Speciation of L-DOPA on nanorutile as a function of pH and surface coverage using surface-enhanced Raman spectroscopy (SERS)

The adsorption configuration of organic molecules on mineral surfaces is of great interest because it can provide fundamental information for both engineered and natural systems. Here we have conducted surface-enhanced Raman spectroscopy (SERS) measurements to probe the attachment configurations of...

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Veröffentlicht in:Langmuir : the ACS journal of surfaces and colloids. - 1992. - 28(2012), 50 vom: 18. Dez., Seite 17322-30
1. Verfasser: Lee, Namhey (VerfasserIn)
Weitere Verfasser: Hummer, Daniel R, Sverjensky, Dimitri A, Rajh, Tijana, Hazen, Robert M, Steele, Andrew, Cody, George D
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2012
Zugriff auf das übergeordnete Werk:Langmuir : the ACS journal of surfaces and colloids
Schlagworte:Journal Article Research Support, Non-U.S. Gov't Research Support, U.S. Gov't, Non-P.H.S. titanium dioxide 15FIX9V2JP Levodopa 46627O600J Titanium D1JT611TNE
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245 1 0 |a Speciation of L-DOPA on nanorutile as a function of pH and surface coverage using surface-enhanced Raman spectroscopy (SERS) 
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520 |a The adsorption configuration of organic molecules on mineral surfaces is of great interest because it can provide fundamental information for both engineered and natural systems. Here we have conducted surface-enhanced Raman spectroscopy (SERS) measurements to probe the attachment configurations of DOPA on nanorutile particles under different pH and surface coverage conditions. The Raman signal enhancement arises when a charge transfer (CT) complex forms between the nanoparticles and adsorbed DOPA. This Raman signal is exclusively from the surface-bound complexes with great sensitivity to the binding and orientation of the DOPA attached to the TiO(2) surface. Our SERS spectra show peaks that progressively change with pH and surface coverage, indicating changing surface speciation. At low pH and surface coverage, DOPA adsorbs on the surface lying down, with probably three points of attachment, whereas at higher pH and surface coverage DOPA stands up on the surface as a species involving two attachment points via the two phenolic oxygens. Our results demonstrate experimentally the varying proportions of the two surface species as a function of environmental conditions consistent with published surface complexation modeling. This observation opens up the possibility to manipulate organic molecule attachment in engineered systems such as biodetection devices. Furthermore, it provides a perspective on the possible role of mineral surfaces in the chemical evolution of biomolecules on the early Earth. Adsorbed biomolecules on mineral surface in certain configurations may have had an advantage for subsequent condensation reactions, facilitating the formation of peptides 
650 4 |a Journal Article 
650 4 |a Research Support, Non-U.S. Gov't 
650 4 |a Research Support, U.S. Gov't, Non-P.H.S. 
650 7 |a titanium dioxide  |2 NLM 
650 7 |a 15FIX9V2JP  |2 NLM 
650 7 |a Levodopa  |2 NLM 
650 7 |a 46627O600J  |2 NLM 
650 7 |a Titanium  |2 NLM 
650 7 |a D1JT611TNE  |2 NLM 
700 1 |a Hummer, Daniel R  |e verfasserin  |4 aut 
700 1 |a Sverjensky, Dimitri A  |e verfasserin  |4 aut 
700 1 |a Rajh, Tijana  |e verfasserin  |4 aut 
700 1 |a Hazen, Robert M  |e verfasserin  |4 aut 
700 1 |a Steele, Andrew  |e verfasserin  |4 aut 
700 1 |a Cody, George D  |e verfasserin  |4 aut 
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773 1 8 |g volume:28  |g year:2012  |g number:50  |g day:18  |g month:12  |g pages:17322-30 
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