Detection of Protein Toxin Simulants from Contaminated Surfaces by Paper Spray Mass Spectrometry
- 252 Downloads
Proteinaceous toxins are harmful proteins derived from plants, bacteria, and other natural sources. They pose a risk to human health due to infection and also as possible biological warfare agents. Paper spray mass spectrometry (PS-MS) with wipe sampling was used to detect proteins from surfaces as a potential tool for identifying the presence of these toxins. Proteins ranging in mass between 12.4 and 66.5 kDa were tested, including a biological toxin simulant/vaccine for Staphylococcal enterotoxin B (SEBv). Various substrates were tested for these representative proteins, including a laboratory bench, a notebook cover, steel, glass, plant leaf and vinyl flooring. Carbon sputtered porous polyethylene (CSPP) was found to outperform typical chromatography paper used for paper spray, as well as carbon nanotube (CNT)-coated paper and polyethylene (PE), which have been previously shown to be well-suited for protein analysis. Low microgram quantities of the protein toxin simulant and other test proteins were successfully detected with good signal-to-noise from surfaces using a porous wipe. These applications demonstrate that PS-MS can potentially be used for rapid, sample preparation-free detection of proteins and biological warfare agents, which would be beneficial to first responders and warfighters.
KeywordsLarge molecule Swabbing Ambient ionization Direct analysis Cartridge prototyping
This work was supported by a grant (CB10238) from the Joint Science and Technology Office (JSTO) and the CBA Division of the Defense Threat Reduction Agency (DTRA). DTRA is a Combat Support Agency and a Defense Agency with a three-pronged mission: (1) to counter the threats posed by the full spectrum of weapons of mass destruction (WMD), including chemical, biological, radiological, nuclear, and high-yield explosives; (2) counter the threats posed by the growing, evolving categories of improvised threats, including improvised explosive devices, car bombs, and weaponized consumer drones, as well as the tactics, technologies, and networks that put them on the battlefield; (3) ensure the U.S. military maintains a safe, secure, effective, and credible nuclear weapons deterrent.
The authors would like to thank Alena Calm (CCDC Chemical Biological Center) for kindly providing all purified SEBv used in this study. The authors would also like to thank the Integrated Nanosystems Development Institute (INDI) for the use of the sputtering and SEM systems, as well as David Heemstra (NDnano) at the University of Notre Dame for his contribution and valuable discussions regarding thin film deposition. Conclusions and opinions presented here are those of the authors and are not the official policy of the US Army, CCDC Chemical Biological Center, or the US Government. Information in this report is cleared for public release and distribution is unlimited.
- 1.Krenzelok, E. P., and American Society of Health-System Pharmacists: Biological and chemicalterrorism : a pharmacy preparedness guide. American Society of Health-System Pharmacists, Bethesda (2003)Google Scholar
- 5.Crowe, K.: Salad bar salmonella. Forensic Examiner. 16, 24 (2007)Google Scholar
- 7.National Research Council: Review of the Scientific Approaches Used During the FBI's Investigation of the 2001 Anthrax Letters. The National Academies Press, Washington, DC (2011). doi: https://doi.org/10.17226/13098
- 8.Roxas-Duncan, V.I., Smith, L.A.: Ricin Perspective in Bioterrorism, Bioterrorism, Stephen A. Morse, IntechOpen (2012). doi: https://doi.org/10.5772/33392
- 11.Dou, K., Chen, G., Yu, F.B., Liu, Y.X., Chen, L.X., Cao, Z.P., Chen, T., Li, Y.L., You, J.M.: Bright and sensitive ratiometric fluorescent probe enabling endogenous FA imaging and mechanistic exploration of indirect oxidative damage due to FA in various living systems. Chem. Sci. 8, 7851–7861 (2017)CrossRefGoogle Scholar
- 13.Mason, J.T., Xu, L., Sheng, Z.M., O’leary, T.: Liposome polymerase chain reaction assay for the high sensitivity detection of biological toxins. Biophys. J. 329A–329A (2007)Google Scholar
- 18.Kilianski, A., Roth, P.A., Liem, A.T., Hill, J.M., Willis, K.L., Rossmaier, R.D., Marinich, A.V., Maughan, M.N., Karavis, M.A., Kuhn, J.H.: Use of unamplified RNA/cDNA–hybrid nanopore sequencing for rapid detection and characterization of RNA viruses. Emerg. Infect. Dis. 22, 1448 (2016)CrossRefGoogle Scholar
- 20.Steinbock, L.J., Radenovic, A.: The emergence of nanopores in next-generation sequencing. Nanotechnology. 26(5), (2015)Google Scholar
- 24.Stevenson, R.L.: Sample preparation for liquid chromatography-mass spectrometry. Am. Lab. 44, 36–38 (2012)Google Scholar
- 36.Dhummakupt, E.S., Mach, P.M., Carmany, D., Demond, P.S., Moran, T.S., Connell, T., Wylie, H.S., Manicke, N.E., Nilles, J.M., Glaros, T.: Direct analysis of aerosolized chemical warfare simulants captured on a modified glass-based substrate by “paper-spray” ionization. Anal. Chem. 89, 10866–10872 (2017)CrossRefGoogle Scholar
- 43.Lowell, G.H., Kaminski, R.W., Grate, S., Hunt, R.E., Charney, C., Zimmer, S., Colleton, C.: Intranasal and intramuscular proteosome-staphylococcal enterotoxin B (SEB) toxoid vaccines: immunogenicity and efficacy against lethal SEB intoxication in mice. Infect. Immun. 64, 1706–1713 (1996)Google Scholar
- 44.Boles, J.W., Pitt, M.L.M., Leclaire, R.D., Gibbs, P.H., Torres, E., Dyas, B., Ulrich, R.G., Bavari, S.: Generation of protective immunity by inactivated recombinant staphylococcal enterotoxin B vaccine in nonhuman primates and identification of correlates of immunity. Clin. Immunol. 108, 51–59 (2003)CrossRefGoogle Scholar
- 56.US Army Publication Directorate: Chemical, biological, radiological, nuclear and explosives command (CBRNE COMMAND). Publication Number ATP 3–37.11 (2018)Google Scholar
- 58.Lawton, Z.E., Traub, A., Fatigante, W.L., Mancias, J., O’leary, A.E., Hall, S.E., Wieland, J.R., Oberacher, H., Gizzi, M.C., Mulligan, C.C.: Analytical validation of a portable mass spectrometer featuring interchangeable, ambient ionization sources for high throughput forensic evidence screening. J. Am. Soc. Mass Spectrom. 28, 1048–1059 (2017)CrossRefGoogle Scholar
- 59.Fedick, P., Fatigante, W., Lawton, Z., O’leary, A., Hall, S., Bain, R., Ayrton, S., Ludwig, J., Mulligan, C.: A low-cost, simplified platform of interchangeable, ambient ionization sources for rapid, forensic evidence screening on portable mass spectrometric instrumentation. Instruments. 2, 5 (2018)CrossRefGoogle Scholar
- 60.Silva, L.C., Pereira, I., Carvalho, T.C., Allochio Filho, J.F., Romão, W., Gontijo Vaz, B.: Paper spray ionization and portable mass spectrometers: a review. Anal. Methods. 11, 999–1013 (2019)Google Scholar
- 61.Devereaux, Z.J., Reynolds, C.A., Fischer, J.L., Foley, C.D., Deleeuw, J.L., Wager-Miller, J., Narayan, S.B., Mackie, K., Trimpin, S.: Matrix-assisted ionization on a portable mass spectrometer: analysis directly from biological and synthetic materials. Anal. Chem. 88, 10831–10836 (2016)CrossRefGoogle Scholar