Development of a Surface-Enhanced Raman Technique for Biomarker Studies on Mars

Abstract

Raman spectroscopy has been identified as a potentially useful tool to collect evidence of past or present life on extraterrestrial bodies. However, it is limited by its inherently low signal strength. In this investigation, laboratory tests were conducted using surface-enhanced Raman spectroscopy (SERS) in an “inverted” mode to detect the presence of organic compounds that may be similar to possible biomarkers present on Mars. SERS was used to overcome the inherently low signal intensity of Raman spectroscopy and was an effective method for detecting small concentrations of organic compounds on a number of surfaces. For small organic molecules, dissolution of the molecule to be analyzed in a suitable solvent and depositing it on a prepared SERS substrate for analysis is possible. However, for larger molecules, an “inverted” SERS (iSERS) technique was shown to be effective. In iSERS, nanoparticles of silver or gold were deposited on the mineral substrate/organic compound to be analyzed. Benzotriazole, benzoic acid, and phthalic acid were used as test organic analogs and the iSERS technique was able to detect femtomole levels of the analytes. The interference from various mineral substrates was also examined. Different methods of depositing silver particles were evaluated, including ion beam-assisted vapor deposition and deposition from aqueous colloidal suspensions.

Keywords

Raman spectroscopy Surface-enhanced Raman spectroscopy SERS Organic biomarkers Mars

Get full access to this article

View all access options for this article.

References

National Aeronautical and Space Administration (NASA), NASA Astrobiology Roadmap, http://astrobiology.arc.nasa.gov/roadmap/roadmap.pdf, Washington, D.C., National Aeronautical and Space Administration (September 2003).

Ellery

Wynn-Williams

Parnell

Edwards

H. G. M.

and Dickensheets

, J. Raman Spectrosc. 35, 441 (2004).

Wang

Haskin

L. A.

and Cortez

, Appl. Spectrosc. 52, 477 (1998).

Wang

Haskin

L. A.

Lane

A. L.

Wdowiak

T. J.

Squyres

S. W.

Wilson

R. J.

Hovland

L. E.

Manatt

K. S.

Raouf

and Smith

C. D

, J. Geophys. Res. 108, 5005, 5–1 (2003).

Sharma

S. K.

Angel

Ghosh

Hubble

H. W.

and Lucey

P. G

, Appl. Spectrosc. 56, 699 (2002).

Ellery

A. A.

Cockell

C. S.

Edwards

H. G. M.

Dickensheets

D. L.

and Welch

C. S

, Int. J. Astrobiol. 1, 191 (2002).

DiGregorio

B. E.

, Spectroscopy 15(9), 49 (2000).

Moskovits

, Rev. Mod. Phys. 57, 783 (1985).

Kiefer

, Special Techniques and Applications Infrared and Raman Spectroscopy Methods and Applications, Schrader

Ed. (Weinheim, Germany VCH, 1994), p. 490.

10.

Zayat

and Einot

, J. Sol-Gel Sci. Technol. 10, 64 (1997).

11.

and Jia

, Appl. Spectrosc. 58, 1 (2004).

12.

Yang

and Chen

S.-H

, Appl. Spectrosc. 55, 399 (2001).

13.

Pastorzia-Santos

and Liz-Marzan

L. M

, Pure Appl. Chem. 72, 83 (2000).

14.

Lee

P. C.

and Meisel

, J. Phys. Chem. 86, 3391 (1982).

15.

Fleischmann

Tian

Z. Q.

and Li

L. J

, J. Electroanal. Chem. 217, 397 (1987).

16.

Creighton

J. A.

, Surf. Sci. 173, 665 (1986).

17.

Creighton

J. A.

, Royal Soc. Chem. 84, 13 (1990).

18.

Oblonsky

L. J.

and Devine

T. M

, Corrosion Sci. 31, 17 (1995).

19.

Gui

and Devine

T. M

, Corrosion Sci. 36, 441 (1994).

20.

Simpson

L. J.

and Melendres

C. A

, J. Electrochem. Soc. 143, 2146 (1996).

21.

Jiang

L.-P.

and Wang

A.-N

, Inorg. Chem. Commun. 7, 506 (2004).

22.

Stockle

R. M.

Deckert

Fokas

and Zenobi

, Appl. Spectrosc. 54, 1577 (2000).

23.

Nepijko

S. A.

Ievlev

D. N.

and Schulze

, Physica B 304, 45 (2001).

24.

D'Urso

and Nicolosi

, Appl. Surf. Sci. 226, 131 (2004).

25.

Kundu

and Madhuri

, J. Photochem. Photobiol., A 162, 625 (2004).

26.

Norrod

K. L.

Sudnik

L. M.

Rousell

and Rowlen

K. L

, Appl. Spectrosc. 51, 994 (1997).

27.

Benner

S. A.

Delvine

K. G.

Matveeva

L. D.

and Powell

D. H

, Proc. Natl. Acad. Sci. U.S.A. 97, 2425 (2000).

28.

Banfield

J. F.

Moreau

J. W.

Chan

C. S.

Welch

S. A.

and Little

, Astrobiology 1, 447 (2001).

29.

Bandfield

J. L.

, J. Geophys. Res. 107, E6, 9.1 (2002).

30.

Christensen

P. R.

Bandfield

J. L.

Clark

R. N.

Edgett

K. S.

Hamilton

V. E.

Hoefen

Kieffer

H. H.

Kuzmin

R. O.

Lane

M. D.

Malin

M. C.

Morris

R. V.

Pearl

J. C.

Pearson

Roush

T. L.

Ruff

S. W.

and Smith

M. D

, J. Geophys. Res. 105, 623 (2000).

31.

Christensen

P. R.

Bandfield

J. L.

Smith

M. D.

Hamilton

V. E.

and Clark

R. N

, J. Geophys. Res. 105, 9609 (2000).

32.

Huang

Chen

E. C. H.

Huang

Lin

E. H.

and Xu

J.-A

, Am. Mineral. 85, 473 (2000).

33.

Tomisaka

and Iishi

, Mineral. J. 10, 84 (1980).

34.

Chamritski

and Burns

, J. Phys. Chem. B 109, 4965 (2005).

35.

Bersani

Lottici

P. P.

and Montenero

, J. Raman Spectrosc. 30, 355 (1999).

36.

Nauer

Strecha

Brinda-Konopik

and Liptay

, J. Therm. Anal. 813 (1985).

37.

Degen

I. A.

and Newman

G. A

, Spectrochim. Acta, Part A 49, 859 (1993).

38.

Herman

R. G.

Bogdan

C. E.

Sommer

A. J.

and Simpson

D. R

, Appl. Spectrosc. 41, 437 (1987).

39.

De Faria

D. L. A.

Silva

S. V.

and De Oliveira

M. T

, J. Raman Spectrosc. 28, 873 (1997).

40.

Oblonsky

L. J.

and Devine

T. M

, J. Electrochem. Soc. 142, 3677 (1995).

41.

Dunn

D. S.

Bogart

M. B.

Brossia

C. S.

and Cragnolino

G. A

, Corrosion 56, 470 (2000).

42.

White

W. B.

, Infrared and Raman Spectroscopy of Lunar and Terrestrial Minerals (Academic Press, New York, 1975), p. 325.

43.

Servion

J. L.

and Piriou

, Phys. Status Solidii B 55, 677 (1973).

44.

Heymann

and Cellucci

T. A

, Raman Spectra of Shocked Minerals 1: Olivine, Meteoritics 23, 353 (1988).

45.

Cao

P. G.

Yao

J. L.

Zheng

J. W.

R. A.

and Tian

Z. Q

, Langmuir 18, 100 (2002).

46.

Trout

C. C.

Tambach

T. J.

and Kubicki

J. D

, Spectrochim. Acta, Part A 61, 2622 (2005).

47.

Joo

S. W.

Han

S. W.

Han

H. S.

and Kim

, J. Raman Spectrosc. 31, 145 (2000).

48.

Xue

and Zhang

, Appl. Spectrosc. 45, 760 (1991).