Density functional study of substituted (–SH, –S, –OH, –Cl) hydrated ions of Hg2+

Afaneh, Akef T.; Schreckenbach, Georg; Wang, Fei

doi:10.1007/s00214-012-1174-2

Cited by 17 publications

(24 citation statements)

References 98 publications

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“…Even slightly shorter r HgÀO(OH) distances were calculated in the Hg II -aqua clusters by using the same DFT functional and different basis set and with the MP2 method. [33,35] Though virtually similar, the slightly longer r HgÀO(OH) distance seemed to be due to the implicit water solvent employed on top of the explicit one in our calculations. The trans-aqua ligand in the Hg II -hydroxo clusters was longer, that is, r HgÀO(H2O) = 2.28-2.56 .…”

Section: Resultsmentioning

confidence: 62%

“…[33] In our case, the trans effect contributed to the stability of the pseudo-base pair and prevented its opening. The release of one of these bridging water molecules in the IS3 state (r (H 2 O)OÀHg = 2.238 and 3.500 ) was accompanied by shortening of the Hg II À N3(T) bond (r HgÀN3(T) = 2.180 ).…”

Section: The Fpmd Simulations Of the [Hg II A C H T U N G T R E N N Umentioning

confidence: 57%

“…[33,35] Though virtually similar, the slightly longer r HgÀO(OH) distance seemed to be due to the implicit water solvent employed on top of the explicit one in our calculations. Even slightly shorter r HgÀO(OH) distances were calculated in the Hg II -aqua clusters by using the same DFT functional and different basis set and with the MP2 method.…”

Section: The Fpmd Simulations Of the [Hg IImentioning

confidence: 62%

“…[33] As can be foreseen, the hydroxo ligand is a much better nucleophile for proton abstraction than the aqua ligand, the possible occurrence of which at neutral pH has to be reflected by using a proper model considered for the mercury reactant. The outer overall hydration of the Hg IIaqua cluster was obtained by using the implicit solvent model.…”

Section: The Fpmd Simulations Of the [Hg IImentioning

confidence: 99%

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Formation of a Thymine‐Hg^II‐Thymine Metal‐Mediated DNA Base Pair: Proposal and Theoretical Calculation of the Reaction Pathway

Šebera

Burda

Straka

et al. 2013

Chemistry A European J

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A reaction mechanism that describes the substitution of two imino protons in a thymine:thymine (T:T) mismatched DNA base pair with a Hg(II) ion, which results in the formation of a (T)N3-Hg(II)-N3(T) metal-mediated base pair was proposed and calculated. The mechanism assumes two key steps: The formation of the first Hg(II)-N3(T) bond is triggered by deprotonation of the imino N3 atom in thymine with a hydroxo ligand on the Hg(II) ion. The formation of the second Hg(II)-N3(T) bond proceeds through water-assisted tautomerization of the remaining, metal-nonbonded thymine base or through thymine deprotonation with a hydroxo ligand of the Hg(II) ion already coordinated to the thymine base. The thermodynamic parameters ΔGR =-9.5 kcal mol(-1), ΔHR =-4.7 kcal mol(-1), and ΔSR =16.0 cal mol(-1) K(-1) calculated with the ONIOM (B3LYP:BP86) method for the reaction agreed well with the isothermal titration calorimetric (ITC) measurements by Torigoe et al. [H. Torigoe, A. Ono, T. Kozasa, Chem. Eur. J. 2010, 16, 13218-13225]. The peculiar positive reaction entropy measured previously was due to both dehydration of the metal and the change in chemical bonding. The mercury reactant in the theoretical model contained one hydroxo ligand in accord with the experimental pKa value of 3.6 known for an aqua ligand of a Hg(II) center. The chemical modification of T:T mismatched to the T-Hg(II)-T metal-mediated base pair was modeled for the middle base pair within a trinucleotide B-DNA duplex, which ensured complete dehydration of the Hg(II) ion during the reaction.

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Section: Resultsmentioning

confidence: 62%

Section: The Fpmd Simulations Of the [Hg II A C H T U N G T R E N N Umentioning

confidence: 57%

Section: The Fpmd Simulations Of the [Hg IImentioning

confidence: 62%

Section: The Fpmd Simulations Of the [Hg IImentioning

confidence: 99%

See 2 more Smart Citations

Formation of a Thymine‐Hg^II‐Thymine Metal‐Mediated DNA Base Pair: Proposal and Theoretical Calculation of the Reaction Pathway

Šebera

Burda

Straka

et al. 2013

Chemistry A European J

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“…[36][37][38][39][40][41][42][43][44] For example, mechanisms associated with the Hg−C bond cleavage by halogenic acids have been investigated by Barone and co-workers. 15 Ni et al 36 investigated possible mechanisms for degrading chloromethylmercury (CH 3 −Hg−Cl) and dimethylmercury (CH 3 −Hg−CH 3 ) involving thiol and ammonium residues.…”

Section: Introductionmentioning

confidence: 99%

Stability of Dimethylmercury and Related Mercury-containing Compounds with Respect to Selected Chemical Species Found in Aqueous Environment

Bytautas¹

2013

Croat. Chem. Acta

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Abstract. Dimethylmercury (CH 3 −Hg−CH 3 ) and other Hg-containing compounds can be found in atmospheric and aqueous environments. These substances are highly toxic and pose a serious environmental and health hazard. Therefore, the understanding of chemical processes that affect the stability of these substances is of great interest. The mercury-containing compounds can be detected in atmosphere, as well as soil and aqueous environments where, in addition to water molecules, numerous ionic species are abundant. In this study we explore the stability of several small, Hg-containing compounds with respect to water molecules, hydronium (H 3 O + ) ions as well as other small molecules/ions using density functional theory and wave function quantum chemistry methods. It is found that the stability of such molecules, most notably of dimethylmercury, can be strongly affected by the presence of the hydronium H 3 O + ions. Although the present theoretical study represents gas phase results, it implies that pH level of a solution should be a major factor in determining the degree of abundance for dimethylmercury in aqueous environment. In particular, it is found that CH 3 −Hg−CH 3 reacts readily with the H 3 O + ion producing CH 3 −Hg−OH 2 + and methane indicating that low-pH levels favor the decomposition of dimethylmercury. On the other hand, our study suggests that high-pH levels in aqueous environment would favor stronglybound complexes of [CH 3 −Hg−CH 3 OH]  species. Overall, the theoretical evidence presented in this study offers an explanation for the available experimental data concerning the stability of dimethylmercury and other mercury-containing compounds having the general structure

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Alkyl mercury compounds: an assessment of DFT methods

Montero‐Campillo

Lamsabhi

Mó

et al. 2012

Highlights in Theoretical Chemistry

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Density functional study of substituted (–SH, –S, –OH, –Cl) hydrated ions of Hg2+

Cited by 17 publications

References 98 publications

Formation of a Thymine‐Hg^II‐Thymine Metal‐Mediated DNA Base Pair: Proposal and Theoretical Calculation of the Reaction Pathway

Formation of a Thymine‐Hg^II‐Thymine Metal‐Mediated DNA Base Pair: Proposal and Theoretical Calculation of the Reaction Pathway

Stability of Dimethylmercury and Related Mercury-containing Compounds with Respect to Selected Chemical Species Found in Aqueous Environment

Alkyl mercury compounds: an assessment of DFT methods

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Density functional study of substituted (–SH, –S, –OH, –Cl) hydrated ions of Hg2+

Cited by 17 publications

References 98 publications

Formation of a Thymine‐HgII‐Thymine Metal‐Mediated DNA Base Pair: Proposal and Theoretical Calculation of the Reaction Pathway

Formation of a Thymine‐HgII‐Thymine Metal‐Mediated DNA Base Pair: Proposal and Theoretical Calculation of the Reaction Pathway

Stability of Dimethylmercury and Related Mercury-containing Compounds with Respect to Selected Chemical Species Found in Aqueous Environment

Alkyl mercury compounds: an assessment of DFT methods

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Product

Resources

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Formation of a Thymine‐Hg^II‐Thymine Metal‐Mediated DNA Base Pair: Proposal and Theoretical Calculation of the Reaction Pathway

Formation of a Thymine‐Hg^II‐Thymine Metal‐Mediated DNA Base Pair: Proposal and Theoretical Calculation of the Reaction Pathway