Reorientation and translation of individual dye molecules in a polymer matrix

Schob, Arne; Cichos, Frank; Schuster, Jörg; Borczyskowski, C. von

doi:10.1016/j.eurpolymj.2004.01.016

Cited by 85 publications

(144 citation statements)

References 26 publications

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“…Singlemolecule imaging studies have been revealing the spatiotemporal heterogeneity of polymer dynamics by visualizing the motion of individual polymer chains [32][33][34][35][36] or small fluorophores embedded in polymer matrices. [37][38][39][40][41][42][43][44] Using single-molecule localization and tracking (SMLT) technique, we previously reported the multimode diffusion of a cyclic and dicyclic polymers under the entangled conditions by incorporating a fluorophore into the chains. 17,45,46 These studies have suggested a direct connection between the conformational state of the chains and the diffusive motion.…”

Section: Introductionmentioning

confidence: 99%

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

2015

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that the method provides an invaluable tool for characterizing topological interaction between the entangled chains. We further demonstrate that the current models proposed for the entanglement between cyclic polymers which are based on cyclic chains moving through an array of fixed obstacles cannot correctly describe the motion of the cyclic chain under the entangled conditions.Our results rather suggest the mutual relaxation of the cyclic chains, which underscore the necessity of developing a new model to describe the motion of cyclic polymer under the entangled conditions based on the mutual interaction of the chains.3

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Section: Introductionmentioning

confidence: 99%

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

2015

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“…Fluorescence microscopy of single molecules confirms the presence of large variations in the local viscosities. [7][8][9][10][11] Zondervan et al observed that these variations can be surprisingly long-lived, even at temperatures well above the glass transition temperature (T g ). 9 This may indicate the existence of a nearly static solid-like network at temperatures above T g , which was also revealed by rheological measurements.…”

Section: Introductionmentioning

confidence: 99%

Communication: Crystallite nucleation in supercooled glycerol near the glass transition

Yuan

Xia

Plazanet

et al. 2012

The Journal of Chemical Physics

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Heterogeneity and solid-like structures found near the glass transition provide a key to a better understanding of supercooled liquids and of the glass transition. However, the formation of solid-like structures and its effect on spatial heterogeneity in supercooled liquids is neither well documented nor well understood. In this work, we reveal the crystalline nature of the solid-like structures in supercooled glycerol by means of neutron scattering. The results indicate that inhomogeneous nucleation happens at temperatures near T g . Nevertheless, the thermal history of the sample is essential for crystallization. This implies such structures in supercooled liquids strongly depend on thermal history. Our work suggests that different thermal histories may lead to different structures and therefore to different length and time scales of heterogeneity near the glass transition.

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“…In their view, glass formation arises from dynamical arrest of cooperative domains, and their spread in sizes leads to an overall nonexponential relaxation. Indeed, spatially inhomogeneous dynamics (5) have been observed with a variety of techniques in many glass formers, including simple liquids (6-10) and polymers (11)(12)(13)(14)(15). Inhomogeneities have been found in the particular case of supercooled glycerol by dielectric hole burning (16), NMR (17), x-ray (18), light scattering (19), and stimulated Brillouin gain spectroscopy experiments (20,21).…”

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“…These observations have to be reconciled with the common view of a supercooled liquid, which is supposed to remain a normal ergodic liquid until the glass transition. Heterogeneous regions with different relaxation dynamics are therefore expected to exchange with one another to restore ergodicity, by processes called environmental exchanges (6,9,10,12,(14)(15)(16). The typical mechanisms, length scales, and time scales of environmental exchanges remain largely unclear.…”

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Local viscosity of supercooled glycerol near T _g probed by rotational diffusion of ensembles and single dye molecules

Zondervan

Kulzer

Berkhout

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

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We probe the rotational diffusion of a perylene dye in supercooled glycerol, 5-25 K above the glass-transition temperature (T g ‫؍‬ 190 K) at the ensemble and the single-molecule level. The singlemolecule results point to a broad distribution of local viscosities that vary by a factor of five or more for different individual fluorophores at a given temperature. By following the same single molecules at various temperatures, we find that the distribution of local viscosities itself broadens upon approaching T g. This spatial heterogeneity is found to relax extremely slowly, persisting over hours or even days. These results convey a picture of heterogeneous liquid pockets separated by solid-like walls, which exist already well above the viscosimetric glass transition.fluorescence ͉ glass transition ͉ anisotropy ͉ correlation G lycerol is an archetypal molecular glass former. Although glycerol crystals can be grown from solution, the pure liquid readily supercools because of its high viscosity [10 3 times that of water at room temperature (1)], which is caused by the formation of a highly branched network of intermolecular hydrogen bonds. The viscosity of supercooled glycerol increases by 10 orders of magnitude between 291.8 K, the melting temperature of crystalline glycerol, and its viscosimetric glass-transition temperature T g ϭ 190 K. Throughout this range of temperatures, macroscopic rheology measurements seem consistent with the expected behavior of a Newtonian liquid, although they also reveal highly nonexponential kinetics (1-3).The necessity for cooperative motion at larger and larger scales on approaching the glass transition was recognized a long time ago by Adam and Gibbs (4). In their view, glass formation arises from dynamical arrest of cooperative domains, and their spread in sizes leads to an overall nonexponential relaxation. Indeed, spatially inhomogeneous dynamics (5) have been observed with a variety of techniques in many glass formers, including simple liquids (6-10) and polymers (11-15). Inhomogeneities have been found in the particular case of supercooled glycerol by dielectric hole burning (16), NMR (17), x-ray (18), light scattering (19), and stimulated Brillouin gain spectroscopy experiments (20, 21). These observations have to be reconciled with the common view of a supercooled liquid, which is supposed to remain a normal ergodic liquid until the glass transition. Heterogeneous regions with different relaxation dynamics are therefore expected to exchange with one another to restore ergodicity, by processes called environmental exchanges (6,9,10,12,(14)(15)(16). The typical mechanisms, length scales, and time scales of environmental exchanges remain largely unclear. NMR and dielectric relaxation point to times comparable to the molecular rotation times (16,22), whereas light scattering and fluorescence show inhomogeneities with exceedingly slow relaxation (9,12,(19)(20)(21).Single-molecule fluorescence is a well established method for studying rotational diffusion (23-26). Linear dichroism...

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Reorientation and translation of individual dye molecules in a polymer matrix

Cited by 85 publications

References 26 publications

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

Communication: Crystallite nucleation in supercooled glycerol near the glass transition

Local viscosity of supercooled glycerol near T _g probed by rotational diffusion of ensembles and single dye molecules

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Reorientation and translation of individual dye molecules in a polymer matrix

Cited by 85 publications

References 26 publications

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

Communication: Crystallite nucleation in supercooled glycerol near the glass transition

Local viscosity of supercooled glycerol near T g probed by rotational diffusion of ensembles and single dye molecules

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Local viscosity of supercooled glycerol near T _g probed by rotational diffusion of ensembles and single dye molecules