The increasing demand for heterogeneous materials prompts the interest for the physics and chemistry of organic–inorganic interfaces. Within this field of interest we have investigated the electronic states of L-cysteine (Cys) adsorbed on Au(111) from aqueous solution with synchrotron-based, high resolution X-ray photoemission spectroscopy. The analysis of the S 2p core level region in pristine samples prepared with purified Cys indicates that Cys adsorbs on gold as a thiolate. The absence of a signal related to physisorbed sulfur indicates that Cys forms a monomolecular layer. The high resolution allowed us to resolve two components in the C 1s spectral region related to carboxyl. The comparative analysis of C 1s, N 1s and O 1s core level regions indicates the presence of the neutral and ionic form for both the carboxyl and the amine groups. From the quantitative analysis of the C 1s and N 1s data we can infer that the zwitterionic form is the prevalent one, with a ratio of zwitterionic to neutral molecules of 3 : 1. This value is quite different from that in the deposition solution. Prolonged exposure to the X-ray beam and thermal annealing induce the formation of atomic sulfur through S–C bond breaking and molecular fragment desorption. This response to X-ray irradiation differs from the results recently reported on long chain alkanethiols.
High resolution X-ray photoelectron spectroscopy of L-cysteine self-assembled films
CAVALLERI, ORNELLA;TERRENI, SILVANA;CANEPA, MAURIZIO;ROLANDI, RANIERI
2004-01-01
Abstract
The increasing demand for heterogeneous materials prompts the interest for the physics and chemistry of organic–inorganic interfaces. Within this field of interest we have investigated the electronic states of L-cysteine (Cys) adsorbed on Au(111) from aqueous solution with synchrotron-based, high resolution X-ray photoemission spectroscopy. The analysis of the S 2p core level region in pristine samples prepared with purified Cys indicates that Cys adsorbs on gold as a thiolate. The absence of a signal related to physisorbed sulfur indicates that Cys forms a monomolecular layer. The high resolution allowed us to resolve two components in the C 1s spectral region related to carboxyl. The comparative analysis of C 1s, N 1s and O 1s core level regions indicates the presence of the neutral and ionic form for both the carboxyl and the amine groups. From the quantitative analysis of the C 1s and N 1s data we can infer that the zwitterionic form is the prevalent one, with a ratio of zwitterionic to neutral molecules of 3 : 1. This value is quite different from that in the deposition solution. Prolonged exposure to the X-ray beam and thermal annealing induce the formation of atomic sulfur through S–C bond breaking and molecular fragment desorption. This response to X-ray irradiation differs from the results recently reported on long chain alkanethiols.
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