Adsorption of beta-adrenergic agonists used in sport doping on metal nanoparticles: a detection study based on surface-enhanced Raman scattering.

The adsorption of beta(2)-adrenergic agonist (βAA) drugs clenbuterol, salbutamol, and terbutaline on metal surfaces has been investigated in this work by means of surface-enhanced Raman scattering (SERS). To assist in this investigation, a previous vibrational (IR and normal Raman) characterization of these drugs was performed, supported by ab initio density functional theory calculations. The application of SERS was aimed to apply this highly sensitive technique, based on localized surface plasmon resonance, in the detection of βAA at trace concentrations and as a possible alternative method which can be postulated in routine antidoping analysis. The adsorption of these drugs was studied in depth at different experimental conditions: on Au and Ag, at different pHs, and with varying adsorbate concentration. Moreover, plasmon resonance spectroscopy was employed to investigate the adsorption of these drugs on the metal nanoparticles as well as their aggregation. It was found that the adsorption of these molecules is more effective on gold nanoparticles and at acidic pH, based on the direct interaction of the aromatic or aliphatic moieties through ionic or coordination bonds with the metal. These drugs followed a Langmuir adsorption model from which the adsorption constant and the limit of detection can be determined.

[1]  C. Domingo,et al.  Sensing polycyclic aromatic hydrocarbons with dithiocarbamate-functionalized ag nanoparticles by surface-enhanced Raman scattering. , 2009, Analytical chemistry.

[2]  Carlo Bicchi,et al.  High-speed gas chromatography in doping control: fast-GC and fast-GC/MS determination of beta-adrenoceptor ligands and diuretics. , 2006, Journal of separation science.

[3]  Y. Yang,et al.  Multiple actions of beta-adrenergic agonists on skeletal muscle and adipose tissue. , 1989, The Biochemical journal.

[4]  M. Moskovits,et al.  A SERS-active system based on silver nanoparticles tethered to a deposited silver film. , 2006, The journal of physical chemistry. B.

[5]  Aiming Liu,et al.  Simultaneous analysis of bambuterol and its active metabolite terbutaline enantiomers in rat plasma by chiral liquid chromatography-tandem mass spectrometry. , 2010, Journal of pharmaceutical and biomedical analysis.

[6]  W. S. Sutherland,et al.  Colloid filtration: A novel substrate preparation method for surface-enhanced Raman spectroscopy , 1992 .

[7]  H. Edwards,et al.  Vibrational spectroscopic study of terbutaline hemisulphate. , 2009, Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy.

[8]  Guonan Chen,et al.  Improved simultaneous enantioseparation of β‐agonists in CE using β‐CD and ionic liquids , 2009, Electrophoresis.

[9]  F. Hartgens,et al.  Inhaled salbutamol and endurance cycling performance in non-asthmatic athletes. , 2004, International journal of sports medicine.

[10]  Guonan Chen,et al.  Electrostacking online sample pre-concentration capillary electrophoresis with amperometric detection for beta2-agonists in human urine. , 2008, Journal of separation science.

[11]  M. Moskovits Surface-enhanced spectroscopy , 1985 .

[12]  N. Shah,et al.  Sensitive and selective chem/bio sensing based on surface-enhanced Raman spectroscopy (SERS) , 2006 .

[13]  H. Fenniri,et al.  SERS Classification of Highly Related Performance Enhancers , 2007, ChemMedChem.

[14]  C. Domingo,et al.  Surface-Enhanced Micro-Raman Detection and Characterization of Calix[4]Arene—Polycyclic Aromatic Hydrocarbon Host—Guest Complexes , 2005, Applied spectroscopy.

[15]  J. Laserna,et al.  Surface-enhanced Raman spectrometry of chiral β-blocker drugs on colloidal silver , 1996 .

[16]  H. Edwards,et al.  Vibrational spectroscopic study of salbutamol hemisulphate. , 2009, Drug testing and analysis.

[17]  M. Moskovits,et al.  Single-molecule surface-enhanced Raman spectroscopy from a molecularly-bridged silver nanoparticle dimer , 2008 .

[18]  Shulin Zhao,et al.  Determination of terbutaline sulfate by capillary electrophoresis with chemiluminescence detection. , 2009, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[19]  C. Domingo,et al.  Functionalization of Ag nanoparticles with dithiocarbamate calix[4]arene as an effective supramolecular host for the surface-enhanced Raman scattering detection of polycyclic aromatic hydrocarbons. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[20]  Siegfried Schneider,et al.  Combination of high-performance liquid chromatography and SERS detection applied to the analysis of drugs in human blood and urine , 2004 .

[21]  M. Yáñez,et al.  Structural and energetic aspects of the protonation of phenol, catechol, resorcinol, and hydroquinone. , 2002, Chemistry.

[22]  Somsak Sirichai,et al.  Rapid analysis of clenbuterol, salbutamol, procaterol, and fenoterol in pharmaceuticals and human urine by capillary electrophoresis. , 2008, Talanta.

[23]  J. Popp,et al.  Surface-enhanced Raman spectroscopy , 2009, Analytical and bioanalytical chemistry.

[24]  Bingcheng Lin,et al.  Integrated microfluidic immunoassay for the rapid determination of clenbuterol. , 2009, Lab on a chip.