Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway
During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe...
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Gespeichert in:
| Autor*in: |
Heeb, Michèle B [verfasserIn] |
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| Format: |
Artikel |
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| Sprache: |
Englisch |
| Erschienen: |
2015 |
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| Schlagwörter: |
Water Pollutants, Chemical - analysis Water Pollutants, Chemical - chemistry Dimethylnitrosamine - chemistry |
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| Übergeordnetes Werk: |
Enthalten in: Environmental science & technology - Washington, DC : ACS Publ., 1967, 49(2015), 7, Seite 4163 |
|---|---|
| Übergeordnetes Werk: |
volume:49 ; year:2015 ; number:7 ; pages:4163 |
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| 520 | |a During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally. | ||
| 650 | 4 | |a Bromides - chemistry | |
| 650 | 4 | |a Bromates - chemistry | |
| 650 | 4 | |a Sulfonamides - chemistry | |
| 650 | 4 | |a Ozone - chemistry | |
| 650 | 4 | |a Water Pollutants, Chemical - analysis | |
| 650 | 4 | |a Water Pollutants, Chemical - chemistry | |
| 650 | 4 | |a Dimethylnitrosamine - chemistry | |
| 650 | 4 | |a Dimethylnitrosamine - analysis | |
| 650 | 4 | |a Sulfonamides - analysis | |
| 650 | 4 | |a Drinking Water - chemistry | |
| 650 | 4 | |a Drinking Water - standards | |
| 650 | 4 | |a Water Purification - methods | |
| 650 | 4 | |a Metabolites | |
| 650 | 4 | |a Molecules | |
| 650 | 4 | |a Drinking water | |
| 650 | 4 | |a Environmental science | |
| 650 | 4 | |a Ozone | |
| 650 | 4 | |a Pesticides | |
| 700 | 1 | |a Mishra, Brijesh Kumar |4 oth | |
| 700 | 1 | |a Arey, J Samuel |4 oth | |
| 700 | 1 | |a Trogolo, Daniela |4 oth | |
| 700 | 1 | |a von Gunten, Urs |4 oth | |
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PQ20160211 (DE-627)OLC196962924X (DE-599)GBVOLC196962924X (PRQ)p1921-4f366708fc73e588cb9943c178a3c09e7ccc55ef72bd14faf8fc2e645c03b3410 (KEY)0072627320150000049000704163molecularmechanismofndmaformationfromnndimethylsul DE-627 ger DE-627 rakwb eng 050 333.7 DNB Heeb, Michèle B verfasserin aut Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway 2015 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally. Bromides - chemistry Bromates - chemistry Sulfonamides - chemistry Ozone - chemistry Water Pollutants, Chemical - analysis Water Pollutants, Chemical - chemistry Dimethylnitrosamine - chemistry Dimethylnitrosamine - analysis Sulfonamides - analysis Drinking Water - chemistry Drinking Water - standards Water Purification - methods Metabolites Molecules Drinking water Environmental science Ozone Pesticides Mishra, Brijesh Kumar oth Arey, J Samuel oth Trogolo, Daniela oth von Gunten, Urs oth Enthalten in Environmental science & technology Washington, DC : ACS Publ., 1967 49(2015), 7, Seite 4163 (DE-627)129852457 (DE-600)280653-8 (DE-576)01515274X 0013-936X nnns volume:49 year:2015 number:7 pages:4163 http://www.ncbi.nlm.nih.gov/pubmed/25772586 http://search.proquest.com/docview/1673516963 GBV_USEFLAG_A SYSFLAG_A GBV_OLC SSG-OLC-UMW SSG-OLC-TEC SSG-OLC-CHE GBV_ILN_23 GBV_ILN_70 GBV_ILN_252 GBV_ILN_2006 GBV_ILN_4323 AR 49 2015 7 4163 |
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PQ20160211 (DE-627)OLC196962924X (DE-599)GBVOLC196962924X (PRQ)p1921-4f366708fc73e588cb9943c178a3c09e7ccc55ef72bd14faf8fc2e645c03b3410 (KEY)0072627320150000049000704163molecularmechanismofndmaformationfromnndimethylsul DE-627 ger DE-627 rakwb eng 050 333.7 DNB Heeb, Michèle B verfasserin aut Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway 2015 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally. Bromides - chemistry Bromates - chemistry Sulfonamides - chemistry Ozone - chemistry Water Pollutants, Chemical - analysis Water Pollutants, Chemical - chemistry Dimethylnitrosamine - chemistry Dimethylnitrosamine - analysis Sulfonamides - analysis Drinking Water - chemistry Drinking Water - standards Water Purification - methods Metabolites Molecules Drinking water Environmental science Ozone Pesticides Mishra, Brijesh Kumar oth Arey, J Samuel oth Trogolo, Daniela oth von Gunten, Urs oth Enthalten in Environmental science & technology Washington, DC : ACS Publ., 1967 49(2015), 7, Seite 4163 (DE-627)129852457 (DE-600)280653-8 (DE-576)01515274X 0013-936X nnns volume:49 year:2015 number:7 pages:4163 http://www.ncbi.nlm.nih.gov/pubmed/25772586 http://search.proquest.com/docview/1673516963 GBV_USEFLAG_A SYSFLAG_A GBV_OLC SSG-OLC-UMW SSG-OLC-TEC SSG-OLC-CHE GBV_ILN_23 GBV_ILN_70 GBV_ILN_252 GBV_ILN_2006 GBV_ILN_4323 AR 49 2015 7 4163 |
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PQ20160211 (DE-627)OLC196962924X (DE-599)GBVOLC196962924X (PRQ)p1921-4f366708fc73e588cb9943c178a3c09e7ccc55ef72bd14faf8fc2e645c03b3410 (KEY)0072627320150000049000704163molecularmechanismofndmaformationfromnndimethylsul DE-627 ger DE-627 rakwb eng 050 333.7 DNB Heeb, Michèle B verfasserin aut Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway 2015 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally. Bromides - chemistry Bromates - chemistry Sulfonamides - chemistry Ozone - chemistry Water Pollutants, Chemical - analysis Water Pollutants, Chemical - chemistry Dimethylnitrosamine - chemistry Dimethylnitrosamine - analysis Sulfonamides - analysis Drinking Water - chemistry Drinking Water - standards Water Purification - methods Metabolites Molecules Drinking water Environmental science Ozone Pesticides Mishra, Brijesh Kumar oth Arey, J Samuel oth Trogolo, Daniela oth von Gunten, Urs oth Enthalten in Environmental science & technology Washington, DC : ACS Publ., 1967 49(2015), 7, Seite 4163 (DE-627)129852457 (DE-600)280653-8 (DE-576)01515274X 0013-936X nnns volume:49 year:2015 number:7 pages:4163 http://www.ncbi.nlm.nih.gov/pubmed/25772586 http://search.proquest.com/docview/1673516963 GBV_USEFLAG_A SYSFLAG_A GBV_OLC SSG-OLC-UMW SSG-OLC-TEC SSG-OLC-CHE GBV_ILN_23 GBV_ILN_70 GBV_ILN_252 GBV_ILN_2006 GBV_ILN_4323 AR 49 2015 7 4163 |
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PQ20160211 (DE-627)OLC196962924X (DE-599)GBVOLC196962924X (PRQ)p1921-4f366708fc73e588cb9943c178a3c09e7ccc55ef72bd14faf8fc2e645c03b3410 (KEY)0072627320150000049000704163molecularmechanismofndmaformationfromnndimethylsul DE-627 ger DE-627 rakwb eng 050 333.7 DNB Heeb, Michèle B verfasserin aut Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway 2015 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally. Bromides - chemistry Bromates - chemistry Sulfonamides - chemistry Ozone - chemistry Water Pollutants, Chemical - analysis Water Pollutants, Chemical - chemistry Dimethylnitrosamine - chemistry Dimethylnitrosamine - analysis Sulfonamides - analysis Drinking Water - chemistry Drinking Water - standards Water Purification - methods Metabolites Molecules Drinking water Environmental science Ozone Pesticides Mishra, Brijesh Kumar oth Arey, J Samuel oth Trogolo, Daniela oth von Gunten, Urs oth Enthalten in Environmental science & technology Washington, DC : ACS Publ., 1967 49(2015), 7, Seite 4163 (DE-627)129852457 (DE-600)280653-8 (DE-576)01515274X 0013-936X nnns volume:49 year:2015 number:7 pages:4163 http://www.ncbi.nlm.nih.gov/pubmed/25772586 http://search.proquest.com/docview/1673516963 GBV_USEFLAG_A SYSFLAG_A GBV_OLC SSG-OLC-UMW SSG-OLC-TEC SSG-OLC-CHE GBV_ILN_23 GBV_ILN_70 GBV_ILN_252 GBV_ILN_2006 GBV_ILN_4323 AR 49 2015 7 4163 |
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We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). 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050 333.7 DNB Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway Bromides - chemistry Bromates - chemistry Sulfonamides - chemistry Ozone - chemistry Water Pollutants, Chemical - analysis Water Pollutants, Chemical - chemistry Dimethylnitrosamine - chemistry Dimethylnitrosamine - analysis Sulfonamides - analysis Drinking Water - chemistry Drinking Water - standards Water Purification - methods Metabolites Molecules Drinking water Environmental science Ozone Pesticides |
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molecular mechanism of ndma formation from n,n-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway |
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Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway |
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During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally. |
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During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally. |
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During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally. |
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Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway |
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