Anisotropic molecular structure

Primary nucleation is the most observable phenomenon for the initiation of polymer crystallization, which can be categorized further into homogeneous nucleation and heterogeneous nucleation. In homogeneous nucleatimi, polymer nuclei can be treated as a cylindrical bunch of stems due to the anisotropic molecular structure, as depicted in Fig. 4.14. 

The molecular structures of many common liquid crystals are long and rodlike. In addition, they contain polar groups. Explain how both characteristics of liquid crystals contribute to their anisotropic nature. 

Crystal data and parameters of the data collection (at -173°, 50 < 20 < 450) are shown in Table I. A data set collected on a parallelopiped of dimensions 0.09 x 0.18 x 0.55 mm yielded the molecular structure with little difficulty using direct methods and Fourier techniques. Full matrix refinement using isotropic thermal parameters converged to R = 0.I7. Attempts to use anisotropic thermal parameters, both with and without an absorption correction, yielded non-positive-definite thermal parameters for over half of the atoms and the residual remained at ca. 0.15. 

The out-of-plane orientation of chromophores can be more easily controlled in LB films as compared with the in-plane orientation. Many chromophores are known to show anisotropic orientation in the surface normal direction. The molecular structure of chromophores and their position in amphiphile molecules, the surface pressure, the subphase conditions are among those affect their out-of-plane orientation. The out-of-plane orientation has been studied by dichroic ratio at 45° incidence, absorbance ratio at normal and 45° incidence, and incident angle dependence of p-polarized absorption [3,4,27,33-41]. The evaluation of the out-of-plane orientation in LB films is given below using amphipathic porphyrin (AMP) as an example [5,10,12]. 

All these advances have resulted not only in increases in resolution but have also alleviated the detection problems to a considerable extent. As a result, the last decade has seen a dramatic growth in 15N- and 170-NMR spectroscopy as a versatile method for studying molecular structure, both in isotropic (liquid) and anisotropic (solid) phases. Studies at a natural abundance level of the nucleides are now commonplace. The scope of chemical applications extends from inorganic, organometallic and organic chemistry to biochemistry and molecular biology, and includes the study of reactive intermediates, biopolymers and enzyme-inhibitor complexes. 

Brushes with long side chains can be synthesized by polymerization of macromonomers [117-119] or by grafting of the side chains to [16-20] or from [21] a main chain. In contrast to globular dendrimers, these molecules have an anisotropic primary structure and experience bending or coiling of the molecular contour. Depending on the relative stiffness of the main and side chains, one may distinguish four types of molecular cylinders (Fig. 20). 

Besides the remarkable directionality of the motion, the images also demonstrate a periodic variation of the cluster from an elongated to a circular shape (Fig. 39). The diagrams in Fig. 39 depict the time dependence of the displacement and the cluster size. Until the cluster was finally trapped, the speed remained fairly constant as can be seen from the constant slope in Fig. 39 a. The oscillatory variation of the cluster shape is shown in Fig. 39b. Although a coarse model for the motion has been presented in Fig. 39, the actual cause of the motion remains unknown. The ratchet model proposed by J. Frost requires a non-equiUb-rium variation in the energetic potential to bias the Brownian motion of a molecule or particle under anisotropic boundary conditions [177]. Such local perturbations of the molecular structure are believed to be caused by the mechanical contact with the scaiming tip. A detailed and systematic study of this question is still in progress. 

Carbon and oxygen atom positions were refined with anisotropic thermal parameters. Hydrogen atoms were not located. Figure 3 shows the molecular structure and the atom numbering scheme utilized for the x-ray data presented in the supplementary material for heritiana acetate. Coordinates, bond length, and bond angles for compound III acetate are available as supplementary material. 

In this book we consider only fluids that are isotropic, meaning that the fluid properties are independent of direction. By contrast, solids can readily have spatially oriented properties. Consider, for example, a common material like graphite, whose molecular structure has strongly oriented layers. Both mechanical and thermal properties are vastly different normal to and parallel to the layers. While ordinary fluids exhibit no such properties, it is possible to have anisotropic fluids. For example, long-chain polymeric fluids can exhibit properties that are oriented relative to the flow directions. 

A pseudo solid-like behavior of the T2 relaxation is also observed in i) high Mn fractionated linear polydimethylsiloxanes (PDMS), ii) crosslinked PDMS networks, with a single FID and the line shape follows the Weibull function (p = 1.5)88> and iii) in uncrosslinked c/.s-polyisoprenes with Mn > 30000, when the presence of entanglements produces a transient network structure. Irradiation crosslinking of polyisoprenes having smaller Mn leads to a similar effect91 . The non-Lorentzian free-induction decay can be a consequence of a) anisotropic molecular motion or b) residual dipolar interactions in the viscoelastic state. 

Differing 7j values for CH3, CH2, and CH carbon nuclei within a molecule can arise not only by methyl rotation or anisotropic molecular motion, but also from the segmental mobility of partial structures, even when the dipolar mechanism predominates. Thus the spin-lattice relaxation times of methylene carbon atoms in long alkane chains pass through a minimum at the middle of the chain. In the presence of heavy nonassociating... 

The unique spectral absorption of the Rhodonines contains two visual band components, an isotropic absorption associated with the conjugated dipole molecular structure of the molecule, and a anisotropic absorption associated with an additional resonant slow-wave stmcture intimately associated with the triplet electrons of the oxygen atoms of the molecule. The unusual relaxation properties of these molecules are also associated with these triplet state electrons. The Rhodonines do not fluoresce or phosphoresce significantly while in a dilute liquid solution. 

Since a charge transfer from TDAE to C60 leads to a partially filled molecular tlu orbital (Fig. 2), and because of the close contacts of the C60 units, it might be expected that TDAE-C60 is a metal with a highly anisotropic electronic structure, displaying itinerant ferromagnetism [2]. However, powder infrared absorption... 

The molecular structure and constitution of the anisotropic mesophase sphere have been analyzed (49,50) NMR, UV, IR, and... 

---