Matches in SemOpenAlex for { <https://semopenalex.org/work/W2057193635> ?p ?o ?g. }
- W2057193635 endingPage "12490" @default.
- W2057193635 startingPage "12480" @default.
- W2057193635 abstract "Reactions of the anticancer active compound cis-[Rh2(DTolF)2(CH3CN)6](BF4)2 with 9-ethyladenine (9-EtAdeH) or the dinucleotide d(ApA) proceed with bridging adenine bases in the rare imino form (A*), spanning the Rh-Rh bond at equatorial positions via N7/N6. The inflection points for the pH-dependent H2 and H8 NMR resonance curves of cis-[Rh2(DTolF)2(9-EtAdeH)2](BF4)2 correspond to N1H deprotonation of the metal-stabilized rare imino tautomer, which takes place at pKa approximately 7.5 in CD3CN-d3, a considerably reduced value as compared to that of the imino form of 9-EtAdeH. Similarly, coordination of the metal atoms to the N7/N6 adenine sites in Rh2(DTolF)2{d(ApA)} induces formation of the rare imino tautomer of the bases with a concomitant substantial decrease in the basicity of the N1H sites (pKa approximately 7.0 in CD3CN-d3), as compared to the imino form of the free dinucleotide. The presence of the adenine bases in the rare imino form, due to bidentate metalation of the N6/N7 sites, is further corroborated by DQF-COSY H2/N1H and ROE N1H/N6H cross-peaks in the 2D NMR spectra of Rh2(DTolF)2{d(ApA)} in CD3CN-d3 at -38 degrees C. Due to the N7/N6 bridging mode of the adenine bases in Rh2(DTolF)2{d(ApA)}, only the anti orientation of the imino tautomer is possible. The imino form A* of adenine in DNA may result in AT-->CG transversions or AT-->GC transitions, which can eventually lead to lethal mutations. The HH arrangement of the bases in Rh2(DTolF)2{d(ApA)} is indicated by the H8/H8 NOE cross-peaks in the 2D ROESY NMR spectrum, whereas the formamidinate bridging groups dictate the presence of one right-handed conformer HH1R in solution. Complete characterization of Rh2(DTolF)2{d(ApA)} by 2D NMR spectroscopy and molecular modeling supports the presence of the HH1R conformer, anti orientation of both sugar residues about the glycosyl bonds, and N-type conformation for the 5'-A base." @default.
- W2057193635 created "2016-06-24" @default.
- W2057193635 creator A5005670674 @default.
- W2057193635 creator A5056201103 @default.
- W2057193635 date "2007-09-21" @default.
- W2057193635 modified "2023-10-02" @default.
- W2057193635 title "Unprecedented Head-to-Head Right-Handed Cross-Links between the Antitumor Bis(μ-<i>N,N</i>‘-di-<i>p</i>-tolylformamidinate) Dirhodium(II,II) Core and the Dinucleotide d(ApA) with the Adenine Bases in the Rare Imino Form" @default.
- W2057193635 cites W1792004940 @default.
- W2057193635 cites W1965074632 @default.
- W2057193635 cites W1965082632 @default.
- W2057193635 cites W1965564256 @default.
- W2057193635 cites W1972917298 @default.
- W2057193635 cites W1973880326 @default.
- W2057193635 cites W1974693247 @default.
- W2057193635 cites W1975253000 @default.
- W2057193635 cites W1975851628 @default.
- W2057193635 cites W1978397881 @default.
- W2057193635 cites W1979124023 @default.
- W2057193635 cites W1980095889 @default.
- W2057193635 cites W1980725587 @default.
- W2057193635 cites W1981388235 @default.
- W2057193635 cites W1981863209 @default.
- W2057193635 cites W1982233717 @default.
- W2057193635 cites W1983846414 @default.
- W2057193635 cites W1985463059 @default.
- W2057193635 cites W1987465704 @default.
- W2057193635 cites W1989163046 @default.
- W2057193635 cites W1990889686 @default.
- W2057193635 cites W1991256096 @default.
- W2057193635 cites W1997161530 @default.
- W2057193635 cites W1997598566 @default.
- W2057193635 cites W2001508352 @default.
- W2057193635 cites W2002588343 @default.
- W2057193635 cites W2003988120 @default.
- W2057193635 cites W2004288169 @default.
- W2057193635 cites W2009180778 @default.
- W2057193635 cites W2010715860 @default.
- W2057193635 cites W2012872666 @default.
- W2057193635 cites W2012999349 @default.
- W2057193635 cites W2014814198 @default.
- W2057193635 cites W2015878863 @default.
- W2057193635 cites W2018522395 @default.
- W2057193635 cites W2019913425 @default.
- W2057193635 cites W2021527389 @default.
- W2057193635 cites W2023562894 @default.
- W2057193635 cites W2023653072 @default.
- W2057193635 cites W2030634561 @default.
- W2057193635 cites W2030971064 @default.
- W2057193635 cites W2032442944 @default.
- W2057193635 cites W2032925684 @default.
- W2057193635 cites W2034175316 @default.
- W2057193635 cites W2039740399 @default.
- W2057193635 cites W2045180147 @default.
- W2057193635 cites W2046159980 @default.
- W2057193635 cites W2048146449 @default.
- W2057193635 cites W2049435597 @default.
- W2057193635 cites W2051941062 @default.
- W2057193635 cites W2052383143 @default.
- W2057193635 cites W2052831849 @default.
- W2057193635 cites W2057321488 @default.
- W2057193635 cites W2058946097 @default.
- W2057193635 cites W2068198075 @default.
- W2057193635 cites W2070953803 @default.
- W2057193635 cites W2071936543 @default.
- W2057193635 cites W2073319135 @default.
- W2057193635 cites W2080354279 @default.
- W2057193635 cites W2083044219 @default.
- W2057193635 cites W2084722290 @default.
- W2057193635 cites W2088764843 @default.
- W2057193635 cites W2089570339 @default.
- W2057193635 cites W2093282189 @default.
- W2057193635 cites W2093765227 @default.
- W2057193635 cites W2093914499 @default.
- W2057193635 cites W2095441700 @default.
- W2057193635 cites W2096847256 @default.
- W2057193635 cites W2106512121 @default.
- W2057193635 cites W2114770190 @default.
- W2057193635 cites W2120115869 @default.
- W2057193635 cites W2121773722 @default.
- W2057193635 cites W2123950781 @default.
- W2057193635 cites W2125639615 @default.
- W2057193635 cites W2126720780 @default.
- W2057193635 cites W2132997348 @default.
- W2057193635 cites W2135879829 @default.
- W2057193635 cites W2142590750 @default.
- W2057193635 cites W2149940432 @default.
- W2057193635 cites W2154967383 @default.
- W2057193635 cites W2167301623 @default.
- W2057193635 cites W2169448795 @default.
- W2057193635 cites W2242788071 @default.
- W2057193635 cites W2414129550 @default.
- W2057193635 cites W271398347 @default.
- W2057193635 cites W280694366 @default.
- W2057193635 cites W2949845980 @default.
- W2057193635 cites W2950585844 @default.
- W2057193635 cites W2951963344 @default.
- W2057193635 cites W47267634 @default.
- W2057193635 doi "https://doi.org/10.1021/ja073422i" @default.