Reversible Excited-State Transient Solvation in Binary Supercritical Fluids Revealed by Multifrequency Phase and Modulation Fluorescence

Abstract

Frequency-domain fluorescence spectroscopy is used to study the transient solvation of 4-amino-N-methylphthalimide (4AMP) in binary supercritical fluids composed of 2-propanol and CO₂. The time-resolved emission spectra are constructed for this system with the use of the wavelength-dependent frequency-domain data. Analysis of the experimental data indicates that: (1) 4AMP is pre-associated with 2-propanol prior to excitation; (2) the 2-propanol-induced spectral relaxation occurs on a nanosecond time scale; and (3) the excited-state reaction between 4AMP and 2-propanol is reversible.

Keywords

Transient solvation Frequency-domain fluorescence Supercritical fluids Matrix modification

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References

Mataga

and Kubota

, Molecular Interactions and Electronic Spectra (Marcel Dekker, New York, 1970).

Seliskar

C. J.

and Brand

, J. Amer. Chem. Soc. 93, 5405 (1971).

Seliskar

C. J.

and Brand

, J. Amer. Chem. Soc. 93, 5414 (1971).

Demas

J. N.

, Excited-State Lifetime Measurements (Academic, New York, 1983).

Turro

N. J.

, Modern Molecular Photochemistry (Benjamin, New York, 1978).

Wahl

, New Techniques in Biophysics and Cell Biology (Wiley, New York, 1975).

Lakowicz

J. R.

, Principles of Fluorescence Spectroscopy (Plenum, New York, 1983).

Ware

W. R.

, in Creation and Detection of the Excited State. LaMola

, Ed. (Marcel Dekker, New York, 1971), Vol. 1, Part A.

DeToma

R. P.

Easter

J. H.

and Brand

, J. Amer. Chem. Soc. 98, 5001 (1976).

10.

Maroncelli

and Fleming

G. R

, J. Chem. Phys. 86, 6221 (1987).

11.

van der Zwan

and Hynes

J. T

, J. Phys. Chem. 89, 4181 (1985).

12.

Galla

H. J.

and Hartman

, Chem. Phys. Lipids 27, 199 (1980).

13.

Yeh

S. M.

and Mears

C. M

, Biochemistry 19, 5057 (1980).

14.

Brand

and Gafni

, Chem. Phys. Lett. 58, 346 (1978).

15.

Lakowicz

J. R.

Gratton

Cherek

Maliwal

B. P.

and Laczko

, J. Biol. Chem. 259, 10967 (1984).

16.

Maroncelli

MacInnis

and Fleming

G. R

, Science 243, 1674 (1989).

17.

Weber

, in Time-Resolved Fluorescence Spectroscopy in Biochemistry and Biology, Cundall

R. B.

and Dale

R. E

, Eds. (Plenum, New York, 1983).

18.

Bakshiev

N. G.

, Opt. Spectrosc. 16, 446 (1964).

19.

Mazurenko

Y. T.

and Bakshiev

N. G

, Opt. Spectrosc. 28, 490 (1970).

20.

Mazurenko

Y. T.

and Udaltsov

V. S

, Opt. Spectrosc. 44, 417 (1978).

21.

Mazurenko

Y. T.

, Opt. Spectrosc. 48, 388 (1980).

22.

Ware

W. R.

Lee

S. K.

Brant

G. J.

and Chow

P. P

, J. Phys. Chem. 54, 4729 (1971).

23.

DeToma

R. P.

and Brand

, Chem. Phys. Lett. 42, 231 (1977).

24.

Castner

E. W.

Jr. Bagchi

Maroncelli

Webb

S. P.

Ruggiero

A. J.

and Fleming

G. R

, Ber. Bunsenges. Phys. Chem. 92, 363 (1988).

25.

Kahlow

M. A.

Jarzeba

DuBruill

T. P.

and Barbara

P. F

, Rev. Sci. Instrumn. 59, 1098 (1988).

26.

Kahlow

M. A.

Jarzeba

Kang

T. J.

and Barbara

P. F

, J. Phys. Chem. 90, 151 (1989).

27.

Jarzeba

Walker

G. C.

Johnson

A. E.

Kahlow

M. A.

and Barbara

P. F

, J. Phys. Chem. 92, 7039 (1988).

28.

Angel

Gagel

and Laubereau

, Chem. Phys. Lett. 156, 169 (1989).

29.

Simon

J. D.

, Ace. Chem. Res. 21, 128 (1988).

30.

S.-G.

and Simon

J. D

, J. Phys. Chem. 90, 6457 (1986).

31.

Barbara

P. F.

and Jarzeba

, Ace. Chem. Res. 21, 195 (1988).

32.

McHugh

M. A.

and Krukonis

V. J

, Supercritical Fluid Extraction: Principles and Practice (Butterworths, Boston, 1986).

33.

Paulaitis

M. E.

Krukonis

V. J.

Kurnik

R. T.

and Reid

R. C

, Rev. Chem. Engr. 1, 179 (1983).

34.

Paulaitis

M. E.

Kander

R. G.

and DiAndreth

J. R

, Ber. Bunsenges. Phys. Chem. 88, 869 (1984).

35.

Supercritical Fluid Chromatography, Smith

R. M.

, Ed. (Royal Society of Chemistry Monograph, London, 1988).

36.

Smith

R. D.

Wright

B. W.

and Yonker

C. R

, Anal. Chem. 60, 1323A (1988).

37.

Eckert

C. A.

Van Alsten

J. G.

and Stoicos

, Environ. Sci. Technol. 20, 2738 (1986).

38.

Supercritical Fluids: Chemical Engineering Principles and Applications, Squires

T. G.

and Paulaitis

M. E

, Eds., ACS Symposium Series 329 (American Chemical Society, Washington, D.C., 1987).

39.

Eckert

C. A.

Ziger

D. H.

Johnston

K. P.

and Kim

, J. Phys. Chem. 90, 2738 (1986).

40.

van Wasen

Swaid

and Schneider

G. M

, Angew. Chem. Int. Ed. Engl. 19, 575 (1980).

41.

Debenedetti

P. G.

, Chem. Engr. Sci. 42, 2203 (1987).

42.

Gouw

T. H.

and Jentoft

R. E

, J. Chrom. Chrom. Rev. 68, 303 (1972).

43.

Smith

R. D.

Chapman

E. G.

and Wright

B. W

, Anal. Chem. 57, 2829 (1985).

44.

Sigman

M. E.

Lindley

S. M.

and Leffler

J. E

, J. Amer. Chem. Soc. 107, 1471 (1985).

45.

Yonker

C. R.

Frye

S. L.

Kalkwarf

D. R.

and Smith

R. D

, J. Phys. Chem. 90, 3022 (1986).

46.

Smith

R. D.

Frye

S. L.

Yonker

C. R.

and Gale

R. W. J

, J. Phys. Chem. 91, 3059 (1987).

47.

Sigman

M. E.

and Leffler

J. E

, J. Phys. Chem. 90, 6063 (1986).

48.

Yonker

C. R.

and Smith

R. D

, J. Phys. Chem. 92, 2374 (1988).

49.

Okada

Kobayashi

Yamasa

and Mataga

, Chem. Phys. Lett. 128, 583 (1986).

50.

Kajimoto

Futakami

Kobayashi

and Yamasaki

, J. Phys. Chem. 92, 1347 (1988).

51.

Hrnjez

B. J.

Yazdi

P. T.

Fox

M. A.

and Johnston

K. P

, J. Amer. Chem. Soc. 111, 1915 (1989).

52.

Radosz

, J. Chem. Engr. Data 31, 43 (1986).

53.

Bright

F. V.

Keimig

T. L.

and McGown

L. B

, Anal. Chim. Acta 175, 189 (1985).

54.

Gratton

Jameson

D. M.

and Hall

R. B

, Ann. Rev. Biophys. Bioengr. 13, 105 (1984).

55.

Bevington

P. B.

, Data Reduction and Error Analysis for Physical Sciences (McGraw-Hill, New York, 1969).

56.

Easter

J. H.

DeToma

R. P.

and Brand

, Biophys. J. 15, 571 (1976).

57.

Lakowicz

J. R.

and Cherek

, Chem. Phys. Lett. 122, 380 (1985).

58.

Betts

T. A.

and Bright

F. V

, Appl. Spectrosc. 44, 1196 (1990).

59.

Lakowicz

J. R.

Cherek

and Balter

, J. Biochem. Biophys. Methods 5, 131 (1981).

60.

Beecham

J. M.

and Gratton

, SPIE Conf. Proc. 909, 70 (1988).

61.

Laws

J. R.

and Brand

, J. Phys. Chem. 83, 795 (1979).

62.

Lakowicz

J. R.

and Balter

, Biophys. Chem. 16, 99 (1982).

63.

Lakowicz

J. R.

and Balter

, Biophys. Chem. 16, 117 (1982).

64.

Bakshiev

N. G.

, Opt. Spectrosc. 13, 104 (1962).

65.

McGown

L. B.

and Bright

F. V

, Anal. Chem. 56, 1400A (1984).

66.

McGown

L. B.

and Bright

F. V

, C.R.C. Crit. Rev. Anal. Chem. 18, 245 (1987).