Synthesis and hybridization of oligonucleotides modified at AMP sites with adenine pyrrolidine phosphonate nucleotides

2009 ◽  
Vol 74 (6) ◽  
pp. 935-955 ◽  
Author(s):  
Dominik Rejman ◽  
Petr Kočalka ◽  
Radek Pohl ◽  
Zdeněk Točík ◽  
Ivan Rosenberg
Keyword(s):  
Solid Phase ◽  
Thermal Characteristics ◽  
Stable Complex ◽  
Modified Oligonucleotides ◽  
Pyrrolidine Ring ◽  
Phosphonic Acids ◽  
Phosphoramidite Chemistry ◽  
Ring Nitrogen ◽  
Ring Nitrogen Atom ◽  
Phosphotriester Method

Three structurally diverse types of the protected pyrrolidine nucleoside phosphonates were prepared as the monomers for the introduction of pyrrolidine nucleotide units into modified oligonucleotides on the solid phase. Two different chemistries were used for incorporation of modified and natural units: the phosphotriester method for the former, i.e., monomers containing N-phosphonoalkyl and N-phosphonoacyl moieties attached to the pyrrolidine ring nitrogen atom, and phosphoramidite chemistry for the latter. Since the synthesized pyrrolidine nucleoside phosphonic acids are close mimics of the 3′-deoxynucleoside 5′-phosphates, the incorporation of one modified unit into oligonucleotides gives rise to one 2′,5′ internucleotide linkage. A series of nonamers containing two or three modified units, as well as the fully modified adenine 15-mer, were synthesized in reverse order, i.e., from the 5′ to the 3′ end of the strand. The measurement of thermal characteristics of the complexes of modified nonamers with the complementary strand revealed a destabilizing effect of the introduced modification. The modified adenine homooligonucleotide, was found to form the most stable complex with oligothymidylate of all the tested modified oligonucleotides in terms of ΔTm per modification.

Synthesis and sequencing of Informational Poly(amino phosphodiester)s

2021 ◽  
Author(s):  
Ian Roszak ◽  
Laurence Oswald ◽  
Abdelaziz AL-OUAHABI ◽  
Annabelle Bertin ◽  
Eline Laurent ◽  
...  
Keyword(s):  
Main Chain ◽  
Solid Phase ◽  
Tertiary Amines ◽  
Phosphoramidite Chemistry

Sequenced-defined poly(amino phosphodiester)s containing main-chain tertiary amines were synthesized by automated solid-phase phosphoramidite chemistry. These polymers were prepared using four monomers with different substituents. The formed polymers were characterized by...

One-pot synthesis of N-substituted-3-hydroxy-4-pyridinone chelate complexes of aluminum, gallium, and indium

1989 ◽  
Vol 67 (11) ◽  
pp. 1708-1710 ◽  
Author(s):  
Zaihui Zhang ◽  
T. L. Thomas Hui ◽  
Chris Orvig
Keyword(s):  
Metal Ions ◽  
Metal Ion ◽  
Nucleophilic Attack ◽  
Electronic Effects ◽  
One Pot ◽  
Group 13 ◽  
Pyrone Ring ◽  
One Pot Synthesis ◽  
Ring Nitrogen ◽  
Ring Nitrogen Atom

A series of tris(3-hydroxy-2-methyl-4-pyridinonato)metal(III) and tris(3-hydroxy-6-hydroxymethyl-4-pyridinonato)metal(III) complexes have been prepared in water by one-pot synthesis directly from maltol and kojic acid, respectively, and the metal ion (M = Al, Ga, In) with an appropriate amine. The pyridinones have substituents at the ring nitrogen atom (CH3, C2H5). The tris(3-hydroxy-4-pyronato)metal(III) complexes are formed insitu and these undergo nucleophilic attack by the primary amine; the appropriate tris(3-hydroxy-4-pyridinonato)metal(III) complexes are obtained. This method bypasses the sequential syntheses of ligand and metal complex, and has improved the yields of the tris(ligand)metal complexes, in particular by making them much more easily accessible. The electronic effects of binding the pyrone to the metal ions and of the substituents on the pyrone ring on the reactivity are discussed. Keywords: 3-hydroxy-4 pyridinone complexes, group 13 metal ions, one-pot synthesis.

Continuous-flow Phosphotriester Method for Solid-phase Synthesis of Oligodeoxyribonucleotides

1983 ◽  
Vol 47 (0) ◽  
pp. 393-401 ◽  
Author(s):  
M.J. Gait ◽  
H.W.D. Matthes ◽  
M. Singh ◽  
B.S. Sproat ◽  
R. Titmas
Keyword(s):  
Continuous Flow ◽  
Solid Phase Synthesis ◽  
Solid Phase ◽  
Phase Synthesis ◽  
Phosphotriester Method

Übergangsmetallkomplexe mit Nitroxidradikalen: Palladium-, Platin-, Pentamethylcyclopentadienyl-rhodium- und -iridium-Komplexe sowie α-Aminocarboxylatkomplexe mit Donor-haltigen Derivaten des 2,5-Dihydroimidazol-l-oxyls / Transition Metal Complexes of Nitroxide Radicals, Palladium, Platinum, Pentamethylcyclopentadienyl Rhodium and Iridium Complexes, and α-Aminocarboxylate Complexes with Derivatives of 2,5-Dihydroimidazole-l-oxyls

1998 ◽  
Vol 53 (1) ◽  
pp. 101-109 ◽  
Author(s):  
Frank Hintermaier ◽  
Sylvia Helding ◽  
Leonid B. Volodarsky ◽  
Karlheinz Sünkel ◽  
Kurt Polbom ◽  
...  
Keyword(s):  
Nitrogen Atom ◽  
Molecular Structures ◽  
Iridium Complexes ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
Ring Nitrogen ◽  
Derivatives Of ◽  
Ring Nitrogen Atom ◽  
Palladium Platinum

2,5-Dihydroimidazoline-l-oxyl radicals I, II with imino substituents coordinate to Pd(II) and Pt(II) complexes with formation of the N,N chelate complexes 1-6. With oxygen containing substituents either monodentate N-coordination to give 8 or N ,O chelate formation to give 9 takes place, depending on the position of the oxygen atom relative to the ring nitrogen atom. With radicals III that also have the second ring nitrogen atom oxidized and the Rh(III) or Ir(III) complexes [Cp*MCl2]2 the O , O chelates 11 -13 could be obtained, while with Na2PdCl4 the heterocycle was destroyed with formation of a N,N chelate complex 10 of an α-nitrosooxime ligand. The orthopalladated 2,2,5,5 tetramethyl-4-phenyl-2,5-dihydroimidazoline-l-oxyl complex 7a reacts with several a-amino acidates under splitting of the dichloro bridge with formation of the C,N/N,O-bis-chelate complexes 7b-f. The molecular structures of 2 and 10 were determined by X-ray diffraction.

Photophysics of some substituted 3H-indole probe molecules and their charged species

1994 ◽  
Vol 72 (11) ◽  
pp. 2239-2248 ◽  
Author(s):  
Michel Belletête ◽  
Ranjit S. Sarpal ◽  
Gilles Durocher
Keyword(s):  
Excited State ◽  
Radiative Decay ◽  
Mirror Image ◽  
Good Tool ◽  
Decay Rate Constant ◽  
Solvent Interactions ◽  
Cationic Species ◽  
Photophysical Parameters ◽  
Ring Nitrogen ◽  
Ring Nitrogen Atom

The spectroscopic and photophysical parameters of neutral and cationic species of the following molecules have been discussed: 2-phenyl-3,3-dimethyl-3H-indole (1), 2-[(p-amino)phenyl]-3,3-dimethyl-3H-indole (2), 2-[(p-dimethylamino)phenyl]-3,3-dimethyl-3H-indole (3), 2-[(p-amino)phenyl]-3,3-dimethyl-5-carboethoxy-3H-indole (4), 2-[(p-methylamino)phenyl]-3,3-dimethyl-5-carboethoxy-3H-indole (5), 2-[(p-dimethylamino)phenyl]-3,3-dimethyl-5-carboethoxy-3H-indole (6). Solvatochromic shifts have been interpreted in terms of the nature of the substituent groups and the state of solute–solvent interactions and complexation. The theoretical radiative decay rate constant [Formula: see text] along with the bandwidth of the absorption profile of the different species involved have been used to discuss the geometrical changes from one species to the other in the ground state. The mirror-image relationship between absorption and fluorescence spectra has proven to be a good tool to discuss any geometrical changes occurring in the excited state. A radiationless torsional mechanism takes place in the excited state relaxation of the various species. The protonation of the ring nitrogen atom generates a highly planar cationic species which retains its conformation in the relaxed excited state. The very effective quenching of the monocation fluorescence is interpreted by the formation of a non-emissive TICT state.

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