430
J. Athilakshmi et al. / Tetrahedron Letters 54 (2013) 427–430
Cysteine
AgNPs
(DMSO)
-COOH
-NH2
-CH2SH
cysteine
Figure 5. Proposed model of the aggregation of AgNPs over time after the addition of cysteine.
2. Jacob, C.; Giles, G. I.; Giles, N. M.; Sies, H. Angew. Chem., Int. Ed. 2003, 42, 4742.
(S-methyl-
O-protected (
L
-cysteine (7), N-protected (N-acetylcysteine) (8), and
-cysteine methylester hydrochloride) (9), and the
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L
dipeptide cys-gly (10). UV–vis spectra (Supplementary Fig. S8)
were recorded for these solutions, and as expected the color
change from yellow to pink (Supplementary Fig. S9) and peak
broadening were observed for the analytes having free thiols (2,
5, 6, 8, 9, and 10) and for the disulfide (3). No change could be seen
after the addition of glycine (4) or S-protected analytes, such as
methyl cysteine (7). This method is thus also effective for the
selective detection of simple thiols and disulfides over sulfide.
We hope that this method can be elaborated further to determine
the presence of free thiols and disulfide moieties in proteins.
Our method involves a simple procedure that can be performed
at room temperature for the detection described. The selectivity of
the detection is controlled by the solvent, DMSO,19 in which the
probable disulfide formation is catalyzed by AgNPs (Fig. 5). The
use of DMSO as a dispersant is also advantageous because DMSO
is a mild oxidizing agent of thiols.
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To conclude, selective detection of cysteine/cystine at a ppm le-
vel was successful by using AgNPs prepared in the presence of the
hexaazamacrocycle L1 in DMSO.
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Acknowledgment
This work was supported by CSIR, India (Project No. 01/(2483)/
11/EMR/II).
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Supplementary data
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Supplementary data (Photograph and UV–vis spectra of the
AgNPs showing the selective detection of cysteine/cystine in
DMSO) associated with this article can be found, in the online ver-
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