Vibrational Spectroscopy, 1 (1990) 225-221 Fkevier Science Publishers B.V..

Amsterdam

225

Short Communication

Spectroscopic studies on /3-cyclodextrin

Orsolya Egyed
Central Research Institute for Chemistty, Hungarian Academy of Sciences, H-1525 Budapest (Hungory)

Abstract Fourier transform infrared and Raman spectra of B-CD are reported, with emphasis on the most important characteristic bands indicating complexation. Assignments are based on literature data for a-D-ghCOpyEUIOSe and curve fitting calculations regarding the OH stretching region. Keywork Raman spectrometry; /3-Cyclodextrin

Since cyclodextrins (CDs) have a rigid, slightly non-polar cavity, they usually act as molecular hosts toward a wide range of guest molecules, ranging from polar compounds such as water to non-polar compounds such as hydrocarbons. They can also act as first- or second-sphere ligands for transition metal complexes [1,2]. While the guest molecules are linked to B-CD mainly by Van der Waals forces, the transition metal complexes may be bonded covalently (first-sphere ligands) or by H-bridges (second-sphere ligands). In this paper Fourier transform infrared (FTIR) and Raman spectroscopic studies on /3-CD

are reported. We also intend to show the application of this method to detect complex formation involving B-CD as a host molecule, or a first or second-sphere ligand. Experimental P-CD was obtained from Chinoin (Hungary). FT-IR spectra were measured on solid samples (1.5 mg sample per 800 mg potassium bromide) with a resolution of ca. 4 cm- (4096 data points) using a Nicolet 170SX Fourier transform spectrometer. Infrared spectra were obtained from 1000 scans in order to get an appropriate signal-

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Fig. 1. Infrared and Raman spectra of &cyclodextrin. 09242031/90/$03.50 0 1990 - Elsevier Science Publishers B.V.

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to-noise ratio for the Fourier self-deconvolution and band fitting. Raman spectra were recorded on a Cary 82 spectrometer by excitation with the 514.5-nm line of a Spectra Physics Ar+ laser. Results and discussion Infrared and Raman spectra of P-CD are shown in Fig. 1, the observed band frequencies compared to literature data are listed in Table 1. Since P-CD is too large for its normal modes to be studied by normal coordinate analysis, our assignments are based on the calculations for smaller analogous compounds such as a-D-glucopyranose [3,4] and amylose [5,6]. These calculations have been done only for the 1500-400 cm- region. As can be expected, none of the modes arise from a single type of molecular vibration in this region. In most of them the C-O-H bending mode contributes to a noticeable degree. Therefore they could be very useful when discussing the complex formation of cyclodextrins with transition metal complexes by H-bridge formation. The three bands which are

TABLE 1 Vibrational band frequencies (cm-) for &CD and pyranose (r = Stretching mode; +I= bending mode) fi-cyclodextrin IR cobs.) 1465 1420 1390 1370 1335 1250 1205 1160 1130 1080 1050 1030 950 860 580 Ram. fobs.) 1455 1415 1390 1350 1340 1250 1205 1160 1130 1080 1050 1010 950 850 580 480 vs.
a-D-ghOpyranOSe (3,4] a-~-glum-

Calculated 1469 1434 1375 1356 1335 1284 1201 1149 1083 1051 1014

Assignment @ OCH, + HCH + OCH, 4 CCH 4 CCH, 4 OCH, 4 COH 4 CCH, 4 OCH, 4 COH 4 CCH, 4 COH, 4 HCH a 4 OCH, 4 COH, 4 CCH a r CO, 4 CCH, 4 COH rCO,rCC,+COHb r CO, 4 COH, r CC rCO,rCC r CC, 4 OCH, 4 CCH, 4 CC0 skeletal vibration involving (r-1,4 linkage cpCCH,rCO,rCC Skeletal vibrations Skeletal vibrations ring vibration.

845

a Complex CH,OH anomeric vibration.

vibration. b pyranose

characteristic for the primary OH groups might have a special importance in distinguishing between the different types of cyclodextrin OH groups. The bands at 1335 and 1250 cm- may be assigned as complex modes of the CH,OH group [4], and the band at 860 cm- as an anomeric band which consists essentially of C-l-H deformation coupled to other motions. Moreover, this anomeric band may be used as a marker of the CH,OH position, similarly to the case of a-D-glucopyranose, where the calculated frequency (845 cm-) shifts to a higher value (866 cm-) on rotation of the CH,OH group around the C-C axis. The 1150 cm- band is observed for most saccharide structures and is assigned as pyranose ring vibrational mode with some C-O-H bending components [4]. In the IR spectrum of P-CD this band shifts to a higher frequency (1160 cm-) and has a shoulder at 1130 cm- probably due to the superimposition of the pyranose ring vibration and the asymmetric stretching vibration of the glycosidic C-O-C bonds. The bands missing from the spectrum of a-D-glucopyranose (950, 580 and 480 cm-) may be attributed to skeletal modes of P-CD involving a-1,4 linkage. The OH stretching region is extremely complicated, because the primary and secondary OH groups of P-CD may be bonded intra- or intermolecularly, and H-bridges may also be formed between the water molecules complexed in the cavity, or between the crystallisation water molecules belonging to P-CD. Since the corresponding OH stretching bands form a broad, stuctureless envelope, we have to decompose it to individual components. The number of the components and the initial band positions for the band fitting calculations were determined by Fourier self-deconvolution [7], using a triangular squared apodization function, 250 cm- spectral line width and a resolution improvement factor K = 2.2. The band positions obtained this way were in good agreement with those of /3-D-glucopyranose measured at liquid helium temperature [8]. Further initial parameters (band intensities and half-widths) were estimated from the original spectra. Band fitting calculations were performed using an iterative curve analysis program based on least squares fitting. The results are shown in Fig. 2. Compo-

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STUDIES

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Fig. 2. Fourier self-deconvolution and band fitting of the OH stretching region of the infrared spectrum of B-CD. (A) Experimental curve; (B) self-deconvoluted curve with 250 cm- line width, triangular squared apodization function. The spectral resolution has been improved by a factor of 2.2; (C) band components: (a) 3504 cm-; (b) 3336 cm-; (c) 3195 cm-; (d) 3109 cm-.

(furanmethanethiol, dimethyldichlorvinylphosphate) other than water. In these cases we obtained two components at 3570 and 3460 cm-r according to the intra- and intermolecular Hbridges. Components b, c and d (at 3336, 3195 and 3109 cm-) are probably due to the stretching vibrations of the secondary OH groups bonded to each other in different ways. It is hoped that our results presented here combined with further investigations at liquid helium temperature will be suitable for the detection of complex formation with cyclodextrins especially for those which act as second-sphere ligands (Hbridge formation). Acknowledgement is made to Prof. Szejtli and Dr. Szente for providing the samples and for valuable comments.

REFERENCES

nent a (at 3504 cm-) may be assigned to the stretching vibrations of primary OH groups (bonded to the ring oxygen intramolecularly or to each other intermolecularly). Unlike the case of 2-hydroxymethyltetrahydropyran [9] we were unable to dinstinguish between these two types of H-bridges, because the OH stretching vibrations of the water molecules existing in the cavities also appear in this region. This assumption is supported by further investigations on some inclusion complexes containing non-polar guest molecules
A further source of water content of samples arises from the preparation process of pellets. This can be eliminated by the subtraction of the spectrum of a pure KBr pellet made under the same conditions.

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