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Fujitake, Masaharu ; Tanaka, Toshihiro ; Ohashi, Nobukimi ; 藤竹, 正晴 ; 大橋, 信喜美
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金沢大学理工研究域数物科学系<br />The rotational spectrum of one conformer of the methyl glycolate-H2O complex has been measured by me
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ans of the pulsed jet Fourier transform microwave spectrometer. The observed a- and b-type transitions exhibit doublet splittings due to the internal rotation of the methyl group. On the other hand, most of the c-type transitions exhibit quartet splittings arising from the methyl internal rotation and the inversion motion between two equivalent conformations. The spectrum was analyzed using parameterized expressions of the Hamiltonian matrix elements derived by applying the tunneling matrix formalism. Based on the results obtained from ab initio calculation, the observed complex of methyl glycolate-H2O was assigned to the most stable conformer of the insertion complex, in which a non-planer seven membered-ring structure is formed by the intermolecular hydrogen bonds between methyl glycolate and H2O subunits. The inversion motion observed in the c-type transitions is therefore a kind of ring-inversion motion between two equivalent conformations. Conformational flexibility, which corresponds to the ring-inversion between two equivalent conformations and to the isomerization between two possible conformers of the insertion complex, was investigated with the help of the ab initio calculation. © 2017 Elsevier Inc.<br />Embargo Period 24 months
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大橋, 信喜美
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大橋, 信喜美 ; Ohashi, Nobukimi
概要:
金沢大学自然科学研究科<br />表記研究課題のもとに金沢大学・神奈川工科大学・総合研究大学院大学さらには海外研究者の協力を得て共同研究を推し進めてきた。金沢大学においては、ノズルジェットフーリェ変換マイクロ波分光器(FTMW)を新たに構築
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し、また、神奈川工科大学では既設のFTMW装置の機能拡張を計り、ペプチド分子など生体機能を解明するのに有用と考えられる分子種をとりあげ、純回転スペクトルの測定・解析から、その内部運動に関する情報を得ることに鋭意努め、情報伝達の機構解明の糸口をつかむべく研究を進めてきた。当該研究機関中(平成14-16年度)に取りくんだ分子種はdimethyl methyl phosphonate, N-methylpropion amide,1,1-dimethylsilacyclobutane, N-methyl acetamide, N-methylaniline, N,N-dimethylacetamide, Ar-dimethylether, Ne-dimethyletherなどである。いずれもメチル基内部回転運動を含む複数の大振幅内部運動を有するものであり、今回の研究を通してこれら内部運動に関する詳しい情報が得られた。ことに各内部運動間の相互作用に関する知見は情報伝達機構と直接深く関連するものと考えられ、有用な情報といえよう。たとえば、N,N-dimethylacetamideでは、コリオリ相互作用項を通して3個のメチル基を内部回転が伝播する遷移確率、また、1,1-dimethylsilacyclobutaneでは内部回転-リングパッカリング間の相互作用の回転定数への寄与、等々の精密な情報が得られており、実験データの解析を通して得られたこれらの知見は情報伝達機構を考える上で貴重な成果と云えよう。<br />In the present project, a nozzle-jet Fourier transform microwave (ETTMW) spectrometer was newly constructed in Kanazawa University, and the FTMW existing already in Kanagawa Institute of Technology was revised. Using these two FTMW spectrometers, and also using the instrument in National Institute of Standards and Technology (NIST) of U.S,A. through collaborative work, pure rotational spectra of peptide molecules and other molecular species involving large-amplitude motions were investigated to obtain information on intra-moleculaar interactions useful for understanding mechanism of biological information transmittance. Molecular species studied in the present project are dimethyl methylphosphonate, N-methylpropionamide, N-methylformamide, N-methylacetamide, 1,1-dimethylsilacyclobutane, N-methylaniline, N,N-dimethylacetamide, Ar-dimethyl ether complex, Ne-dimethyl ether complex etc. For examples, a transition probability relating to transmittanee of the three CH_3-internal rotations occurring through Coriolis interaction between overall-rotation and internal-rotation was obtained for the N,N-dimethylacetamide, and a contribution to a rotational constant of the interaction between CH_3-internal rotation and ring-puckering motion was determined for the 1,1-dimethylsilacyclobutane molecule. Information involved in these quantities is useful, which are considered to be strongly related to information transmittance of fiologically related molecules.<br />研究課題/領域番号:14340177, 研究期間(年度):2002 – 2004<br />出典：「高分解能分子分光学的手法を活用した生体機能とくに情報伝達の機構の解明」研究成果報告書 課題番号14340177（KAKEN：科学研究費助成事業データベース（国立情報学研究所））（https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-14340177/143401772004kenkyu_seika_hokoku_gaiyo/)を加工して作成
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