Hostname: page-component-78c5997874-t5tsf Total loading time: 0 Render date: 2024-11-19T08:23:13.307Z Has data issue: false hasContentIssue false

Solutochromic Molecular Spectroscopy with a Reference Hydrogen-Bond Acid Dendrimer

Published online by Cambridge University Press:  30 April 2012

R. Andrew McGill
Affiliation:
Naval Research Laboratory, Codes a6365, b5654, Washington, DC 20375 USA
Duane Simonson
Affiliation:
Naval Research Laboratory, Codes a6365, b5654, Washington, DC 20375 USA
Julie H. Ta
Affiliation:
Naval Research Laboratory, Codes a6365, b5654, Washington, DC 20375 USA
Viet Nguyen
Affiliation:
Naval Research Laboratory, Codes a6365, b5654, Washington, DC 20375 USA
Yasar Ozten
Affiliation:
Naval Research Laboratory, Codes a6365, b5654, Washington, DC 20375 USA Federal Office of Defense Technology, Ferdi-Sauerbruch-Str. 1, 56073 Koblenz, Germany
Chris Kendziora
Affiliation:
Naval Research Laboratory, Codes a6365, b5654, Washington, DC 20375 USA
Todd H. Stievater
Affiliation:
Naval Research Laboratory, Codes a6365, b5654, Washington, DC 20375 USA
Get access

Abstract

A zeroth order dendritic carbosilane structure, SiFA4H with four hexafluoroisopropanol (HFIP) functional groups attached via propyl ligand arms to a central silicon atom, has been developed as a model hydrogen-bond (HB) acid sorbent coating and candidate reference HB acid. The HB donor interaction, through the hydroxyl of the HFIP moiety, with a solute HB base can be monitored by observing the hydroxyl stretching frequency through measurements of SiFA4H FTIR spectra before and during vapor exposure. HFIP hydroxyl stretch shifts, upwards of 700 cm-1 have been observed depending on the HB base. For a range of HB bases, the resulting hydroxyl stretch shifts correlate directly with the solute HB basicity scale, “B”, developed by Abraham et al [1]. A variety of techniques exist to measure solute HB basicity, however, the applicability to examine HB bases delivered as vapors or gases and the simplicity of the measurements described herein, with a reusable reference HB acid sorbent coating and standard FTIR spectrophotometer techniques is attractive for some applications including those with hazardous chemicals. Moreover, as an extension of this work we propose employing SiFA4H or related sorbents as molecular sensing coatings, where the semi-selective sorbent is examined by various infrared (IR) spectroscopic techniques to monitor and identify hazardous chemicals, taking advantage of molecular binding phenomena which occur in the sorbent [2].

Type
Research Article
Copyright
Copyright © Materials Research Society 2012

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1. Abraham, M.H., Chem. Soc. Rev. 22, 7383 (1993).Google Scholar
2. Stievater, T.H., Papanicolaou, N. A., Bass, R., Rabinovich, W. S. and McGill, R. A., Opt. Lett. (accepted, 2012).Google Scholar
3. Latimer, W. M. and Rodebush, W.H., J. Amer. Chem. Soc. 42, 1419–33 (1920).Google Scholar
4. Kamlet, M.J. and Taft, R.W., J. Amer. Chem. Soc. 98, 377 (1976).Google Scholar
5. Kamlet, M.J. and Taft, R.W., J. Amer. Chem. Soc. 98, 2886 (1976).Google Scholar
6. Higgins, B.A. Simonson, D.L., Houser, E.J., Kohl, J.G. and McGill, R.A, J. Pol. Sci. Part A-Pol. Chem. 48, 30003009, (2010).Google Scholar
7. McGill, R.A., Abraham, M.H. and Grate, J.W., CHEMTECH 24, 2737, (1994).Google Scholar
8. Purcell, K.F., Stikeleather, J.A. and Brunk, S.D., J. Mol. Spec. 32, 202213 (1969).Google Scholar
9. Houser, E.J., Mlsna, T.E., Nguyen, V.K., Chung, R., Mowery, R.L., McGill, R.A., Talanta 54, 469485 (2001).Google Scholar
10. Vuluga, D., Legros, J., Crousse, B., Slawin, A.M.Z., Laurence, C., Nicolet, P., Bonnet-Delpon, D., J. Org. Chem. 76, 11261133, (2011).Google Scholar