Nature of Subdiffusion Crossover in Molecular and Polymeric Glassformers.

A crossover from a non-Gaussian to Gaussian subdiffusion has been observed ubiquitously in various polymeric and molecular glassformers. We have developed a framework that generalizes the fractional Brownian motion model to incorporate non-Gaussian features by introducing a jump kernel. We illustrate that the non-Gaussian fractional Brownian motion model accurately characterizes the subdiffusion crossover. From the solutions of the non-Gaussian fractional Brownian motion model, we gain insights into the nature of van Hove self-correlation in non-Gaussian subdiffusive regime, which is found to exhibit exponential tails, providing first such experimental evidence in molecular glassformers. The validity of the model is supported by comparison with incoherent quasielastic neutron scattering data obtained from several molecular and polymeric glassformers.

Cellular dynamics as a marker of normal-to-cancer transition in human cells.

Normal-to-cancer (NTC) transition is known to be closely associated to cell´s biomechanical properties which are dependent on the dynamics of the intracellular medium. This study probes different human cancer cells (breast, prostate and lung), concomitantly to their healthy counterparts, aiming at characterising the dynamical profile of water in distinct cellular locations, for each type of cell, and how it changes between normal and cancer states. An increased plasticity of the cytomatrix is observed upon normal-to-malignant transformation, the lung carcinoma cells displaying the highest flexibility followed by prostate and breast cancers. Also, lung cells show a distinct behaviour relative to breast and prostate, with a higher influence from hydration water motions and localised fast rotations upon NTC transformation. Quasielastic neutron scattering techniques allowed to accurately distinguish the different dynamical processes taking place within these highly heterogeneous cellular systems. The results thus obtained suggest that intracellular water dynamics may be regarded as a specific reporter of the cellular conditions-either healthy or malignant.

On the crystal structures and phase transitions of hydrates in the binary dimethyl sulfoxide-water system.

Neutron powder diffraction data have been collected from a series of flash-frozen aqueous solutions of dimethyl sulfoxide (DMSO) with concentrations between 25 and 66.7 mol% DMSO. These reveal the existence of three stoichiometric hydrates, which crystallize on warming between 175 and 195 K. DMSO trihydrate crystallizes in the monoclinic space group P21/c, with unit-cell parameters at 195 K of a = 10.26619 (3), b = 7.01113 (2), c = 10.06897 (3) Å, ß = 101.5030 (2)° and V = 710.183 (3) Å3 (Z = 4). Two of the symmetry-inequivalent water molecules form a sheet of tiled four- and eight-sided rings; the DMSO molecules are sandwiched between these sheets and linked along the b axis by the third water molecule to generate water-DMSO-water tapes. Two different polymorphs of DMSO dihydrate have been identified. The α phase is monoclinic (space group P21/c), with unit-cell parameters at 175 K of a = 6.30304 (4), b = 9.05700 (5), c = 11.22013 (7) Å, ß = 105.9691 (4)° and V = 615.802 (4) Å3 (Z = 4). Its structure contains water-DMSO-water chains, but these are polymerized in such a manner as to form sheets of reniform eight-sided rings, with the methyl groups extending on either side of the sheet. On warming above 198 K, α-DMSO·2H2O undergoes a solid-state transformation to a mixture of DMSO·3H2O + anhydrous DMSO, and there is then a stable eutectic between these two phases at ∼203 K. The ß-phase of DMSO dihydrate has been observed in a rapidly frozen eutectic melt and in very DMSO-rich mixtures. It is observed to be unstable with respect to the α-phase; above ∼180 K, ß-DMSO·2H2O converts irreversibly to α-DMSO·2H2O. At 175 K, the lattice parameters of ß-DMSO·2H2O are a = 6.17448 (10), b = 11.61635 (16), c = 8.66530 (12) Å, ß = 101.663 (1)° and V = 608.684 (10) Å3 (Z = 4), hence this polymorph is just 1.16% denser than the α-phase under identical conditions. Like the other two hydrates, the space group appears likely, on the basis of systematic absences, to be P21/c, but the structure has not yet been determined. Our results reconcile 60 years of contradictory interpretations of the phase relations in the binary DMSO-water system, particularly between mole fractions of 0.25-0.50, and confirm empirical and theoretical studies of the liquid structure around the eutectic composition (33.33 mol% DMSO).

Dioctadecyldimethylammonium bromide, a surfactant model for the cell membrane: Importance of microscopic dynamics.

Cationic lipid membranes have recently attracted huge attention both from a fundamental point of view and due to their practical applications in drug delivery and gene therapy. The dynamical behavior of the lipids in the membrane is a key parameter controlling various physiological processes and drug release kinetics. Here, we review the dynamical and thermotropic phase behavior of an archetypal cationic lipid membrane, dioctadecyldimethylammonium bromide (DODAB), as studied using neutron scattering and molecular dynamics simulation techniques. DODAB membranes exhibit interesting phase behavior, specifically showing coagel, gel, and fluid phases in addition to a large hysteresis when comparing heating and cooling cycles. The dynamics of the lipid membrane is strongly dependent on the physical state of the bilayer. Lateral diffusion of the lipids is faster, by an order of magnitude, in the fluid phase than in the ordered phase. It is not only the characteristic times but also the nature of the segmental motions that differ between the ordered and fluid phases. The effect of different membrane active molecules including drugs, stimulants, gemini surfactants, and unsaturated lipids, on the dynamical and thermotropic phase behavior of the DODAB membrane, is also discussed here. Various interesting features such as induced synchronous ordering between polar head groups and tails, sub diffusive behavior, etc., are observed. The results shed light on the interaction between these additives and the membrane, which is found to be a complex interplay between the physical state of the membrane, charge, concentration, molecular architecture of the additives, and their location within the membrane.

Role of intracellular water in the normal-to-cancer transition in human cells-insights from quasi-elastic neutron scattering.

The transition from normal to malignant state in human cells is still a poorly understood process. Changes in the dynamical activity of intracellular water between healthy and cancerous human cells were probed as an innovative approach for unveiling particular features of malignancy and identifying specific reporters of cancer. Androgen-unresponsive prostate and triple-negative breast carcinomas were studied as well as osteosarcoma, using the technique of quasi-elastic neutron scattering. The cancerous cells showed a considerably higher plasticity relative to their healthy counterparts, this being more significant for the mammary adenocarcinoma. Also, the data evidence that the prostate cancer cells display the highest plasticity when compared to triple-negative mammary cancer and osteosarcoma, the latter being remarkably less flexible. Furthermore, the results suggest differences between the flexibility of different types of intracellular water molecules in normal and cancerous cells, as well as the number of molecules involved in the different modes of motion. The dynamics of hydration water molecules remain virtually unaffected when going from healthy to cancer cells, while cytoplasmic water (particularly the rotational motions) undergoes significant changes upon normal-to-cancer transition. The results obtained along this study can potentially help to understand the variations in cellular dynamics underlying carcinogenesis and tumor metastasis, with an emphasis on intracellular water.

Ubiquicidin-Derived Peptides Selectively Interact with the Anionic Phospholipid Membrane.

Ubiquicidin (UBI)/ribosomal protein S30 (RS30) is an intracellular protein with antimicrobial activities against various pathogens. UBI (29-41) and UBI (31-38) are two crucial peptides derived from Ubiquicidin, which have shown potential as infection imaging probes. Here, we report the interactions of UBI-derived peptides with anionic and zwitterionic phospholipid membranes. Our isothermal titration calorimetry results show that both peptides selectively interact with the anionic phospholipid membrane (a model bacterial membrane) and reside mainly on the membrane surface. The interaction of UBI-derived peptides with the anionic phospholipid membrane is exothermic and driven by both enthalpy (ΔH) and entropy (ΔS), with the entropic term TΔS being greater than ΔH. This large entropic term can be a result of the aggregation of the anionic vesicles, which is confirmed by dynamic light scattering (DLS) measurements. DLS data show that vesicle aggregation is enhanced with increasing peptide-to-lipid molar ratios (P/L) and is found to be more pronounced in the case of UBI (29-41). DLS results are found to be consistent with independent transmission measurements. To study the effects of UBI-derived peptides on the microscopic dynamics of the model bacterial membrane, quasielastic neutron scattering (QENS) measurements have been carried out. The QENS results show that both peptides restrict the lateral motion of the lipid within the leaflet. UBI (29-41) acts as a stronger stiffening agent, hindering the lateral diffusion of lipids more efficiently than UBI (31-38). To our knowledge, this is the first report illustrating the mechanism of interaction of UBI-derived peptides with model membranes. This study also has implications for the improvement and design of antimicrobial peptide-based infection imaging probes.

Analysis of elastic incoherent neutron scattering data beyond the Gaussian approximation.

This work addresses the use of the Gaussian approximation as a common tool to extract atomic motions in proteins from elastic incoherent neutron scattering and whether improvements in data analysis and additional information can be obtained when going beyond that. We measured alpha-lactalbumin with different levels of hydration on three neutron backscattering spectrometers, to be able to resolve a wide temporal and spatial range for dynamics. We demonstrate that the Gaussian approximation gives qualitatively similar results to models that include heterogeneity, if one respects a certain procedure to treat the intercept of the elastic intensities with the momentum transfer axis. However, the inclusion of motional heterogeneity provides better fits to the data. Our analysis suggests an approach of limited heterogeneity, where including only two kinds of motions appears sufficient to obtain more quantitative results for the mean square displacement. Finally, we note that traditional backscattering spectrometers pose a limit on the lowest accessible momentum transfer. We therefore suggest that complementary information about the spatial evolution of the elastic intensity close to zero momentum transfer can be obtained using other neutron methods, in particular, neutron spin-echo together with polarization analysis.

Effects of Hydrotropic Salt on the Nanoscopic Dynamics of DTAB Micelles.

Effects of a hydrotropic salt, sodium salicylate (NaSal), on the dynamic behavior of cationic dodecyltrimethylammonium bromide (DTAB) micelles as studied using dynamic light scattering (DLS) and quasielastic neutron scattering (QENS) techniques are reported here. DLS study showed that the addition of NaSal leads to a decrease in the apparent diffusion coefficient of the whole micelle indicating micellar growth. QENS data analysis suggested that observed dynamics involves two distinct motions, lateral motion of the surfactant over the curved micellar surface and localized segmental motion of the surfactant. It is found that the addition of NaSal slows down the lateral motion of DTAB while the localized segmental motion of the DTAB chain is not affected much. An atomistic molecular dynamics (MD) simulation was performed to gain further insight into the underlying phenomena. MD simulation results are found to be consistent with the experimental observations. MD simulation revealed that location of the salicylate ions on the micellar surface and their strong electrostatic association with their oppositely charged surfactant headgroup are the major factors in slowing down the lateral motion of the DTAB molecule. In the present work, a quantitative description of the effects of NaSal on the nanoscopic dynamics of DTAB micelles and its correlation with the microstructure of the micelle is provided.

Neutron Radiation Tolerance of Two Benchmark Thiophene-Based Conjugated Polymers: the Importance of Crystallinity for Organic Avionics.

Aviation and space applications can benefit significantly from lightweight organic electronics, now spanning from displays to logics, because of the vital importance of minimising payload (size and mass). It is thus crucial to assess the damage caused to such materials by cosmic rays and neutrons, which pose a variety of hazards through atomic displacements following neutron-nucleus collisions. Here we report the first study of the neutron radiation tolerance of two poly(thiophene)s-based organic semiconductors: poly(3-hexylthiophene-2,5-diyl), P3HT, and the liquid-crystalline poly(2,5-bis (3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene), PBTTT. We combine spectroscopic investigations with characterisation of intrinsic charge mobility to show that PBTTT exhibits significantly higher tolerance than P3HT. We explain this in terms of a superior chemical, structural and conformational stability of PBTTT, which can be ascribed to its higher crystallinity, in turn induced by a combination of molecular design features. Our approach can be used to develop design strategies for better neutron radiation-tolerant materials, thus paving the way for organic semiconductors to enter avionics and space applications.

Enhancement of Lateral Diffusion in Catanionic Vesicles during Multilamellar-to-Unilamellar Transition.

Catanionic vesicles are formed spontaneously by mixing cationic and anionic dispersions in aqueous solution in suitable conditions. Because of spontaneity in formation, long-term stability, and easy modulation of size and charge, they have numerous advantages over conventional lipid-based vesicles. The dynamics of such vesicles is of interest in the field of biomedicine, as they can be used to deliver drug molecules into the cell membrane. Dynamics of catanionic vesicles based on sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) have been studied using incoherent elastic and quasielastic neutron scattering (QENS) techniques. Neutron scattering experiments have been carried out on two backscattering spectrometers, IRIS and IN16B, which have different energy resolutions and energy transfer windows. An elastic fixed-window scan carried out using IN16B shows a phase transition at ∼307 K during the heating cycle, whereas on cooling the transition occurred at ∼294 K. DSC results are found to be in close agreement with the elastic scan data. This transition is ascribed to a structural rearrangement from a multilamellar to a unilamellar phase [ Andreozzi J. Phys. Chem. B 2010 , 114 , 8056 - 8060 ]. It is found that a model in which the surfactant molecules undergo both lateral and internal motions can describe the QENS data quite well. While the data from IRIS have contributions from both dynamical processes, the data from IN16B probe only lateral motions, as the internal motions are too fast for the energy window of the spectrometer. It is found that, through the transition, the fraction of surfactant molecules undergoing lateral motion increases of a factor of 2 from the multilamellar to the unilamellar phase, indicating an enhanced fluidity of the latter. The lateral motion is found to be Fickian in nature, while the internal motion has been described by a localized translational diffusion model. The results reported here could have direct interest for a number of applications, such as molecular transport, and the effect of specific drug molecules or hormones through the membrane.

Dynamical features in cationic micelles of varied chain length.

Chain length is one of the parameters controlling the structural arrangement of micelle monomers, such that one can tailor the monomers for different applications, but the effect of chain length on the dynamical behavior of micelles is unknown. In this article, we report a study on the effect of varying chain length on the dynamical behavior of alkyltrimethylammonium bromide (C(n)TAB) micelles (n = 10, 12, 14, and 16) using incoherent quasielastic neutron scattering (QENS). The data analysis clearly shows the presence of two distinct motions: global motion of whole micelles and faster internal motions of the C(n)TAB monomers. The global diffusion is Fickian in nature, whereas the internal motions can be described with a model that considers the motions of the headgroup and the hydrophobic alkyl chain separately. Methyl groups in the headgroup undergo 3-fold jump rotations, and the hydrogen atoms belonging to the alkyl chain undergo localized translational diffusion. The hydrogen atoms belonging to the alkyl chain are confined within spherical volumes that increase linearly along the C(n)TAB chain: the hydrogen atoms closer to the headgroup move within smaller spheres with lower diffusion coefficients than those farther from the headgroup. The main result is that, with increasing chain length, the dynamics of the C(n)TAB monomer is greatly affected: diffusion is reduced and occurs in smaller spheres, and residence times are increased. Global motion is also hindered with increased chain length.

Internal dynamics in SDS micelles: neutron scattering study.

The molecular dynamics of sodium dodecyl sulfate (SDS) micelle has been investigated using high-resolution incoherent quasielastic neutron scattering technique. Data analysis clearly shows presence of two distinct motions: whole micellar motion or global diffusion and faster internal motion of the SDS monomer. The global diffusion associated with the whole micelle is found to be Fickian in nature, and the corresponding diffusion coefficients are found to be consistent with those obtained from dynamic light scattering measurements. The internal motion is described with a model consistent with the structure of the micelle and which accounts for the flexibility of the chains. The SDS monomer consists of a head group, which lies on the surface of the globular micelle, and a tail that hangs from the head toward the center of the globule. Considering various factors like conformational changes of the SDS chains, bending, stretching of the chemical bonds, etc., the dynamics of the SDS molecules is successfully described by a model in which the hydrogen atoms undergo localized translational motion confined within spherical volumes. This volume increases linearly along the SDS chain such that the hydrogen atoms closer to the head group move within smaller spheres with lower diffusion constant than the hydrogen atoms away from the head group. This model is found to be consistent with the data over the whole temperature and concentration range. Diffusivity and the volume of the spheres are also found to increase with temperature. The effect of lowering the SDS concentration is found to be similar to that of increasing the temperature.

The origin of the dynamic transition in proteins.

Despite extensive efforts in experimental and computational studies, the microscopic understanding of dynamics of biological macromolecules remains a great challenge. It is known that hydrated proteins, DNA and RNA, exhibit a so-called "dynamic transition." It appears as a sharp rise of their mean-squared atomic displacements r2 at temperatures above 200-230 K. Even after a long history of studies, this sudden activation of biomolecular dynamics remains a puzzle and many contradicting models have been proposed. By combining neutron and dielectric spectroscopy data, we were able to follow protein dynamics over an extremely broad frequency range. Our results show that there is no sudden change in the dynamics of the protein at temperatures around approximately 200-230 K. The protein's relaxation time exhibits a smooth temperature variation over the temperature range of 180-300 K. Thus the experimentally observed sharp rise in r2 is just a result of the protein's structural relaxation reaching the limit of the experimental frequency window. The microscopic mechanism of the protein's structural relaxation remains unclear.

Observation of a dynamic crossover in water confined in double-wall carbon nanotubes.

High-resolution quasielastic neutron scattering spectroscopy was used to measure H2O hydrated double-wall carbon nanotubes (DWNT). The measurements were made at a series of temperatures from 250 K down to 150 K. The relaxing-cage model was used to analyze the quasielastic spectra. We observed clear evidence of a fragile-to-strong dynamic crossover (FSC) at T(L) = 190 K in the confined water. We further show that the mean-square atomic displacement of the hydrogen atoms in water exhibits a sharp change in slope at approximately the same temperature 190 K. Comparing the result with that obtained from the confined water in hydrophilic porous silica material MCM-41, we demonstrate experimentally that water confined in a hydrophobic substrate exhibits a lower dynamic crossover temperature by deltaT(L) approximately = 35 K.