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  1. 020 学位論文
  2. 物理科学研究科
  3. 08 機能分子科学専攻

金属イオンにより誘起される人工DNAの自発的集合化

https://ir.soken.ac.jp/records/311
https://ir.soken.ac.jp/records/311
d7f3d9fe-50d8-43e6-b72c-39b638ceca0f
名前 / ファイル ライセンス アクション
甲488_要旨.pdf 要旨・審査要旨 / Abstract, Screening Result (282.2 kB)
甲488_本文.pdf 本文 / Thesis (5.6 MB)
Item type 学位論文 / Thesis or Dissertation(1)
公開日 2010-02-22
タイトル
タイトル 金属イオンにより誘起される人工DNAの自発的集合化
タイトル
タイトル Self-Assembly of Artificial DNA induced by Metal Coordination
言語 en
言語
言語 jpn
資源タイプ
資源タイプ識別子 http://purl.org/coar/resource_type/c_46ec
資源タイプ thesis
著者名 幡野, 明彦

× 幡野, 明彦

幡野, 明彦

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フリガナ ハタノ, アキヒコ

× ハタノ, アキヒコ

ハタノ, アキヒコ

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著者 HATANO, Akihiko

× HATANO, Akihiko

en HATANO, Akihiko

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学位授与機関
学位授与機関名 総合研究大学院大学
学位名
学位名 博士(理学)
学位記番号
内容記述タイプ Other
内容記述 総研大甲第488号
研究科
値 数物科学研究科
専攻
値 08 機能分子科学専攻
学位授与年月日
学位授与年月日 2000-09-29
学位授与年度
値 2000
要旨
内容記述タイプ Other
内容記述 The self-assembly of noncovalently linked molecular clusters of unique building blocks has currently received considerable attention. In particular, "template-directed" approaches are becoming common and have been accepted promising for the construction of the ideally predesigned assembly. One of the most appealing paradigms of self-assembly in biological system is sequence-specific association between two complementary nucleic acid strands, and such processes play essential roles in most genetic events. DNA oligonucleotides have been intensively used as templates for reaction control on the template such as self-replication of the guest DNA components.

(Chart 1 was abbreviated.)

As an approach to novel metal-assembled systems directed to a single-stranded DNA as the template (Chart 1), they have synthesized "chelator-type" nucleic acids mimics 1 - 4 (Scheme 1). Two metal binding sites and one nucleobase moiety were introduced into compound 1 - 4 so that they can undergo strand formation by intermolecular metal coordination thereby possibly interacting with a natural DNA strand through Watson-Crick base pairing.

(Scheme 1 was abbreviated.)

Compound 1 was synthesized from 3,5-dimethylphenol, according to Scheme 1. The phenolic intermediate serves as a common intermediate for the introduction of each nucleobase at the phenolic position. Here they present the experimental data with respect to an adenine mimic 1. The adenine mimic 1 reacted with Zn<SUP>II</SUP>(NO<SUB>3</SUB>)<SUB>2</SUB> in water to form Zn<SUP>II</SUP> complex 2. The molecular structure of the Zn<SUP>II</SUP> complex was characterized by single-crystal X-ray crystallography. Each ethylenediamine moiety binds to Zn<SUP>II</SUP> to form a trans-N<SUB>4</SUB>-plane, and two water molecules at the axial positions complete the octahedral structure (Figure 1).

(Figure 1 was abbreviated.)

Adenine analogues 1 are intermolecularly linked together by Zn<SUP>II</SUP> ions that provide the driving force for polymerization by imposing an octahedral coordination geometry at each site. Although the Zn<SUP>II</SUP>-Zn<SUP>II</SUP> distance of 7.718Å is rather longer than the average distance between adjacent phosphodiester groups in the same chain of B-DNA (ca. 6Å), molecular modeling studies indicated that this complex is structurally flexible enough for complementary binding to a single-stranded natural DNA.
They then examined interactions of the Zn<SUP>II</SUP> - assembled adenine polymer with oligo (dT)<SUB>70</SUB> using UV absorption changes. Figure 2 shows the temperature-dependency of the absorption at 260 nm for a 1 : 1 mixture of Zn<SUP>II</SUP> complex and (dT)<SUB>70</SUB> ([Zn<SUP>II</SUP> complex] = [(dT)<SUB>70</SUB>] = 15 μM/base, 1 mM Mops buffer at pH 7.0) when the solution temperature was elevated from 0 □C to 80 □C. An absorption break was observed at 39 □C, and almost the same curve was obtained even when the temperature was changed downwardly. This behavior is common in the naturally occurring nucleic acids.

(Figure 2 was abbreviated.)

The Zn<SUP>II</SUP> complex thus preferably associates with a natural DNA oligomer probably through electrostatic and hydrogen bonding interactions accompanied by hydrophobic effects. Such artificially-designed nucleic acid components that can undergo metal-assisted assembly in a reversible fashion would provide novel molecular array systems directed to information-bearing DNA or RNA for applications not only to metallo-antisenses for gene regulation but also to molecular memory devices or molecular wires.
所蔵
値 有
フォーマット
内容記述タイプ Other
内容記述 application/pdf
著者版フラグ
出版タイプ AM
出版タイプResource http://purl.org/coar/version/c_ab4af688f83e57aa
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