A carbon-13 nuclear magnetic resonance study of thiol-exchange reactions of gold(I) thiomalate ('Myocrisin') including applications to cysteine derivatives

Anvarhusein A. Isab; Peter J. Sadler

doi:10.1039/DT9820000135

A carbon-13 nuclear magnetic resonance study of thiol-exchange reactions of gold(I) thiomalate ('Myocrisin') including applications to cysteine derivatives

Anvarhusein A. Isab
, Peter J. Sadler^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

102 Scopus citations

Abstract

Reactions at pH 7 between gold(I) thiomalate and a variety of thiols with pK_SH values ranging from 7.6 (thioglucose) to 10.2 (mercaptoacetate) have been studied by ¹³C n.m.r. spectroscopy. New species [Au(SR)_n]^1-n, where n appears to be less than 2, are formed and thiomalate is readily displaced, especially by thiols with low pK_SH. The latter are in fast exchange with Au^I on the n.m.r. time scale. Similar activation parameters have been derived for thiomalate, N-acetyl-L-cysteine, and mercaptoacetate exchange (ΔG‡ 63 kJ mol^-1, ΔS‡ -145 J K^-1 mol^-1, E_A 22 kJ mol^-1) via a line-shape analysis of ¹³C n.m.r. spectra at different temperatures. Thiol exchange rates increase at high pH, but at low pH 1:1 polymers are more stable than [Au(SR)_n]^1-n species.

Original language	English
Pages (from-to)	135-141
Number of pages	7
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	1
DOIs	https://doi.org/10.1039/DT9820000135
State	Published - 1982
Externally published	Yes

Bibliographical note

Funding Information:
Thisparallels the pKa order, see Table 1. We note the use ofD-penicillamine to reverse toxicity due to gold drugs.The most strongly bound thiols are those with the lowestPKa values.Figure 6 shows the shifts of the 13C resonances of gold-bound thiomalate as a function of the concentration ofadded thiol. The pattern of shifts is similar in all cases:a small shift of the CH, resonance of thiomalate to lowWe thank the British Council (grant to A. A. I.) and theCentral Research Fund of the University of London (n.m.r.crystal fitter) for support, May and Baker Ltd. (Dagenham)for their gifts of Myocrisin, and Professor D. L. Rabenstein(University of Edmonton, Alberta) for stimulating discus-sion.[1/916 Received, 8th June, 19811REFERENCES1 P. J. Sadler, Struct. Bonding ( B e r l i n ) , 1976, 29, 171.2 C. F. Shaw, Inorg. Perspec. Biol. Med., 1979, 2, 287.3 D. H. Brown and W. E. Smith, Chem. Soc. Rev., 1980,9,217141A. A. Isab and P. J. Sadler, J . Chem. SOC., Dalton Trans.,1981, 1657.M. A. Mazid, T. R. Razi, P. J. Sadler, G. N. Greaves, S .Gurman, M. H. J. Koch, and J. C . Phillips, J . Chem. SOC., Chem.Commun., 1980, 1261.A. A. Isab and P. J. Sadler, J . Chem. SOC., Chem. Commun.,1976, 1051.I. G. Dance, J . Chem. SOC., Chem. Commun., 1976, 68.I. G. Dance, J . Chem. SOC., Chem. Commun., 1976, 103.E. H. Griffith, G. W. Hunt, and E. L. Amma, J . Chem. SOC.,Chem. Commun., 1976, 432.lo G. A. Bowmaker and B. C . Dobson, J . Chem. Soc., Daltonl1 R. D. Bach and A. T. Weibel, J . Am. Chem. SOC., 1976, 98,l2 D. H. Brown, G. C. McKinley, and W. E. Smith, J . Chem.l3 F. F. Brown, I. D. Campbell, P. W. Kuchel, and D. L.Trans., 1981, 267.6241.SOC., Dalton Trans., 1978, 199.Rabenstein, FEBS Lett., 1977, 82, 12

ASJC Scopus subject areas

General Chemistry

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10.1039/DT9820000135

Cite this

@article{ecdfaf615f0543a5acf7bfb91db4febd,

title = "A carbon-13 nuclear magnetic resonance study of thiol-exchange reactions of gold(I) thiomalate ('Myocrisin') including applications to cysteine derivatives",

abstract = "Reactions at pH 7 between gold(I) thiomalate and a variety of thiols with pKSH values ranging from 7.6 (thioglucose) to 10.2 (mercaptoacetate) have been studied by 13C n.m.r. spectroscopy. New species [Au(SR)n]1-n, where n appears to be less than 2, are formed and thiomalate is readily displaced, especially by thiols with low pKSH. The latter are in fast exchange with AuI on the n.m.r. time scale. Similar activation parameters have been derived for thiomalate, N-acetyl-L-cysteine, and mercaptoacetate exchange (ΔG‡ 63 kJ mol-1, ΔS‡ -145 J K-1 mol-1, EA 22 kJ mol-1) via a line-shape analysis of 13C n.m.r. spectra at different temperatures. Thiol exchange rates increase at high pH, but at low pH 1:1 polymers are more stable than [Au(SR)n]1-n species.",

author = "Isab, \{Anvarhusein A.\} and Sadler, \{Peter J.\}",

note = "Funding Information: Thisparallels the pKa order, see Table 1. We note the use ofD-penicillamine to reverse toxicity due to gold drugs.The most strongly bound thiols are those with the lowestPKa values.Figure 6 shows the shifts of the 13C resonances of gold-bound thiomalate as a function of the concentration ofadded thiol. The pattern of shifts is similar in all cases:a small shift of the CH, resonance of thiomalate to lowWe thank the British Council (grant to A. A. I.) and theCentral Research Fund of the University of London (n.m.r.crystal fitter) for support, May and Baker Ltd. (Dagenham)for their gifts of Myocrisin, and Professor D. L. Rabenstein(University of Edmonton, Alberta) for stimulating discus-sion.[1/916 Received, 8th June, 19811REFERENCES1 P. J. Sadler, Struct. Bonding ( B e r l i n ) , 1976, 29, 171.2 C. F. Shaw, Inorg. Perspec. Biol. Med., 1979, 2, 287.3 D. H. Brown and W. E. Smith, Chem. Soc. Rev., 1980,9,217141A. A. Isab and P. J. Sadler, J . Chem. SOC., Dalton Trans.,1981, 1657.M. A. Mazid, T. R. Razi, P. J. Sadler, G. N. Greaves, S .Gurman, M. H. J. Koch, and J. C . Phillips, J . Chem. SOC., Chem.Commun., 1980, 1261.A. A. Isab and P. J. Sadler, J . Chem. SOC., Chem. Commun.,1976, 1051.I. G. Dance, J . Chem. SOC., Chem. Commun., 1976, 68.I. G. Dance, J . Chem. SOC., Chem. Commun., 1976, 103.E. H. Griffith, G. W. Hunt, and E. L. Amma, J . Chem. SOC.,Chem. Commun., 1976, 432.lo G. A. Bowmaker and B. C . Dobson, J . Chem. Soc., Daltonl1 R. D. Bach and A. T. Weibel, J . Am. Chem. SOC., 1976, 98,l2 D. H. Brown, G. C. McKinley, and W. E. Smith, J . Chem.l3 F. F. Brown, I. D. Campbell, P. W. Kuchel, and D. L.Trans., 1981, 267.6241.SOC., Dalton Trans., 1978, 199.Rabenstein, FEBS Lett., 1977, 82, 12",

year = "1982",

doi = "10.1039/DT9820000135",

language = "English",

pages = "135--141",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1472-7773",

publisher = "Royal Society of Chemistry",

number = "1",

}

TY - JOUR

T1 - A carbon-13 nuclear magnetic resonance study of thiol-exchange reactions of gold(I) thiomalate ('Myocrisin') including applications to cysteine derivatives

AU - Isab, Anvarhusein A.

AU - Sadler, Peter J.

N1 - Funding Information: Thisparallels the pKa order, see Table 1. We note the use ofD-penicillamine to reverse toxicity due to gold drugs.The most strongly bound thiols are those with the lowestPKa values.Figure 6 shows the shifts of the 13C resonances of gold-bound thiomalate as a function of the concentration ofadded thiol. The pattern of shifts is similar in all cases:a small shift of the CH, resonance of thiomalate to lowWe thank the British Council (grant to A. A. I.) and theCentral Research Fund of the University of London (n.m.r.crystal fitter) for support, May and Baker Ltd. (Dagenham)for their gifts of Myocrisin, and Professor D. L. Rabenstein(University of Edmonton, Alberta) for stimulating discus-sion.[1/916 Received, 8th June, 19811REFERENCES1 P. J. Sadler, Struct. Bonding ( B e r l i n ) , 1976, 29, 171.2 C. F. Shaw, Inorg. Perspec. Biol. Med., 1979, 2, 287.3 D. H. Brown and W. E. Smith, Chem. Soc. Rev., 1980,9,217141A. A. Isab and P. J. Sadler, J . Chem. SOC., Dalton Trans.,1981, 1657.M. A. Mazid, T. R. Razi, P. J. Sadler, G. N. Greaves, S .Gurman, M. H. J. Koch, and J. C . Phillips, J . Chem. SOC., Chem.Commun., 1980, 1261.A. A. Isab and P. J. Sadler, J . Chem. SOC., Chem. Commun.,1976, 1051.I. G. Dance, J . Chem. SOC., Chem. Commun., 1976, 68.I. G. Dance, J . Chem. SOC., Chem. Commun., 1976, 103.E. H. Griffith, G. W. Hunt, and E. L. Amma, J . Chem. SOC.,Chem. Commun., 1976, 432.lo G. A. Bowmaker and B. C . Dobson, J . Chem. Soc., Daltonl1 R. D. Bach and A. T. Weibel, J . Am. Chem. SOC., 1976, 98,l2 D. H. Brown, G. C. McKinley, and W. E. Smith, J . Chem.l3 F. F. Brown, I. D. Campbell, P. W. Kuchel, and D. L.Trans., 1981, 267.6241.SOC., Dalton Trans., 1978, 199.Rabenstein, FEBS Lett., 1977, 82, 12

PY - 1982

Y1 - 1982

N2 - Reactions at pH 7 between gold(I) thiomalate and a variety of thiols with pKSH values ranging from 7.6 (thioglucose) to 10.2 (mercaptoacetate) have been studied by 13C n.m.r. spectroscopy. New species [Au(SR)n]1-n, where n appears to be less than 2, are formed and thiomalate is readily displaced, especially by thiols with low pKSH. The latter are in fast exchange with AuI on the n.m.r. time scale. Similar activation parameters have been derived for thiomalate, N-acetyl-L-cysteine, and mercaptoacetate exchange (ΔG‡ 63 kJ mol-1, ΔS‡ -145 J K-1 mol-1, EA 22 kJ mol-1) via a line-shape analysis of 13C n.m.r. spectra at different temperatures. Thiol exchange rates increase at high pH, but at low pH 1:1 polymers are more stable than [Au(SR)n]1-n species.

AB - Reactions at pH 7 between gold(I) thiomalate and a variety of thiols with pKSH values ranging from 7.6 (thioglucose) to 10.2 (mercaptoacetate) have been studied by 13C n.m.r. spectroscopy. New species [Au(SR)n]1-n, where n appears to be less than 2, are formed and thiomalate is readily displaced, especially by thiols with low pKSH. The latter are in fast exchange with AuI on the n.m.r. time scale. Similar activation parameters have been derived for thiomalate, N-acetyl-L-cysteine, and mercaptoacetate exchange (ΔG‡ 63 kJ mol-1, ΔS‡ -145 J K-1 mol-1, EA 22 kJ mol-1) via a line-shape analysis of 13C n.m.r. spectra at different temperatures. Thiol exchange rates increase at high pH, but at low pH 1:1 polymers are more stable than [Au(SR)n]1-n species.

UR - https://www.scopus.com/pages/publications/37049110799

U2 - 10.1039/DT9820000135

DO - 10.1039/DT9820000135

M3 - Article

AN - SCOPUS:37049110799

SN - 1472-7773

SP - 135

EP - 141

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 1

ER -

A carbon-13 nuclear magnetic resonance study of thiol-exchange reactions of gold(I) thiomalate ('Myocrisin') including applications to cysteine derivatives

Abstract

Bibliographical note

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