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Journal of Molecular Structure 524 (2000) 201215 www.elsevier.

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Phase transitions in oleic acid as studied by X-ray diffraction and FT-Raman spectroscopy
rster b, R. Neubert a,*, S. Wartewig c P. Tandon 1,a, G. Fo
a

t Halle-Wittenberg, Wolfgang-Langenbeck-Str.4, D-06120 Halle/Saale, Germany Department of Pharmacy, Martin-Luther-Universita b t Halle-Wittenberg, Mu hlpforte 1, D-06108 Halle/Saale, Germany Department of Physical Chemistry, Martin-Luther-Universita c Institute of Applied Dermatopharmacy, Wolfgang-Langenbeck-Str. 4, D-06120 Halle/Saale, Germany Received 4 October 1999; received in revised form 1 December 1999; accepted 1 December 1999

Abstract The solidsolid g 0 to a 0 transition in the melt crystallized oleic acid has been investigated using X-ray diffraction, Fourier transform (FT) -Raman spectroscopy and differential scanning calorimetry (DSC). The spectroscopic study indicates that in the g 0 to a 0 transition the conformation of the olen group changes from skew cis skew 0 to skew cis trans. The observed splitting of many of the crystalline peaks in the wide angle region of X-ray pattern, including the ngerprint reections could be simulated on the assumption that the unit cell of the melt crystallized g 0 polymorph is monoclinic with b 91 and the other unit cell parameters are as given by Abrahamsson and Ryder-Nahringbauer for the solvent crystallized g phase. In the X-ray diffraction studies the ngerprint reections are used to deduce the subcell structure for the carboxyl- and methylsided chains in both phases. They indicate that the carboxyl-sided chains keep a modied O 0 k (orthorhombic) subcell, while the change in the conformation of the olen group results in the transformation of the subcell of the methyl-sided chains to modied M (monoclinic). The methyl-sided hydrocarbon chains are partially disordered in the a 0 phase with a high content of gauche conformers, but the CC bonds near the methyl end are mostly in the tt conformation. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Oleic acid; X-ray diffraction; FT-Raman spectroscopy; Phase transition; Subcell polymorphism

1. Introduction Oleic acid (cis-9-octadecenoic acid: OA) is one of the major component of oils (olive, castor and peanut oil) used in pharmacy and medicine. OA is widely used in pharmaceutics as ingredient of semisolid formulation, e.g. ointments, lotions, emulsions and
* Corresponding author. Tel.: 49-345-5525000; fax: 49345-5527292. E-mail address: neubert@pharmazie.uni-halle.de (R. Neubert). 1 Permanent address: Physics Department, Lucknow University, Lucknow 226 007, India.

gels. It is also the major unsaturated fatty acid of stratum corneum, the outermost layer of human skin. It is proposed that OA modulates the properties of the stratum corneum lipid bilayer [1,2]. It is assumed that oleic acid uidizes the close packing of the bilayer due to the kink structure of its hydrocarbon chain residue [3]. Generally, it is known that oleic acid acts as an efcient penetration enhancer for percutaneous drug delivery [4,5]. OA crystallizes in three modications a, b and g [6]. The crystal structures of the g and b phases have already been reported [7,8]. However, no information is available on the packing of hydrocarbon chains in

0022-2860/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved. PII: S0022-286 0(00)00378-1

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the a phase. In the g phase the unit cell is pseudoorthorhombic (space group P21 =a with four molecules (or two hydrogen bonded dimers) per unit cell. The molecules are bent at the CyC bond, and the hydrocarbon chains pack according to the orthorhombic O 0 k subcell (space group Pma2 [7,9]. The b phase could be classied into two modications stable b1 and metastable b2. In the b1 phase the unit cell belongs to a triclinic system of P1; and the asymmetric unit contains two crystallographically independent molecules A and B. The molecular layer is a unique interdigitated structure, where the methyl group of the molecule A and the carboxyl group of the molecule B are located in the same plane. The methyl- and the carboxyl-sided chains together form a Tk subcell [8]. Vibrational spectra of the three crystalline phases of oleic acid are reported in the literature [1012]. Kobayashi et al. [10] found that the solid state phase transition between the g and the a phase at 2.2C is an orderdisorder type and concluded that, in the a phase, the segment of the alkyl chain on the methylside of the C y C bond exhibits conformational disorder, while the segment on the carboxyl-side of C y C bond remains in the ordered all-trans conformation. Kim et al. [12] pointed out that the degree of disorder is highly temperature dependent and at a temperature just above the g to a phase transition temperature, the amount of disorder is small and appears to be conned in the region of the chain near the methyl end. In continuation of our studies on the thermotropic phase behaviour of binary mixtures of stratum corneum lipids [1315] we report in the present communication temperature dependent X-ray diffraction and FT-Raman spectroscopic studies of polymorphism of the melt crystallized OA. Using the combination of these methods we have tried to obtain a rened insight into the molecular nature of the g to a transition.

was used as received. The sample was sealed in an Xray glass capillary tube for X-ray diffraction measurements. For Raman scattering experiments the sample was placed in glass tubes and was sealed into aluminium pans for DSC measurements. All investigations were performed on melt crystallized samples, therefore, in order to differentiate it from the solvent crystallized sample in the literature [7], we prefer to use the notations a 0 and g 0 for the two polymorphs. 2.2. Differential scanning calorimetry The thermograms in the temperature range from 30 to 40C were recorded with a DSC 2 (Perkin Elmer Corp., Norwalk, USA) differential scanning calorimeter, where the scan rate was 5 K min 1. The enthalpy was obtained by integrating the area under the transition peak by comparison with that of an indium standard. 2.3. X-ray diffraction The experiments were carried out on a stage with a primary beam monochromator, high temperature attachment and a stationary curved position sensitive detector (STOE & CIE, Darmstadt, Germany) working with CuKa1 radiation l 0:154058 nm; 35 kV, 60 mA) in transmission technique. The intensities were recorded in the scattering angle range of 0 2q 44: The OA sample was heated from room temperature up to 30C, cooled down to 40C and then again heated up to 20C stability ^ 0:2C: The X-ray diffraction patterns are normalized with respect to the primary beam intensity and corrected with respect to background scattering. Each diffraction pattern is presented here as scattering intensity Icorr in arbitrary units versus the reciprocal spacing s nl= 2 sin q: 2.4. Molecular simulations Simulations of the powder pattern from single crystal data were performed by the Cerius 2 programme (Molecular Simulations Inc., San Diego, USA). This programme is also used to handle the subcell data and to calculate the lattice energy. 2.5. Fourier transform Raman spectroscopy

2. Materials and methods 2.1. Sample Oleic acid with a purity above 99% was purchased from Sigma Chemical Co. (St Louis, MO, USA) and

Vibrational Raman spectra were collected using a

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Fig. 1. Representative X-ray diffraction patterns of oleic acid in the g 0 polymorph (12C), a 0 polymorph (6C), and isotropic phase (16C).

Bruker FT-IR spectrometer IFS 66 equipped with the Raman module FRA 106. A diode pumped Nd:YAG laser which emits at a wavelength 1064 nm was used as the excitation source. The scattered radiation was collected at 180 to the source. Typical spectra were recorded with 400 scans and a laser power of 300 mW. The interferograms were apodized with the BlackmanHarris-4 term function and Fourier transformed to give spectra of 4 cm 1 resolution. Using the temperature control accessory R 495 (Bruker, Karlsruhe, Germany) the temperature dependence of the spectra was studied in the range from 30 to 40C stability ^ 0:2C: After each temperature step, the sample was allowed to equilibrate for 10 min to stabilize the temperature before recording each spectra. The manipulation and evaluation of the spectra, in particular, integration and curve tting were carried out using the Bruker opus 2.2 software. Generally, Raman intensities were determined as integrated band intensities.

sharp endothermic transition at 12:3 ^ 0:1C with an enthalpy change DH 8:2 ^ 0:4 kJ mol1 : This peak reects the melting of the a 0 phase [10]. Another peak at 5:3 ^ 0:4C with DH 37:3 ^ 0:5 kJ mol1 involves the solidsolid transition from the g 0 to the a 0 phase. 3.2. X-ray diffraction pattern 3.2.1. Polymorphism The X-ray diffraction patterns for the a 0 ,g 0 polymorphs and the melt phase (see Fig. 1) are representative for the melt crystallized OA. At temperatures above 12C, an isotropic phase exists without any scattering in the small angle range (SAXS). However, the molten hydrocarbon chains give rise to a broad halo in the wide angle region (WAXS) with a maximum at s 2:23 nm1 d 0:45 nm: At temperatures below 12C, the a 0 polymorph crystalline phase is observed with a very strong reection in the SAXS region, corresponding to the lamellar repeat distance d 4:14 nm; followed by at least eight of its higher orders. In the WAXS region there are three strong ngerprint reections surrounded by weak crystalline peaks. The reections from chain packing lattices (subcells) are termed as ngerprint

3. Results and discussion 3.1. DSC measurements The DSC thermogram for OA sample exhibits a

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Fig. 2. Indexing of the X-ray diffraction pattern of g 0 polymorph of oleic acid at 12C. Note the logarithmic scale for the intensity.

reections. At temperatures below 5C the g 0 polymorph phase is formed with the orders of the repeat distance d 4:07 nm in the SAXS region showing changed intensity relations and weak crystalline peaks in the WAXS region including only two strong ngerprint reections. 3.2.2. Main cell scattering The simulation and indexing of the powder pattern of the low temperature polymorph (Fig. 2) is based on the single crystal data of the solvent crystallized g oleic acid [7], but has to be modied. The observed splitting of many of the crystalline peaks including the ngerprint reections could be simulated on the assumption that in the melt crystallized g 0 polymorph the unit cell is monoclinic with b 91: The diffraction pattern for the crystalline a 0 phase is not very different from that of the g 0 phase (Fig. 1). The relative intensities of the reection in the SAXS region show only little changes, but the repeat distance in z-axis increases from 4.07 nm for g 0 to 4.14 nm for a 0 . Recently, Kaneko et al. [16] have

reported a similar feature in the g to a transitions of erucic acid (cis-13 docosenoic acid). Kobayashi et al. [10] have found that single crystal specimens of OA show no morphological changes under optical microscopic observation and suggested that on the phase transition no large molecular displacements take place except for the conformational disordering of the hydrocarbon chain, which is connected with the change in lattice parameters. However, we observed a  and 207  reecdecrease in intensity for the 206  tions, and an increase of the 204 reection due to the g 0 to the a 0 transition (see Fig. 3). The intensity of the (206) and (207) reections remains unchanged. This strongly suggests that some structural changes are involved in the g 0 to a 0 transition. As shown in Fig.  planes in the g 0 phase nearly 4, the (206) and 206 correspond to the planes where the carboxyl-terminal chain and the methyl-terminal chain are placed, respectively. The concentration of the electron density of the chain fragments parallel to the corresponding Miller planes strongly inuences the scattered intensity. Therefore, the unchanged intensity of the (206)

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Fig. 3. WAXS pattern of oleic acid showing intensity changes during the g 0 to a 0 transition. Upward arrows: the ngerprint reections of the modied O 0 k subcell (methyl-sided chain in the g 0 phase); Downward arrows: the ngerprint reections of the M subcell (methyl-sided chain in the a 0 phase); Vertical lines: carboxyl-sided chain in both phases.

 reection, the decrease in intensity of the 206  reection reection, and the increase of the 204 are interpreted by the assumption that the methylterminal chain is displaced from the vicinity of the  plane toward the 204  plane due to the trans206 ition, while there is no change in inclination of the carboxyl-sided chain. From our spectroscopic measurements we found that there is a change in the conformation of the olen group due to the g 0 to a 0 transition which results in a change in the orientation of methyl-sided chains. But there is no change in the orientation of the carboxylsided chains. 3.2.3. Subcell scattering The most intense peaks in the wide angle range belong to the ngerprint reections of the subcell packing of the hydrocarbon chains [1719], and different packing modes may appear on both sides of the double bond. It is clear from spectroscopic

data that the conformation and orientation of methyl-sided chain change due to the transition, while that for carboxyl-sided chain remains unchanged. This is in agreement with the nding that the ngerprint reections (marked in Fig. 3 by straight lines) which are related to the carboxylsided chain fragments are less affected by the phase transition. These chain fragments are connected by strong hydrogen bonds with the adjacent carboxyl groups, and the packing of the resulting dimer of oleic acid forms the hard core of the bilayers. Nevertheless, some strong ngerprint reections change their position and intensity during the phase transition (arrows in Fig. 3). It is assumed that these are related to the methyl-sided chain fragments, which are able to change their packing mode during the phase transition. The indexing of the ngerprint reections of the g 0 polymorph gives subcell parameters (Table 1) which are different from the data reported from the single crystal study (orthorhombic parallel O 0 k) [7].

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Fig. 4. Schematic representation of conformational changes during the g 0 to a 0 transition. The COOH-sided chain in both g 0 and a 0 phase lies in Miller plane (206). The CH3-sided chain in g 0 and a 0  and 204 ; respectively. phases lies in Miller planes 206

Especially, the observed increase in the a axis parameter is not allowed in the space group Pma2 as it would mean that the CH bond length is inuenced. Therefore, two modied packing models with a parallel orientation of neighbouring zig-zag planes in a subcell are created (modied O 0 k subcell, model I and II, Fig. 5) and their lattice energy was minimized with the help of the Cerius 2 software. Further, it is

possible to simulate the X-ray diffraction pattern and to compare the intensity of the observed and calculated peaks. The model I of the modied O 0 k subcell shows an agreement with the observed reections (Table 1). The modied O 0 k subcell was found in the carboxyl-sided chain fragments of both a 0 and g 0 polymorphs of OA with similar lattice constants (Tables 1 and 2). It is also found in the methyl-sided chain fragments of the g 0 polymorph but with enlarged lattice parameters (Table 3). The calculated lattice energy of this enlarged subcell shows that this packing is not favoured, and therefore model I is a candidate for changes during a phase transition on heating. In the phase transition the disappearance of the ngerprint reections of the modied O 0 k subcell is coupled with the appearance of three reections which are representative for the subcell of the a 0 polymorph of oleic acid (Fig. 3). Indexing tests show that they are not in accordance with the orthorhombic subcell packing O [20,21] which was found in the a polymorph of erucic acid [16] and was assumed to be the most probable packing also in OA [6]. For the methyl-sided chain fragments in the a 0 polymorph new models of the subcell packing are considered that include both packing principles, namely the angular orientation of neighbouring zig-zag planes and a pronounced tendency for a parallel alignment of the chains as in O 0 k. These modied subcell packings were build by the introduction of an angle of 100.8 in the modied O 0 k packing and a rotation of about 90 of the chain in the middle of the cell (see Fig. 6). It is therefore named M. The cell parameters given in Table 4 were calculated by least squares procedure from the observed reections, and four variations were created and optimized in packing by the lattice energy minimization (Fig. 6). Differences

Table 1 The indexing of the g 0 polymorph (carboxyl-sided chain) of oleic acid and the comparison of observed and simulated peak position Observed Position (nm) (010) (200) (110) Lattice energy (kJ/CH2 group) Lattice parameters 0.410 0.389 0.367 Intensity (%) 30.8 100.0 92.9 Simulated for two models of modied O 0 k subcell Position (nm) 0.413 0.390 0.365 Intensity (Model I, %) Intensity (Model II, %)

9.0 56.6 100.0 100.0 78.6 12.4 5.284 5.309 a 0:778 nm; b 0:413 nm; c 0:258 nm; g 90

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Fig. 5. Two models of modied O 0 k subcell packing with energy minimized arrangement of chains. Table 2 The indexing of the a 0 polymorph (carboxyl-sided chain) of oleic acid and the comparison of observed and simulated peak position Observed Position (nm) (010) (200) (110) Lattice energy (kJ/CH2 group) Lattice parameters 0.410 0.389 0.367 Intensity (%) 50.9 100.0 85.9 Simulated for two models of modied O 0 k subcell Position (nm) 0.414 0.390 0.366 Intensity (Model I, %) Intensity (Model II, %)

9.1 56.5 100.0 100.0 78.5 12.5 5.493 5.506 a 0:780 nm; b 0:414 nm; c 0:258 nm; g 90

in the intensity of the simulated X-ray pattern result from the fact, that the overall orientation of zig-zag planes are different (pair I, III other than II, IV), and that there exists different tendencies for centring within the subcells (pair I, II other than III, IV). The model I in Fig. 6, shows the best t to the experimental scattering data, which, however, has the

worst energy (6.830 kJ/CH2 group) and is very close to the data of model IV. 3.2.4. Background scattering A tting procedure of the X-ray pattern of the a 0 and g 0 polymorph of OA shows a broad background halo besides of the crystal reections in the overall

Table 3 The indexing of the g 0 polymorph (methyl-sided chain) of oleic acid and the comparison of observed and simulated peak position Observed Position (nm) (010) (200) (110) Lattice energy (kJ/CH2 group) Lattice parameters 0.417 0.395 0.374 Intensity (%) 42.6 100.0 86.33 Simulated for two models of modied O 0 k subcell Position (nm) 0.420 0.396 0.371 Intensity (Model I, %) Intensity (Model II, %) 56.9 100.0 14.1 6.859 g 90

10.6 100.0 78.3 6.792 a 0:792 nm; b 0:420 nm; c 0:258 nm;

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Fig. 6. Four models of the M subcell packing with energy minimized arrangement of chains.

Table 4 The indexing of a 0 polymorph (methyl-sided chain) of oleic acid and the comparison of observed and simulated peak position Observed Position (nm) (200) (110) 0) (21 Lattice energy (kJ/CH2 group) Lattice parameters 0.425 0.403 0.360 Intensity (%) 100.0 16.2 20.9 Simulated for four models of M subcell Peak position (nm) 0.421 0.403 0.360 Intensity (Model I, %) 100.0 42.0 45.0 6.830 Intensity (Model II, %) 100.0 94.2 33.3 7.098 Intensity (Model III, %) 100.0 94.2 33.3 7.098 Intensity (Model IV, %) 100.0 44.6 44.9 6.805

a 0:864 nm; b 0:515 nm; c 0:258 nm; g 100:8

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Fig. 7. Fitting procedure of the X-ray diffraction pattern of oleic acid: (a) a 0 polymorph at 6C, dark: modied O 0 k subcell reections, light: M subcell reections; (b) g 0 polymorph at 12C, dark and light: modied O 0 k subcell reections from two different subcells.

wide angle range (Fig. 7(a) and (b)). It is remarkable that the position of the maximum, the height, and the line width of this background halo are very similar in the low temperature and high temperature polymorphs, respectively. This scattering phenomenon usually is very sensitive to the occurrence of amorphous chain segments (partially crystalline polymers) [22] or partially uid chain segments (liquid crystal-

line phase in lipids). The observed proles conrm the crystalline character in both the a 0 and the g 0 polymorphs, and exclude the existence of compact domains with disorder of the mentioned types. 3.3. FT-Raman spectroscopy The Raman spectra of OA recorded at different

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Table 5 Assignment of selected Raman bands of oleic acid according to literature data [1012], vs very strong, s strong, m medium, mw medium weak, sh shoulder, w weak g 0 -Phase at 30C (cm 1) 188w;207w; 231w;245w 700w 890mw 971w 910mw 1062m 1095m a 0 -Phase at 5C (cm 1) 207w; 237w 686w 889mw 966w 909mw 1063m 1094m Melt (cm 1) 239w 970w 1082w 1118w 1265mw 1298m 1438s; 1454sh 1654w 1654m 2852s 3006w Assignments LAM Disordered LAM CyCH out-of-plane CH3 rocking, chain-end tt CyCH out-of-plane n (CC), Ca-atom n as(CC), chain ordered n (CC), chain disordered n s(CC), COOH-sided chain ordered n (CC), chain disordered n s(CC), CH3-sided chain ordered CyCH in-plane-bending CH2 twisting CH2 scissoring n (CyO) n (CyC) n s(CH2) n as(CH2), chain ordered n (yCH)

1122m 1274m 1296s 1448s;1468s 1638mw 1660m 2841s 2879vs 2995m

1121w 1266mw 1297s 1433s;1444sh; 1461sh 1643w 1656m 2846s 2881vs 3002w

temperatures are in accordance with those reported in the literature [1012]. The literature data are also related to the a 0 and g 0 phases because no solvent crystallized material was used. The Raman band positions observed and the vibrational assignments according to literature data [1012] are summarized in Table 5. In the course of the phase transitions, we have observed various changes in the spectra. 3.3.1. CH2 stretching modes As with other lipids [23,24], the spectra in the CH stretching region exhibits distinct temperature induced changes (see Fig. 8(b)). As shown in Fig. 9 the thermotropic response of the band position of the symmetric CH2 stretching mode clearly reveals the phase transitions of OA. The g 0 to a 0 transition, characterized by a wave number increase of 3 cm 1, occurs with a midpoint of about 5C from a lowtemperature value of 2842 cm 1. The melting of the a 0 phase appears with a midpoint of about 12C with a jump of the wave number from 2846 to 2851 cm 1. The intensity ratio I[n as(CH2)]/I[n s(CH2)] also shows two transitions (see Fig. 10).

3.3.2. CyO stretching mode The band positions of the CyO stretching vibration shifts abruptly from 1638 to 1643 cm 1 at the solid solid transition (see Fig. 11), indicating rearrangements within the hydrogen bonds between COOH groups of the dimers. It coincides with the CyC stretching mode (1654 cm 1) in the molten state.

3.3.3. CH2 scissoring modes The spectral feature in the CH2 scissoring region, displayed in Fig. 8(a) for the g 0 and a 0 phase, is also temperature dependent. The spectral changes in this region suggest that there is a change in the subcell structure. In the g 0 phase, the spectral features are characteristic of the modied O 0 k subcell structure. In the a 0 phase, a shoulder appears in the broad peak around 1443 cm 1. Our X-ray diffraction studies combined with molecular simulations suggest that the subcell of the methyl-sided chains transforms to the M due to the a 0 to g 0 transition. So it is concluded that in the a 0 phase the spectrum is a superposition of those of the modied O 0 k and M subcells.

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Fig. 8. Temperature dependence of the Raman spectra of oleic acid in the spectral ranges: (a) 6001800 cm 1; and (b) 28003030 cm 1. From bottom to top T 20; 6, 0 and 12C.

3.3.4. CC stretching modes In the course of g 0 to a 0 transition, the intensity of the symmetric CC stretching band at 1122 cm 1 (methylsided chain) and of the asymmetric CC stretching band at 1062 cm 1 clearly decreases, while on the contrary that of the symmetric CC stretching band at 1095 cm 1 (carboxyl-sided) remains constant. In order to quantify this nding, the intensity ratio I[n s(CC, CH3-sided)]/

I[n s(CC, COOH-sided)] is plotted versus temperature in Fig. 12, where the ratio at 30C was considered to be unity for the sake of simplicity. This curve demonstrates that the concentration of gauche conformers in the methyl-sided chains drastically increases in the course of the g 0 to a 0 transition, but a certain number of trans segments remains. That is consistent with the observations of Kobayashi et al. [10].

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Fig. 9. Band position of the symmetric stretching mode n s(CH2) versus temperature for oleic acid.

3.3.5. Methyl rocking modes The methyl rocking mode associated with the tt chain-end conformation occurs as a sharp 890 cm 1 band in both solid phases. But, there is a small decrease in intensity of this band during the transition. This nding is noteworthy, because it demonstrates that the end of the methyl-sided chain remains in mostly the ordered tt conformation in the a 0 phase, too.

3.3.6. Olen group modes The bands associated with the cis olen group show changes due to the solidsolid transition. Fig. 8(a) reproduces the spectral changes of the band belonging to the out-of-plane bending mode of CyCH. The frequency of this band reects sensitively the conformation of the CCyCC group. In the solvent crystallized g phase it is in the skew cis skew 0

Fig. 10. Intensity ratio I[n as(CH2)]/I[n s(CH2)] versus temperature for oleic acid.

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Fig. 11. Band positions of the n (CyO) [B] and n (CyC) [X] modes versus temperature for oleic acid.

conformation [7]. In the g 0 phase, it is observed at 700 cm 1 which is typical of the skew cis skew 0 conformation. At the g 0 to a 0 transition point this band shifts to 686 cm 1 accompanying with an abrupt intensity decrease. The out-of-plane bending at 970 cm 1 shifts to 966 cm 1, the in-plane bending from 1274 to 1266 cm 1. The band position of the

CyC stretching vibration shifts abruptly from 1660 to 1656 cm 1, indicating conformational changes close to the cis formed CyC bond in the middle of the chain. Similar features are observed in the band due to the yCH stretching mode. This band shifts from 2995 to 3002 cm 1 and broadens greatly at the g 0 to a 0 transition (see Fig. 8(b)). Kaneko et al. [16]

Fig. 12. Intensity ratio I[n as(CC,CH3-sided)]/I[(n s(CC,COOH-sided)] versus temperature for oleic acid.

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have reported similar spectral changes in the g to a transitions of erucic acid. Our studies suggest that the conformation of the olen group changes from skew cis skew 0 to skew cis trans accompanying with an increase in thermal motion. 3.3.7. Longitudinal acoustic modes The weak bands in the low frequency region between 150 and 250 cm 1, tentatively assigned to longitudinal acoustic modes (LAM) [25] of the alkyl chain residues (see Table 5), indicate the planar alltrans conformation of the chains both in the g 0 and a 0 phase. In the melt the LAM disappear and the socalled disorder LAM rises at 239 cm 1 [26]. 4. Conclusions Our X-ray diffraction and molecular simulation studies indicate that the packing of the hydrocarbon chain fragments for the g 0 phase of melt crystallized OA is different from that crystallized from the solvent. The characteristic splitting of ngerprint reections are the consequence of the angle b 90: The FTRaman studies indicate that the conformation of the olen group changes from skew cis skew 0 to skew cis trans due to the g 0 to a 0 transition and this change results in a different orientation and subcell packing of the methyl-sided chain fragments, whereas the orientation and packing of the carboxyl-sided chain fragments remain the same. The indexing of ngerprint reections and the simulation studies indicate that in the g 0 phase the methylene chains at both sides of the double bond form a modied O 0 k subcell. During the g 0 to a 0 transition only the subcell of methyl-sided chains transforms to the M one, while the carboxyl-terminal chains keep the modied O 0 k subcell. The indexing of the methyl-sided chain fragment within a M subcell gives enlarged subcell parameters. This enlarged value has the capacity to involve a great amount of kinks within an overall crystal packing. The FT-Raman studies indicate that the number of gauche conformers in the methylterminal alkyl chains drastically increases in the course of the g 0 to a 0 transition, but the end of the methyl-sided chain remains mostly in the ordered tt conformation in the a 0 phase, too. However, the carboxyl-sided alkyl chains exist in the ordered

conformation in both the a 0 and g 0 phases. The overall character of the a 0 phase too remains crystalline.

Acknowledgements This work was supported by the Deutsche Forschungsgemeinschaft (DFG), Sonderforschungsbereich 197, project A8 and B1. Financial assistance to P.T. (Humboldt research fellow) from the Alexander von Humboldt Foundation (AvH) is gratefully acknowledged. The authors would like to thank D. Woetzel for technical assistance.

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