Radu Silaghi-Dumitrescu
SMALL MOLECULE
ACTIVATION BY metalloproteins and related systems
Our main research interest is currently in
small molecule activation by biological metal centers, with emphasis on hemes
and hemoproteins, using computational chemistry as well as experimental
methods. Hemes, i.e., complexes of iron with protoporphyrin IX and its
derivatives, have been some of the most studied prosthetic groups in
biochemistry. This has been due to their spectroscopic accessibility, as well
as to their ubiquitous involvement in processes central to life (e.g. energy
transport, energy storage, respiration, defence mechanisms). See here a general
overview of structures and functions for hemes and heme proteins in biology.
Besides hemes, other biological/biomimetic systems of interest for us have been
non-heme iron, copper, and cobalt centers.
Research projects:
Computational:
Experimental:
Participation in projects led elsewhere:
Relevant research
publications:
50. Svistunenko,
Dimitri A.; Reeder, Brandon J.; Wankasi, Mieebi M.; Silaghi-Dumitrescu, Radu; Cooper, Chris E. Rinaldo, Serena;
Cutruzzolà, Francesca; Wilson, Michael T. Interaction
of Aplysia limacina metmyoglobin with
hydrogen peroxide. Dalton
Transactions, (2007), 10.1039/b615770j.
49. Silaghi-Dumitrescu, Radu; Reeder,
Brandon; Nicholls, Peter; Cooper, Chris E.; Wilson, Michael T. Ferryl haem protonation gates peroxidatic
reactivity in globins. Biochemical
Journal, (2007), 10.1042/BJ20061421.
48. Schwartz, Jennifer K.; Liu XF; Albetel AN;
Silaghi-Dumitrescu, Radu, Kurtz, Donald
M, Jr.; Theil, Elizabeth C; Solomon, Edward I; Structure/function
correlations in binuclear non-heme ferrous sites: Specific characterization of
the active sites in m-Ferritin and nitric oxide reductases Abstracts of Papers, 231st ACS National
Meeting, United States, March 26, 2006
(2006), INOR-89
47. Silaghi-Dumitrescu, Radu. Hemes Revisited by Density Functional
Approaches. 2. A Paradigm for Axial Ligation In Hemoproteins. Studia Universitatis Babes-Bolyai, Chemia
(2006), in press.
46. Silaghi-Dumitrescu, Radu. Fe(IV)-Fe(II) electromerism in hemoprotein
complexes: implications for ferryl chemistry. Proc. Rom. Acad. Series B (2006), in press.
45. Silaghi-Dumitrescu, Radu;
Silaghi-Dumitrescu, Ioan; Editorial –
special issue on Computational Inorganic Chemistry. Chemtracts – Inorganic Chemistry (2005), 50,
11-16.
44. Silaghi-Dumitrescu, Radu;
Silaghi-Dumitrescu, Ioan; Computational
Inorganic Chemistry – a useful tool, and more. Chemtracts – Inorganic Chemistry (2005),
684-708.
43. Isaza, Clara E.; Silaghi-Dumitrescu, Radu; Iyer,
Ramesh B.; Kurtz, Donald M. Jr.; Chan, Michael K. Structural Basis
for O2 Sensing by the Hemerythrin-like Domain of a Bacterial Chemotaxis
Protein: Substrate Tunnel and Fluxional N Terminus. Biochemistry, (2006), 45(30), 9023-9031.
42. Dunne, Jacqueline; Caron, Alexis; Menu, Patrick;
Alayash, Abdu I.; Buehler, Paul W.; Wilson, Michael T.; Silaghi-Dumitrescu, Radu; Faivre, Beatrice; Cooper, Chris E. Ascorbate removes key precursors to oxidative
damage by cell free hemoglobin in vitro and in vivo. Biochemical Journal, (2006), 399(3), 513-24.
41. Silaghi-Dumitrescu,
Radu; Copper-containing nitrite
reductase: a DFT study of nitrite and nitric oxide adducts. Journal of Inorganic Biochemistry, (2006),
100(3), 396-402.
40. Silaghi-Dumitrescu,
Radu; Silaghi-Dumitrescu, Ioan; DFT
and the electromerism in complexes of iron with diatomic ligands. Journal of Inorganic Biochemistry, (2006),
100(1), 161-166.
39. Silaghi-Dumitrescu,
Radu; Cooper, Chris E., Transient
species involved in catalytic dioxygen/peroxide activation by hemoproteins:
possible involvement of protonated compound I species.
38. Iyer, Ramesh B.; Silaghi-Dumitrescu, Radu;
Lanzilotta, William N.; Kurtz, Donald M.
Novel non-heme diiron bacterial peroxidases. Abstracts of Papers, 229th ACS National
Meeting, San Diego, CA, United States, March 13-17, 2005 (2005),
INOR-556
37. Iyer, Ramesh,*
Silaghi-Dumitrescu, Radu,* Lanzilotta, William N. Kurtz, Donald M.
Jr. High-resolution
crystal structures of Desulfovibrio vulgaris (Hildenborough) nigerythrin:
facile, redox-dependent iron movement, domain interface variability, and
peroxidase activity in the rubrerythrins
J. Biol. Inorg. Chem. (2005),
10, 407-416. (*authors marked “contributed equally to this work”)
36. Silaghi-Dumitrescu, Radu, Kurtz, Donald M. Jr., Ljungdahl,| Lars
G., Lanzilotta, William N. X-ray
35. Silaghi-Dumitrescu, Radu. A density functional study of
heme-peroxynitrite adducts. J. Mol.
Struct. THEOCHEM, (2005), 722,
233-237.
34. Silaghi-Dumitrescu, Radu. “High-valent” ferryl-oxo complexes: how
“high” are they really? Studia
Universitatis Babes-Bolyai, Chemia (2005),
50, 17-21.
33. Silaghi-Dumitrescu, Radu. Discontinuum between ferrous-superoxo and
ferric-peroxo in heme
32. Silaghi-Dumitrescu, Radu. Nitrile
hydration by the cobalt-containing nitrile hydratase. DFT investigation of the mechanism Revista de Chimie (2005), 56(4), 359-362.
31. Silaghi-Dumitrescu, Radu; Ng, Kim Yong;
Viswanathan, Rathinam, Kurtz, Donald M. Jr. A Flavo-diiron protein from Desulfovibrio
vulgaris with oxidase and nitric oxide reductase activities. Evidence for
an In vivo nitric oxide scavenging function. Biochemistry, (2005), 44(9),
3572-9.
30. Das, Amaresh; Silaghi-Dumitrescu, Radu; Ljungdahl,
Lars G.; Kurtz, Donald M., Jr., Cytochrome bd oxidase, oxidative stress and
dioxygen tolerance of the strictly anaerobic bacterium, Moorella thermoacetica. Journal
of Bacteriology, (2005), 187(6), 2020-2029.
29. Kurtz,
Donald M.; Lanzilotta, William N.; Silaghi-Dumitrescu,
Radu. How microbes detoxify superoxide, hydrogen peroxide, and nitric oxide:
The non-heme iron reductive paradigm.
Abstracts of Papers, 227th ACS National Meeting, Anaheim, CA, United
States, March 28-April 1, 2004
(2004), INOR-418
28. Silaghi-Dumitrescu, Radu. Factors controlling O-O bond cleavage in
ferric-hydroperoxo complexes. Proc.
Rom. Acad. Series B, (2004), 3, 155-163.
27. Silaghi-Dumitrescu, Radu. Bioorganometallic
complexes relevant to the “push effect” in hemoproteins. Proc.
Rom. Acad. Series B, (2004), 3, 149-154.
26. Silaghi-Dumitrescu, Radu. Bonding in
ferric-oxo complexes. Studia
Universitatis Babes-Bolyai, Chemia (2004),
49(2), 235-240.
25. Silaghi-Dumitrescu, Radu; Linkage isomerism in nitrite reduction
by cytochrome cd1 nitrite reductase. Inorganic Chemistry (2004), 43(12),
3715-3718.
24. Silaghi-Dumitrescu, Radu; The nature of the “high-valent” complexes
in the catalytic cycles of hemoproteins.
Journal of Biological Inorganic Chemistry (2004), 9, 471-476.
23. Silaghi-Dumitrescu, Radu; The nitric
oxide adducts of cytochrome cd1 nitrite reductase. Revista de Chimie (2004), 55, 496-498.
22. Silaghi-Dumitrescu, Radu; On the performance of the PM3
semiempirical method with heme complexes relevant to dioxygen and peroxide
activation. Revista de Chimie
(2004), 55, 304-307.
21. Silaghi-Dumitrescu, Radu; Heme ferrous-hydroperoxo complexes: some
theoretical considerations.
Archives of Biochemistry and Biophysics (2004), 424, 137-140.
20. Silaghi-Dumitrescu, Radu;
Silaghi-Dumitrescu, Ioan. Hemes revisited by density functional
approaches. 1. The axial ligand and the dioxygen-peroxo chemistry.
Revue Roumaine de Chimie (2004), 3-4, 257-268.
19. Silaghi-Dumitrescu, Radu;
Amthor, Stephan; Paizs, Csaba; Majdik, Cornelia; Tosa, Monica; Moldovan, Paula;
Sas, Angela; Tamas, Liana; Irimie,
Florin-Dan. Horseradish
peroxidase - catalyzed oxidation of water - insoluble phenothiazines.
Studia Universitatis Babes-Bolyai, Chemia (2003), 48, 165.
18. Kurtz,
Donald M., Jr.; Emerson, Joseph P; Silaghi-Dumitrescu, Radu; Kung, Irene;
Das, Amaresh; Ljungdahl, Lars; How
microbes detoxify superoxide, hydrogen peroxide and nitric oxide. The non-heme
iron reductive paradigm Journal of Inorganic Biochemistry
(2003), 96, 69.
17. Kurtz,
Donald M., Jr.; Silaghi-Dumitrescu, Radu; Das, Amaresh; Jameson, Guy; Ljungdahl,
Lars; Huynh, Boi Hanh A non-heme iron nitric oxide reductase that
protects against nitrosative stress in acetogenic bacteria
Journal of Inorganic Biochemistry
(2003), 96, 174.
16. Silaghi-Dumitrescu, Radu; Kurtz, Donald
M., Jr. High-resolution crystal structures and spectroscopy of native and
Compound I Cytochrome c Peroxidase Chemtracts
– Inorganic Chemistry (2003), 16, 722-728 – Commentary.
15. Silaghi-Dumitrescu, Radu; Irimie, Florin-Dan; Paizs, Csaba; Majdik,
Cornelia; Tosa, Monica; Moldovan, Paula; Sas, Angela; Tamas, Liana. Horseradish peroxidase catalyzed oxidation
of some benzyl-type alcohols.
Studia Universitatis Babes-Bolyai, Chemia (2003),
48, 177-182.
14. Silaghi-Dumitrescu, Radu; Kurtz, Donald
M., Jr. Tuning the electronic
structure of octahedral iron complexes {FeL(X)} (L =
1-alkyl-4,7-bis(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane, X = Cl,
CH3O, CN, NO): the S = 1/2 - S = 3/2 spin equilibrium of {FeLPr(NO)}. Chemtracts – Inorganic Chemistry (2003),
16(8), 468-473 – Commentary.
13. Silaghi-Dumitrescu, Radu. Nitric oxide reduction by heme-thiolate
enzymes (P450nor): A reevaluation of the mechanism. European Journal of Inorganic Chemistry
(2003), (6), 1048-1052.
12. Silaghi-Dumitrescu, Radu; Coulter, Eric
D.; Das, Amaresh; Ljungdahl, Lars G.; Jameson, Guy N. L.; Huynh, Boi Hanh;
Kurtz, Donald M., Jr. A flavodiiron
protein and high molecular weight rubredoxin from Moorella thermoacetica with nitric oxide reductase activity. Biochemistry (2003), 42(10), 2806-2815.
11. Silaghi-Dumitrescu, Radu;
Silaghi-Dumitrescu, Ioan; Coulter, Eric D.; Kurtz, Donald M., Jr. Computational study of the non-heme iron
active site in superoxide reductase and its reaction with superoxide. Inorganic Chemistry (2003), 42(2), 446-456.
10.Silaghi-Dumitrescu,
Luminita; Silaghi-Dumitrescu, Radu;
Blake, Alexander J; Cooke, Paul A.; Sowerby, D. Bryan, Chlorination of (AsPh2)2O:
Supramolecular structure of dihydroxodiphenylarsonium hydrogensulfate
9. Irimie,
Florin-Dan; Paizs, Csaba; Majdik, Cornelia; Tosa, Monica; Misca, Radu; Silaghi-Dumitrescu, Radu. Bioorganic synthesis of some
(5-benzothiazol-2-yl-furan-2-yl)-methanols in cell catalysis using
Saccharomyces cerevisiae.
Heterocyclic Communications (2002), 8(5), 489-492.
8. Silaghi-Dumitrescu, Radu;
Silaghi-Dumitrescu, Ioan; Coulter, Eric D.; Emerson, Joseph P; Kurtz, Donald
M., Jr. Computational study of the
non-heme iron active site in superoxide reductase and its reaction with superoxide. Journal of Inorganic Biochemistry (2001),
86(1), 432.
7.
Silaghi-Dumitrescu, Luminita; Silaghi-Dumitrescu, Ioan; Silaghi-Dumitrescu, Radu; Haiduc, Ionel; Blake, Alexander J.;
Sowerby, D. Bryan. Bromination of
(AsPh2)2O: the structure of tribromo-diphenylarsenic(V). Revista de la Sociedad Quimica de Mexico
(2000), 44(2), 134-138.
6. Irimie,
Florin-Dan; Paisz, Csaba; Joo, Francisc; Silaghi-Dumitrescu,
Radu; Tosa, Monica; Majdik, Cornelia.
Biocatalytical reduction of some 5-(carboxyethyl-phenyl)-furyl-2-carboxaldehydes
mediated by baker's yeast.
Progress in Catalysis (1999), 8(2), 70-73.
5. Irimie,
Florin-Dan; Paizs, Csaba; Joo, Francisc; Silaghi-Dumitrescu,
Radu; Tosa, Monica; Majdik, Cornelia.
Bioorganic reduction of some 5-phenyl-furyl-2-carboxaldehydes
mediated by bakers' yeast.
Roumanian Biotechnological Letters (1999), 4(1), 71-74.
4. Irimie,
Florin-Dan; Paizs, Csaba; Silaghi-Dumitrescu,
Radu; Damian, G.; Majdik, Cornelia; Tosa, Monica. Mass spectrometry of some new 2-hydroxymethyl-5-phenyl-furans
obtained through cell catalysis.
Studia Universitatis Babes-Bolyai, Chemia (1998), 43(1-2),
173-177.
3. Majdik,
Cornelia; Irimie, Florin-Dan; Paizs, Csaba; Silaghi-Dumitrescu, Radu; Joo, Francisc; Tosa, Monica. Synthesis and reduction of some
nitro-benzofurans. Studia
Universitatis Babes-Bolyai, Chemia (1998), 43(1-2), 115-120.
2. Irimie,
Florin-Dan; Paizs, Csaba; Chender, C.; Joo, Francisc; Silaghi-Dumitrescu, Radu; Majdik, Cornelia; Tosa, Monica. Furyl-benzothiazoles. Synthesis and
reactivity. Studia Universitatis
Babes-Bolyai, Chemia (1998), 43(1-2), 109-114.
1. Silaghi-Dumitrescu, Radu; Paisz, Csaba;
Irimie, Florin-Dan; Joo, Francisc; Majdik, Cornelia; Tosa, Monica. Biotransformation of nitroso naphthols
bioassisted by Baker's yeast.
Studia Universitatis Babes-Bolyai, Chemia (1998), 43(1-2), 83-90.
Book:
Radu Silaghi-Dumitrescu, Horseradish
peroxidase – a versatile catalyst
2006, Research
Publication on the World
Wide Web:
HRP: A Summary of its
Structure, Mechanism and Substrate Diversity - International Working Group on Plant Peroxidases
(IWGPP)
http://www.unige.ch/LABPV/perox.html
Links:
Romanian
institutions:
Romanian
chemistry/biochemistry journals
Studia Universitatis
Babes-Bolyai
Proceedings of the Romanian Academy