Submolecular scale

Phase-locked electronics are used to record the dynamic IR spectral change in-phase and out of phase with the applied mechanical field. The method provides insight to the response to the external stress on the molecular and submolecular scale. Rheooptical FTIR spectroscopy is one of the few techniques providing data on the crystallisation, orientation and conformational changes of a polymer during mechanical treatment (83). Two dimensional correlation analysis is utilised to enhance the information derived from the vibrational spectroscopic data. 

At the submolecular scale, the thermochemical properties of the reactions are influenced by quantum mechanics. 

T, Fukuma, K. Kobayashi, H. Yamada, and K Matsushige, Non-contact atomic force microscopy study of copper-phthalocyanines Submolecular-scale contrasts in topography and energy dissipation,/ Appl Phys. 95, 4742 (2004). 

Up to this poinL we have primarily focused our attention on the application of theo-oprical characterization techniques for monitoring the dynamics of supramolecular stmctures, such as the spatial reorganization of crystals and microphase-separated domains, in various polymeric systems under the influence of flow, deformation, and relaxation. We now shift our attention to rheo-oprical analysis at submolecular scale by using molecular spectroscopic probes. In particular, a rheo-oprical technique called dynamic infrared linear dichroism (DIRLD) spectroscopy, capable of monitoring segmental dynamits of polymer chains, is described. 

In this chapter, the rheo-optical methods in the mesoscopic scale were described in Section 2.30.2 and those in the sub-molecular scale in Section 2.30.3, for separate systems. The authors would like to encourage the next generation of rheo-optics researchers to simultaneously apply the two methods, covering both the mesoscopic and the submolecular scales, to the same system. This is indispensable for a further integral and systematic understanding of the structural and rheological responses against applied fields. 

Once the synthetic methodologies were developed, the research efforts were focused on the preparation of photoactive systems where fullerenes had already shown potential applicability, such as organic photovoltaic materials. In these molecular-scale engineered systems, a fullerene electron acceptor contained in one submolecular fragment is coupled with an electron donor contained in the opposite component. Zinc porphyrins were thus coupled to in many different architectures such as, for instance, in that shown in Scheme 9.11, where the ZnP was appended to... 

K. Ariga, Template-Assisted Nano-Patterning from Submicron-Scale to Submolecular-Level , J. Nanosci. Nanotech., 4, 23 (2004)... 

Figure 3.4 A high resoLution contact mode AFM image of a native photosynthetic membrane (128 nm) of i 5p. photometricum at submoLecuLar resoLution (scale bar 20 nm z-scale 6 nm) (From Scheuring et al. The EMBO J. (2004) 23, 4127, Reproduced by permission of the Nature Publishing Group)...

In the very dilute polymer solutions the macromolecules practically do not interact with one another, submolecular structures are absent. In the solution at rest long linear molecules are rolled up into slightly asymmetric balls saturated by the solvent. Their sizes are small as compared with characteristic scales of the wall turbulence. 

A rigorous definition of miscibility is used in the following tables. In order to be classified as miscible polymers, there must be some evidence in the literature that the polymers are miscible on a submolecular (segmental) scale. If the polymer mixture contains several phases, the polymers will be listed as miscible even if segmental miscibility data... 

In Section 2.30.3 of this chapter, attention was focused on the rheo-optical study of polymers at the submolecular and segmental scale. Optical spectroscopy, especially infrared dichroism spectroscopy, was utilized in conjunction with the application of a small-amplitude oscillatory dynamic strain to probe the local dynamics of molecular constituents of polymers undergoing reorientation process. The insights obtained by such measurements were somewhat unexpected, such as the observation that macromolecules exhibit considerable local flexibility and individual rotational freedom with respect to the dynamics of various mesoscopic-scale supramolecular structures. 

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