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Sodium terbium(III) polyphosphate.

ABSTRACT: Single crystals of the title compound, NaTb(PO(3))(4), were obtained by solid-state reaction. This compound belongs to type II of long-chain polyphosphates with the general formula A(I)B(III)(PO(3))(4). It is isotypic with the NaNd(PO(3))(4) and NaEr(PO(3))(4) homologues. The crystal structure is built up of infinite crenelated chains of corner-sharing PO(4) tetra-hedra with a repeating unit of four tetra-hedra. These chains, extending parallel to [100], are linked by isolated TbO(8) square anti-prisms, forming a three-dimensional framework. The Na(+) ions are located in channels running along [010] and are surrounded by six oxygen atoms in a distorted octa-hedral environment within a cut-off distance <2.9?Å.

SUBMITTER: Oudahmane A

PROVIDER: S-EPMC2983799 | biostudies-literature | 2010

REPOSITORIES: biostudies-literature

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Sodium terbium(III) polyphosphate.

Oudahmane Abdelghani A Daoud Mohamed M Tanouti Boumediene B Avignant Daniel D Zambon Daniel D

Acta crystallographica. Section E, Structure reports online 20100324 Pt 4

Single crystals of the title compound, NaTb(PO(3))(4), were obtained by solid-state reaction. This compound belongs to type II of long-chain polyphosphates with the general formula A(I)B(III)(PO(3))(4). It is isotypic with the NaNd(PO(3))(4) and NaEr(PO(3))(4) homologues. The crystal structure is built up of infinite crenelated chains of corner-sharing PO(4) tetra-hedra with a repeating unit of four tetra-hedra. These chains, extending parallel to [100], are linked by isolated TbO(8) square anti ...[more]

PMID: 21580462

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Project description:Reaction of terbium triflate with a heptadentate ligand derivative of cyclen, L1 = 2-[7-ethyl-4,10-bis(isopropylcarbamoylmethyl)-1,4,7,10-tetraazacyclododec-1-yl]-N-isopropyl-acetamide, produced a new synthetic ribonuclease, [Tb(L1)(OTf)(OH(2))](OTf)(2).MeCN (C1). X-ray crystal structure analysis indicates that the terbium(III) center in C1 is 9-coordinate, with a capped square-antiprism geometry. While the terbium(III) center is tightly bound by the L1 ligand, two of the coordination sites are occupied by labile water and triflate ligands. In water, the triflate ligand is likely to be displaced, forming [Tb(L1)(OH(2))(2)](3+), which is able to effectively promote RNA cleavage. This complex greatly accelerates the rate of intramolecular transesterification of an activated model RNA phosphodiester, uridine-3'-p-nitrophenylphosphate (UpNP), with k(obs) = 5.5(1) x 10(-2) s(-1) at 21 degrees C and pH 7.5, corresponding to an apparent second-order rate constant of 277(5) M(-1) s(-1). By contrast, the analogous complex of an octadentate derivative of cyclen featuring only a single labile coordination site, [Tb(L2)(OH(2))](OTf)(3) (C2), where L2 = 2-[4,7,10-tris(isopropylcarbamoylmethyl)-1,4,7,10-tetraazacyclododec-1-yl]-N-isopropyl-acetamide, is inactive. [Tb(L1)(OH(2))(2)](3+) is also capable of hydrolyzing short transcripts of the HIV-1 transactivation response (TAR) element, HIV-1 dimerization initiation site (DIS) and ribosomal A-site, as well as formyl methionine tRNA (tRNA(fMet)), albeit at a considerably slower rate than UpNP transesterification (k(obs) = 2.78(8) x 10(-5) s(-1) for TAR cleavage at 37 degrees C, pH 6.5, corresponding to an apparent second-order rate constant of 0.56(2) M(-1)s(-1)). Cleavage is concentrated at the single-stranded "bulge" regions of these RNA motifs. Exploiting this selectivity, [Tb(L1)(OH(2))(2)](3+) was successfully employed in footprinting experiments, in which binding of the Tat peptide and neomycin B to the bulge region of the TAR stem-loop was confirmed.

Dataset Information

Sodium terbium(III) polyphosphate.

Publications

Sodium terbium(III) polyphosphate.

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