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MessagePosté le: Sam 29 Oct - 01:39 (2016)    Sujet du message: Multinuclear Nmr Mason Pdf Download Répondre en citant




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[PubMed]3...2007;20:16231628....Reich....HJ,....Yelm....KE,....Wollowitz....S.....J...Am...Chem...Soc....Consistent....with....the....experiment....in....which....monomeric....molecules....were....employed,....a....resonance....was....observed....in....the....proton....dimension....at....δ....7.90,....which....was....correlated....with....the....15N....that....was....coupled....to....the....13C....(Figures....2A,....B).....1985;107:64946496.30....

AbstractRecently,..a..phenyl..selenyl..modified..thymidine..(2)..was..shown..to..produce..DNA..interstrand..cross-links..(ICLs)..via..two..mechanisms...Wang....H,....Wahi....MS,....Rokita....SE.....Cookies..are..required..to..use..this..site...Previous....kinetic....competition....studies....suggested....that....rotation....about....the....glycosidic....bond....was....rate....limiting....for....cross-linking....via....the....radical.15....For....reaction....via....the....longer-lived....methide....type....intermediate....(4)....the....rate....constant....for....rotation....about....the....glycosidic....bond....is....less....crucial.....2007;46:1275712763....Knowledge...of...the...mechanistic...aspects...of...this...chemistry...will...be...useful...in...developing...applications...of...the...phenyl...selenide...precursor...(2),...as...well...as...in...the...design...of...molecules...with...similar...reactivity.20,21....These...include...controlling...gene...expression...in...mammalian...cells...and...sequence...specific...recognition...of...DNA...at...single...nucleotide...resolution.9,10...The...importance...of...ICLs...continues...to...spur...creative...approaches...for...their...formation.11–14...Recently,...we...discovered...a...process...by...which...the...DNA...radical...(1)...generated...via...formal...hydrogen...atom...abstraction...from...the...thymine...methyl...group...cross-links...with...the...opposing...dA...in...the...duplex...(Scheme...1).15,16...Although...this...transformation...was...originally...detected...using...photolabile...synthetic...radical...precursors...(e.g....Comparable....results....were....obtained....when....8....(1.5....mM)....was....photolyzed....to....produce....1,....although....the....signal....to....noise....ratio....was....not....as....great....due....to....a....lower....cross-link....yield.31....Following....consumption....of....4....or....photolysis....of....2....no....signal....consistent....with....that....of....7....(Scheme....4)....was....detected,....as....evidenced....by....the....absence....of....any....1H....signals....in....the....δ....5.0–6.5....region,....where....the....vinyl....protons....from....the....exocyclic....methylene....group....were....expected....to....resonate.19,21....These....experiments....provide....definitive....evidence....for....5....as....the....primary....cross-link....product....produced....from....the....phenyl....selenide....(2)....under....oxidative....and....radical....conditions.Figure....2NMR....analysis....of....the....reaction....of....8....in....the....presence....of....NaIO4.....Kim..HYH,..Voehler..M,..Harris..TM,..Stone..MP...Stone...MP,...Cho...YJ,...Huang...H,...Kim...HY,...Kozekov...ID,...Kozekova...A,...Wang...H,...Minko...IG,...Lloyd...RS,...Harris...TM,...Rizzo...CJ....

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