Two time scales for self and collective diffusion near the critical point in a simple patchy model for proteins with floating bonds.

Using dynamic Monte Carlo and Brownian dynamics, we investigate a floating bond model in which particles can bind through mobile bonds. The maximum number of bonds (here fixed to 4) can be tuned by appropriately choosing the repulsive, nonadditive interactions among bonds and particles. We compute the static and dynamic structure factor (intermediate scattering function) in the vicinity of the gas-liquid critical point. The static structure exhibits a weak tetrahedral network character. The intermediate scattering function shows a temporal decay deviating from a single exponential, which can be described by a double exponential decay where the two time scales differ approximately by one order of magnitude. This time scale separation is robust over a range of wave numbers. The analysis of clusters in real space indicates the formation of noncompact clusters and shows a considerable stretch in the instantaneous size distribution when approaching the critical point. The average time evolution of the largest subcluster of given initial clusters with 10 or more particles also shows a double exponential decay. The observation of two time scales in the intermediate scattering function at low packing fractions is consistent with similar findings in globular protein solutions with trivalent metal ions that act as bonds between proteins.

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.

Dynamic footprint of sequestration in the molecular fluctuations of osteopontin.

The sequestration of calcium phosphate by unfolded proteins is fundamental to the stabilization of biofluids supersaturated with respect to hydroxyapatite, such as milk, blood or urine. The unfolded state of osteopontin (OPN) is thought to be a prerequisite for this activity, which leads to the formation of core-shell calcium phosphate nanoclusters. We report on the structures and dynamics of a native OPN peptide from bovine milk, studied by neutron spectroscopy and small-angle X-ray and neutron scattering. The effects of sequestration are quantified on the nanosecond- ångström resolution by elastic incoherent neutron scattering. The molecular fluctuations of the free phosphopeptide are in agreement with a highly flexible protein. An increased resilience to diffusive motions of OPN is corroborated by molecular fluctuations similar to those observed for globular proteins, yet retaining conformational flexibilities. The results bring insight into the modulation of the activity of OPN and phosphopeptides with a role in the control of biomineralization. The quantification of such effects provides an important handle for the future design of new peptides based on the dynamics-activity relationship.

Investigation of the relationship between hydrogen bonds and macroscopic properties in hybrid core-shell gamma-Fe2O3-P(NIPAM-AAS) microgels.

We investigate in a hybrid material the interactions existing between magnetic nanoparticles of gamma-Fe(2)O(3) and the polymer matrix constituted by core-shell poly(N-isopropylacrylamide-sodium acrylate) microgels. These interactions provoke the shifting of the microgel volume phase transition to higher temperatures when the amount of gamma-Fe(2)O(3) increases. The study was performed using different techniques such as incoherent quasi-elastic neutron scattering (IQNS), infrared spectroscopy (FTIR-ATR), and dynamic light scattering (DLS). Below the low critical solution temperature (LCST) of the polymer, the IQNS data confirm that the presence of inorganic nanoparticles affects the PNIPAM chain motions. Thus, in the swollen state both the mean-square displacement of the polymer segments and the diffusive motion of the polymer chains decrease as the iron oxide content increases. The FTIR-ATR study indicates that the reduction of vibrational and diffusional motions of the polymer chains is due to the formation of hydrogen bonds between the amide groups of the polymer matrix and the OH groups of the magnetic nanoparticles. The creation of this hybrid complex would explain the reduction of the swelling capacity with increasing the iron content in the microgels. Furthermore, this interaction could also explain the shift of the polymer LCST to higher temperatures as due to the extra energy required by the system to break the hydrogen bonds prior to the PNIPAM collapse.

X-ray diffraction and inelastic neutron scattering study of 1:1 tetramethylpyrazine chloranilic acid complex: temperature, isotope, and pressure effects.

The x-ray diffraction studies of the title complex were carried out at room temperature and 14 K for H/D (in hydrogen bridge) isotopomers. At 82 K a phase transition takes place leading to a doubling of unit cells and alternation of the hydrogen bond lengths linking tetramethylpyrazine (TMP) and chloranilic acid molecules. A marked H/D isotope effect on these lengths was found at room temperature. The elongation is much smaller at 14 K. The infrared isotopic ratio for O-H(D)...N bands equals to 1.33. The four tunnel splittings of methyl librational ground states of the protonated complex required by the structure are determined at a temperature T=4.2 K up to pressures P=4.7 kbars by high resolution neutron spectroscopy. The tunnel mode at 20.6 microeV at ambient pressure shifts smoothly to 12.2 microeV at P=3.4 kbars. This is attributed to an increase of the strength of the rotational potential proportional to r(-5.6). The three other tunnel peaks show no or weak shifts only. The increasing interaction with diminishing intermolecular distances is assumed to be compensated by a charge transfer between the constituents of deltae/e approximately 0.02 kbar(-1). The phase transition observed between 3.4 and 4.7 kbars leads to increased symmetry with only two more intense tunneling bands. In the isotopomer with deuterated hydrogen bonds and P=1 bar all tunnel intensities become equal in consistency with the low temperature crystal structure. The effect of charge transfer is confirmed by a weakening of rotational potentials for those methyl groups whose tunnel splittings were independent of pressure. Density functional theory calculations for the model TMP.(HF)2 complex and fully ionized molecule TMP+ point out that the intramolecular rotational potential of methyl groups is weaker in the charged species. They do not allow for the unequivocal conclusions about the role of the intermolecular charge transfer effect on the torsional frequencies.

Dynamics of propylene glycol and its oligomers confined to a single molecular layer.

The dynamics of propylene glycol (PG) and its oligomers 7-PG and poly-propylene glycol (PPG), with M(w) = 4000 (approximately 70 monomers), confined in a Na-vermiculite clay have been investigated by quasielastic neutron scattering. The liquids are confined to single molecular layers between clay platelets, giving a true two-dimensional liquid. Data from three different spectrometers of different resolutions were Fourier transformed to S(Q,t) and combined to give an extended dynamical time range of 0.3-2000 ps. An attempt was made to distinguish the diffusive motion from the methyl group rotation and a fast local motion of hydrogen in the polymer backbone. The results show that the average relaxation time tau(d) of this diffusive process is, as expected, larger than the relaxation time tau averaged over all dynamical processes observed in the experimental time window. More interesting, it is evident that the severe confinement has a relatively small effect on tau(d) at T = 300 K, this holds particularly for the longest oligomer, PPG. The most significant difference is that the chain-length dependence of tau(d) is weaker for the confined liquids, although the slowing down in bulk PG due to the formation of a three-dimensional network of OH-bonded end groups reduces this difference. The estimated average relaxation time tau at Q = 0.92 Angstroms(-1) for all the observed processes is in excellent agreement with the previously reported dielectric alpha relaxation time in the studied temperature range of 260-380 K. The average relaxation time tau (as well as the dielectric alpha relaxation time) is also almost unaffected by the confinement to a single molecular layer, suggesting that the interaction with the clay surfaces is weak and that the reduced dimensionality has only a weak influence on the time scale of all the dynamical processes observed in this study.

Surface roughness of supercooled polymer melts.

We report on in situ x-ray reflectivity measurements of the surface roughness of supercooled glass forming polymers in a temperature range from 190 to 330 K. The experimentally determined rms roughness has been found to obey the capillary wave model of a single liquid/vapor interface over the entire temperature range. An expression for the surface roughness below the bulk glass transition (T(G) approximately equal to 200 K) is deduced from the viscoelastic theory of surface fluctuations; however, no indication of a frozen-in surface roughness has been observed in the experiment. Additionally, it is shown that precise values of the surface tension of highly viscous liquids in the supercooled state can be determined by x-ray reflectivity.

Capillary waves at the transition from propagating to overdamped behavior.

We measure the dispersion relation of capillary waves on a liquid surface by heterodyne x-ray photon correlation spectroscopy near the transition from propagating to overdamped dynamic behavior. A strong deviation of the propagation frequency from the small-damping result omega(p) proportional, variant k(3/2) is observed long before the actual transition where ( partial differential omega(p)/ partial differential k)<0 and omega(p) tends to zero. This behavior is successfully described by expressions derived within linear response theory.

Observation of heterodyne mixing in surface x-ray photon correlation spectroscopy experiments.

We report measurements of propagating capillary waves on a liquid water surface at T=5 degrees C with x-ray photon correlation spectroscopy. The experiment has been performed under grazing incidence conditions with an incoming x-ray beam below the critical angle of total external reflection. In the q region investigated the measured intensity-intensity autocorrelation functions of the liquid water surface were found to be heterodyne signals, i.e., a combination of first- and second-order correlation functions g(1)(tau) and g(2)(tau).