7,158 research outputs found
Financing the Investment Projects in Regions in globalization
The urgent problems of financing the investment strategy in the regions of Ukraine are examined in globalization. The directions of further development of the investment resources mobilization system and their management are determined in order to apply innovative models of structural reorganization of the economy and to ensure social and economic development of region
Structural reorganization of the cerebral cortex after vestibulo-cerebellar stroke
Objective: Structural reorganization following cerebellar infarcts is not yet known. This study aimed to demonstrate structural volumetric changes over time in the cortical vestibular and multisensory areas (i.e., brain plasticity) after acute cerebellar infarcts with vestibular and ocular motor symptoms. Additionally, we evaluated whether structural reorganization in the patients topographically correlates with cerebello-cortical connectivity that can be observed in healthy participants.
Methods: We obtained high-resolution structural imaging in seven patients with midline cerebellar infarcts at two time points. These data were compared to structural imaging of a group of healthy age-matched controls using voxel-based morphometry (2×2 ANOVA approach). The maximum overlap of the infarcts was used as a seed region for a separate resting-state functional connectivity analysis in healthy volunteers.
Results: Volumetric changes were detected in the multisensory cortical vestibular areas around the parieto-opercular and (retro-) insular cortex. Furthermore, structural reorganization was evident in parts of the frontal, temporal, parietal, limbic, and occipital lobes and reflected functional connections between the main infarct regions in the cerebellum and the cerebral cortex in healthy individuals.
Conclusions: This study demonstrates structural reorganization in the parieto-opercular insular vestibular cortex after acute vestibulo-cerebellar infarcts. Additionally, the widely distributed structural reorganization after midline cerebellar infarcts provides additional in vivo evidence for the multifaceted contribution of cerebellar processing to cortical functions that extend beyond vestibular or ocular motor function
Structural Reorganization of Parallel Actin Bundles by Crosslinking Proteins: Incommensurate States of Twist
We construct a coarse-grained model of parallel actin bundles crosslinked by
compact, globular bundling proteins, such as fascin and espin, necessary
components of filapodial and mechanosensory bundles. Consistent with structural
observations of bundles, we find that the optimal geometry for crosslinking is
overtwisted, requiring a coherent structural change of the helical geometry of
the filaments. We study the linker-dependent thermodynamic transition of
bundled actin filaments from their native state to the overtwisted state and
map out the "twist-state'' phase diagram in terms of the availability as well
as the flexibility of crosslinker proteins. We predict that the transition from
the uncrosslinked to fully-crosslinked state is highly sensitive to linker
flexibility: flexible crosslinking smoothly distorts the twist-state of bundled
filaments, while rigidly crosslinked bundles undergo a phase transition,
rapidly overtwisting filaments over a narrow range of free crosslinker
concentrations. Additionally, we predict a rich spectrum of intermediate
structures, composed of alternating domains of sparsely-bound (untwisted) and
strongly-bound (overtwisted) filaments. This model reveals that subtle
differences in crosslinking agents themselves modify not only the detailed
structure of parallel actin bundles, but also the thermodynamic pathway by
which they form.Comment: Main Text (25 pages, 7 figures) with supporting material (12 pages, 9
figures, 2 tables
Structural reorganization in a hydrogen-bonded organic framework
Self-recognition of 3,3′,5,5′-azobenzenetetracarboxylic acid drives the formation of a grid-like anionic hydrogen-bonded framework with channels occupied by organic cations. This supramolecular solid is capable of reorganizing its connectivity in the presence of specific guests into a different crystalline architecture by sequential dissolution and recrystallization
Structural reorganization of cylindrical nanoparticles triggered by polylactide stereocomplexation
YesCo-crystallization of polymers with different configurations/tacticities provides access to materials with enhanced performance. The stereocomplexation of isotactic poly(L-lactide) and poly(D-lactide) has led to improved properties compared with each homochiral material. Herein, we report the preparation of stereocomplex micelles from a mixture of poly(L-lactide)-b-poly(acrylic acid) and poly(D-lactide)-b-poly(acrylic acid) diblock copolymers in water via crystallization-driven self-assembly. During the formation of these stereocomplex micelles, an unexpected morphological transition results in the formation of dense crystalline spherical micelles rather than cylinders. Furthermore, mixture of cylinders with opposite homochirality in either THF/H2O mixtures or in pure water at 65 °C leads to disassembly into stereocomplexed spherical micelles. Similarly, a transition is also observed in a related PEO-b-PLLA/PEO-b-PDLA system, demonstrating wider applicability. This new mechanism for morphological reorganization, through competitive crystallization and stereocomplexation and without the requirement for an external stimulus, allows for new opportunities in controlled release and delivery applications.University of Warwick, Swiss National Science Foundation and the EPSRC. The Royal Society - an Industry Fellowship to A.P.D. The Engineering and Physical Sciences Research Council (EP/G004897/1) - funding to support postdoctoral fellowships for A.P.B. as well as funding for J.S. and M.A.D. through the Warwick Centre for Analytical Science (EP/F034210/1). The Science City Research Alliance and the HEFCE Strategic Development Fund - funding support. Some items of equipment that were used in this research were funded by Birmingham Science City, with support from Advantage West Midlands and part-funded by the European Regional Development Fund
Vertical vs. Adiabatic Ionization Energies in Solution and Gas-Phase: Probing Ionization-Induced Reorganization in Conformationally-Mobile Bichromophoric Actuators Using Photoelectron Spectroscopy, Electrochemistry and Theory
Ionization-induced structural and conformational reorganization in various π-stacked dimers and covalently linked bichromophores is relevant to many processes in biological systems and functional materials. In this work, we examine the role of structural, conformational, and solvent reorganization in a set of conformationally mobile bichromophoric donors, using a combination of gas-phase photoelectron spectroscopy, solution-phase electrochemistry, and density functional theory (DFT) calculations. Photoelectron spectral analysis yields both adiabatic and vertical ionization energies (AIE/VIE), which are compared with measured (adiabatic) solution-phase oxidation potentials (Eox). Importantly, we find a strong correlation of Eox with AIE, but not VIE, reflecting variations in the attendant structural/conformational reorganization upon ionization. A careful comparison of the experimental data with the DFT calculations allowed us to probe the extent of charge stabilization in the gas phase and solution and to parse the reorganizational energy into its various components. This study highlights the importance of a synergistic approach of experiment and theory to study ionization-induced structural and conformational reorganization
Two\u27s Company, Three\u27s a Crowd: Exciton Localization in Cofacially Arrayed Polyfluorenes
Understanding the mechanisms of long-range energy transfer through polychromophoric assemblies is critically important in photovoltaics and biochemical systems. Using a set of cofacially arrayed polyfluorenes (Fn), we investigate the mechanism of (singlet) exciton delocalization in π-stacked polychromophoric assemblies. Calculations reveal that effective stabilization of an excimeric state requires an ideal sandwich-like arrangement; yet surprisingly, emission spectroscopy indicates that exciton delocalization is limited to only two fluorene units for all n. Herein, we show that delocalization is determined by the interplay between the energetic gain from delocalization, which quickly saturates beyond two units in larger Fn, and an energetic penalty associated with structural reorganization, which increases linearly with n. With these insights, we propose a hopping mechanism for exciton transfer, based upon the presence of multiple excimeric tautomers of similar energy in larger polyfluorenes (n ≥ 4) together with the anticipated low thermal barrier of their interconversion
Multiple Scale Reorganization of Electrostatic Complexes of PolyStyrene Sulfonate and Lysozyme
We report on a SANS investigation into the potential for these structural
reorganization of complexes composed of lysozyme and small PSS chains of
opposite charge if the physicochemical conditions of the solutions are changed
after their formation. Mixtures of solutions of lysozyme and PSS with high
matter content and with an introduced charge ratio [-]/[+]intro close to the
electrostatic stoichiometry, lead to suspensions that are macroscopically
stable. They are composed at local scale of dense globular primary complexes of
radius ~ 100 {\AA}; at a higher scale they are organized fractally with a
dimension 2.1. We first show that the dilution of the solution of complexes,
all other physicochemical parameters remaining constant, induces a macroscopic
destabilization of the solutions but does not modify the structure of the
complexes at submicronic scales. This suggests that the colloidal stability of
the complexes can be explained by the interlocking of the fractal aggregates in
a network at high concentration: dilution does not break the local aggregate
structure but it does destroy the network. We show, secondly, that the addition
of salt does not change the almost frozen inner structure of the cores of the
primary complexes, although it does encourage growth of the complexes; these
coalesce into larger complexes as salt has partially screened the electrostatic
repulsions between two primary complexes. These larger primary complexes remain
aggregated with a fractal dimension of 2.1. Thirdly, we show that the addition
of PSS chains up to [-]/[+]intro ~ 20, after the formation of the primary
complex with a [-]/[+]intro close to 1, only slightly changes the inner
structure of the primary complexes. Moreover, in contrast to the synthesis
achieved in the one-step mixing procedure where the proteins are unfolded for a
range of [-]/[+]intro, the native conformation of the proteins is preserved
inside the frozen core
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