Development of TfOH-Catalyzed Spirocyclization by Intramolecular Friedel-Crafts-type 1,4-Addition: Application to the Total Synthesis of the Unusual Proaporphine Alkaloid (±)-Misrametine

An effective method was developed for TfOH-catalyzed construction of spiroindanes and spirotetralines containing an all-carbon quaternary stereocenter. Intramolecular Friedel-Crafts-type 1,4-addition of the substrates which were di- or trimethoxybenzene and 2-cyclohexenone linked by an alkyl chain proceeded smoothly in the presence of 30 mol % of TfOH. A variety of spiroindanes and spirotetralines were obtained with moderate to excellent yield by this method. The reaction was successfully applied in the first total synthesis of the unusual proaporphine alkaloid (±)-misrametine, which included the gram-scale spirocyclization and selective O-demethylation used KCN in DMSO condition as key steps.     

The tetraalkylammonium-accelerated Norrish-Yang photocyclization of 2-substituted acetophenones

The tetrabutylammonium-accelerated Norrish-Yang cyclization of 2-ethoxycarbonylmethyloxy- and 2-cyanomethyloxyacetophenones afforded trans-dihydrobenzofuranols in good stereoselectivities through cation-π interactions between the ammonium and the carbonyl and cyano groups. Furthermore, a new type of organocatalyst possessing both conformation-controlling and triplet-sensitizing units was developed, and was found to be effective in accelerating the Norrish-Yang photocyclization of 2-cyanomethyloxyacetophenone.     

Establishing a “Ring-Size-Divergent” Synthetic Strategy: Synthesis,Structural Revision,and Absolute Configuration of Feroniellins

Feroniellin analogs isolated from Feroniella lucida possess a furanocoumarin skeleton connected to monoterpenic five- to seven-membered ethereal rings by an ether linkage and exhibit a broad spectrum of biological activities. In this contribution, we intended to establish a “ring-size-divergent” synthetic strategy for the monoterpenic five- to seven-membered ethereal rings through the chemical sythesis of feroniellins. The short and comprehensive synthesis of feroniellins was achieved in only two steps from easily available bergamottin based on the “ring-size-divergent” strategy. In addition, these syntheses resulted in revision of the proposed structures for feroniellins A and B and the determination of all the absolute configurations of feroniellins; their preliminary anti-inflammatory activities were investigated as well.     

Controlling apatite microparticles formation by calcining electrospun sol–gel derived ultrafine silica fibers

Electrospun ultrafine silica fibers were calcined at 150–800 °C. The relation of calcination temperature to the ability to form biomimetic apatite in a simulated body fluid solution (SBF) was evaluated. The largest apatite particles, formed on non-calcined fibers after 1 week of soaking in SBF, were 10 μm in diameter, had a narrow size distribution (coefficient of variation 9%), and were similar to pearls on string. The particles size decreased with increasing calcination temperature below 250 °C and the particles formed on the fibers calcined at 250 °C were 4.5 μm in diameter. No particles were found on those calcined above 500 °C. By using a concentrated SBF at 1.5-times higher ionic concentrations than SBF, the size of apatite microparticles increased about 50%. The fibrous substrate covered with apatite particles was effective for osteoblastic differentiation of pre-osteoblastic cells.     

An approximation algorithm for the traveling tournament problem

This paper describes the traveling tournament problem, a well-known benchmark problem in the field of tournament timetabling. We propose a new lower bound for the traveling tournament problem, and construct a randomized approximation algorithm yielding a feasible solution whose approximation ratio is less than 2+(9/4)/(n−1), where n is the number of teams. Additionally, we propose a deterministic approximation algorithm with the same approximation ratio using a derandomization technique. For the traveling tournament problem, the proposed algorithms are the first approximation algorithms with a constant approximation ratio, which is less than 2+3/4.     

Long-term fluctuations in globally coupled phase oscillators with general coupling: finite size effects

We investigate the diffusion coefficient of the time integral of the Kuramoto order parameter in globally coupled nonidentical phase oscillators. This coefficient represents the deviation of the time integral of the order parameter from its mean value on the sample average. In other words, this coefficient characterizes long-term fluctuations of the order parameter. For a system of N coupled oscillators, we introduce a statistical quantity D, which denotes the product of N and the diffusion coefficient. We study the scaling law of D with respect to the system size N. In other well-known models such as the Ising model, the scaling property of D is D～O(1) for both coherent and incoherent regimes except for the transition point. In contrast, in the globally coupled phase oscillators, the scaling law of D is different for the coherent and incoherent regimes: D～O(1/N(a)) with a certain constant a>0 in the coherent regime and D～O(1) in the incoherent regime. We demonstrate that these scaling laws hold for several representative coupling schemes.     

Performance test of passive radon–thoron discriminative detectors on environmental parameters

This paper describes how humidity, wind and ambient aerosols in air influence the detection responses of passive detectors. Two types of alpha track detectors based on a passive radon (²²²Rn)–thoron (²²⁰Rn) discriminative measurement technique were used: the Raduet and Radopot detectors that were developed and calibrated by the National Institute of Radiological Sciences, Japan. The initial experiment showed that the infiltration rate of ²²⁰Rn onto sponges with a high air exchange rate for the Raduet detectors was one third lower than that onto filters for the Radopot detectors. Little distinct dependence on humidity was observed for the ²²²Rn detection responses of both detectors. For ²²⁰Rn, the detection responses of both detectors for the high air exchange rate seemed to decrease slightly at high humidity conditions. The ²²⁰Rn detection responses of the Radopot detectors had little influence from wind speed. The ²²⁰Rn detection responses of the Raduet detectors for the high air exchange rate seemed to decrease at low wind speeds. Furthermore, there was little difference between the detection responses in the presence and absence of ambient aerosol particles because the ambient aerosols were filtered out during their passive diffusion through the sponges and filters for the Raduet and Radopot detectors, respectively.     

Direct Observation of Fluorescently Labeled Single-stranded λDNA Molecules in a Micro-Flow Channel

We developed two labeling methods for the direct observation of single-stranded DNA (ssDNA), using a ssDNA binding protein and a ssDNA recognition peptide. The first approach involved protein fusion between the 70-kDa ssDNA-binding domain of replication protein A and enhanced yellow fluorescent protein (RPA-YFP). The second method used the ssDNA binding peptide of Escherichia coli RecA labeled with Atto488 (ssBP-488; Atto488-IRMKIGVMFGNPETTTGGNALKFY). The labeled ssλDNA molecules were visualized over time in micro-flow channels. We report substantially different dynamics between these two labeling methods. When ssλDNA molecules were labeled with RPA-YFP, terminally bound fusion proteins were sheared from the free ends of the ssλDNA molecules unless 25-mer oligonucleotides were annealed to the free ends. RPA-YFP-ssλDNA complexes were dissociated by the addition of 0.2 M NaCl, although complex reassembly was possible with injection of additional RPA-YFP. In contrast to the flexible dynamics of RPA-YFP-ssλDNA complexes, the ssBP-488-ssλDNA complexes behaved as rigid rods and were not dissociated even in 2 M NaCl.     

Crystal Structures and Phase Transformations of the Fluorinated Fullerenes

Abstract

In situ x-ray diffraction experiments of the fluorinated fullerenes, C₆₀F _x (x = 0, 36 and 48) at high temperatures have been undertaken. The structural phase transformation of C₆₀F₄₈ was observed at about 358 K. It was also found that the lattice parameters of the low temperature phase of C₆₀F₄₈ show anomalous change at about 310 K. The thermal expansion coefficients of the fluorinated fullerenes were determined by using the change of the lattice parameters with temperature.