Clavicipitic Acid from Asparagine via Ir‐Catalyzed CH bond Activation as a Key Step

4‐Substituted tryptophan derivatives and the total synthesis of cis‐clavicipitic acid were achieved in reactions in which Ir‐catalyzed C?H bond activation was a key step. The starting material for these reactions is asparagine, which is a cheap natural amino acid. The reductive amination step from the 4‐substituted tryptophan derivative gave cis‐clavicipitic acid with perfect diastereoselectivity.     

Swelling-shrinking behavior of chemically cross-linked polypeptide gels from poly(α-L-lysine), poly(α-DL-lysine), poly(ɛ-L-lysine) and thermally prepared poly(lysine): effects of pH, temperature and additives in the solution

We synthesized the glutaraldehyde cross-linked hydrogels using four kinds of poly(lysine)s (PLs) and measured the equilibrium swelling ratio (Q) as a function of pH. Also measured was the temperature change of Q at a fixed pH (11.6) in the absence and presence of additives (LiBr, methanol and urea) that affect the secondary structure of PLs. The swelling data were examined using a force balance approach in which the repulsive and attractive interactions among the cross-linked PL chains were considered based on the conformational properties of PLs in aqueous solutions. It was found that the formation of the helical segments in the cross-linked chain has little effect in the gel collapse, but their association acts as the attractive interaction causing the gel to shrink. The formation of the beta-sheet structure within the network also acts as the attractive interaction. These attractive interactions are mainly due to the hydrogen bonding, but hydrophobic interactions between the lysine side chains should be considered. In addition, in the swelling behavior of all the PL gels the polyampholyte nature appears due to electrostatic interactions of the basic groups with the C-terminal carboxyl group.     

Reorganization energy of supramolecular donor–acceptor dyad of octaethylporphyrin isomers and axial-coordinated acceptor: Experimental and computational study

The internal reorganization energy (λ_V) of photoinduced electron transfer (ET) in the supramolecular donor–acceptor dyads of 2,3,7,8,12,13,17,18-octaethylporphinatozinc(II) (ZnOEP) and electron acceptor ligands was compared with those of structural isomers, 2,3,7,8,11,12,17,18-octaethylhemiporphycenatozinc(II) (ZnHPc) and 2,3,6,7,12,13,16,17-octaethylporphycenatozinc(II) (ZnPcn). First, ET process of the supramolecular donor–acceptor dyads of ZnOEP was investigated by means of the transient absorption spectroscopy mainly. The formation of supramolecular dyads was confirmed by absorption spectral change, from which the association constant was estimated. The ET process was confirmed by the observation of radical cation of ZnOEP during the laser flash photolysis. The ET rates of these dyads are in the order of ZnOEP > ZnHPc > ZnPcn, when the driving forces for ET are similar to each other. From the free energy dependence of ET rates, the λ_V values of OEP and its isomers were estimated. The estimated λ_V value was in the order of ZnOEP < ZnHPc < ZnPcn. This tendency was reproduced by calculation at B3LYP/6-31G(d) and BHandHLYP/6-31G(d) levels. The origin of this tendency was discussed on the basis of the structural change during the ET process.     

Proposition of Single Molecular Orientation Determination Using polarization Controlled Beam by Liquid Crystal Spatial Light Modulators

We have proposed a method to control the three-dimensional electric field in the focus of an optical microscope using two non-twisted liquid crystal spatial light modulators, and to detect the molecular orientation of a single molecule. The three-dimensional electric field is generated by focusing the beam with two dimensional spatial distribution of polarization. The possibility of detection of three-dimensional single molecular orientation was shown by numerical calculations. © 2005 The Optical Society of Japan     

Behavior strategies,mixed strategies and perfect recall

When perfect recall is not satisfied, the informational contents of mixed and behavior strategies differ and are more than what the information partition describes. First, we consider two kinds of additional information strategies may carry, and show that such information leads to theperfect recall refinement of a given information partition. This does not, however, imply that the strategies compensate fully for the lack of perfect recall. We give a necessary and sufficient condition on an information partition, calledA-loss, for the informational content of mixed strategies to fully compensate for the lack of perfect recall. The informational content of behavior strategies never fully compensates.     

Preferential Alignment of Hydroxyapatite Crystallites in Nanocomposites with Chemically Disintegrated Silk Fibroin

Hydroxyapatite (HAp) nanocrystals were prepared at room temperature by a coprecipitation method from Ca(OH)₂ and H₃PO₄, in the presence of chemically disintegrated silk fibroin (SF). Adsorbed amounts of cations on SF and crystallinity of HAp in the composite were increased by the chemical disintegration of SF higher order structure. Preferential alignment of c-axis of HAp crystallites along the longitudinal direction of ca. 150nm SF fibril was observed. These changes due to disintegration of SF were discussed in terms of the chemical interaction between HAp and SF. The resulted composite with preferential alignment of HAp nanocrystals is a good candidate as a starting material for bone substitutes.     

Investigation of the ηη system in π − p interactions at a momentum of 32.5 GeV/c at the GAMS-4π spectrometer

The ηη system produced in charge-exchange π ^? p interaction at a momentum of 32.5 GeV/c is studied in an experiment performed with the GAMS-4π spectrometer at the 70-GeV accelerator of the Institute for High-Energy Physics (IHEP, Protvino). A partial-wave analysis is performed in the mass range between 1.1 and 3.9 GeV for ?t <0.2 (GeV/c)², S, D, G, and J waves being taken into account in this analysis. The S wave has a complicated structure, displaying peaks at about 1.5 and 1.7 GeV. These peaks are associated with the f ₀(1500) and f ₀(1710) mesons. One of the solutions (preferable one) involves the f ₀(2200) and f ₂(1950) resonances. The mass region above 2.4 GeV is dominated by the G wave. A broad state of mass about 3 GeV and width 0.7 GeV is found in the J wave. The parameters of the resonances in question and their production cross sections are measured.     

Synthesis of well‐defined polymers end‐functionalized with crosslinkable aziridine groups by living anionic polymerization

Well‐defined end‐functionalized polystyrene, poly(α‐methylstyrene), and polyisoprene with polymerizable aziridine groups were synthesized by the termination reactions of the anionic living polymers of styrene, α‐methylstyrene, and isoprene with 1‐[2‐(4‐chlorobutoxy)ethyl]aziridine in tetrahydrofuran at ?78 °C. The resulting polymers possessed the predicted molecular weights and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.1) as well as aziridine terminal moieties. The cationic ring‐opening polymerization of the ω‐monofunctionalized polystyrene having an aziridinyl group with Et₃OBF₄ gave the polymacromonomer, whereas the α,ω‐difunctional polystyrene underwent crosslinking reactions to afford an insoluble gel. Crosslinking products were similarly obtained by the reaction of the α,ω‐diaziridinyl polystyrene with poly(acrylic acid)‐co‐poly(butyl acrylate). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4126–4135, 2005     

Finding of Optimal Calcium Ion Probes for Fluorescence Lifetime Measurement

We have investigated the fluorescence lifetime properties of 8 calcium ion probes, calcium-green-1, calcium green-2, calcium green-5N, calcium orange, oregon green 488 BAPTA-6F, fluo-3, fluo-4, and fluo-5N. We found that the decay time of calcium green-5N varied more sensitively with calcium concentration than calcium green-1 which was known to be a highly sensitive probe. We have also found that the center of observable range of calcium concentration by fluorescence lifetime measurement is lower than that by fluorescence intensity measurement.