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61.
An 8-endo selective Friedel-Crafts cyclization of vinyloxirane 8 with Co2(CO)6-complexed benzeneacetylene was found to give poly-functional eight-membered cyclic compound 9 in high yields. 相似文献
62.
Norio Kitadai Tadashi Yokoyama Satoru Nakashima 《Journal of colloid and interface science》2009,338(2):395-401
The adsorption behavior of lysine on montmorillonite in aqueous solution was investigated by in situ attenuated total reflectance infrared (ATR-IR) spectroscopy. To distinguish the protonation states of α-amino group, side-chain amino group and carboxyl group in lysine structure using ATR-IR spectra (i.e., NH2 versus and COO− versus COOH), pH-induced spectral changes of dissolved lysine were firstly measured and correlated with the thermodynamically calculated dissociation states of lysine (di-cationic, cationic, zwitterionic and anionic states). The obtained result was applied to interpret the ATR-IR spectra of lysine adsorbed on montmorillonite. We found that the adsorbed lysine was dominantly present as cationic state over the whole range of tested pH (pH = 4.9–9.7). This indicates that the adsorption is mainly driven by electrostatic interaction between the negatively charged montmorillonite surface and positively charged cationic lysine. We also found that lysine interacts with montmorillonite surface through the protonated side-chain amino group. This result suggests that lysine has a preferred vertical orientation, with the side-chain amino group pointing toward the surface. 相似文献
63.
Polypropylene (PP) has become an indispensable material in our daily lives. Annual worldwide production of PP is now more than 30000000 tons and is predicted to grow at an annual rate of about 6% during the first decade of the 21st century. Commercial production of PP began in 1957 with the use of TiCl(3) catalysts established by Ziegler and Natta. However, the low activities and low stereospecificities of the catalysts resulted in large amounts of catalyst residue and atactic PP in the product, necessitating steps for their removal in commercial production. As a means of finding appropriate catalysts, we developed MgCl(2)-supported TiCl(4) catalysts, which basic concept was introduction of organic compounds onto the inorganic crystal catalyst surface. This addition led to remarkable enhancements in stereospecificity with extremely high activity. Use of the new catalysts enlarged and simplified the PP production process by eliminating the steps previously required for removal of catalyst residue and atactic PP. In addition, it greatly improved the properties of the PP, enabling a much wider range of PP applications by replacing metal and engineering plastics with the highly stereoregular PP. Therefore, these catalysts helped the rapid establishment of the current PP industry and now play a major role in production. The latest MgCl(2)-supported TiCl(4) catalyst is providing precise control of the isotactic PP structure. Future expectations for this type of catalyst are to acquire a single-site nature and to contribute to the creation of a new class of hybrid materials. 相似文献
64.
Yasunori Yamamoto Dr. Kazunori Kurihara Dr. Norio Miyaura Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(24):4414-4416
Ligand design by‐pam : A ruthenium‐catalyzed asymmetric arylation of aldehydes with arylboronic acids has been developed, giving chiral diarylmethanols in good yields. The use of a chiral bidentate phosphoramidite ligand ((R,R)‐Me‐bipam) led to excellent enantioselectivities.
65.
Sato Y Nishizawa S Teramae N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(41):11650-11656
A new class of label-free molecular beacon (MB) system based on DNA strands that contain abasic (AP) sites (AP-DNA) and adopt stem-loop structures, in combination with fluorescent ligands that bind these AP sites, has been developed. Unlike a conventional MB, which requires covalent labeling of the MB with a fluorophore and a quencher, the developed system (APMB) does not require covalent attachment of signal transduction units. Detailed sensing functions of a series of APMB systems were examined with the aid of the fluorescent ligand named ATMND to provide insight into the design strategy for APMB systems. The effects of the stem length and the position of the AP site in the stem moiety on the fluorescence response of the APMB system were examined. Genotyping of a G/C SNP of PCR amplification products was successfully demonstrated with the APMB system and blue-fluorescent ATMND as a ligand. The APMB system was further extended to a system that utilized green-fluorescent lumiflavin. 相似文献
66.
Miura S Nishizawa S Suzuki A Fujimoto Y Ono K Gao Q Teramae N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(50):14104-14110
A surface plasmon resonance (SPR) biosensor that carries DNA-binding small ligands has been developed for the detection of single-nucleotide polymorphisms (SNPs). 3,5-Diaminopyrazine derivatives, with a hydrogen-bonding profile fully complementary to the thymine base, were utilized as recognition elements on the sensor surface, and a target single-stranded DNA sequence was hybridized with a DNA probe containing an abasic site to place this site opposite a nucleobase to be detected. In a continuous flow of sample solutions buffered to pH 6.4 (0.25 M NaCl), the 3,5-diaminopyrazine-based SPR sensor can detect an orphan nucleobase in the duplex with a clear selectivity for thymine over cytosine, guanine, and adenine (5'-GTT GGA GCT GXG GGC GTA GGC-3'/3'-CAA CCT CGA CNC CCG CAT CCG-5'; X=abasic site, N=target nucleobase G, C, A, or T). The SPR response was linear in the concentration range 10-100 nM. Allele discrimination is possible based on the combination of different binding surfaces in a flow cell of the SPR system, which is demonstrated for the analysis of the thymine/cytosine mutation present in 63-meric polymerase chain reaction (PCR) amplification products (Ha-ras gene, codon 12, antisense strand). Comparison with a bulk assay based on 3,5-diaminopyrazine/DNA binding shows that the immobilization of 3,5-diaminopyrazine derivatives on the SPR sensor allows more sensitive detection of the target DNA sequence, and binding selectivity can be tuned by controlling the salt concentration of sample solutions. These features of the DNA-binding small-molecule-immobilized SPR sensor are discussed as a basis for the design of SPR biosensors for SNP genotyping. 相似文献
67.
Shuichi Nakamura Masashi Hayashi Yasutoshi Kamada Ryosuke Sasaki Yuichi Hiramatsu Norio Shibata Takeshi Toru 《Tetrahedron letters》2010,51(29):3820-3823
A catalytic enantioselective desymmetrization of meso-N-(heteroarenesulfonyl)aziridines with TMSN3 using chiral Lewis acids afforded products with high enantioselectivity. As proof of the utility of this procedure, the precursor of selective κ-opioid agonist (1S,2S)-(−)-U-50,488 was synthesized. 相似文献
68.
In this Review, we summarize the current state of the art in late‐transition‐metal‐catalyzed reactions of acyl fluorides, covering both their synthesis and further transformations. In organic reactions, the relationship between stability and reactivity of the starting substrates is usually characterized by a trade‐off. Yet, acyl fluorides display a very good balance between these properties, which is mostly due to their moderate electrophilicity. Thus, acyl fluorides (RCOF) can be used as versatile building blocks in transition‐metal‐catalyzed reactions, for example, as an “RCO” source in acyl coupling reactions, as an “R” source in decarbonylative coupling reactions, and as an “F” source in fluorination reactions. Starting from the cleavage of the acyl C?F bond in acyl fluorides, various transformations are accessible, including C?C, C?H, C?B, and C?F bond‐forming reactions that are catalyzed by transition‐metal catalysts that contain the Group 9–11 metals Co, Rh, Ir, Ni, Pd, or Cu. 相似文献
69.
Oshima S Kashihara I Moritani K Inui N Mochiji K 《Rapid communications in mass spectrometry : RCM》2011,25(8):1070-1074
In secondary ion mass spectrometry (SIMS) of organic substances, the dissociation of the sample molecules is crucial. We have developed SIMS equipment capable of bombardment, where the primary ions are argon cluster ions with kinetic energy per atom controllable down to 1 eV. We previously reported the detection of intact ions of insulin and cytochrome C using this equipment. In this paper, we present a detailed characterization of the emission of secondary ions from insulin, focusing on the difference in secondary ion yield between intact ions and fragment ions by varying the incident angle of the cluster ions. The emission intensity of the intact ions was changed drastically due to the exposed dosage and incident angle of the cluster ions in contrast to the fragment ions. We discuss these results based on the manner in which the argon-cluster ions collide with the organic solid. 相似文献
70.
Stereoselective catalytic synthesis of 3-trifluoromethyl indolines through the [4+1] cycloaddition of benzoxazinones and sulfur ylides in a transition-metal-free manner was developed. In the presence of a catalytic amount of sodium hydride, aza-ortho-quinone methide intermediates were formed from trifluoromethyl benzoxazinones through decarboxylation after the first nucleophilic attack of sulfur ylides, which progressed to a second nucleophilic attack of sulfur ylides, resulting in the [4+1] cycloaddition. The key for this catalytic transformation is the dual attack of sulfur ylides on substrates. This unique transition-metal-free protocol is applicable to the synthesis of non-fluorinated vinyl-, ethynyl- or methyl-substituted indolines. The synthesis of 3-trifluoromethyl indoles was also achieved described under stoichiometric conditions. 相似文献