2391-46-0Relevant articles and documents
Efficient and selective cleavage of RNA oligonucleotides by calix[4]arene-based synthetic metallonucleases
Cacciapaglia, Roberta,Casnati, Alessandro,Mandolini, Luigi,Peracchi, Alessio,Reinhoudt, David N.,Salvio, Riccardo,Sartori, Andrea,Ungaro, Rocco
, p. 12512 - 12520 (2007)
Di- and trinuclear copper(II) complexes of [12]aneN3 macrocycles anchored at the upper rim of cone calix[4]arenes in 1,2-, 1,3-, and 1,2,3-positions were investigated as cleaving agents of 6-, 7-, and 17-meric oligoribonucleotides. A kinetic investigation of the cleavage reactions was carried out using gel electrophoresis to separate and analyze reactants and products having a radioactive phosphate label in the terminal opposition. The degree of cooperation was assessed on the basis of a comparison with rates of cleavage by mononuclear controls. A remarkable selectivity of cleavage of the CpA phosphodiester bond was observed for all metal complexes, in sharp contrast with the UpU and UpG selectivity previously observed in the cleavage of diribonucleoside monophosphates by the same metal complexes. The highest rate acceleration, brought about in the cleavage of the 5′-pCpA bond in hexanucleotide 9 by 50 μM trinuclear complex 5-Cu3 (water solution, pH 7.4, 50°C), amounts to 5 × 105-fold, as based on the estimated background reactivity of the CpA dimer. Selectivity in the cleavage of oligoribonucleotides by copper(II) complexes closely resembles that experienced by ribonuclease A and by a number of metal-independent RNase A mimicks. The possible role of the dianionic phosphate at the 5′-terminal positions as a primary anchoring site for the metal catalyst is discussed.
Synthesis and enzymatic deprotection of biodegradably protected dinucleoside-2′,5′-monophosphates: 3-(Acetyloxy)-2,2- bis(ethoxycarbonyl)propyl phosphoesters of 3′-O-(acyloxymethyl)adenylyl- 2′,5′-adenosines
Kiuru, Emilia,Ora, Mikko,Beigelman, Leonid,Blatt, Lawrence,Loennberg, Harri
experimental part, p. 266 - 286 (2011/10/05)
As a first step towards a viable prodrug strategy for short oligoribonucleotides, such as 2-5A and its congeners, adenylyl-2′, 5′-adenosines bearing a 3-(acetyloxy)-2,2-bis(ethoxycarbonyl)propyl group at the phosphate moiety, and an (acetyloxy)methyl- or a (pivaloyloxy)methyl- protected 3′-OH group of the 2′-linked nucleoside have been prepared. The enzyme-triggered removal of these protecting groups by hog liver carboxyesterase at pH 7.5 and 37° has been studied. The (acetyloxy)methyl group turned out to be too labile for the 3′-O-protection, being removed faster than the phosphate-protecting group, which results in 2′,5′- to 3′,5′-isomerization of the internucleosidic phosphoester linkage. In addition, the starting material was unexpectedly converted to the 5′-O-acetylated derivative. (Pivaloyloxy)methyl group appears more appropriate for the purpose. The fully deprotected 2′,5′-ApA was accumulated as a main product, although, even in this case, the isomerization of the starting material takes place.
THE RAPID CHEMICAL SYNTHESIS OF ARABINONUCLEOTIDES
Damha, Masad J.,Usman, Nassim,Ogilvie, Kelvin K.
, p. 1633 - 1636 (2007/10/02)
A fast and convenient procedure for the chemical synthesis of arabinonucleotides which eliminates the multistep protection of the arabinonucleoside building blocks is described.Both solution and solid phase phosphite triester procedures are described.
