Detection and analysis of cyclotrimethylenetrinitramine (RDX) in environmental samples by surface-enhanced Raman spectroscopy

Techniques for rapid and sensitive detection of energetics such as cyclotrimethylenetrinitramine (RDX) are needed both for environmental and security screening applications. Here we report the use of surface enhanced Raman spectroscopy (SERS) to detect traces of RDX with good sensitivity and reproducibility. Using gold (Au) nanoparticles (~90-100 nm in diameter) as SERS substrates, RDX was detectable at concentrations as low as 0.15 mg/L in a contaminated groundwater sample. This detection limit is about two orders of magnitude lower than those reported previously using SERS techniques. A surface enhancement factor of ~6x104 was obtained. This research further demonstrates the potential for using SERS as a rapid, in-situ field screening tool for energetics detection when coupled with a portable Raman spectrometer.

[1]  M. Natan,et al.  Seeding of Colloidal Au Nanoparticle Solutions. 2. Improved Control of Particle Size and Shape , 2000 .

[2]  N. Shah,et al.  Surface-enhanced Raman spectroscopy. , 2008, Annual review of analytical chemistry.

[3]  M. Klempner,et al.  Characterization of the surface enhanced raman scattering (SERS) of bacteria. , 2005, The journal of physical chemistry. B.

[4]  S. Ahn,et al.  Controlled Synthesis of Icosahedral Gold Nanoparticles and Their Surface-Enhanced Raman Scattering Property , 2007 .

[5]  C. Ruan,et al.  Determination of technetium and its speciation by surface-enhanced Raman spectroscopy. , 2007, Analytical chemistry.

[6]  K. Murakoshi,et al.  Control of near-infrared optical response of metal nano-structured film on glass substrate for intense Raman scattering. , 2006, Faraday discussions.

[7]  J. Janni,et al.  Surface-enhanced raman detection of 2,4-dinitrotoluene impurity vapor as a marker to locate landmines. , 2000, Analytical chemistry.

[8]  C. Ruan,et al.  Perchlorate Detection at Nanomolar Concentrations by Surface-Enhanced Raman Scattering , 2009, Applied spectroscopy.

[9]  Xiaoyu Zhang,et al.  Wavelength-Scanned Surface-Enhanced Resonance Raman Excitation Spectroscopy , 2008 .

[10]  A. Wei,et al.  Tunable surface-enhanced Raman scattering from large gold nanoparticle arrays. , 2001, Chemphyschem : a European journal of chemical physics and physical chemistry.

[11]  W. Smith,et al.  Selective functionalisation of TNT for sensitive detection by SERRS. , 2002, Chemical communications.

[12]  L. Pacheco-Londoño,et al.  Nanotechnology-Based Detection of Explosives and Biological Agents Simulants , 2008, IEEE Sensors Journal.

[13]  Mustafa Çulha,et al.  Characterization of Thermophilic Bacteria Using Surface-Enhanced Raman Scattering , 2008, Applied spectroscopy.

[14]  R. Guo,et al.  Adsorption characteristics of thionine on gold nanoparticles. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[15]  C. Ruan,et al.  Surface-enhanced Raman spectroscopy for uranium detection and analysis in environmental samples. , 2007, Analytica chimica acta.

[16]  T. Brill,et al.  Comparison of the molecular structure of hexahydro-1,3,5-trinitro-s-triazine in the vapor, solution and solid phases , 1984 .

[17]  B. Parkinson,et al.  Surface-Enhanced Raman Spectroscopy in the Near-Infrared , 1988 .

[18]  Stephan Link,et al.  Optical properties and ultrafast dynamics of metallic nanocrystals. , 2003, Annual review of physical chemistry.

[19]  Weiqi Wang,et al.  Single‐molecule detection of thionine on aggregated gold nanoparticles by surface enhanced Raman scattering , 2007 .

[20]  Catherine J. Murphy,et al.  Wet Chemical Synthesis of High Aspect Ratio Cylindrical Gold Nanorods , 2001 .

[21]  Hongjun Gao,et al.  Monodisperse Noble-Metal Nanoparticles and Their Surface Enhanced Raman Scattering Properties , 2008 .

[22]  Tao Zhu,et al.  Raman scattering enhancement contributed from individual gold nanoparticles and interparticle coupling , 2004 .

[23]  M. Natan,et al.  Self-Assembled Metal Colloid Monolayers: An Approach to SERS Substrates , 1995, Science.

[24]  George C. Schatz,et al.  Electromagnetic mechanism of SERS , 2006 .

[25]  H. Craig,et al.  Overview of On-Site Analytical Methods for Explosives in Soil. , 1998 .

[26]  Frank Seifert,et al.  Near-infrared excitation profile study of surface-enhanced hyper-Raman scattering and surface-enhanced Raman scattering by means of tunable mode-locked Ti: sapphire laser excitation , 1995 .

[27]  Duncan Graham,et al.  SERRS. In situ substrate formation and improved detection using microfluidics. , 2002, Analytical chemistry.

[28]  Mustafa Culha,et al.  Experimental parameters influencing surface-enhanced Raman scattering of bacteria. , 2007, Journal of biomedical optics.

[29]  K. Kneipp,et al.  Near-infrared excited surface-enhanced Raman spectroscopy of rhodamine 6G on colloidal silver , 1993 .

[30]  L. Brus Noble metal nanocrystals: plasmon electron transfer photochemistry and single-molecule Raman spectroscopy. , 2008, Accounts of chemical research.

[31]  Louis E. Brus,et al.  Single Molecule Raman Spectroscopy at the Junctions of Large Ag Nanocrystals , 2003 .

[32]  M. Godejohann,et al.  Comprehensive non-targeted analysis of contaminated groundwater of a former ammunition destruction site using 1H-NMR and HPLC-SPE-NMR/TOF-MS. , 2009, Environmental science & technology.

[33]  Yang Wang,et al.  Near-infrared surface-enhanced Raman scattering of trinitrotoluene on colloidal gold and silver , 1995 .

[34]  C. Murphy,et al.  Room temperature, high-yield synthesis of multiple shapes of gold nanoparticles in aqueous solution. , 2004, Journal of the American Chemical Society.

[35]  O. M. Primera-Pedrozo,et al.  Enhanced Raman Scattering of 2,4,6-TNT Using Metallic Colloids , 2008, IEEE Sensors Journal.

[36]  M. El-Sayed,et al.  Chemistry and properties of nanocrystals of different shapes. , 2005, Chemical reviews.

[37]  R. J. Scharff,et al.  Portable Raman explosives detection , 2009, Analytical and bioanalytical chemistry.

[38]  Nairmen Mina,et al.  Vibrational Spectroscopy Study of β and α RDX Deposits , 2004 .

[39]  Louis E. Brus,et al.  Ag Nanocrystal Junctions as the Site for Surface-Enhanced Raman Scattering of Single Rhodamine 6G Molecules , 2000 .

[40]  Yang Wang,et al.  Near-Infrared Surface-Enhanced Raman Scattering (NIR SERS) on Colloidal Silver and Gold , 1994 .

[41]  Baohua Gu,et al.  One-dimensional arrays of nanoshell dimers for single molecule spectroscopy via surface-enhanced Raman scattering. , 2006, The Journal of chemical physics.