Sage Journals: Discover world-class research

Abstract

Thermodynamics of inclusion of α- and β-cyclodextrins (CDs) with three diester precursors of polyesters, dimethyl terephthalate (DMT), dimethyl isophthalate (DMI), and dimethyl phthalate (DMP) were studied with different fluorescence spectroscopy techniques. The stoichiometry, association constants, and other thermodynamics parameters were investigated from the fluorescence intensity decrease that takes place upon CD addition and temperature changes. Apart from DMP, which did not form a complex with αCD, all other systems showed 1:1 stoichiometry complexes with different stabilities. The complexes formed with the DMT guest are the most stable, whereas the stability constant for DMP: βCD is the lowest. Binding constants are also larger for complexes formed with βCD than for those formed with αCD. Fluorescence polarization, quenching, and lifetime measurements provide information about the structure of the complexes formed. This geometry explains the values of enthalpy and entropy changes during complexation. Van der Waals interactions seem to be involved in the formation of these complexes.

Keywords

Cyclodextrins Inclusion complex Fluorescence Dimethyl terephthalate Dimethyl isophthalate Dimethyl phthalate

Get full access to this article

View all access options for this article.

References

“Cyclodextrins”, in Comprehensive Supramolecular Chemistry, Szejtli

and Osa

, Eds. (Elsevier, Oxford, 1996), vol. 3.

D'Souza

V. T.

and Lipkowitz

K. B

, Chem. Rev. 98, 5 (1998).

Harada

, Adv. Polym. Sci. 133, 141 (1997).

Harada

, Acc. Chem. Res. 34, 456 (2001).

Takahashi

, J. Chem. Soc., Chem. Commun., 929 (1991).

Flamigni

, J. Phys. Chem. 97, 9566 (1993).

Monti

Köhler

and Grabner

, J. Phys. Chem. 97, 13011 (1993).

Schuette

J. M.

and Warner

I. M

, Talanta 41, 647 (1994).

Fraiji

E. K.

Jr. Cregan

T. R.

and Werner

T. C

, Appl. Spectrosc. 48, 79 (1994).

10.

Nakamura

Sato

Hamasaki

Ueno

and Toda

, J. Phys. Chem. 99, 10952 (1995).

11.

Madrid

J. M.

Villafruela

Serrano

and Mendicuti

, J. Phys. Chem. B 103, 4847 (1999).

12.

Turro

N. J.

Okubo

and Weed

G. C

, Photochem. Photobiol. 35, 325 (1982).

13.

Kano

Takenoshita

and Ogawa

, Chem. Lett., 321 (1982).

14.

Hamai

, Bull. Chem. Soc. Jpn. 55, 2721 (1982).

15.

Hamai

, J. Phys. Chem. 93, 6527 (1989).

16.

Street

K. W.

Jr. Acree

W. E.

Jr. , Appl. Spectrosc. 43, 1315 (1988).

17.

Muñoz de la Peña

Ndou

T. T.

Zung

J. B.

and Warner

I. M

, J. Phys. Chem. 95, 3330 (1991).

18.

Muñoz de la Peña

Ndou

T. T.

Zung

J. B.

Greene

K. L.

Live

D. H.

and Warner

I. M

, J. Am. Chem. Soc. 113, 1572 (1991).

19.

Will

A. Y.

Muñoz de la Peña

Ndou

T. T.

and Warner

I. M

, Appl. Spectrosc. 47, 277 (1993).

20.

Madrid

J. M.

and Mendicuti

, Appl. Spectrosc 51, 1621 (1997).

21.

Madrid

J. M.

Mendicuti

and Mattice

W. L

, J. Phys. Chem. B 102, 2037 (1998).

22.

Cervero

and Mendicuti

, J. Phys. Chem. B 104, 1572 (2000).

23.

Pastor

Di Marino

and Mendicuti

, J. Phys. Chem. B 106, 1995 (2002).

24.

Di Marino

and Mendicuti

, Appl. Spectrosc. 56, 1579 (2002).

25.

Catena

G. C.

and Bright

F. V

, Anal. Chem. 61, 905 (1989).

26.

Nelson

Patonay

and Warner

I. M

, Appl. Spectrosc. 41, 1235 (1987).

27.

Yorozu

Hoshino

and Imamura

, J. Phys. Chem. 86, 4426 (1982).

28.

Mendicuti

Viswanadhan

V. N.

and Mattice

W. L

, Polymer 29, 875 (1988).

29.

Mendicuti

Patel

Viswanadhan

V. N.

and Mattice

W. L

, Polymer 29, 1669 (1988).

30.

Mendicuti

Patel

Waldeck

D. H.

and Mattice

W. L

, Polymer 30, 1680 (1989).

31.

Mendicuti

Saiz

Patel

Dodge

and Mattice

W. L

, J. Phys. Chem. 94, 8374 (1990).

32.

Job

, Ann. Chim. 9, 113 (1928).

33.

O'Connor

D. V.

Ware

W. R.

and André

J. C

, J. Phys. Chem. 83, 1333 (1979).

34.

Patonay

Shapira

Diamond

and Warner

I. M

, J. Phys. Chem. 90, 1963 (1987).

35.

MicroCal Origin, version 6.0 (MicroCal Software, Inc, Northampton, MA).

36.

Kitano

Taira

and Yamamoto

, Anal. Chem. 72, 2976 (2000).

37.

Hirose

, J. Inclus. Phenom. Macroc. Chem. 39, 193 (2001).

38.

Loukas

Y. L.

, J. Phys. Chem. B 101, 4843 (1997).

39.

Lakowicz

J. R.

, Principles of Fluorescence Spectroscopy (Kluwer Academic/Plenum, New York, 1999), 2nd ed., p. 298.

40.

Lakowicz

J. R.

, Principles of Fluorescence Spectroscopy (Kluwer Academic/Plenum, New York, 1999), 2nd ed., p. 240.

Thermodynamics of Complexation of Dimethyl Esters of Tere-,Iso-,and Phthalic Acids with α- and β-Cyclodextrins

Abstract

Keywords

Get full access to this article

References