COMMUNICATIONS
B. J. Dunne, R. B. Morris, A. G. Orpen, J. Chem. Soc. Dalton Trans.
1991, 653, and references therein.
[2] a) X. Li, S. I. Weissman, T.-S. Lin, P. P. Gaspar, J. Am. Chem. Soc.
1994, 116, 7899, and references therein; b) E. Niecke, J. Böske, D.
Gudat, W. Güth, M. Lysek, E. Symalla, Nova Acta Leopold. 1985, 59,
83.
Study of the Interactions between Poly(vinyl
pyrrolidone) and Sodium Dodecyl Sulfate by
Fluorescence Correlation Spectroscopy
Ralf Nörenberg,* Jürgen Klingler, and Dieter Horn
[3] a) X. Li, K. D. Robinson, P. P. Gaspar, J. Org. Chem. 1996, 61, 7702; b)
N. Mezailles, P. E. Fanwick, C. P. Kubiak, Organometallics 1997, 16,
1526.
Dedicated to Professor Hans-Jürgen Quadbeck-Seeger
on the occasion of his 60th birthday
[4] A. Marinetti, F. Mathey, L. Ricard, Organometallics 1993, 12, 1207.
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[5] a) See stable isomers of phosphabenzenes and oligomers of tBuC P
Interactions between polymers and surfactants in aqueous
solutions are attracting much attention at present as many
formulations and industrial processes make simultaneous use
of polymers and surfactants for their complementary or even
synergistic roles.[1] In many of these applications the optimi-
zation of the properties of the polymer in the presence of
interference from other chemicals demands a method that is
capable of monitoring the association behavior in complex
media, in a wide concentration regime, and with less effort
than the presently available methods permit. There have been
a lot of experimental techniques explored in the past to study
the complex formation.[2±6] All of them, however, have their
specific limitations. The first method used to study the
complex formation was NMR-self-diffusion by monitoring
the hydrodynamic size of surfactant molecules.[7] However,
this method is limited in the concentration range accessible
and also takes a lot of effort.
containing PC2 rings: M. Regitz in Multiple Bonds and Low
Coordination in Phosphorus Chemistry (Eds.: M. Regitz, O. Scherer),
Thieme, Stuttgart, 1990, p. 79; b) D. Hu, H. Schäufele, H. Pritzkow, U.
Zenneck, Angew. Chem. 1989, 101, 929; Angew. Chem. Int. Ed. Engl.
1989, 28, 900. Also, P4 is a quite stable molecule.
[6] a) (Hoffmann-La Roche), NL-B 6600093, 1966, [Chem. Abstr. 1967,
66, 2426]; b) H. Kessler, Methoden der Organischen Chemie (Houben-
Weyl), 4th ed. 1952 ± , Vol. 5/1d, 1972, pp. 301.
[7] P-Amino phosphiranes see: a) E. Niecke, W. W. Schoeller, D.-A.
Wildbredt, Angew. Chem. 1981, 93, 119; Angew. Chem. Int. Ed. Engl.
1981, 20, 131; b) E. Niecke, M. Leuer, M. Nieger, Chem. Ber. 1989, 122,
453.
Ã
[8] J. Thomaier, S. Boulmaaz, H. Schönberg, H. Rüegger, A. Currao, H.
Grützmacher, H. Hillebrecht, H. Pritzkow, New J. Chem. 1998, 21, 947.
[9] D. C. R. Hockless, M. A. McDonald, M. Pabel, S. B. Wild, J. Chem.
Soc. Chem. Commun. 1995, 257.
[10] a) D. Carmichael, P. B. Hitchcock, J. F. Nixon, F. Mathey, L. Ricard, J.
Chem. Soc. Dalton Trans. 1993, 1811, and references therein; b) S. S.
Al Juaid, D. Carmichael, P. B. Hitchcock, A. Marinetti, F. Mathey, J. F.
Nixon, J. Chem. Soc. Dalton Trans. 1991, 905.
With the ongoing development of optical correlation
techniques, measurements of the self-diffusion coefficient of
fluorescing molecules by fluorescence correlation spectro-
scopy (FCS)[8] became a practical laboratory technique in the
last few years.[9] Since fluorescence is a very sensitive technique
measurements of the self-diffusion coefficient can be extended
to very low concentrations.[10] We present herein the first study
of the complex formation of sodium dodecyl sulfate (SDS) with
poly(vinyl pyrrolidone) (PVP) by FCS to demonstrate its
applicability for associating colloidal systems. The complexes
of SDS with PVP belong to the best studied model systems in
the literature and often serve as a reference system.
Fluorescence correlation spectroscopy uses fluctuations in
the numbers of fluorescent molecules (or particles) in a very
small observation volume to obtain information on the
diffusive properties of these molecules.[11] The resulting
autocorrelation functions G(t) were fitted to the theoretical
Equation (1).[10]
[11] a) All structures were solved by direct methods and refined against
full-matrix (versus F2) with SHELXTL (Version 5.0). 5b: orthorhom-
bic, space group P212121; a 8.829(1), b 8.887(1), c 25.544(4) ;
V 2004.3(5) 3; Z 4, MoKa radiation, 2Vmax 56.68. 16654 reflec-
tions, 4975 independent (Rint. 0.0543); R1 0.0531, wR2 0.1136
(based on F2) for 309 parameters and 3598 reflections with I > 2s(I). 6:
monoclinic, space group P21/n; a 14.260(3), b 16.088(3), c
17.062(3) , b 95.14(3)8; V 3899(1) 3; Z 4, MoKa radiation,
2Vmax 48.28. 21835 reflections, 6088 independent (Rint. 0.0747);
R1 0.549, wR2 0.1251 (based on F2) for 501 parameters and 3837
refelctions with I > 2s(I). 7: monoclinic, space group C2/m; a
13.819(1), b 19.796(1), c 45.796(3) , b 95.725(1)8; V
12466(1) 3; Z 8, MoKa radiation, 2Vmax 55.38. 34197 reflections,
12836 independent (Rint. 0.0433); R1 0.0508, wR2 0.0665 (based
on F2) for 739 parameters and 9882 reflections with I > 2s(I). 10a:
monoclinic, space group P21/c; a 9.102(5), b 8.629(5), c
35.300(20) , b 95.93(5)8; V 2757(3) 3; Z 4, CuKa radiation,
2Vmax 100.08. 2829 reflections, 2829 independent (Rint. 0.0); R1
0.0327, wR2 0.0910 (based on F2) for 290 parameters and 2434
reflections with I > 2s(I). All non-hydrogen atoms in 5b, 6, 7 and 10a
were refined with anisotropic, hydrogen atoms at calculated positions
with common isotropic parameters (riding model). One CF3 group in
5b, and the BF4 ion in 6 were refined as rigid bodies on two positions.
Crystallographic data (excluding structure factors) for the structures
reported in this paper have been deposited with the Cambridge
Crystallographic Data Center as supplementary publication no.
CCDC-106557 (6), 106559 (5b), 106560 (7) and 113781 (10a). Copies
of the data can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB21EZ, UK (fax: ( 44)1223-336-033;
e-mail: deposit
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1
1
G(t) 1
(1)
N
4 D t
1
r2
In this equation N is the average number of fluorescent
molecules, D the thermal diffusion coefficient of the mole-
cules and r the radial width of the laser focus. The value of r
was obtained by calibrating the instrument with the dye
Rhodamin 6G, by assuming a diffusion coefficient of this dye
@ccdc.cam.ac.uk). b) ORTEP drawings of the molecular structures of
5b, 6, and 7 are available from the author on request.
[12] a) G. Chandra, P. Y. Lo, P. B. Hitchcock, M. F. Lappert, Organo-
metallics 1987, 6, 191; b) P. B. Hitchcock, M. F. Lappert, N. J. W.
Warhurst, Angew. Chem. 1991, 103, 439; Angew. Chem. Int. Ed. Engl.
1991, 30, 438.
of 2.8 Â 10 10 m2 s . The diffusion coefficients in this study
1
[*] Dr. R. Nörenberg, Dr. J. Klingler, Dr. D. Horn
BASF Aktiengesellschaft
Polymerphysik, Festkörperphysik
D ± 67056 Ludwigshafen (Germany)
Fax: (49)621-60-92281
1626
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1433-7851/99/3811-1626 $ 17.50+.50/0
Angew. Chem. Int. Ed. 1999, 38, No. 11