Low-Temperature Dynamical Transition in Lipid Bilayers Detected by Spin-Label ESE Spectroscopy

Data on neutron scattering in biological systems show low-temperature dynamical transition between 170 and 230 K manifesting itself as a drastic increase of the atomic mean-squared displacement, 〈x²〉, detected for hydrogen atoms in the nano- to picosecond time scale. For spin-labeled systems, electron spin echo (ESE) spectroscopy—a pulsed version of electron paramagnetic resonance—is also capable of detection of dynamical transition. A two-pulse ESE decay in frozen matrixes is induced by spin relaxation arising from stochastic molecular librations, and allows to obtain the 〈α²〉τ_c parameter, where 〈α²〉 is a mean-squared angular amplitude of the motion and τ_c is the correlation time lying in the sub- and nanosecond time ranges. In this work, the ESE technique was applied to spin-labeled amphiphilic molecules of three different kinds embedded in bilayers of fully saturated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and mono-unsaturated 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) lipids. Two-pulse ESE data revealed the appearance of stochastic librations above 130 K, with the parameter 〈α²〉τ_c obeying the Arrhenius type of temperature dependence and increasing remarkably above 170–180 K. A comparison with a dry sample suggests that onset of motions is not related with lipid internal motions. Three-pulse ESE experiments (resulting in stimulated echos) in DPPC bilayers showed the appearance of slow molecular rotations above 170–180 K. For D₂O-hydrated bilayers, ESE envelope modulation experiments indicate that isotropic water molecular motions in the nearest hydration shell of the bilayer appear with a rate of ~?10⁵ s^?1 in the narrow temperature range between 175 and 179 K. The similarity of the experimental data found for three different spin-labeled compounds suggests a cooperative character for the ESE-detected molecular motions. The data were interpreted within a model suggesting that dynamical transition is related with overcoming barriers, of 10–20 kJ/mol height, existing in the system for the molecular reorientations.     

fMRI study of motor cortex activity modulation in early Parkinson's disease

Parkinson's disease is a neurological disorder associated with the disfunction of dopaminergic pathways of the basal ganglia, mainly resulting in a progressive alteration in the execution of voluntary movements. We present a functional magnetic resonance imaging (fMRI) study on cortical activations during simple motor task performance, in six early–stage hemiparkinsonian patients and seven healthy volunteers. We acquired data in three sessions, during which subjects performed the task with right or left hand, or bimanually. We observed consistent bilateral activations in cingulate cortex and dorsolateral prefrontal cortex of Parkinsonian subjects during the execution of the task with the affected hand. In addition, patients showed both larger and stronger activations in motor cortex of the affected hemisphere with respect to the healthy hemisphere. Compared with the control group, patients showed a hyperactivation of the dorsolateral prefrontal cortex of the affected hemisphere. We concluded that a presymptomatic reorganization of the motor system is likely to occur in Parkinson's disease at earlier stages than previously hypothesized. Moreover, our results support fMRI as a sensitive technique for revealing the initial involvement of motor cortex areas at the debut of this degenerative disorder.     

Percept-related activity in the human somatosensory system: functional magnetic resonance imaging studies

In this paper, we review blood oxygenation level-dependent (BOLD) functional magnetic resonance imaging (fMRI) studies addressing the neural correlates of touch, thermosensation, pain and the mechanisms of their cognitive modulation in healthy human subjects. There is evidence that fMRI signal changes can be elicited in the parietal cortex by stimulation of single mechanoceptive afferent fibers at suprathreshold intensities for conscious perception. Positive linear relationships between the amplitude or the spatial extents of BOLD fMRI signal changes, stimulus intensity and the perceived touch or pain intensity have been described in different brain areas. Some recent fMRI studies addressed the role of cortical areas in somatosensory perception by comparing the time course of cortical activity evoked by different kinds of stimuli with the temporal features of touch, heat or pain perception. Moreover, parametric single-trial functional MRI designs have been adopted in order to disentangle subprocesses within the nociceptive system.

Available evidence suggest that studies that combine fMRI with psychophysical methods may provide a valuable approach for understanding complex perceptual mechanisms and top-down modulation of the somatosensory system by cognitive factors specifically related to selective attention and to anticipation. The brain networks underlying somatosensory perception are complex and highly distributed. A deeper understanding of perceptual-related brain mechanisms therefore requires new approaches suited to investigate the spatial and temporal dynamics of activation in different brain regions and their functional interaction.     

EPR Equilibration Measurement of the C–H Bond Enthalpy in the Methylene Groups of 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (Irganox)

On the basis of previous and current studies, it has been possible to evaluate and compare the bond dissociation energies of the phenol (O–H) bond and of the methylene and methyl (C–H) bonds in Irganox (trade name) by means of electron paramagnetic resonance records of galvinoxyl–irganoxyl hydrogen transfer reaction equilibria. The bond dissociation enthalpy of the C–H methylene and methyl bonds in Irganox was found to be 339.0 ± 3.0 kJ/mol, very close to the previously found value of 340.7 ± 3.0 kJ/mol for the O–H bond of some benzyl–phenolic antioxidant.     

One single-step synthesis of multifunctional methylene blue-coated magnetite nanoparticles

This work reports the preparation of hybrid nanoparticles with magnetic and fluorescent properties. The material is based on magnetite nanoparticles (NPs) coated with fluorophore methylene blue (MB). The synthesis of a multifunctional material with magnetic and fluorescent features is carried out in a single step by electrooxidation. The effect of the presence of methylene blue in the synthetic medium is discussed. The presence of MB polymer at the NP surface is demonstrated with visible UV, infrared and Raman spectroscopy. The NPs morphology, structure and size are determined by transmission electron microscopy (TEM) and X-ray diffraction. The magnetic properties are measured with a vibrating sample magnetometer (VMS). In overall, the results show that magnetite NPs generated electrochemically in the presence of MB present a core/shell structure, being the NP at the core surrounded by methylene blue polymer, leading to a nanocomposite or hybrid material.     

Isomonodromic deformations and twisted Yangians arising in Teichmüller theory

In this paper we build a link between the Teichmüller theory of hyperbolic Riemann surfaces and isomonodromic deformations of linear systems whose monodromy group is the Fuchsian group associated to the given hyperbolic Riemann surface by the Poincaré uniformization. In the case of a one-sheeted hyperboloid with n orbifold points we show that the Poisson algebra Dn of geodesic length functions is the semiclassical limit of the twisted q-Yangian for the orthogonal Lie algebra on defined by Molev, Ragoucy and Sorba. We give a representation of the braid-group action on Dn in terms of an adjoint matrix action. We characterize two types of finite-dimensional Poissonian reductions and give an explicit expression for the generating function of their central elements. Finally, we interpret the algebra Dn as the Poisson algebra of monodromy data of a Frobenius manifold in the vicinity of a non-semi-simple point.     

Interaction enthalpy of lysozyme with vesicles

Negatively charged vesicles made of non-stoichiometric amounts of sodium dodecylsulfate and cetyltrimethylammonium bromide were characterised by physico-chemical methods. Interactions with lysozyme were examined by calorimetry. A remarkable heat effect is observed upon diluting the protein with the vesicular pseudo-solvent. The maximum ΔH_bind value occurs at complete vesicle charge neutralisation by the protein.     

Modeling NMR chemical shifts: a comparison of charge models for solid state effects on N chemical shift tensors

This paper presents results from applying different point charge models to take into account intermolecular interactions to model the solid state effects on the ¹⁵N NMR chemical shifts tensors. The DFT approach with the BLYP gradient corrected exchange correlation functional has been used because it can include electron correlation effects at a reasonable cost and is able to reproduce ¹⁵N NMR chemical shifts with reasonable accuracy. The results obtained with the point charge models are compared with the experimental data and with results obtained using the cluster model, which includes explicitly neighboring molecular fragments. The results show that the point charge models can take into account solid state effects at a cost much lower than the cluster methods.