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Crystal Fluidity Reflected by Fast Rotational Motion at the Core, Branches, and Peripheral Aromatic Groups of a Dendrimeric Molecular Rotor.

ABSTRACT: Low packing densities are key structural features of amphidynamic crystals built with static and mobile components. Here we report a loosely packed crystal of dendrimeric rotor 2 and the fast dynamics of all its aromatic groups, both resulting from the hyperbranched structure of the molecule. Compound 2 was synthesized with a convergent strategy to construct a central phenylene core with stators consisting of two layers of triarylmethyl groups. Single crystal X-ray diffraction analysis confirmed a low-density packing structure consisting of one molecule of 2 and approximately eight solvent molecules per unit cell. Three isotopologues of 2 were synthesized to study the motion of each segment of the molecule in the solid state using variable temperature quadrupolar echo (2)H NMR spectroscopy. Line shape analysis of the spectra reveals that the central phenylene, the six branch phenylenes, and the 18 periphery phenyls all display megahertz rotational dynamics in the crystals at ambient temperature. Arrhenius analysis of the data gives similar activation energies and pre-exponential factors for different parts of the structure. The observed pre-exponential factors are 4-6 orders of magnitude greater than those of elementary site-exchange processes, indicating that the dynamics are not dictated by static energetic potentials. Instead, the activation energies for rotations in the crystals of 2 are controlled by temperature dependent local structural fluctuations and crystal fluidity.

SUBMITTER: Jiang X

PROVIDER: S-EPMC5155508 | biostudies-literature | 2016 Apr

REPOSITORIES: biostudies-literature

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Crystal Fluidity Reflected by Fast Rotational Motion at the Core, Branches, and Peripheral Aromatic Groups of a Dendrimeric Molecular Rotor.

Jiang Xing X O'Brien Zachary J ZJ Yang Song S Lai Lan Huong LH Buenaflor Jeffrey J Tan Colleen C Khan Saeed S Houk K N KN Garcia-Garibay Miguel A MA

Journal of the American Chemical Society 20160325 13

Low packing densities are key structural features of amphidynamic crystals built with static and mobile components. Here we report a loosely packed crystal of dendrimeric rotor 2 and the fast dynamics of all its aromatic groups, both resulting from the hyperbranched structure of the molecule. Compound 2 was synthesized with a convergent strategy to construct a central phenylene core with stators consisting of two layers of triarylmethyl groups. Single crystal X-ray diffraction analysis confirmed ...[more]

PMID: 26973017

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Project description:Objective Rotational Chair Test (RCT) is considered one of the most critical measures for vestibular functionality, which generally includes the sinusoidal harmonic acceleration test (SHAT), velocity step test (VST), and visual suppression (VS). The purpose of this study was to establish normal values for different age groups on the RCT and investigate whether motion susceptibility, such as with a history of motion sickness or migraine, has any effects on test metrics. Methods One hundred and nine subjects aged from 20 to 59 years who were free from neurotological and vestibular disorders were enrolled. According to the history of motion sickness or migraine, participants were divided into four groups: the motion sickness (MS) group (n = 13), the migraine group (n = 8), comorbidity group (n = 11), and the control group (n = 77). The 77 subjects without any history of MS and migraine were then further separated into four age groups: youth group (20–29 years), young and middle-aged group (30–39 years), middle-age group (40–49 years), and middle-age and elderly group (50–59 years). All participants underwent SHAT, VST, and VS, and a comprehensive set of metrics including gain, phase, asymmetry, time constant (TC), and Fixation Index were recorded. Results Regarding the VST and VS, no significant differences were observed either across the four groups (MS, migraine, comorbidity, and control group) or four age categories within the control group. For SHAT, VOR gain at the frequency of 0.01 Hz, VOR phase from 0.08 to 0.64 Hz, and asymmetry at 0.01, 0.16, and 0.64 Hz indicated significant differences among various age groups (P < 0.05 for all comparisons). The VOR phase lead was lower in the migraine and comorbidity group than that in the control group at 0.64 Hz (P = 0.027, P = 0.003, respectively). Conclusions Age slightly affects the result of SHAT, but not for VST and VS. VOR gain is more susceptible to aging at low frequency, while the phase is opposite. Subjects with both migraine and motion sickness show abnormal velocity storage mechanisms. Phase bias should be considered when assessing motion susceptibility with the RCT. SHAT is more sensitive than VST in terms of reflecting motion susceptibility.

Dataset Information

Crystal Fluidity Reflected by Fast Rotational Motion at the Core, Branches, and Peripheral Aromatic Groups of a Dendrimeric Molecular Rotor.

Publications

Crystal Fluidity Reflected by Fast Rotational Motion at the Core, Branches, and Peripheral Aromatic Groups of a Dendrimeric Molecular Rotor.

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