Simultaneous measurements dichroism

The optical apparatus used in this study was designed according to the strategy described in section 8.4.3, which permits the simultaneous measurement of birefringence and dichroism. The source was a infrared diode laser that generates light at a wavelength in the... 

A review of rheo-optical techniques by Sherman et al. (1996) notes that there has been an increase in the use of rheo-optic set-ups both for FT-IR dichroism and for dynamic IR dichroism spectroscopies for polymer melts and polymer blends. Skytt et al. (1996) highlight the use of simultaneous measurement of the transient or steady-state rheological properties and IR dichroism to characterize orientation in polymer melts. However, there is little reference to dual spectroscopic-rheological techniques for reactive polymer systems in the literature. 

Gotoh, R., Takenaka, T., Hagama, N. Simultaneous measurements of stress and infrared dichroism on polymers I. Kolloid-Z. 205, 18 (1965). 

Simultaneous measurements of electrophoretic mobility, self-diffusion coefficient, and fluorescence-detected linear dichroism indicate that, with a polymer... 

Dynamic mechanical techniques are important in the characterization of the rheological properties of polymers. In dynamic mechanical analysis, a small-amplitude oscillatory strain is applied to a sample, and the resulting dynamic stress is measured as a function of time. The dynamic mechanical technique allows the simultaneous measurement of both the elastic and the viscous components of the stress response. Typically, the temperature and deformation frequencies are changed in order to determine the mechanical relaxation spectrum of the system. The molecular basis of changes in the dynamic mechanical properties can be investigated using dynamic IR dichroism. 

A two-state transition is usually identified by all spectroscopic probes changing simultaneously as the equilibrium changes. The far ultraviolet circular dichroism signals, which are a measure of secondary structure, should change in parallel with the near ultraviolet, which are a measure of tertiary structure. Fluorescence and near ultraviolet absorbance spectra also probe tertiary structure and should change in parallel with each other and the circular dichroism spectra. Ideally, there should be isosbestic or isodichroic points where spectra converge. 

The integration of the optics within the stress rheometer allows the simultaneous acquisition of optical and mechanical properties of the sample, which can be important for determining the relationship between a material s microstructure and its rheological response. The particular rheometer used here has an open construction that easily accommodates the insertion of an optical train for the purpose of birefringence and dichroism measurements. The optical train consisted of a helium-neon light source with a (P/RII)/)(,G... 

S. J. Johnson, P. L. Frattini and G. G. Fuller, Simultaneous dichroism and birefringence measurements of dilute colloidal suspensions in transient shear flow, J. Colloid Interface Sci., 104,440 (1985) S. J. Johnson and G. G. Fuller, Flowing colloidal suspensions in non-Newtonian suspending fluids decoupling the composite birefringence, Rheol. Acta, 25, 405 (1986). 

Practical problems associated with infrared dichroism measurements include the requirement of a band absorbance lower than 0.7 in the general case, in order to use the Beer-Lambert law in addition infrared bands should be sufficently well assigned and free of overlap with other bands. The specificity of infrared absorption bands to particular chemical functional groups makes infrared dichroism especially attractive for a detailed study of submolecular orientations of materials such as polymers. For instance, information on the orientation of both crystalline and amorphous phases in semicrystalline polymers may be obtained if absorption bands specific of each phase can be found. Polarized infrared spectroscopy can also yield detailed information on the orientational behavior of each component of a pol3mier blend or of the different chemical sequences of a copoljnner. Infrar dichroism studies do not require any chain labelling but owing to the mass dependence of the vibrational frequency, pronounced shifts result upon isotopic substitution. It is therefore possible to study binary mixtures of deuterated and normal polymers as well as isotopically-labelled block copolymers and thus obtain information simultaneously on the two t3q>es of units. 

In order that an relevant to the CD study may be experimentally obtained, it is important to have the same beam collimation and sample-phototube configuration for the absorption and CD measurements. This problem is well solved by simultaneously determining absorption and circular dichroism on the same phototube with a single beam and sample. A relatively simple modification of the Cary instrument allows this to be achieved. ... 

Rheo-optical techniques (46 8) afford information on the strain dependence not only of stress but also of optical quantities associated directly with the structure or molecular morphology. The techniques were developed extensively for crystalline polymers to investigate the molecular deformation mechanism underlying the tensile elongation. In this part, the chain orientation behavior is characterized by infrared dichroism measured simultaneously with tensile deformation at a constant rate of elongation. 

Circular dichroism (CD) is much more useful than any other spectroscopic technique in controlling the sterospecificity of the reactions in the total synthesis of steroids. Prednisolone can be determined simultaneously along hydrocortisone. Hydrocortisone can be measured selectively at 326 nm where prednisolone does not show dichroism, while at 314 nm prednisolone can be measured on the basis of its selective dichroism (27, 28). 

Generally, from spectroscopic data such as frequency position, band shape, intensity and dichroism of specific absorption bands conclusions can be derived in terms of the applied mechanical stress and the state of order and orientation of the polymer under investigation. An extremely powerful method for the study of transient phenomena in polyuMr deformation and relaxation is rheo-optics which describes the relation between stress, strain and an optical quantity (for example birefringence, infrared absorption, light scattering. X-ray diffraction) measured simultaneously with stress and strain as a function of time In a given rheo-optical method therefore, a mechanical test is combined with one of these various types of optical measurements. 

Figure 1-3 shows a schematic diagram of a dynamic IR linear dichroism (DIRLD) experiment [20-25] which provided the foundation for the 2D IR analysis of polymers. In DIRLD spectroscopy, a small-amplitude oscillatory strain (ca. 0.1% of the sample dimension) with an acoustic-range frequency is applied to a thin polymer film. The submolecular-level response of individual chemical constituents induced by the applied dynamic strain is then monitored by using a polarized IR probe as a function of deformation frequency and other variables such as temperature. The macroscopic stress response of the system may also be measured simultaneously. In short, a DIRLD experiment may be regarded as a combination of two well-established characterization techniques already used extensively for polymers dynamic mechanical analysis (DMA) [26, 27] and infrared dichroism (IRD) spectroscopy [10, 11]. 

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