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Broadband Dielectric Spectroscopy was applied to investigate molecular dynamics of two anhydrosaccharides, i.e., 1,6-anhydro-β-D-mannopyranose, anhMAN (hydrogen-bonded system) and 2,3,4-tri-O-acetyl-1,6-anhydro-β-D-glucopyranose, ac-anhGLU (van der Waals material), at different thermodynamic conditions. Moreover, the reported data were compared with those recently published for two other H-bonded systems, i.e., 1,6-anhydro-β-D-glucopyranose (anhGLU) and D-glucose (D-GLU). A direct comparison of the dynamical behavior of the materials with a similar chemical structure but significantly differing by the degrees of freedom, complexity, and intermolecular interactions made it possible to probe the impact of compression on the fragility, Temperature-Pressure Superpositioning and pressure coefficient of the glassy crystal/glass transition temperatures ( d T g c / d p ; d T g / d p ). Moreover, the correlation between d T g c / d p determined experimentally from the high-pressure dielectric data and the Ehrenfest equation has been tested for the plastic crystals (anhGLU and anhMAN) for the first time. Interestingly, a satisfactory agreement was found between both approaches. It is a quite intriguing finding which can be rationalized by the fact that the studied materials are characterized by the low complexity (lower degrees of freedom with respect to the molecular mobility) as well as ordered internal structure. Therefore, one can speculate that in contrast to the ordinary glasses the dynamics of the plastic crystals might be described with the use of a single order parameter. However, to confirm this thesis further, pressure-volume-temperature (PVT) experiments enabling calculations of the Prigogine Defay ratio are required. [ABSTRACT FROM AUTHOR]

In this paper, broadband dielectric spectroscopy was applied to investigate molecular dynamics of 1,2,3,4,6-penta-O-(trimethylsilyl)-D-glucopyranose (S-GLU) at ambient and elevated pressures. Our studies showed that apart from the structural relaxation, one well resolved asymmetric secondary process (initially labeled as β) is observed in the spectra measured at p = 0.1 MPa. Analysis with the use of the coupling model and criterion proposed by Ngai and Capaccioli indicated that the β-process in S-GLU is probably a Johari-Goldstein relaxation of intermolecular origin. Further high pressure experiments demonstrated that there are in fact two secondary processes contributing to the β-relaxation. Therefore, one can postulate that the coupling model is a necessary, but not sufficient criterion to identify the true nature of the given secondary relaxation process. The role of pressure experiments in better understanding of the molecular origin of local mobility seems to be much more important. Interestingly, our research also revealed that the structural relaxation in S-GLU is very sensitive to compression. It was reflected in an extremely high pressure coefficient of the glass transition temperature (dTg/dp = 412 K/GPa). According to the literature data, such a high value of dTg/dp has not been obtained so far for any H-bonded, van der Waals, or polymeric glassformers. [ABSTRACT FROM AUTHOR]

Single-walled carbon nanotubes (SWCNTs) are synthesized as mixtures of various SWCNT types, exhibiting drastically different properties, and thereby making the material of limited use. Fluorene-based polymers are successful agents for purifying such blends by means of conjugated polymer extraction (CPE), greatly increasing their application potential. However, a limited number of studies have devoted attention to understanding the effects of the polyfluorene backbone and side chain structure on the selectivity and separation efficiency of SWCNTs. Regarding the impact of the polymer backbone, it was noted that the ability to extract SWCNTs with conjugated polymers could be significantly enhanced by using fluorene-based copolymers that exhibit dramatically different interactions with SWCNTs depending on the types of monomers combined. However, the role of monomer side chains remains much less explored, and the knowledge generated so far is fragmentary. Herein, we present a new approach to tailor polymer selectivity by creating copolymers of polyfluorene bearing mixed-length alkyl chains. Their thorough and systematic analysis by experiments and modeling revealed considerable insight into the impact of the attached functional groups on the capacity of conjugated polymers for the purification of SWCNTs. Interestingly, the obtained results contradict the generally accepted conclusion that polyfluorene-based polymers and copolymers with longer chains always prefer SWCNTs of larger diameters. Besides that, we report that the capacity of such polymers for sorting SWCNTs may be substantially enhanced using specific low molecular weight compounds. The carried-out research provides considerable insight into the behavior of polymers and carbon-based materials at the nanoscale.