Sason Shaik

Summary

Affiliation: The Hebrew University
Country: Israel

Publications

  1. ncbi request reprint A valence bond study of the dioxygen molecule
    Peifeng Su
    Department of Chemistry, State Key Laboratory of Physical Chemistry of Solid Surfaces, Center for Theoretical Chemistry, Xiamen University, Xiamen 361005, People s Republic of China
    J Comput Chem 28:185-97. 2007
  2. ncbi request reprint A tutorial for understanding chemical reactivity through the valence bond approach
    Dandamudi Usharani
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904, Jerusalem, Israel
    Chem Soc Rev 43:4968-88. 2014
  3. doi request reprint One molecule, two atoms, three views, four bonds?
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, 91904, Jerusalem Israel
    Angew Chem Int Ed Engl 52:3020-33. 2013
  4. ncbi request reprint Quadruple bonding in C2 and analogous eight-valence electron species
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, 91904, Jerusalem, Israel
    Nat Chem 4:195-200. 2012
  5. ncbi request reprint The valence bond way: reactivity patterns of cytochrome P450 enzymes and synthetic analogs
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    Acc Chem Res 43:1154-65. 2010
  6. ncbi request reprint One oxidant, many pathways: a theoretical perspective of monooxygenation mechanisms by cytochrome P450 enzymes
    Sason Shaik
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904 Jerusalem, Israel
    J Biol Inorg Chem 9:661-8. 2004
  7. ncbi request reprint Valence bond all the way: from the degenerate H-exchange to cytochrome P450
    Sason Shaik
    The Institute of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University, 91904, Jerusalem, Israel
    Phys Chem Chem Phys 12:8706-20. 2010
  8. ncbi request reprint Theoretical perspective on the structure and mechanism of cytochrome P450 enzymes
    Sason Shaik
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Israel
    Chem Rev 105:2279-328. 2005
  9. ncbi request reprint A valence bond modeling of trends in hydrogen abstraction barriers and transition states of hydroxylation reactions catalyzed by cytochrome P450 enzymes
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 130:10128-40. 2008
  10. doi request reprint Lessons on O2 and NO bonding to heme from ab initio multireference/multiconfiguration and DFT calculations
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904, Jerusalem, Israel
    J Biol Inorg Chem 16:841-55. 2011

Collaborators

Detail Information

Publications90

  1. ncbi request reprint A valence bond study of the dioxygen molecule
    Peifeng Su
    Department of Chemistry, State Key Laboratory of Physical Chemistry of Solid Surfaces, Center for Theoretical Chemistry, Xiamen University, Xiamen 361005, People s Republic of China
    J Comput Chem 28:185-97. 2007
    ....
  2. ncbi request reprint A tutorial for understanding chemical reactivity through the valence bond approach
    Dandamudi Usharani
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904, Jerusalem, Israel
    Chem Soc Rev 43:4968-88. 2014
    ..The tutorial projects the unity of reactivity treatments, following Coulson's dictum "give me insight, not numbers", albeit with its modern twist: giving numbers and insight. ..
  3. doi request reprint One molecule, two atoms, three views, four bonds?
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, 91904, Jerusalem Israel
    Angew Chem Int Ed Engl 52:3020-33. 2013
    ..Join the three authors in their lively debate, light a candle, as Faraday did, and see the excited states of C !..
  4. ncbi request reprint Quadruple bonding in C2 and analogous eight-valence electron species
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, 91904, Jerusalem, Israel
    Nat Chem 4:195-200. 2012
    ..In contrast, the analogues of C(2) that contain higher-row elements, such as Si(2) and Ge(2), exhibit only double bonding...
  5. ncbi request reprint The valence bond way: reactivity patterns of cytochrome P450 enzymes and synthetic analogs
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    Acc Chem Res 43:1154-65. 2010
    ..The VB diagram model leads to a unified understanding of complex bioinorganic transformations, creates order in the data, and provides an important framework for making useful predictions...
  6. ncbi request reprint One oxidant, many pathways: a theoretical perspective of monooxygenation mechanisms by cytochrome P450 enzymes
    Sason Shaik
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904 Jerusalem, Israel
    J Biol Inorg Chem 9:661-8. 2004
    ..If and when Compound I is absent, P450 oxidation will logically proceed by another form, but this has to be more reactive than ferric(III)-hydroperoxide. Theoretical studies are conducted to pinpoint such an oxidant for P450...
  7. ncbi request reprint Valence bond all the way: from the degenerate H-exchange to cytochrome P450
    Sason Shaik
    The Institute of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University, 91904, Jerusalem, Israel
    Phys Chem Chem Phys 12:8706-20. 2010
    ..Phys. Org. Chem. 1985, 15, 197; Angew. Chem., Int. Ed., 1999, 38, 586)...
  8. ncbi request reprint Theoretical perspective on the structure and mechanism of cytochrome P450 enzymes
    Sason Shaik
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Israel
    Chem Rev 105:2279-328. 2005
  9. ncbi request reprint A valence bond modeling of trends in hydrogen abstraction barriers and transition states of hydroxylation reactions catalyzed by cytochrome P450 enzymes
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 130:10128-40. 2008
    ..This treatment can be generalized to the reactivity patterns of nonheme systems and synthetic iron-oxo porphyrin reagents...
  10. doi request reprint Lessons on O2 and NO bonding to heme from ab initio multireference/multiconfiguration and DFT calculations
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904, Jerusalem, Israel
    J Biol Inorg Chem 16:841-55. 2011
    ..The insight provided by "reading" the VB content of the MC wave functions highlights the potential of this approach as a general paradigm in future computational bioinorganic chemistry. A great deal of insight lies in this road...
  11. doi request reprint Exchange-enhanced reactivity in bond activation by metal-oxo enzymes and synthetic reagents
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    Nat Chem 3:19-27. 2011
    ..We discuss the interplay between orbital- and exchange-controlled principles, and how this depends on the identity of the transition metal, its oxidation number and its coordination sphere...
  12. doi request reprint Charge-shift bonding and its manifestations in chemistry
    Sason Shaik
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904, Jerusalem, Israel
    Nat Chem 1:443-9. 2009
    ..1.1]propellane). Here, we discuss experimental manifestations of CS bonding in chemistry, and outline new directions demonstrating the portability of the new concept...
  13. ncbi request reprint Reactivity patterns of cytochrome P450 enzymes: multifunctionality of the active species, and the two states-two oxidants conundrum
    Sason Shaik
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram, 91904 Jerusalem, Israel
    Nat Prod Rep 24:533-52. 2007
  14. ncbi request reprint Reactivity of high-valent iron-oxo species in enzymes and synthetic reagents: a tale of many states
    Sason Shaik
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    Acc Chem Res 40:532-42. 2007
    ..Experimental trends that demonstrate TSR and MSR are discussed. Diagnostic mechanistic probes are proposed for the TSR/MSR scenario, based on kinetic isotope effect, stereochemical studies, and magnetic- and electric-field effects...
  15. ncbi request reprint Sulfoxidation mechanisms catalyzed by cytochrome P450 and horseradish peroxidase models: spin selection induced by the ligand
    Devesh Kumar
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    Biochemistry 44:8148-58. 2005
    ..S., Rock, D. A., Rock, D. A., Jones, J. P. (2004) J. Am. Chem. Soc. 126, 8868-8869]. Theory shows that intrinsically, HRP should be as reactive as P450 toward sulfoxidation...
  16. doi request reprint Compound I in heme thiolate enzymes: a comparative QM/MM study
    Kyung Bin Cho
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Phys Chem A 112:13128-38. 2008
    ..These results are discussed in the broader context of recent findings of Cpd I species that exhibit large variations in the electronic structure due to the presence of the substrate...
  17. ncbi request reprint New features in the catalytic cycle of cytochrome P450 during the formation of compound I from compound 0
    Devesh Kumar
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Phys Chem B 109:19946-51. 2005
    ..The paper also addresses the essential role of Thr(252) as a hydrogen-bond acceptor (in accord with mutation studies of the OH group to OMe)...
  18. ncbi request reprint Two-state reactivity in alkane hydroxylation by non-heme iron-oxo complexes
    Hajime Hirao
    Department of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 128:8590-606. 2006
    ..c) In situations where the two surfaces contribute to the rate, one expects intermediate KIEs and radical scrambling patterns that reflect the two processes. (d) Solvent effects on these reactions are expected to be very large...
  19. ncbi request reprint Computer-generated high-valent iron--oxo and manganese--oxo species with polyoxometalate ligands: how do they compare with the iron--oxo active species of heme enzymes?
    Samuël P de Visser
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904 Jerusalem, Israel
    Angew Chem Int Ed Engl 43:5661-5. 2004
  20. ncbi request reprint Effects of substrate, protein environment, and proximal ligand mutation on compound I and compound 0 of chloroperoxidase
    Wenzhen Lai
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Phys Chem A 113:11763-71. 2009
    ..This surprising finding shows that the polar CPO pocket applies a leveling effect that stabilizes the anionic forms of the proximal ligands (CysS(-) and CysSe(-)). This in turn means that the Se-Cpd I of the mutant CPO is observable...
  21. ncbi request reprint Two-state reactivity mechanisms of hydroxylation and epoxidation by cytochrome P-450 revealed by theory
    Sason Shaik
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904 Jerusalem, Israel
    Curr Opin Chem Biol 6:556-67. 2002
    ..In both states, bond activation proceeds in a manner akin to the rebound mechanism, but the LS mechanism is effectively concerted, whereas the HS is stepwise with incursion of radical intermediates...
  22. ncbi request reprint An efficient proton-coupled electron-transfer process during oxidation of ferulic acid by horseradish peroxidase: coming full cycle
    Etienne Derat
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Am Chem Soc 128:13940-9. 2006
    ..M., Smith, K. M., Guilard, R., Eds.; Academic Press: New York, 2000; Vol. 4, pp 189). In view of the results, the possibility of manipulating substrate oxidation by magnetic fields is an intriguing possibility...
  23. ncbi request reprint Two states and two more in the mechanisms of hydroxylation and epoxidation by cytochrome P450
    Hajime Hirao
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 127:13007-18. 2005
    ....
  24. ncbi request reprint What factors affect the regioselectivity of oxidation by cytochrome p450? A DFT study of allylic hydroxylation and double bond epoxidation in a model reaction
    Sam P de Visser
    Department of Organic Chemistry, The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 124:11809-26. 2002
    ..The model is used to discuss the computed results and to relate them to experimental findings...
  25. ncbi request reprint Is the ruthenium analogue of compound I of cytochrome p450 an efficient oxidant? A theoretical investigation of the methane hydroxylation reaction
    Pankaz K Sharma
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 125:2291-300. 2003
    ..As such, the ruthenium-oxo species is predicted to be a more robust catalyst than its iron-oxo analogue...
  26. doi request reprint Theoretical and experimental studies of the conversion of chromopyrrolic acid to an antitumor derivative by cytochrome P450 StaP: the catalytic role of water molecules
    Yong Wang
    The Institute of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Am Chem Soc 131:6748-62. 2009
    ..This highlights the role of water molecules as biological catalysts that transform a P450 to a peroxidase-type (Derat, E.; Shaik, S. J. Am. Chem. Soc. 2006, 128, 13940-13949)...
  27. ncbi request reprint NR transfer reactivity of azo-compound I of P450. How does the nitrogen substituent tune the reactivity of the species toward C-H and C=C activation?
    Yohann Moreau
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Phys Chem B 111:10288-99. 2007
    ..Finally, the study predicts (i) that the reactions of RN-Cpd I will be less stereospecific than those of O-Cpd I and (ii) that aziridination will be more stereoselective than amidation...
  28. doi request reprint Quantum mechanical/molecular mechanical study of mechanisms of heme degradation by the enzyme heme oxygenase: the strategic function of the water cluster
    Hui Chen
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Am Chem Soc 130:1953-65. 2008
    ..R. Acc. Chem. Res. 1998, 31, 543). Differences/similarities with P450 and HRP are discussed...
  29. ncbi request reprint Porphyrin traps its terminator! Concerted and stepwise porphyrin degradation mechanisms induced by heme-oxygenase and cytochrome p450
    Pankaz K Sharma
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    Angew Chem Int Ed Engl 43:1129-32. 2004
  30. ncbi request reprint Theory favors a stepwise mechanism of porphyrin degradation by a ferric hydroperoxide model of the active species of heme oxygenase
    Devesh Kumar
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem 91904, Israel
    J Am Chem Soc 127:8204-13. 2005
    ..95-0.98), but much less so than the experimental value (0.7). Possible reasons for this quantitative difference are discussed. Some probes are suggested that may enable experiment to distinguish the stepwise from the concerted mechanism...
  31. ncbi request reprint A predictive pattern of computed barriers for C-h hydroxylation by compound I of cytochrome p450
    Sam P de Visser
    Department of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 126:8362-3. 2004
    ..This facility is demonstrated be estimating the barrier of camphor hydroxylation by P450cam...
  32. pmc Dichotomous hydrogen atom transfer vs proton-coupled electron transfer during activation of X-H bonds (X = C, N, O) by nonheme iron-oxo complexes of variable basicity
    Dandamudi Usharani
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 135:17090-104. 2013
    ..A valence bond model is used to link the observed results with the basicity/acidity of the reactants. ..
  33. ncbi request reprint Gauging the relative oxidative powers of compound I, ferric-hydroperoxide, and the ferric-hydrogen peroxide species of cytochrome P450 toward C-H hydroxylation of a radical clock substrate
    Etienne Derat
    Department of Organic Chemistry, The Hebrew University of Jerusalem, Israel
    J Am Chem Soc 128:473-84. 2006
    ..Typically both Cpd 0 and Fe(H(2)O(2)) will lead to a [2/3] ratio < 1, while Cpd I will lead to ratios > 1. In addition, the product isotope effect (KIE(2)/KIE(3) not equal 1) is expected from the reactivity of Cpd I...
  34. doi request reprint What kinds of ferryl species exist for compound II of chloroperoxidase? A dialog of theory with experiment
    Wenzhen Lai
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Phys Chem B 113:7912-7. 2009
    ..In addition, since 3c possesses an additional proton, its identity can be revealed by pH-dependent yield. All in all, the present paper shows that QM/MM calculations can conduct a useful dialogue with experiment in this complex field...
  35. ncbi request reprint Quantum mechanical/molecular mechanical study on the mechanisms of compound I formation in the catalytic cycle of chloroperoxidase: an overview on heme enzymes
    Hui Chen
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel
    J Phys Chem B 112:9490-500. 2008
    ..By contrast, the absence of PCET in HO, along with the robust water cluster, prefers a homolytic cleavage mechanism...
  36. ncbi request reprint Two-state reactivity, electromerism, tautomerism, and "surprise" isomers in the formation of compound II of the enzyme horseradish peroxidase from the principal species, compound I
    Etienne Derat
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Am Chem Soc 128:8185-98. 2006
    ..Our suggested multi-state reactivity scheme provides a paradigm for Compound II species. The calculated Mössbauer parameters may be helpful toward eventual characterization of these missing isomers of Compound II...
  37. ncbi request reprint Radical clock substrates, their C-H hydroxylation mechanism by cytochrome P450, and other reactivity patterns: what does theory reveal about the clocks' behavior?
    Devesh Kumar
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 126:1907-20. 2004
    ....
  38. ncbi request reprint Compound I of nitric oxide synthase: the active site protonation state
    Kyung Bin Cho
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 129:3182-8. 2007
    ..The Mössbauer parameters are calculated and may serve as experimental probes in attempts to characterize NOS Cpd I...
  39. ncbi request reprint On the identity and reactivity patterns of the "second oxidant" of the T252A mutant of cytochrome P450cam in the oxidation of 5-methylenenylcamphor
    Hajime Hirao
    Department of Chemistry and the Lise Meitner Minerva Center for Computational, Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Inorg Biochem 100:2054-68. 2006
    ..If this product can be found in T252A P450(cam) or in similar mutants of other P450 isozymes, this will constitute a more definitive proof for the action of Cpd 0 in P450 enzymes...
  40. ncbi request reprint The intrinsic axial ligand effect on propene oxidation by horseradish peroxidase versus cytochrome P450 enzymes
    Devesh Kumar
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Israel
    J Biol Inorg Chem 10:181-9. 2005
    ..In the enzyme, HRP is much less reactive than cytochrome P450, presumably because HRP reactivity is limited by the access of the substrate to compound I...
  41. ncbi request reprint In silico design of a mutant of cytochrome P450 containing selenocysteine
    Shimrit Cohen
    Department of Organic Chemistry, The Hebrew University, Jerusalem, Israel
    J Am Chem Soc 128:2649-53. 2006
    ..Chem. Rev. 2005, 105, 2253-2277). Spectral features of Se-Cpd I were calculated and may assist such eventual characterization. The observation of Se-Cpd I will resolve the major puzzle in the catalytic cycle of a key enzyme in nature...
  42. ncbi request reprint How does product isotope effect prove the operation of a two-state "rebound" mechanism in C-H hydroxylation by cytochrome P450?
    Devesh Kumar
    Department of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 125:13024-5. 2003
    ..This match between experiment and theory makes a strong case that the reaction occurs via TSR mechanism...
  43. ncbi request reprint Proton-shuffle mechanism of O-O activation for formation of a high-valent oxo-iron species of bleomycin
    Devesh Kumar
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem 91904, Israel
    J Am Chem Soc 128:16148-58. 2006
    ..It suggests that the high-valence Cpd I species of BLM participates in the DNA cleavage. This is an alternative mechanistic hypothesis to the exclusive reactivity scenario based on ABLM (FeIII-OOH)...
  44. ncbi request reprint Theoretical investigation of C--H hydroxylation by (N4Py)Fe(IV)=O(2+): an oxidant more powerful than P450?
    Devesh Kumar
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 127:8026-7. 2005
    ..This nonheme iron oxidant is predicted to exhibit stereoselective reactions, strong solvent effect, and involve multistate reactivity with spin-state crossing...
  45. doi request reprint A two-state reactivity rationale for counterintuitive axial ligand effects on the C-H activation reactivity of nonheme FeIV=O oxidants
    Hajime Hirao
    Department of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    Chemistry 14:1740-56. 2008
    ..The calculated barriers predict the dichotomic experimental trends and the counterintuitive behavior of the H-abstraction series. The TSR approaches make a variety of testable predictions...
  46. doi request reprint Can ferric-superoxide act as a potential oxidant in P450(cam)? QM/MM investigation of hydroxylation, epoxidation, and sulfoxidation
    Wenzhen Lai
    Institute of Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 133:5444-52. 2011
    ..Other options for nascent superoxo reactivity in P450 are discussed...
  47. doi request reprint First half-reaction mechanism of nitric oxide synthase: the role of proton and oxygen coupled electron transfer in the reaction by quantum mechanics/molecular mechanics
    Kyung Bin Cho
    Institute of Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Phys Chem B 113:336-46. 2009
    ..Alternative mechanistic hypotheses are tested and excluded, and a new mechanism for the NOS second half-reaction is proposed...
  48. doi request reprint Enzymatic ring-opening mechanism of verdoheme by the heme oxygenase: a combined X-ray crystallography and QM/MM study
    Wenzhen Lai
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 132:12960-70. 2010
    ....
  49. ncbi request reprint Brain chemistry: how does P450 catalyze the O-demethylation reaction of 5-methoxytryptamine to yield serotonin?
    Patric Schyman
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91940 Jerusalem, Israel
    J Phys Chem B 114:7078-89. 2010
    ..The study further shows that the H-abstraction follows two-state reactivity (TSR), whereas the rebound path may involve more states due to the appearance of both Fe(IV) and Fe(III) electromers during the reaction of 5-MTH(+)...
  50. ncbi request reprint Oxygen economy of cytochrome P450: what is the origin of the mixed functionality as a dehydrogenase-oxidase enzyme compared with its normal function?
    Devesh Kumar
    Department of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Israel
    J Am Chem Soc 126:5072-3. 2004
    ....
  51. ncbi request reprint Electron transfer activation of chromopyrrolic acid by cytochrome p450 en route to the formation of an antitumor indolocarbazole derivative: theory supports experiment
    Yong Wang
    The Institute of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 130:7170-1. 2008
    ..The electron transfer is enabled by His250, the presence of carboxylate groups in CPA, and by the H-bonding network that tunes the energetic of the process. Theory supports experiment but reveals some novel aspects of this unusual P450...
  52. ncbi request reprint Nature of the Fe-O2 bonding in oxy-myoglobin: effect of the protein
    Hui Chen
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Am Chem Soc 130:14778-90. 2008
    ..The VB model is generalized, showing how the protein or the axial ligand of the oxyheme complex can determine the nature of its bonding in terms of the blend of the three bonding models: Weiss, Pauling, and McClure-Goddard...
  53. ncbi request reprint Multistate reactivity in styrene epoxidation by compound I of cytochrome p450: mechanisms of products and side products formation
    Devesh Kumar
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    Chemistry 11:2825-35. 2005
    ..This resembles the internally mediated NIH-shift observed during benzene hydroxylation...
  54. ncbi request reprint Active species of horseradish peroxidase (HRP) and cytochrome P450: two electronic chameleons
    Sam P de Visser
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 125:15779-88. 2003
    ..A comparative discussion of Cpd I species follows for the enzymes HRP, CcP, APX, CAT (catalase), and P450...
  55. ncbi request reprint How do aldehyde side products occur during alkene epoxidation by cytochrome P450? Theory reveals a state-specific multi-state scenario where the high-spin component leads to all side products
    Sam P de Visser
    Department of Organic Chemistry, Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Inorg Biochem 98:1183-93. 2004
    ..Factors controlling the competition between these processes are discussed...
  56. ncbi request reprint External electric field will control the selectivity of enzymatic-like bond activations
    Sason Shaik
    Contribution from the Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 126:11746-9. 2004
    ..Thus, the choice of the orientation and direction of the field vis-à-vis the molecular axes drives the reaction in the direction of complete C-H hydroxylation or complete C=C epoxidation...
  57. ncbi request reprint Theoretical analysis of the structural and electronic properties of metalloporphyrin pi-cation radicals
    Hajime Hirao
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Phys Chem A 110:6091-9. 2006
    ..Both techniques produce very similar results, pointing out that the frontier orbital, which becomes empty upon electron removal, plays a critical role in determining electronic properties...
  58. ncbi request reprint Can a single oxidant with two spin states masquerade as two different oxidants? A study of the sulfoxidation mechanism by cytochrome p450
    Pankaz K Sharma
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram 91904, Jerusalem, Israel
    J Am Chem Soc 125:8698-9. 2003
    ..The calculations rule out the possibility that a second oxidant (the ferric peroxide, Cpd 0 species) interferes in the observed results of Jones et al...
  59. ncbi request reprint The 'push' effect of the thiolate ligand in cytochrome P450: a theoretical gauging
    François Ogliaro
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University, 91904 Jerusalem, Israel
    J Inorg Biochem 91:554-67. 2002
    ..In an environment with a dielectric constant of 5.7, the total 'push' effect is reduced to 29-33 kcal/mol. Manifestations of the 'push' effect on other properties of thiolate enzymes are discussed...
  60. ncbi request reprint Formation of the active species of cytochrome p450 by using iodosylbenzene: a case for spin-selective reactivity
    Kyung Bin Cho
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904 Jerusalem, Israel
    Chemistry 13:4103-15. 2007
    ..The effect of PhIO is compared with N,N-dimethylaniline-N-oxide (DMAO), which acts both as the oxygen donor and the substrate and leads to the same KIE values as the native route...
  61. ncbi request reprint QM/MM theoretical study of the pentacoordinate Mn(III) and resting states of manganese-reconstituted cytochrome P450(cam)
    Hajime Hirao
    Department of Chemistry, The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Biol Inorg Chem 13:521-30. 2008
    ..The TDDFT results enabled us to assign the origins of the peaks observed in optical absorption spectra (Makris et al. in J. Inorg. Biochem. 100:507-518, 2006)...
  62. ncbi request reprint Does the TauD enzyme always hydroxylate alkanes, while an analogous synthetic non-heme reagent always desaturates them?
    Dandamudi Usharani
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 133:176-9. 2011
    ..Testable predictions are outlined...
  63. ncbi request reprint Principal active species of horseradish peroxidase, compound I: a hybrid quantum mechanical/molecular mechanical study
    Etienne Derat
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 127:13611-21. 2005
    ..Including this network in the QM region was found to be essential for reproducing the experimental Mössbauer parameters. The protein environment shapes most of the subtle features of Compound I of HRP...
  64. ncbi request reprint A proton-shuttle mechanism mediated by the porphyrin in benzene hydroxylation by cytochrome p450 enzymes
    Sam P de Visser
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 125:7413-24. 2003
    ..de Visser, S. P.; Ogliaro, F.; Schwarz, H.; Schröder, D. Curr. Opin. Chem. Biol. 2002, 6, 556-567) in olefin epoxidation and alkane hydroxylation is traced to the loss of benzene resonance energy during the bond activation step...
  65. ncbi request reprint A theory for bioinorganic chemical reactivity of oxometal complexes and analogous oxidants: the exchange and orbital-selection rules
    Dandamudi Usharani
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    Acc Chem Res 46:471-82. 2013
    ..The concepts used in this Account might also be applicable in other areas such as in f-block chemistry and excited-state reactivity of 4d and 5d OMCs...
  66. doi request reprint The directive of the protein: how does cytochrome P450 select the mechanism of dopamine formation?
    Patric Schyman
    Institute of Chemistry and The Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 133:7977-84. 2011
    ..Furthermore, it is shown that external electric fields can either catalyze or inhibit the process depending on their directionality...
  67. ncbi request reprint Searching for the second oxidant in the catalytic cycle of cytochrome P450: a theoretical investigation of the iron(III)-hydroperoxo species and its epoxidation pathways
    François Ogliaro
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904 Jerusalem
    J Am Chem Soc 124:2806-17. 2002
    ..It is therefore concluded that iron(III)-hydroperoxo, as such, cannot be a second oxidant, in line with its significant basicity and poor electron-accepting capability. Possible versions of a second oxidant are discussed...
  68. ncbi request reprint The Poulos-Kraut mechanism of Compound I formation in horseradish peroxidase: a QM/MM study
    Etienne Derat
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Phys Chem B 110:10526-33. 2006
    ..The structures of the intermediate and the transition state reveal the manner by which the Arg-His residues promote cooperatively the electronic reorganization that is required to attend the heterolytic O-O cleavage...
  69. doi request reprint The reaction mechanism of allene oxide synthase: Interplay of theoretical QM/MM calculations and experimental investigations
    Kyung Bin Cho
    Institute of Chemistry and The Lise Meitner Minerva Center for Quantum Computational Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel
    Arch Biochem Biophys 507:14-25. 2011
    ....
  70. ncbi request reprint The effect of a water molecule on the mechanism of formation of compound 0 in horseradish peroxidase
    Etienne Derat
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 129:6346-7. 2007
  71. ncbi request reprint Does substrate oxidation determine the regioselectivity of cyclohexene and propene oxidation by cytochrome p450?
    Shimrit Cohen
    Department of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
    J Am Chem Soc 128:11028-9. 2006
    ..The model expression for the effective barrier of the cycle forms a general basis for understanding and predicting the selectivity of P450 isozymes...
  72. ncbi request reprint Chemistry--a central pillar of human culture
    Sason Shaik
    Department of Organic Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904, Jerusalem, Israel
    Angew Chem Int Ed Engl 42:3208-15. 2003
  73. doi request reprint Multireference and multiconfiguration ab initio methods in heme-related systems: what have we learned so far?
    Hui Chen
    Institute of Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel
    J Phys Chem B 115:1727-42. 2011
    ..Comparisons with corresponding DFT results are also made wherever available. Potential future directions are proposed...
  74. ncbi request reprint Quantum mechanical/molecular mechanical investigation of the mechanism of C-H hydroxylation of camphor by cytochrome P450cam: theory supports a two-state rebound mechanism
    Jan C Schöneboom
    Max Planck Institut fur Kohlenforschung, Kaiser Wilhelm Platz 1, D 45470 Mulheim an der Ruhr, Germany
    J Am Chem Soc 126:4017-34. 2004
    ....
  75. ncbi request reprint Kinetic isotope effect is a sensitive probe of spin state reactivity in C-H hydroxylation of N,N-dimethylaniline by cytochrome P450
    Chunsen Li
    State Key Laboratory of Physical Chemistry of Solid Surfaces, Center for Theoretical Chemistry, and Department of Chemistry, Xiamen University, PR China
    J Am Chem Soc 128:394-5. 2006
    ..The calculations demonstrate that the kinetic isotope effects (KIEs) of the two processes are very different, and only KIELS fits the experimental datum. As such, KIE can be a sensitive probe of spin state reactivity...
  76. ncbi request reprint What is the active species of cytochrome P450 during camphor hydroxylation? QM/MM studies of different electronic states of compound I and of reduced and oxidized iron-oxo intermediates
    Ahmet Altun
    Max Planck Institut fur Kohlenforschung, Kaiser Wilhelm Platz 1, D 45470 Mulheim an der Ruhr, Germany
    J Am Chem Soc 129:8978-87. 2007
    ....
  77. ncbi request reprint Which oxidant is really responsible for sulfur oxidation by cytochrome P450?
    Chunsen Li
    The State Key Laboratory of Physical Chemistry of Solid Surfaces, Center for Theoretical Chemistry, and Department of Chemistry, Xiamen University, Xiamen 361005, China
    Angew Chem Int Ed Engl 46:8168-70. 2007
  78. ncbi request reprint Structural characterization of the fleeting ferric peroxo species in myoglobin: experiment and theory
    Masaki Unno
    Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980 8577, Japan
    J Am Chem Soc 129:13394-5. 2007
  79. pmc Axial ligand tuning of a nonheme iron(IV)-oxo unit for hydrogen atom abstraction
    Chivukula V Sastri
    Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120 750, Korea
    Proc Natl Acad Sci U S A 104:19181-6. 2007
    ....
  80. ncbi request reprint The elusive oxidant species of cytochrome P450 enzymes: characterization by combined quantum mechanical/molecular mechanical (QM/MM) calculations
    Jan C Schöneboom
    Max Planck Institut fur Kohlenforschung, Mulheim an der Ruhr, Germany
    J Am Chem Soc 124:8142-51. 2002
    ....
  81. ncbi request reprint Systematic QM/MM investigation of factors that affect the cytochrome P450-catalyzed hydrogen abstraction of camphor
    Ahmet Altun
    Max Planck Institut fur Kohlenforschung, Kaiser Wilhelm Platz 1, D 45470 Mulheim an der Ruhr, Germany
    J Comput Chem 27:1324-37. 2006
    ....
  82. pmc The effect of heme environment on the hydrogen abstraction reaction of camphor in P450cam catalysis: a QM/MM study
    Ahmet Altun
    Max Planck Institut fur Kohlenforschung, Kaiser Wilhelm Platz 1, D 45470 Mulheim an der Ruhr, Germany
    J Am Chem Soc 128:3924-5. 2006
    ..Spin density at the A-propionate side chain of heme can occur in the case of incomplete screening but has no major effect on the computed barrier...
  83. ncbi request reprint Ferromagnetic bonding: high spin copper clusters (n+1)Cu(n); n = 2-14) devoid of electron pairs but possessing strong bonding
    Sam P de Visser
    The Manchester Interdisciplinary Biocenter, School of Chemical Engineering and Analytical Science, The University of Manchester, Sackville Street, PO Box 88, Manchester M60 1QD, UK
    J Phys Chem A 110:8510-8. 2006
    ..This is achieved because the growing number of VB structures exerts a cumulative effect of stabilization that is maximized when the cluster has a compact structure with an optimal coordination number for the atoms...
  84. ncbi request reprint Theoretical study of N-demethylation of substituted N,N-dimethylanilines by cytochrome P450: the mechanistic significance of kinetic isotope effect profiles
    Yong Wang
    State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People s Republic of China
    J Phys Chem B 111:7700-10. 2007
    ..e) The generated carbinolaniline can readily dissociate from the heme and decomposes in a nonenzymatic environment, which involves water assisted proton shift...
  85. ncbi request reprint Structural dynamics of the cooperative binding of organic molecules in the human cytochrome P450 3A4
    Dan Fishelovitch
    Department of Human Genetics, Sackler Institute of Molecular Medicine, Sackler Faculty of Medicine, Tel Aviv University, Tel Aviv 69978, Israel
    J Am Chem Soc 129:1602-11. 2007
    ..In addition, in one conformer of the enzyme, residue R212 may strongly interact with F304 and counteract the effector's impact on the enzyme...
  86. ncbi request reprint Mechanism of oxidation reactions catalyzed by cytochrome p450 enzymes
    Bernard Meunier
    Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France
    Chem Rev 104:3947-80. 2004
  87. ncbi request reprint The Menshutkin reaction in the gas phase and in aqueous solution: a valence bond study
    Peifeng Su
    Department of Chemistry, College of Chemistry and Chemical Engineering and State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen, Fujian 361005, China
    Chemphyschem 8:2603-14. 2007
    ..Shaik, A. Shurki, Angew. Chem. Int. Ed. 1999, 38, 586). It is shown that the reactivity parameters along with their semiempirical derivations provide together a satisfactory qualitative and quantitative account of the barriers...
  88. ncbi request reprint QM/MM study of mechanisms for compound I formation in the catalytic cycle of cytochrome P450cam
    Jingjing Zheng
    Max Planck Institut fur Kohlenforschung, Kaiser Wilhelm Platz 1, D 45470 Mulheim an der Ruhr, Germany
    J Am Chem Soc 128:13204-15. 2006
    ..According to the QM/MM calculations, the favored low-energy pathway to Cpd I is provided by mechanism II in the Asp(251) channel. Cpd 0 and Cpd I are of similar energies, with a slight preference for Cpd I...
  89. doi request reprint Experiment and theory reveal the fundamental difference between two-state and single-state reactivity patterns in nonheme Fe(IV)=O versus Ru(IV)=O oxidants
    Sunder N Dhuri
    Department of Chemistry, Division of Nano Sciences, and Centre for Biomimetic Systems, Ewha Womans University, Seoul 120 750, Korea
    Angew Chem Int Ed Engl 47:3356-9. 2008
  90. ncbi request reprint A new mechanism for ethanol oxidation mediated by cytochrome P450 2E1: bulk polarity of the active site makes a difference
    Yong Wang
    State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
    Chembiochem 8:277-81. 2007