PMID- 29227104
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20180102
LR  - 20180102
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 57
IP  - 1
DP  - 2018 Jan 2
TI  - X-ray Absorption Spectroscopy Combined with Time-Dependent Density Functional 
      Theory Elucidates Differential Substitution Pathways of Au(I) and Au(III) with 
      Zinc Fingers.
PG  - 218-230
LID - 10.1021/acs.inorgchem.7b02406 [doi]
AB  - A combination of two elements' (Au, Zn) X-ray absorption spectroscopy (XAS) and 
      time-dependent density functional theory (TD-DFT) allowed the elucidation of 
      differential substitution pathways of Au(I) and Au(III) compounds reacting with 
      biologically relevant zinc fingers (ZnFs). Gold L(3)-edge XAS probed the 
      interaction of gold and the C-terminal Cys(2)HisCys finger of the HIV-1 
      nucleocapsid protein NCp7, and the Cys(2)His(2) human transcription factor Sp1. 
      The use of model compounds helped assign oxidation states and the identity of the 
      gold-bound ligands. The computational studies accurately reproduced the 
      experimental XAS spectra and allowed the proposition of structural models for the 
      interaction products at early time points. The direct electrophilic attack on the 
      ZnF by the highly thiophilic Au(I) resulted in a linear P-Au-Cys coordination 
      sphere after zinc ejection whereas for the Sp1, loss of PEt(3) results in linear 
      Cys-Au-Cys or Cys-Au-His arrangements. Reactions with Au(III) compounds, on the 
      other hand, showed multiple binding modes. Prompt reaction between 
      [AuCl(dien)](2+) and [Au(dien)(DMAP)](3+) with Sp1 showed a partially reduced Au 
      center and a final linear His-Au-His coordination. Differently, in the presence 
      of NCp7, [AuCl(dien)](2+) readily reduces to Au(I) and changes from square-planar 
      to linear geometry with Cys-Au-His coordination, while [Au(dien)(DMAP)](3+) 
      initially maintains its Au(III) oxidation state and square-planar geometry and 
      the same first coordination sphere. The latter is the first observation of a 
      "noncovalent" interaction of a Au(III) complex with a zinc finger and confirms 
      early hypotheses that stabilization of Au(III) occurs with N-donor ligands. 
      Modification of the zinc coordination sphere, suggesting full or partial zinc 
      ejection, is observed in all cases, and for [Au(dien)(DMAP)](3+) this represents 
      a novel mechanism for nucleocapsid inactivation. The combination of XAS and 
      TD-DFT presents the first direct experimental observation that not only compound 
      reactivity, but also ZnF core specificity, can be modulated on the basis of the 
      coordination sphere of Au(III) compounds.
FAU - Abbehausen, Camilla
AU  - Abbehausen C
AUID- ORCID: 0000-0002-8410-2252
AD  - Institute of Chemistry, University of Campinas-UNICAMP , P.O. Box 6154, CEP, 
      13083-970 Campinas, Sao Paulo, Brazil.
FAU - de Paiva, Raphael Enoque Ferraz
AU  - de Paiva REF
AUID- ORCID: 0000-0003-2549-0344
AD  - Institute of Chemistry, University of Campinas-UNICAMP , P.O. Box 6154, CEP, 
      13083-970 Campinas, Sao Paulo, Brazil.
FAU - Bjornsson, Ragnar
AU  - Bjornsson R
AUID- ORCID: 0000-0003-2167-8374
AD  - Science Institute, University of Iceland , Dunhagi 3, IS-107 Reykjavik, Iceland.
FAU - Gomes, Saulo Quintana
AU  - Gomes SQ
AD  - Institute of Chemistry, University of Campinas-UNICAMP , P.O. Box 6154, CEP, 
      13083-970 Campinas, Sao Paulo, Brazil.
FAU - Du, Zhifeng
AU  - Du Z
AD  - Department of Chemistry, Virginia Commonwealth University , 1001 W. Main Street, 
      Richmond, Virginia 23284-2006, United States.
FAU - Corbi, Pedro Paulo
AU  - Corbi PP
AD  - Institute of Chemistry, University of Campinas-UNICAMP , P.O. Box 6154, CEP, 
      13083-970 Campinas, Sao Paulo, Brazil.
FAU - Lima, Frederico Alves
AU  - Lima FA
AD  - Centro Nacional de Pesquisa em Energia e Materiais, Brazilian Synchrotron Light 
      Laboratory-LNLS , CP 6192, 13084-971 Campinas, Sao Paulo, Brazil.
FAU - Farrell, Nicholas
AU  - Farrell N
AUID- ORCID: 0000-0001-7160-7182
AD  - Department of Chemistry, Virginia Commonwealth University , 1001 W. Main Street, 
      Richmond, Virginia 23284-2006, United States.
LA  - eng
PT  - Journal Article
DEP - 20171211
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
EDAT- 2017/12/12 06:00
MHDA- 2017/12/12 06:01
CRDT- 2017/12/12 06:00
PHST- 2017/12/12 06:00 [pubmed]
PHST- 2017/12/12 06:01 [medline]
PHST- 2017/12/12 06:00 [entrez]
AID - 10.1021/acs.inorgchem.7b02406 [doi]
PST - ppublish
SO  - Inorg Chem. 2018 Jan 2;57(1):218-230. doi: 10.1021/acs.inorgchem.7b02406. Epub 
      2017 Dec 11.