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Title: Site-selective hydrolysis of tRNA by lanthanide metal complexes

Abstract

tRNA[sup Phe] is site-selectively hydrolyzed by lanthanide metal complexes (Ce(III), Eu(III), La(III)) of hexaimine macrocyclic ligands. The selectivities of the complexes are much higher than those of the metal ions and are strongly dependent on the ligand structure. The tertiary structure of tRNA is essential for the site-selective scission.

Authors:
 [1]; ; ; ;  [2];  [3]
  1. (Tokyo Institute of Technology, Yokohama (Japan))
  2. (Univ. of Tokyo (Japan))
  3. (Univ. of Tsukuba, Ibaraki (Japan))
Publication Date:
OSTI Identifier:
5110094
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; (United States); Journal Volume: 32:26
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CERIUM COMPLEXES; CATALYTIC EFFECTS; EUROPIUM COMPLEXES; LANTHANUM COMPLEXES; TRANSFER RNA; HYDROLYSIS; CHELATES; ORGANIC NITROGEN COMPOUNDS; CHEMICAL REACTIONS; COMPLEXES; DECOMPOSITION; LYSIS; NUCLEIC ACIDS; ORGANIC COMPOUNDS; RARE EARTH COMPLEXES; RNA; SOLVOLYSIS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Hayashi, Nobuhiro, Takeda, Naoya, Yashiro, Morio, Watanabe, Kimitsuna, Komiyama, Makoto, and Shiiba, Tetsuro. Site-selective hydrolysis of tRNA by lanthanide metal complexes. United States: N. p., 1993. Web. doi:10.1021/ic00078a002.
Hayashi, Nobuhiro, Takeda, Naoya, Yashiro, Morio, Watanabe, Kimitsuna, Komiyama, Makoto, & Shiiba, Tetsuro. Site-selective hydrolysis of tRNA by lanthanide metal complexes. United States. doi:10.1021/ic00078a002.
Hayashi, Nobuhiro, Takeda, Naoya, Yashiro, Morio, Watanabe, Kimitsuna, Komiyama, Makoto, and Shiiba, Tetsuro. 1993. "Site-selective hydrolysis of tRNA by lanthanide metal complexes". United States. doi:10.1021/ic00078a002.
@article{osti_5110094,
title = {Site-selective hydrolysis of tRNA by lanthanide metal complexes},
author = {Hayashi, Nobuhiro and Takeda, Naoya and Yashiro, Morio and Watanabe, Kimitsuna and Komiyama, Makoto and Shiiba, Tetsuro},
abstractNote = {tRNA[sup Phe] is site-selectively hydrolyzed by lanthanide metal complexes (Ce(III), Eu(III), La(III)) of hexaimine macrocyclic ligands. The selectivities of the complexes are much higher than those of the metal ions and are strongly dependent on the ligand structure. The tertiary structure of tRNA is essential for the site-selective scission.},
doi = {10.1021/ic00078a002},
journal = {Inorganic Chemistry; (United States)},
number = ,
volume = 32:26,
place = {United States},
year = 1993,
month =
}
  • Lanthanide(III) Cryptate (2.2.1) chlorides (Ln(2.2.1)Cl{sub 3}; Ln = La (1a), Ce(1b), and Eu(1c); (2.2.1) = 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8.8.5]tricosane) are effective for the catalytic hydrolysis of bis(4-nitrophenyl) phophate. Kinetic studies reveal that the europium(III) complex (1c) catalyzes the hydrolysis to produce 6 equiv of 4-nitrophenol with a significant rate (k{sub 1} = 1.5 x 10{sup {minus}4} s{sup {minus}1} at 0.40 mM) at pH 8.5 and 50 {degrees}C. The catalytic activity of the complexes is increased with decreasing the ionic size, i.e. La < Ce < Eu. While the use of hydrogen peroxide further increases the activity of 1b (k{sub 1} = 1.6 xmore » 10{sup {minus}3},at 0.40 mM), the presence of molecular oxygen does not affect the activity at all.« less
  • Molecular mechanics methods have been used to calculate the diverse geometries found in 58 known structures of 8- to 12-coordinate aqua- and nitratolanthanide(III) complexes. A simple model based on the replacement of L-M-L bending interactions with nonbonded interactions between the ligand donor atoms and the use of harmonic M-L stretching potentials is shown to yield very reasonable geometric results. A method of structure specification for coordination compounds is presented that allows these calculations to be carried out by using the MM2 program without requiring any software modification. 52 refs., 9 figs., 7 tabs.
  • The lanthanide and Th{sup 4+} complexes with calix[4]arene ligands substituted either on the narrow or at the wide rim by four coordinating groups behave totally differently as shown by an NMR investigation of the dia- and paramagnetic complexes. Solutions of complexes were prepared by reacting anhydrous metal perchlorate salts with the ligands in dry acetonitrile (CAUTION). Relaxation time T{sub 1} titrations of acetonitrile solutions of Gd{sup 3+} by calixarenes indicate that ligands substituted on the narrow rim form stable 1:1 complexes whether they feature four amide groups (1) or four phosphine oxide functions. In contrast, a ligand substituted by fourmore » (carbamoylmethyl)-diphenylphosphine oxide moieties on the wide rim (3) and its derivatives form polymeric species even at a 1:1 ligand/metal concentration ratio. Nuclear magnetic relaxation dispersion (NMRD) curves (relaxation rates 1/T{sub 1} vs magnetic field strength) of Gd{sup 3+}, Gd{sup 3+}{center_dot}1 and Gd{sup 3+}{center_dot}3 perchlorates in acetonitrile are analyzed by an extended version of the Solomon-Bloembergen-Morgan equations. A comparison of the calculated rotational correlation times {tau}{sub r} shows that ligand 3 forms oligomeric Gd{sup 3+} species. The chelates of ligand 1 are axially symmetric (C{sub 4} symmetry), and the paramagnetic shifts induced by the Yb{sup 3+} ion are accounted for quantitatively. The addition of water or of nitrate ions does not modify the geometry of the complex. The metal chelates of 3 and its derivatives adopt a C{sub 2} symmetry, and the paramagnetic shifts are interpreted on a semiquantitative basis only. Water and NO{sub 3}{sup {minus}} ions completely labilize the complexes of the heavy lanthanides. The very high selectivity of ligand 3 through the lanthanide series stems from a complex interplay of factors.« less
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