有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
54 巻, 5 号
選択された号の論文の12件中1~12を表示しています
  • 多糖誘導体型固定相の開発と分割特性および大量分取への応用
    大西 敦, 市田 昭人, 牧野 成夫
    1996 年 54 巻 5 号 p. 344-353
    発行日: 1996/05/01
    公開日: 2010/01/28
    ジャーナル フリー
    The importance of optically active compounds for pharmaceutical usages has increased. High-performance liquid chromatographic (HPLC) resolution on chiral stationary phases (CSPs) is useful for the analysis of the compounds as well the sample preparations to estimate in the developing stages. CSPs consisting of polysaccharide derviatives were developed by adsorbing them on silica gel on the basis of information obtained from cellulose triacetate. The characteristics of cellulosic esters (OA, OB, OJ, OK) and carbamtes (OC, OF, OG, OD), and amylosic carbamtes (AS, AD) in chiral recognition were introduced with many examples. The optimization of sepqrating conditions are discussed in mentioning the differences among the acidic, neutral or basic compounds. Furthermore, we introduced the principle and applications on the Simulated Moving Bed process to produce optically active compounds in the industrial scale as one of the HPLC methods.
  • 鵜澤 洵, 越野 広雪
    1996 年 54 巻 5 号 p. 354-366
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    NMRの歴史の中で「もうNMRは終わり」と言われた時期が何回かあった。有機化学への応用に限っても, 1960年代半ばが一つの時期であった。この時期はCW (continuous-wave) 機の簡易型が普及し多くの経験則が生まれ, 数々の名著が出版された。1966年, ErnstとAndersonはFT-NMRの実験に成功し, 様々なパルステクニックの発展につながった。1970年代は13CNMRの実用化で始まり, 超伝導磁石による高磁場化とJeenerの二次元NMRの提起と実現化への競争の時代となった。1980年代初期, 二次元 (三次元も二次元の延長と考える) もそろそろ限界かと思えた頃, 多量子NMRとかHOHAHA (TOCSY) の概念の実用化が提起され, そしてインバース法が生まれた。これらは驚くほど早いスピードで普及した。90年代初期は磁場勾配という一部の人にしか興味のなかった技術が中心に躍り出てきた。これら高分解能溶液NMRの進歩においては, 周辺にある固体NMR, MRIなどの技術や考え方が持ち込まれた場合が多いことに気がつく。もちろん逆の動きも当然あるのだが。こうしてみると, 視野を広くもってそれぞれの進歩に目を配る必要性を痛感する。本文では触れなかったが, データ処理を行うコンピュータの進歩は目覚ましく正に日進月歩である。これらの最良の果実はNMRの世界にもすぐに入ってくる。ここで紹介したPFGの高分解能溶液NMRへの導入はこの分野に新しい測定法をもたらしてくれた。NMRの進歩は不可能であったことを可能にしてくれる。NMRの発展にはそれを利用する研究者のNMRへの期待と要求が必須である。そのためには多くのNMR利用者がNMRデータのみでなく, NMRそのものに興味を持ち, NMRについて理解することが必要である。本解説が少しでもその手助けになれば幸いである。
  • 黒子 弘道, 安藤 勲
    1996 年 54 巻 5 号 p. 367-374
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    The application of high-resolution solid-state NMR spectroscopy to structural and dynamical analyses of solid peptides, polypeptides, calixalene, conductive polymers, polyesters and poly (ethylene oxide) in the solid state have been introduced. It has been demonstrated that the high-resolution solid-state NMR spectroscopy is a very powerful means for elucidating the structure and dynamics of molecules in the solid state.
  • 絹見 朋也, 窪田 雅之, 大橋 守
    1996 年 54 巻 5 号 p. 375-383
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    This review describes modern mass spectrometric techniques which make it possible to apply to highly polar and large biomolecules. In recent years, the use of mass spectrometry has dramatically expanded in biochemical and medical fields.
    Significant developments in these techniques have been established by ESI/MS (electrospray ionization mass spectrometry) and MALDI-TOF/MS (matrix-assisted laser desorption ionization time-of-flight mass spectrometry). ESI can detect weak interactions such as cyclodextrin inclusion complexes, enzyme-substrate complexes, double stranded DNA and its intercalation with a ligand. It is expected to be a powerful tool for study of molecular recognition at the picomolar level. ESI can also be easily interfaced with liquid chromatography (LC/MS). On-line LC/MS is widely applicable for mixture analysis. MALDI-TOF provides extremely high sensitivity such as sub picomolar level analysis. PSD-MS (post source decay-mass spectrometry) gives structural information, which is a technique similar to CID-MS/MS with extremely high sensitivity.
  • 中川 敦史
    1996 年 54 巻 5 号 p. 384-394
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    The synchrotron radiation (SR), which is produced in circular electron/positron accelerator, is high brilliance and pulsed white light with wide wavelength range, from infrared to γ-rays. Synchrotron radiation is the only light source which produce high intensity white light in hard X-ray region. Thus, it is used in various scientific field, such as physics, chemistry, biology, medical application, industrial application and so on. Many experiments, such as X-ray absorption fine structure (XAFS), X-ray fluorescence analysis and small angle X-ray scattering etc., are being worked with synchrotron radiation as light source. Biological macromolecular crystallography is one of the main application of synchrotron radiation. High intensity and high brilliance of synchrotron radiation is indispensable to collect good high resolution diffraction data from small crystals with large unit cell. Wavelength tunability can be applied to determine crystallographic phases using anomalous dispersion effect. White X-ray light opens a new field of crystallography, time-resolved dynamic structure determination using Laue technique. A next generation ultra-light source, SPring -8, is now under construction.
  • 山内 芳雄
    1996 年 54 巻 5 号 p. 395-399
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    Utilization of supercritical fluids includes two methods;extraction (SFE) and chromatography (SFC). The most populer fluid may be carbon dioxide due to its easiness in control in the supercritical state. As a new concept of SFE using carbon dioxide, the programmed extraction elution method (PEEM) that enhances extraction efficiency and selectivity is presented, demonstrating the micro scale SFE preparation of naphthalene and anthracene.
    Recently, SFC has been developed in various fields as HPLC. The author describes various applications;analysis of a surfactant uising negative temperature gradient elution method, chiral prep-separation of t-stilbene oxide, and separation and detection of SFC-MS.
  • 菅野 祐一
    1996 年 54 巻 5 号 p. 401-409
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    To allow non-invasive radiotracer studies in human, the emitted radiation must be detected outside the body. PET technique employs tracers labeled with short-lived positron emitting radionuclides that produce externally detectable two anti-parallel gamma photons by collision with an electron. By computerized reconstruction, cross section images of the distribution of the radioactivity can be created.
    The short half-lives of the radionuclides minimize radiation-exposure and allow tht repetitive PET-investigations within short time intervals. The high specific radioactivity makes it possible to work with small concentration of the tracers.
    PET has become increasingly important in biological and medical research. The development of new synthetic methods is eagerly desired to produce new tracers labeled with positron emitting radionuclides.
  • 大内 秋比古
    1996 年 54 巻 5 号 p. 410-418
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    Utilization of lasers in organic syntheses is reviewed. Firstly, characteristics of laser light are summarized. Secondly, photochemical processes of laser reactions are outlined with some examples of reactions. Thirdly, experimental apparatus and techniques in laser reactions are introduced.
  • 深澤 義正, 灰野 岳晴
    1996 年 54 巻 5 号 p. 419-426
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    有機合成の標的化合物は複雑な構造を持っているものが多く一般に多段階の反応を経て合成されることが多い。それらの合成経路のうち重要な反応についてその生成物が立体化学を含めて正しく予測されれば, 合成経路の確立に大いに役立ち有機合成の経済効率の向上に著しく寄与するものと思われる。したがって, 信頼性の高い反応予測技術の開発は非常に重要である。ここで紹介した非経験的分子軌道計算と分子力学計算を組み合わせた遷移状態モデリング法やMC法を用いた溶媒和計算は, その信頼性の高さからいって十分現実的な使用に耐え得るものと思われ今後の発展が期待される。
  • 石黒 正路, 今城 精一
    1996 年 54 巻 5 号 p. 427-436
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    Complex structures of neocarzinostatin (NCS) and β-lactamase/β-lactam antibiotics were built using NMR and crystallographic data of the proteins. On binding of ligands to proteins, particular amino acid side chains as well as ligands show dynamic character to exhibit specific molecular recognition. NMR studies and conformational analysis of the Phe 78 side chain of NCS revealed that the Phe 78 residue plays a major role on the chromophore binding through conformational change of the side chain aromatic moiety. Crystal structures and computational modeling of the enzyme-ligand complexes indicated that at the active site, the carboxylate of β-lactam antibiotics induces the conformational change of the Lys 73 residue and acts as a trigger of the hydrolytic reaction (acylation). Modeling of the acyl-enzyme structures also suggested the role of a mobile water molecule at the active site for deacylation. Experimental (NMR and X-ray crystallography) and computational results provided a fruitful information about molecular interaction between proteins and ligands.
  • 笹井 宏明
    1996 年 54 巻 5 号 p. 437-444
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
    Internet makes it possible to send and receive data in high speed and in high quality. Now, sounds, graphics, and even movies can send over internet very easily. Herein, I would like to introduce some tips to use internet efficiently. With using internet, leaving scientists free to consider more important issues.
  • 鵜沢 洵, 大橋 守, 大内 秋比古, 灰野 岳晴
    1996 年 54 巻 5 号 p. 456
    発行日: 1996/05/01
    公開日: 2009/11/16
    ジャーナル フリー
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