Prediction of the pH-rate profile for dimethyl sulfide oxidation by hydrogen peroxide: The role of elusive H3
O2
 +
 Ion

Silva, Carlos M.; Silva, Poliana L.; Pliego, Josefredo R.

doi:10.1002/qua.24594

Cited by 21 publications

(16 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The physical and chemical stimuli associated with re-submersion following air exposure could result in a burst of H 2 O 2 production. DMSO is the first product of the aqueous phase reaction between DMS and H 2 O 2 5152, so coincident release of H 2 O 2 could result in rapid oxidation of dissolved DMS to DMSO.…”

Section: Discussionmentioning

confidence: 99%

Air exposure of coral is a significant source of dimethylsulfide (DMS) to the atmosphere

Hopkins

Bell

Yang

et al. 2016

Sci Rep

View full text Add to dashboard Cite

Corals are prolific producers of dimethylsulfoniopropionate (DMSP). High atmospheric concentrations of the DMSP breakdown product dimethylsulfide (DMS) have been linked to coral reefs during low tides. DMS is a potentially key sulfur source to the tropical atmosphere, but DMS emission from corals during tidal exposure is not well quantified. Here we show that gas phase DMS concentrations (DMSgas) increased by an order of magnitude when three Indo-Pacific corals were exposed to air in laboratory experiments. Upon re-submersion, an additional rapid rise in DMSgas was observed, reflecting increased production by the coral and/or dissolution of DMS-rich mucus formed by the coral during air exposure. Depletion in DMS following re-submersion was likely due to biologically-driven conversion of DMS to dimethylsulfoxide (DMSO). Fast Repetition Rate fluorometry showed downregulated photosynthesis during air exposure but rapid recovery upon re-submersion, suggesting that DMS enhances coral tolerance to oxidative stress during a process that can induce photoinhibition. We estimate that DMS emission from exposed coral reefs may be comparable in magnitude to emissions from other marine DMS hotspots. Coral DMS emission likely comprises a regular and significant source of sulfur to the tropical marine atmosphere, which is currently unrecognised in global DMS emission estimates and Earth System Models.

show abstract

Section: Discussionmentioning

confidence: 99%

Air exposure of coral is a significant source of dimethylsulfide (DMS) to the atmosphere

Hopkins

Bell

Yang

et al. 2016

Sci Rep

View full text Add to dashboard Cite

show abstract

“…As a final example, the hybrid cluster‐continuum approach was used to predict the pH‐rate profile for the oxidation of the dimethyl sulfide by hydrogen peroxide, using high level MP4/TZVPP+diff calculations on the CPCM/X3LYP/DZ+P(d)+diff optimized geometries, corresponding to the reaction:

{CH}_{3} {SCH}_{3} + H_{2} O_{2} \to {CH}_{3} normalS ((), = normalO) {CH}_{3} + H_{2} normalO

In acidic medium, the calculations have indicated that the “protonated” peroxide ion is better represented by the H 3 O + (H 2 O 2 )(H 2 O) 2 ionic cluster, because the proton stays bound to the water molecule. In the transition state, two water molecules are lost to form the most stable transition state.…”

Section: Applicationsmentioning

confidence: 99%

Hybrid discrete‐continuum solvation methods

Pliego

Riveros

2019

WIREs Comput Mol Sci

Self Cite

View full text Add to dashboard Cite

Hybrid discrete‐continuum approaches for solvation have been widely applied for diverse problems in chemistry suck as pKa calculation in aqueous and nonaqueous solvents, activation free energy barriers for ionic processes in solution, and surface reactions. A special version of this approach, the cluster‐continuum quasichemical model, has also been used for establishing a single‐ion solvation free energy scale in different solvents compatible with the tetraphenylarsonium tetraphenylborate assumption. The use of discrete‐continuum solvation methods can lead to meaningful improvement with respect to pure continuum solvation models for modeling diverse chemical process in solution. In the case of pKa calculations, there are cases where the root mean squared error is as large as 7 pKa units with pure continuum solvation model and becomes around 1 pKa unit with the hybrid approach. For complex reactions in solution, errors as large as 10 kcal/mol for activation free energies with the pure continuum approach can be substantially reduced with the inclusion of explicit solvent molecules. A discussion of the theory of hybrid discrete‐continuum methods is also presented and further development is expected in the coming years. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Software > Quantum Chemistry Molecular and Statistical Mechanics > Free Energy Methods

show abstract

“…24,[33][34][35][36][37][38] In the cases that free ionic species are involved, the method is less reliable and may be needed to use hybrid clustercontinuum approaches. 39,40 In the application of continuum models for chemical reactions, it is important to take care about the type of reaction is being considered. Scheme 1 present some cases.…”

Section: Introductionmentioning

confidence: 99%

Solvent selection for chemical reactions: automated computational screening of solvents using the SMD model

Dalessandro¹,

Pliego²

2018

Quim. Nova

View full text Add to dashboard Cite

Finding the most efficient solvent for a chemical reaction can demand costly experimental procedure and the screening is usually limited to few solvents. The use of theoretical methods could accelerate the search for the best solvent, able to promote most effective kinetics and thermodynamics of a reaction. In this work, it was proposed an automated procedure that calculates the solvent effect for a chemical reaction using all the 179 solvents available in SMD (solvation model density). The reaction of 2-bromoacetophenone with pyridine was used as a test. The SMD model correctly predicts the reactivity trends for five solvents, which experimental data are available. We have found that sulfolane, a less usual solvent, is the best one for this reaction. The present study points out that computational screening of large set of solvents using the SMD model is a viable approach and could be useful for chemical reactions optimization.

show abstract

Prediction of the pH-rate profile for dimethyl sulfide oxidation by hydrogen peroxide: The role of elusive H₃ O₂ ⁺ Ion

Cited by 21 publications

References 44 publications

Air exposure of coral is a significant source of dimethylsulfide (DMS) to the atmosphere

Air exposure of coral is a significant source of dimethylsulfide (DMS) to the atmosphere

Hybrid discrete‐continuum solvation methods

Solvent selection for chemical reactions: automated computational screening of solvents using the SMD model

Contact Info

Product

Resources

About

Prediction of the pH-rate profile for dimethyl sulfide oxidation by hydrogen peroxide: The role of elusive H3 O2 + Ion

Cited by 21 publications

References 44 publications

Air exposure of coral is a significant source of dimethylsulfide (DMS) to the atmosphere

Air exposure of coral is a significant source of dimethylsulfide (DMS) to the atmosphere

Hybrid discrete‐continuum solvation methods

Solvent selection for chemical reactions: automated computational screening of solvents using the SMD model

Contact Info

Product

Resources

About

Prediction of the pH-rate profile for dimethyl sulfide oxidation by hydrogen peroxide: The role of elusive H₃ O₂ ⁺ Ion