Oriented samples

The difficulties associated with the preparation of samples suitable for diffraction studies has led to much interest in the application of solid-state NMR to the investigation of the three-dimensional structure adopted by membrane proteins in their functional environment of phospholipid bilayers [14]. As an oriented sample, the NMR spectrum of a membrane protein is much simplified as compared to the case of a powder sample for perfect ordering, all structurally equivalent nuclei have the same orientation with respect to Bq, and hence the same anisotropic resonance frequency (see Section 9.2.1). This phenomenon is taken advantage of in the PISEMA (polarisation inversion with spin exchange at the magic angle) experiment [150]. This technique is closely related to the experiments described in Section 9.6.2, although it is to be noted that it is applied to static samples. 

PISEMA experiments yield the local dipolar field experienced by the or nucleus. Perhaps counter intuitively, it has been shown that better resolution is obtained by using experiments which detect the local dipolar field on protons [129, 

As specific examples, the detected local field experiment has recently successfully been applied to the characterisation of liquid crystals [155, 156] and membranes [157]. As illustrated by Fig. 9.33, this approach has even been shown to yield sufficient resolution in 3D versions to allow the direct measurement of internuclear dipolar couplings between nuclei separated by up to five bonds in liquid crystals, thereby providing very strong conformational constraints [158]. 

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Anisotropic behaviour is also exhibited in optical properties and orientation effects can be observed and to some extent measured by birefringence methods. In such oriented materials the molecules are in effect frozen in an unstable state and they will normally endeavour to take up a more coiled conformation due to rotation about the single bonds. If an oriented sample is heated up the molecules will start to coil as soon as they possess sufficient energy and the mass will often distort. Because of this oriented materials usually have a lower heat distortion temperature than non-oriented polymers. 

Certainly the most prominent feature of the breakdown process is its dependence on the polarity of the electric field relative to the shock-velocity vector. This effect is manifest in current pulse anomalies from minus-x orientation samples or positively oriented samples subjected to short-pulse loading (see Fig. 4.8). The individual effects of stress and electric field may be delineated with short-pulse loadings in which fields can be varied by utilizing stress pulses of various durations [72G03]. 

The [111] orientation samples were found to be n-type with impurity carrier concentrations of from 2.4 to 8 x 10 m . The [100] samples had... 

A limited number of minus-x orientation samples were impact loaded in the vicinity of the Hugoniot elastic limit at stresses from 5.9 to 6.7 GPa. The principal observation of these experiments was that positive currents were observed from negative polarity disks when a stress of 5.9 GPa was exceeded. Such an observation confirms that quartz responds as predicted by the model, and that the elastic limit is in the vicinity of 6 GPa. 

Hence, the extension of an isotropic unoriented partially crystalline polymer leads to the formation of a highly organized material with a characteristic fibrillar structure. The anisotropy of the sample as a whole is expressed by a higher modulus, tenacity and optical anisotropy. It would seem that the increase in strength in the drawing direction suggests that the oriented samples consist of completely extended chains. However, while the strength of such perfect structure for polyethylene has been evaluated as 13000 MPas), the observed values for an oriented sample are 50 to 30 MPa. 

In spite of the presence of ECC, the sample exhibiting a domain structure remains unoriented on the macroscopic level. Figure 3 c shows a great difference in the structures obtained, if molecular orientation exists and if hydrostatic compression is applied. Although the method of hydrostatic compression of the melt is of paramount importance from the scientific view point just for samples crystallized under pressure it was possible to prove unequivocally the existence of ECC), it does not allow a direct preparation of oriented samples of high strength (they are brittle and readily crumble to powder under minimum strain). However, the material obtained in this way can probably serve as a semi-finished product for further technological treatment that would improve its mechanical properties. 

First of all the term stress-induced crystallization includes crystallization occuring at any extensions or deformations both large and small (in the latter case, ECC are not formed and an ordinary oriented sample is obtained). In contrast, orientational crystallization is a crystallization that occurs at melt extensions corresponding to fi > when chains are considerably extended prior to crystallization and the formation of an intermediate oriented phase is followed by crystallization from the preoriented state. Hence, orientational crystallization proceeds in two steps the first step is the transition of the isotropic melt into the nematic phase (first-order transition of the order-disorder type) and the second involves crystallization with the formation of ECC from the nematic phase (second- or higher-order transition not related to the change in the symmetry elements of the system). 

For a uniaxially oriented sample, with the electric vector parallel to the symmetry axis (parallel dichroism), the absorption A ( will be given by... 

Fig. 3a. P200 and P400 as a function of draw ration for the pseudo-affine deformation scheme (uniaxially oriented sample) b P20o and P400 as a function of draw ratio X for the rubber network affine deformation scheme (N = 6, uniaxially oriented sample). Reproduced from Journal of Polymer Science by permission of the publishers, John Wiley Sons Incs (C)...

FIG. 33 X-Ray Diffraction Patterns of Ammonium Dodecane 1-Sulfonate. 2-D (a) and 3-D plots (b) of oriented samples. Both pictures show the presence of a nonordered smectic phase, since the diffuse, weak, wide-angle diffraction indicates only an average distance between the molecules and the sharp, intense small angle reflections a very well defined layer distance. The reflections are perpendicular to each other, so the structure should correspond to an orthogonal smectic A type. The pictures were obtained using an x-1000 area detector from Siemens. 

The classical scheme for dichroism measurements implies measuring absorbances (optical densities) for light electric vector parallel and perpendicular to the orientation of director of a planarly oriented nematic or smectic sample. This approach requires high quality polarizers and planarly oriented samples. The alternative technique [50, 53] utilizes a comparison of the absorbance in the isotropic phase (Dj) with that of a homeotropically oriented smectic phase (Dh). In this case, the apparent order parameter for each vibrational oscillator of interest S (related to a certain molecular fragment) may be calculated as S = l-(Dh/Di) (l/f), where / is the thermal correction factor. The angles of orientation of vibrational oscillators (0) with respect to the normal to the smectic layers may be determined according to the equation... 

Ever since Pasteur s work with enantiomers of sodium ammonium tartrate, the interaction of polarized light has provided a powerful, physical probe of molecular chirality [18]. What we may consider to be conventional circular dichroism (CD) arises from the different absorption of left- and right-circularly polarized light by target molecules of a specific handedness [19, 20]. However, absorption measurements made with randomly oriented samples provide a dichroism difference signal that is typically rather small. The chirally induced asymmetry or dichroism can be expressed as a Kuhn g-factor [21] defined as ... 

This forward-backward asymmetry of the photoelectron distribution, expected when a randomly oriented sample of molecular enantiomers is ionized by circularly polarized light, is central to our discussion. The photoelectron angular... 

The experimental dichroism is seen to have its greatest magnitude some 5 eV above threshold, where 0.10. This corresponds to an asymmetry factor in the forward-backward scattering of y 20%. Such a pronounced PECD asymmetry from a randomly oriented sample looks to comprehensively better the amazingly high 10% chiral asymmetry recorded with highly ordered nanocrystals of tyrosine enantiomer [25] or the spectacular 12.5% asymmetry reported from an oriented single crystal of a cobalt complex [28]. 

Figure 5. Room-temperature, wide-angle X-ray diffraction (WAXD) pictures of stretch-oriented samples of PDHS (left) and PDPS (right).

Molecular orientation and the testing direction strongly influence the observed modulus of a polymer sample. Fibers are typically highly oriented and exhibit much higher modulus values than non-oriented samples prepared from the same polymer. In the case of films, we typically observe anisotropy a film exhibits a range of modulus values depending upon the testing direction. 

Normal incidence measurements are sufficient for uniaxially oriented samples, but a third spectrum along the ND (Y) is necessary to describe the orientation in biaxially oriented samples or in the case of uniaxial anisotropy in the thickness... 

A more complex but faster and more sensitive approach is polarization modulation (PM) IRLD. For such experiments, a photoelastic modulator is used to modulate the polarization state of the incident radiation at about 100 kHz. The detected signal is the sum of the low-frequency intensity modulation with a high-frequency modulation that depends on the orientation of the sample. After appropriate signal filtering, demodulation, and calibration [41], a dichroic difference spectrum can be directly obtained in a single scan. This improves the time resolution to 400 ms, prevents artifacts due to relaxation between measurements, and improves sensitivity for weakly oriented samples. However, structural information can be lost since individual polarized spectra are not recorded. Pezolet and coworkers have used this approach to study the deformation and relaxation in various homopolymers, copolymers, and polymer blends [15,42,43]. For instance, Figure 7 shows the relaxation curves determined in situ for miscible blends of PS and PVME [42]. The (P2) values were determined... 

Finally, Frisk et al. have proposed a third method, the "depolarization" method, that does not need the assumption of a cylindrical Raman tensor [56]. A randomly oriented sample is again necessary but the depolarization ratio takes the general form... 

At first glance, it would appear that all orientation dependence should be lost in the spectrum of a randomly oriented sample and that location of the g- and hyperfine-matrix principal axes would be impossible. While it is true that there is no way of obtaining matrix axes relative to molecular axes from a powder pattern, it is frequently possible to find the orientation of a set of matrix axes relative to those of another matrix. 

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