Polarizers/Polarization dichroism

Probing Metalloproteins Electronic absorption spectroscopy of copper proteins, 226, 1 electronic absorption spectroscopy of nonheme iron proteins, 226, 33 cobalt as probe and label of proteins, 226, 52 biochemical and spectroscopic probes of mercury(ii) coordination environments in proteins, 226, 71 low-temperature optical spectroscopy metalloprotein structure and dynamics, 226, 97 nanosecond transient absorption spectroscopy, 226, 119 nanosecond time-resolved absorption and polarization dichroism spectroscopies, 226, 147 real-time spectroscopic techniques for probing conformational dynamics of heme proteins, 226, 177 variable-temperature magnetic circular dichroism, 226, 199 linear dichroism, 226, 232 infrared spectroscopy, 226, 259 Fourier transform infrared spectroscopy, 226, 289 infrared circular dichroism, 226, 306 Raman and resonance Raman spectroscopy, 226, 319 protein structure from ultraviolet resonance Raman spectroscopy, 226, 374 single-crystal micro-Raman spectroscopy, 226, 397 nanosecond time-resolved resonance Raman spectroscopy, 226, 409 techniques for obtaining resonance Raman spectra of metalloproteins, 226, 431 Raman optical activity, 226, 470 surface-enhanced resonance Raman scattering, 226, 482 luminescence... 

Yu. E. Perlin and B. S. Tsukerblat, Optical bands and polarization dichroism of Jahn-Teller Centers, Dynamical Jahn-Teller Effect in Localized Systems, Elsevier, Amsterdam, 1984, pp. 251-346. 

Five different optical phenomena are used for producing linear polarization dichroism, birefringence, reflection, reflection-transmission by metal gratings (grids), and scattering. 

Electrochromism-driven linearly and circularly polarized dichroism of poly(3,4-ethylenedioxythiophene) derivatives with chirality and liquid crystallinity 13CC1883. 

In the limiting case of high voltage applied to a "perfect" cell between crossed polars, the transmittance should be dictated by the dichroism of the polars. Defining dichroism of a polar as the difference between absorbances of the polar in crossed and parallel orientations to a perfectly polarized beam, it should be apparent that polar dichroism would have to be somewhat greater than 5 to achieve a contrast ratio of 10 under the above conditions. Literature on commercially available polars does... 

CDAD Circular dichroism photo- Uses circularly polarized Orientation of adsorbed... 

Che D P, Shapiro D B, Esquerra R M and Kliger D S 1994 Ultrasensitive time-resolved linear dichroism spectral measurements using near-crossed linear polarizers Chem. Rhys. Lett. 224 145-54... 

Molecular chirality is most often observed experimentally through its optical activity, which is the elfect on polarized light. The spectroscopic techniques for measuring optical activity are optical rotary dispersion (ORD), circular di-chroism (CD), and vibrational circular dichroism (VCD). 

The UV spectrum of a complex conjugated molecule is usually observed to consist of a few broad band systems, often with fine structure, which may be sharpened up in non-polar solvents. Such a spectrum can often be shown to be more complex than it superficially appears, by investigation of the magnetic circular dichroism (MCD) spectrum, or by introduction of dissymmetry and running the optical rotatory dispersion (ORD) or circular dichroism (CD) spectrum. These techniques will frequently separate and distinguish overlapping bands of different symmetry properties <71PMH(3)397). 

Thus, the process of PAN transformation under the effect of IR radiation proceeds with considerable self-acceleration. The irradiation of uniaxially oriented PAN films gives a polymer with a distinct anisotropy of optical properties, dichroism in the visible spectral region in particular. Figure 8 presents dichroism curves [D =/(X)] at various angles (ip) between the polarization plane and the orientation axis. The same figure shows the dependence D =f(uniaxially oriented film. 

Fig. 8. Dichroism of electronic absorption spectra of oriented and nonoriented PAN films after IR irradiation, (a) Dependence of optical density ( >) on the wavelength for various values of (angle between film orientation axis and light polarization plane).

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... 

Recently, peptoid-based mimics of both SP-C and SP-B have been designed to adopt helical secondary structures, and also mimic (to varying degrees) the sequence patterning of hydrophobic and polar residues found in the natural surfactant proteins. Peptoid-based SP-C mimics of up to 22 monomers in length, were synthesized and characterized by in vitro experimental methods [67, 68] (Fig. 1.8). The secondary structure of all molecules was assessed by circular dichroism and found to be helical. The surface activities of these peptoids, in comparison to the actual SP peptides described above, were characterized by surfactometry using... 

Circular dichroism (c.d.) spectroscopy measures the difference in absorption between left- and right-circularly polarized light by an asymmetric molecule. The spectrum results from the interaction between neighboring groups, and is thus extremely sensitive to the conformation of a molecule. Because the method may be applied to molecules in solution, it has become popular for monitoring the structure of biological molecules as a function of solvent conditions. 

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 ... 

Unfortunately, in the VUV region no polarimetry data are available, but calculations indicate the degree of circular polarization achieved by the wiggler may be 80%, estimated to be no worse than 70% delivered at the experimental chamber [95, 96]. In PECD experiments, we have calibrated the polarization state by deduction from cross-comparison of results at a few fixed energies previously studied on the SU5 beamline where accurate polarimetry data was available [36]. Because the horizontal magnetic field array in the insertion device is electromagnetic, fast current reversal to switch left- and right-handed elliptical polarizations is possible, with the usual potential benefit for dichroism measurements. 

Figure 15. Circular dichroism of the C=0 C li peak (BE = 292.7 eV) in fenchone at three different photon energies, indicated, (a) Photoelectron spectrum of the carbonyl peak of the (1S,4R) enantiomer, recorded with right (solid line) and left (broken line) circularly polarized radiation at the magic angle, 54.7° to the beam direction, (b) The circular dichroism signal for fenchone for (1R,4A)-fenchone (x) and the (lS,41 )-fenchone (+) plotted as the raw difference / p — /rep of the 54.7° spectra, for example, as in the row above, (c) The asymmetry factor, F, obtained by normalizing the raw difference. In the lower rows, error bars are included, but are often comparable to size of plotting symbol (l/ ,4S)-fenchone (x), (lS,4R)-fenchone (+). Data are taken from Ref. [38],...

The availability of the purified transporter in large quantity has enabled investigation of its secondary structure by biophysical techniques. Comparison of the circular dichroism (CD) spectrum of the transporter in lipid vesicles with the CD spectra of water-soluble proteins of known structure indicated the presence of approximately 82% a-helix, 10% ) -turns and 8% other random coil structure [97]. No / -sheet structure was detected either in this study or in a study of the protein by the same group using polarized Fourier transform infrared (FTIR) spectroscopy [98]. In our laboratory FTIR spectroscopy of the transporter has similarly revealed that... 

Of the visible spectroscopic techniques, CD spectroscopy has seen the most rapid and dramatic growth. The far-UV circular dichroism spectrum of a protein is a direct reflection of its secondary structure [71]. An asymmetrical molecule, such as a protein macromolecule, exhibits circular dichroism because it absorbs circularly polarized light of one rotation differently from circularly polarized light of the other rotation. Therefore, the technique is useful in determining changes in secondary structure as a function of stability, thermal treatment, or freeze-thaw. 

We now report that in the region of the absorption band the flow linear dichroism of a solution of 1 is positive (Fig. 3). Assuming that the nature of the flow orientation is of the usual kind, i.e., that the polymer chains in a random coil conformation which dominates in solution (34) tend to align with the flow direction, this observation provides additional support for the absolute assignment of the transition moment direction along the chain direction, even in solution. Similar conclusions based on polarization studies on a stretched film of poly(di-n-hexyl silane) have recently been reported (36). 

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