PMID- 17506550
OWN - NLM
STAT- MEDLINE
DCOM- 20070706
LR  - 20121115
IS  - 0020-1669 (Print)
IS  - 0020-1669 (Linking)
VI  - 46
IP  - 12
DP  - 2007 Jun 11
TI  - fac-[Re(CO)3(H2O)3]+ nucleoside monophosphate adducts investigated in aqueous 
      solution by multinuclear NMR spectroscopy.
PG  - 4926-36
AB  - The fac-[Re(CO)3(H2O)3]+ cation, the putative DNA-binding species accounting for 
      the biological activity of related Re(I) complexes, binds reversibly to N7 of 
      6-oxopurine nucleotide monophosphates (NMPs), in contrast to Pt(II) anticancer 
      drugs. A relatively high amount of NMP is needed to convert all of the 
      fac-[Re(CO)3(H2O)3]+ to adducts. The Re/nucleotide 1:1 adduct forms more rapidly 
      and builds up to a higher concentration for guanosine 5'-monophosphate (5'-GMP) 
      and inosine 5'-monophosphate (5'-IMP) than for the respective 3'-monophosphates 
      (3'-GMP and 3'-IMP). These results are attributable to the 5'-positioning of the 
      5'-NMP phosphate group that allows it to approach the metal inner sphere for more 
      favorable cation electrostatic and aqua ligand H-bonding interactions, both in 
      the initial productive ion pair encounter complexes and in the N7-bound 1:1 
      adducts. A higher reactivity of 5'-GMP over 3'-GMP is known for cisplatin. In 
      contrast, more Re/nucleotide 1:2 adduct was formed by 3'-GMP (and 3'-IMP) than by 
      5'-GMP (and 5'-IMP). Because the 3'-phosphate group cannot closely approach the 
      metal inner coordination sphere, the greater stability for the 3'-GMP 1:2 adduct 
      reflects the more favorable G N1H-phosphate interligand GMP-GMP interactions for 
      3'-GMP vs 5'-GMP (G=guanine base derivative). This type of interaction is known 
      for platinum adducts. In 1:2 adducts the bound nucleotides are inequivalent, 
      prompting us to perform mixed 5'-GMP/3'-GMP experiments, leading to the 
      observation of major (M) and minor (m) mixed Re/5'-GMP/3'-GMP 1:1:1 adducts. The 
      order of abundance at equilibrium in a typical experiment was M>bis 
      3'-GMP>m>or=bis 5'-GMP. This stability order was rationalized by invoking the 
      phosphate interactions described above. When methionine and 5'-GMP were allowed 
      to compete for fac-[Re(CO)3(H2O)3]+, the Re/5'-GMP 1:1 adduct was the kinetic 
      product and the S-bound Re/methionine adduct was the thermodynamic product, a 
      result opposite to that typically found for cisplatin.
FAU - Adams, Kristie M
AU  - Adams KM
AD  - Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 
      70803, USA.
FAU - Marzilli, Luigi G
AU  - Marzilli LG
LA  - eng
GR  - GM 29222/GM/NIGMS NIH HHS/United States
PT  - Journal Article
PT  - Research Support, N.I.H., Extramural
DEP - 20070517
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
RN  - 0 (Antineoplastic Agents)
RN  - 0 (Nucleotides)
RN  - 0 (Organometallic Compounds)
RN  - 0 (Solutions)
RN  - 131-99-7 (Inosine Monophosphate)
RN  - 7440-15-5 (Rhenium)
RN  - 85-32-5 (Guanosine Monophosphate)
SB  - IM
MH  - Antineoplastic Agents/chemistry
MH  - Drug Stability
MH  - Guanosine Monophosphate/chemistry
MH  - Inosine Monophosphate/chemistry
MH  - Magnetic Resonance Spectroscopy/*methods
MH  - Nucleotides/*chemistry
MH  - Organometallic Compounds/chemistry
MH  - Rhenium/*chemistry
MH  - Solutions
EDAT- 2007/05/18 09:00
MHDA- 2007/07/07 09:00
CRDT- 2007/05/18 09:00
PHST- 2007/05/18 09:00 [pubmed]
PHST- 2007/07/07 09:00 [medline]
PHST- 2007/05/18 09:00 [entrez]
AID - 10.1021/ic062410f [doi]
PST - ppublish
SO  - Inorg Chem. 2007 Jun 11;46(12):4926-36. doi: 10.1021/ic062410f. Epub 2007 May 17.