Arriving at the most plausible interpretation of the dielectric spectra of glycerol with help from quasielastic γ-ray scattering time-domain interferometry.

Glycerol is one of the glass-forming liquids selected by Robert H. Cole in 1950 to start his study of molecular dynamics by dielectric spectroscopy. Seventy-one years have gone by and remarkably no consensus has been reached on the nature and identity of the relaxation processes observed in the dielectric spectra. The macroscopic dielectric relaxation data allow different interpretations to yield contrasting results, and it is not possible to determine which one is most plausible. Coming to the rescue is the application of the nuclear γ-resonance time-domain interferometry (TDI) to glycerol by Saito et al. [Phys. Rev. E 105, L012605 (2022)10.1103/PhysRevE.105.L012605]. Their microscopic TDI data potentially can decide which interpretation of the dielectric spectra of glycerol is most plausible. The attempt was made by Saito et al., but there is a problem in their analysis of the dielectric data of glycerol and hence their conclusion is untenable. In this paper, we critically compare four major interpretations with the TDI data in an effort to identify the most plausible interpretation of the relaxation processes constituting the dielectric spectra of glycerol.

Intermittent-contact local dielectric spectroscopy of nanostructured interfaces.

Local dielectric spectroscopy (LDS) is a scanning probe method, based on dynamic-mode atomic force microscopy (AFM), to discriminate dielectric properties at surfaces with nanometer-scale lateral resolution. Until now a sub-10 nm resolution for LDS has not been documented, that would give access to the length scale of fundamental physical phenomena such as the cooperativity length related to structural arrest in glass formers (2-3 nm). In this work, LDS performed by a peculiar variant of intermittent-contact mode of AFM, named constant-excitation frequency modulation, was introduced and extensively explored in order to assess its best resolution capability. Dependence of resolution and contrast of dielectric imaging and spectroscopy on operation parameters like probe oscillation amplitude and free amplitude, the resulting frequency shift, and probe/surface distance-regulation feedback gain, were explored. By using thin films of a diblock copolymer of polystyrene (PS) and polymethylmethacrylate (PMMA), exhibiting phase separation on the nanometer scale, lateral resolution of at least 3 nm was demonstrated in both dielectric imaging and localized spectroscopy, by operating with optimized parameters. The interface within lamellar PS/PMMA was mapped, with a best width in the range between 1 and 3 nm. Changes of characteristic time of the secondary (ß) relaxation process of PMMA could be tracked across the interface with PS.

Tuning-fork-based piezoresponse force microscopy.

Surface displacements of a few picometers, occurring after application of an electric potential to piezoelectric materials, can be detected and mapped with nanometer-scale lateral resolution by scanning probe methods, the most notable being piezoresponse force microscopy (PFM). Yet, absolute determination of such displacements, giving access for instance to materials' piezoelectric coefficients, are hindered by both mechanical and electrostatic side-effects, requiring complex experimental and/or post-processing procedures for carrying out reliable results. The employment of quartz tuning-fork force sensors in an intermittent contact mode PFM is able to provide measurements of electrically-induced surface displacements that are not influenced by electrostatic side-effects typical of more conventional cantilever-based PFM. The method is shown to yield piezoeffect mapping on standard ferroelectric test crystals (periodically-poled lithium niobate and triglycine sulfate), as well as on a ferroelectric polymer (PVDF), with no visible influence from the applied dc electric potential.

Experimental evidence of mosaic structure in strongly supercooled molecular liquids.

When a liquid is cooled to produce a glass its dynamics, dominated by the structural relaxation, become very slow, and at the glass-transition temperature Tg its characteristic relaxation time is about 100 s. At slightly elevated temperatures (~1.2 Tg) however, a second process known as the Johari-Goldstein relaxation, ßJG, decouples from the structural one and remains much faster than it down to Tg. While it is known that the ßJG-process is strongly coupled to the structural relaxation, its dedicated role in the glass-transition remains under debate. Here we use an experimental technique that permits us to investigate the spatial and temporal properties of the ßJG relaxation, and give evidence that the molecules participating in it are highly mobile and spatially connected in a system-spanning, percolating cluster. This correlation of structural and dynamical properties provides strong experimental support for a picture, drawn from theoretical studies, of an intermittent mosaic structure in the deeply supercooled liquid phase.

Lateral resolution of electrostatic force microscopy for mapping of dielectric interfaces in ambient conditions.

The attainable lateral resolution of electrostatic force microscopy (EFM) in an ambient air environment on dielectric materials was characterized on a reference sample comprised of two distinct, immiscible glassy polymers cut in a cross-section by ultramicrotomy. Such a sample can be modeled as two semi-infinite dielectrics with a sharp interface, presenting a quasi-ideal, sharp dielectric contrast. Electric polarizability line profiles across the interface were obtained, in both lift-mode and feedback-regulated dynamic mode EFM, as a function of probe/surface separation, for different cases of oscillation amplitudes. We find that the results do not match predictions for dielectric samples, but comply well or are even better than predicted for conductive interfaces. A resolution down to 3 nm can be obtained by operating in feedback-regulated EFM realized by adopting constant-excitation frequency-modulation mode. This suggests resolution is ruled by the closest approach distance rather than by average separation, even with probe oscillation amplitudes as high as 10 nm. For better comparison with theoretical predictions, effective probe radii and cone aperture angles were derived from approach curves, by also taking into account the finite oscillation amplitude of the probe, by exploiting a data reduction procedure previously devised for the derivation of interatomic potentials.

Piezoelectric displacement mapping of compliant surfaces by constant-excitation frequency-modulation piezoresponse force microscopy.

A simple experimental method for piezoresponse force microscopy (PFM) measurements for reliable evaluation of piezoelectric surface displacements even on compliant surfaces is proposed based on atomic force microscopy (AFM) operated in frequency-modulation (FM) dynamic mode with constant excitation (CE), by using non-contact mode cantilevers. Surface displacement by piezoelectric effect after application of an electric potential to the conductive AFM probe translates into a likewise variation of the probe oscillation amplitude, while the related electrostatic forces mainly affect the oscillator resonant frequency, and cantilever bending is limited due to their high stiffness. Our non-contact CE-FM-PFM method is shown to reduce electrostatic force contributions as compared to contact-PFM modes. Converse piezoelectric effect mapping is demonstrated on poly(vinylidenefluoride) nanofibers obtained by electrospinning.

A microscopic look at the Johari-Goldstein relaxation in a hydrogen-bonded glass-former.

Understanding the glass transition requires getting the picture of the dynamical processes that intervene in it. Glass-forming liquids show a characteristic decoupling of relaxation processes when they are cooled down towards the glassy state. The faster (ßJG) process is still under scrutiny, and its full explanation necessitates information at the microscopic scale. To this aim, nuclear γ-resonance time-domain interferometry (TDI) has been utilized to investigate 5-methyl-2-hexanol, a hydrogen-bonded liquid with a pronounced ßJG process as measured by dielectric spectroscopy. TDI probes in fact the center-of-mass, molecular dynamics at scattering-vectors corresponding to both inter- and intra-molecular distances. Our measurements demonstrate that, in the undercooled liquid phase, the ßJG relaxation can be visualized as a spatially-restricted rearrangement of molecules within the cage of their closest neighbours accompanied by larger excursions which reach out at least the inter-molecular scale and are related to cage-breaking events. In-cage rattling and cage-breaking processes therefore coexist in the ßJG relaxation.

The JG ß-relaxation in water and impact on the dynamics of aqueous mixtures and hydrated biomolecules.

Although by now the glass transition temperature of uncrystallized bulk water is generally accepted to manifest at temperature Tg near 136 K, not much known are the spectral dispersion of the structural α-relaxation and the temperature dependence of its relaxation time τα,bulk(T). Whether bulk water has the supposedly ubiquitous Johari-Goldstein (JG) ß-relaxation is a question that has not been answered. By studying the structural α-relaxation over a wide range of temperatures in several aqueous mixtures without crystallization and with glass transition temperatures Tg close to 136 K, we deduce the properties of the α-relaxation and the temperature dependence of τα,bulk(T) of bulk water. The frequency dispersion of the α-relaxation is narrow, indicating that it is weakly cooperative. A single Vogel-Fulcher-Tammann (VFT) temperature dependence can describe the data of τα,bulk(T) at low temperatures as well as at high temperatures from neutron scattering and GHz-THz dielectric relaxation, and hence, there is no fragile to strong transition. The Tg-scaled VFT temperature dependence of τα,bulk(T) has a small fragility index m less than 44, indicating that water is a "strong" glass-former. The existence of the JG ß-relaxation in bulk water is supported by its equivalent relaxation observed in water confined in spaces with lengths of nanometer scale and having Arrhenius T-dependence of its relaxation times τconf(T). The equivalence is justified by the drastic reduction of cooperativity of the α-relaxation in nanoconfinement and rendering it to become the JG ß-relaxation. Thus, the τconf(T) from experiments can be taken as τß,bulk(T), the JG ß-relaxation time of bulk water. The ratio τα,bulk(Tg)/τß,bulk(Tg) is smaller than most glass-formers, and it corresponds to the Kohlrausch α-correlation function, exp[-(t/τα,bulk)1-n], having (1-n) = 0.90. The dielectric data of many aqueous mixtures and hydrated biomolecules with Tg higher than that of water show the presence of a secondary ν-relaxation from the water component. The ν-relaxation is strongly connected to the α-relaxation in properties, and hence, it belongs to the special class of secondary relaxations in glass-forming systems. Typically, its relaxation time τν(T) is longer than τß,bulk(T), but τν(T) becomes about the same as τß,bulk(T) at sufficiently high water content. However, τν(T) does not become shorter than τß,bulk(T). Thus, τß,bulk(T) is the lower bound of τν(T) for all aqueous mixtures and hydrated biomolecules. Moreover, it is τß,bulk(T) but not τα(T) that is responsible for the dynamic transition of hydrated globular proteins.

Contrasting two different interpretations of the dynamics in binary glass forming mixtures.

In a series of papers on binary glass-forming mixtures of tripropyl phosphate (TPP) with polystyrene (PS), Kahlau et al. [J. Chem. Phys. 140, 044509 (2014)] and Bock et al. [J. Chem. Phys. 139, 064508 (2013); J. Chem. Phys. 140, 094505 (2014); and J. Non-Cryst. Solids 407, 88-97 (2015)] presented the data on the dynamics of the two components studied over the entire composition range by several experimental methods. From these sets of data, obtained by multiple experimental techniques on mixtures with a large difference ΔTg ≈ 200 K between the glass transition temperatures of two starting glass formers, they obtained two α-relaxations, α1 and α2. The temperature dependence of the slower α1 is Vogel-Fulcher like, but the faster α2 is Arrhenius. We have re-examined their data and show that their α2-relaxation is the Johari-Goldstein (JG) ß-relaxation with Arrhenius T-dependence admixed with a true α2-relaxation having a stronger temperature dependence. In support of our interpretation of their data, we made dielectric measurements at elevated pressures P to show that the ratio of the α1 and α2 relaxation times, τα1(T,P)/τα2(T,P), is invariant to variations of T and P, while τα1(T,P) is kept constant. This property proves unequivocally that the α2-relaxation is the JG ß-relaxation, the precursor of the α1-relaxation. Subsequently, the true but unresolved α2-relaxation is recovered, and its relaxation times with much stronger temperature dependence are deduced, as expected for the α-relaxation of the TPP component. The results are fully compatible with those found in another binary mixture of methyltetrahydrofuran with tristyrene and PS with ΔTg ≈ 283 K, even larger than ΔTg ≈ 200 K of the mixture of TPP with PS, and in several polymer blends. The contrast between the two very different interpretations brought out in this paper is deemed beneficial for further progress in this research area.

Dynamics of hydrated proteins and bio-protectants: Caged dynamics, ß-relaxation, and α-relaxation.

BACKGROUND: The properties of the three dynamic processes, α-relaxation, ν-relaxation, and caged dynamics in aqueous mixtures and hydrated proteins are analogous to corresponding processes found in van der Waals and polymeric glass-formers apart from minor differences. METHODS: Collection of various experimental data enables us to characterize the structural α-relaxation of the protein coupled to hydration water (HW), the secondary or ν-relaxation of HW, and the caged HW process. RESULTS: From the T-dependence of the ν-relaxation time of hydrated myoglobin, lysozyme, and bovine serum albumin, we obtain Ton at which it enters the experimental time windows of Mössbauer and neutron scattering spectroscopies, coinciding with protein dynamical transition (PDT) temperature Td. However, for all systems considered, the α-relaxation time at Ton or Td is many orders of magnitude longer. The other step change of the mean-square-displacement (MSD) at Tg_alpha originates from the coupling of the nearly constant loss (NCL) of caged HW to density. The coupling of the NCL to density is further demonstrated by another step change at the secondary glass temperature Tg_beta in two bio-protectants, trehalose and sucrose. CONCLUSIONS: The structural α-relaxation plays no role in PDT. Since PDT is simply due to the ν-relaxation of HW, the term PDT is a misnomer. NCL of caged dynamics is coupled to density and show transitions at lower temperature, Tg_beta and Tg_alpha. GENERAL SIGNIFICANCE: The so-called protein dynamical transition (PDT) of hydrated proteins is not caused by the structural α-relaxation of the protein but by the secondary ν-relaxation of hydration water. "This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo".

Thermodynamic scaling of vibrational dynamics and relaxation.

We investigate by thorough molecular dynamics simulations the thermodynamic scaling (TS) of a polymer melt. Two distinct models, with strong and weak virial-energy correlations, are considered. Both evidence the joint TS with the same characteristic exponent γts of the fast mobility-the mean square amplitude of the picosecond rattling motion inside the cage-and the much slower structural relaxation and chain reorientation. If the cage effect is appreciable, the TS master curves of the fast mobility are nearly linear, grouping in a bundle of approximately concurrent lines for different fragilities. An expression of the TS master curve of the structural relaxation with one adjustable parameter less than the available three-parameter alternatives is derived. The novel expression fits well with the experimental TS master curves of thirty-four glassformers and, in particular, their slope at the glass transition, i.e., the isochoric fragility. For the glassformer OTP, the isochoric fragility allows to satisfactorily predict the TS master curve of the fast mobility with no adjustments.

Coupling of Caged Molecule Dynamics to JG ß-Relaxation III: van der Waals Glasses.

In the first two papers separately on the polyalcohols and amorphous polymers of this series, we demonstrated that the fast dynamics observed in the glassy state at high frequencies above circa 1 GHz is the caged dynamics. We showed generally the intensity of the fast caged dynamics changes temperature dependence at a temperature THF nearly coincident with the secondary glass transition temperature Tgß lower than the nominal glass transition temperature Tgα. The phenomenon is remarkable, since THF is determined from measurements of fast caged dynamics at short time scales typically in the ns to ps range, while Tgß characterizes the secondary glass transition at which the Johari-Goldstein (JG) ß-relaxation time τJG reaches a long time of ∼10(3) s, determined directly either by positronium annihilation lifetime spectroscopy, calorimetry, or low frequency dielectric and mechanical relaxation spectroscopy. The existence of the secondary glass transition originates from the dependence of τJG on density, previously proven by experiments performed at elevated pressure. The fact that THF ≈ Tgß reflects the density dependence of the caged dynamics and coupling to the JG ß-relaxation. The generality of the phenomenon and its theoretical rationalization implies the same should be observable in other classes of glass-formers. In this paper, III, we consider two archetypal small molecular van der Waals glass-formers, ortho-terphenyl and toluene. The experimental data show the same phenomenon. The present paper extends the generality of the phenomenon and explanation from the polyalcohols, a pharmaceutical, and many polymers to the small molecular van der Waals glass-formers.

Coupling of Caged Molecule Dynamics to JG ß-Relaxation II: Polymers.

At temperatures below the nominal glass transition temperature Tgα, the structural α-relaxation and the Johari-Goldstein (JG) ß-relaxation are too slow to contribute to susceptibility measured at frequencies higher than 1 GHz. This is particularly clear in the neighborhood of the secondary glass transition temperature Tgß, which can be obtained directly by positronium annihilation lifetime spectroscopy (PALS) and adiabatic calorimetry, or deduced from the temperature at which the JG ß-relaxation time τß reaches 1000 s. The fast process at such high frequencies comes from the vibrations and caged molecules dynamics manifested as the nearly constant loss (NCL) in susceptibility measurements, elastic scattering intensity, I(Q, T), or the mean-square-displacement, ⟨u(2)(T)⟩, in quasielastic neutron scattering experiment. Remarkably, we find for many different glass-formers that the NCL, I, or ⟨u(2)⟩ measured in the glassy state changes its temperature dependence at temperature THF near Tgß. In paper I (Capaccioli, S.; et al. J. Phys. Chem. B 2015, 119 (28), 8800-8808) we have made known this property in the case of the polyalcohols and a pharmaceutical glass former, flufenamic acid studied by THz dielectric spectroscopy, and explained it by the coupling of the NCL to the JG ß-relaxation, and the density dependence of these processes. In this paper II, we extend the consideration of the high frequency response to broader range from 100 MHz to THz in the glassy state of many polymers observed by quasielastic light scattering, Brillouin scattering, quasielastic neutron scattering, and GHz-THz dielectric relaxation. In all cases, the NCL changes its T-dependence at some temperature, THF, below Tgα, which is approximately the same as Tgß. The latter is independently determined by PALS, or adiabatic calorimetry, or low frequency dielectric and mechanical spectroscopy. The property, THF ≈ Tgß, had not been pointed out before by others or in any of the quasielastic neutron and light scattering studies of various amorphous polymers and van der Waals small molecular glass-formers over the past three decades. The generality and fundamental importance of this novel property revitalize the data from these previous publications, making it necessary to be reckoned with in any attempt to solve the glass transition problem. In our rationalization, the property arises first from the fact that the JG ß-relaxation and the caged dynamics both depends on density and entropy. Second, the JG ß-relaxation is the terminator of the caged dynamics, and hence the two processes are inseparable or effectively coupled. Consequently, the occurrence of the secondary glass transition at Tgß necessarily is accompanied by corresponding change in the temperature dependence of the NCL, I, or ⟨u(2)⟩ of the fast caged dynamics at THF ≈ Tgß.

Coupling of Caged Molecule Dynamics to JG ß-Relaxation: I.

The paper (Sibik, J.; Elliott, S. R.; Zeitler, J. A. J. Phys. Chem. Lett. 2014, 5, 1968-1972) used terahertz time-domain spectroscopy (THz-TDS) to study the dynamics of the polyalcohols, glycerol, threitol, xylitol, and sorbitol, at temperatures from below to above the glass transition temperature Tg. On heating the glasses, they observed the dielectric losses, ε″(ν) at ν = 1 THz, increase monotonically with temperature and change dependence at two temperatures, first deep in the glassy state at TTHz = 0.65Tg and second at Tg. The effects at both temperatures are most prominent in sorbitol but become progressively weaker in the order of xylitol and threitol, and the sub-Tg change was not observed in glycerol. They suggested this feature originates from the high-frequency tail of the Johari-Goldstein (JG) ß-relaxation, and the temperature region near 0.65Tg is the universal region for the secondary glass transition due to the JG ß-relaxation. In this paper, we first use isothermal dielectric relaxation data at frequencies below 10(6) Hz to locate the "second glass transition" temperature Tß at which the JG ß-relaxation time τJG reaches 100 s. The value of Tß is close to TTHz = 0.65Tg for sorbitol (0.63Tg) and xylitol (0.65Tg), but Tß is 0.74Tg for threitol and 0.83Tg for glycerol. Notwithstanding, the larger values of Tß of glycerol are consistent with the THz-TDS data. Next, we identify the dynamic process probed by THz-TDS as the caged molecule dynamics, showing up in susceptibility spectra as nearly constant loss (NCL). The caged molecule dynamics regime is terminated by the onset of the primitive relaxation of the coupling model, which is the precursor of the JG ß-relaxation. From this relation, established is the connection of the magnitude and temperature dependence of the NCL and those of τJG. This connection explains the monotonic increase of NCL with temperature and change to a stronger dependence after crossing Tß giving rise to the sub-Tg behavior of ε″(ν) observed in experiment. Beyond the polyalcohols, we present new dielectric relaxation measurements of flufenamic acid and recall dielectric, NMR, and calorimetric data of indomethacin. The data of these two pharmaceuticals enables us to determine the value of Tß = 0.67Tg for flufenamic acid and Tß = 0.58Tg or Tß = 0.62Tg for indomethacin, which can be compared with experimental values of TTHz from THz-TDS measurements when they become available. We point out that the sub-Tg change of NCL at Tß found by THz-TDS can be observed by other high frequency spectroscopy including neutron scattering, light scattering, Brillouin scattering, and inelastic X-ray scattering. An example from neutron scattering is cited. All the findings demonstrate the connection of all processes in the evolution of dynamics ending at the structural α-relaxation.

Reconsidering the dynamics in mixtures of methyltetrahydrofuran with tristyrene and polystyrene.

Mixtures of methyltetrahydrofuran (MTHF) with tristyrene and high molecular weight polystyrene involve an exceptionally large difference in the glass transition temperatures of the two components not realized in other binary mixtures studied before. The extensive study of the molecular dynamics of these mixtures by various experimental techniques by Blochowicz et al. has revealed the presence of a new α'-relaxation not found before in other mixtures and also the more familiar α- and ß-relaxations, but their properties are more extreme. Attention was focused on the new α'-relaxation by Blochowicz et al. in interpreting it to originate from MTHF in confinement and explaining its properties by the Mode Coupling Theory. In a different direction, we concentrate on the highly unusual properties of the α- and ß-relaxations. Earlier, we had success in explaining the properties of these two relaxations and their connection in other mixtures by the coupling model. In this paper, we apply the same model to explain the highly unusual dynamics of the α- and ß-relaxations found in the mixtures of MTHF with tristyrene and polystyrene. Possible relation between the α'- and the ß-relaxations also is explored.

Change of caged dynamics at T(g) in hydrated proteins: trend of mean squared displacements after correcting for the methyl-group rotation contribution.

The question whether the dynamics of hydrated proteins changes with temperature on crossing the glass transition temperature like that found in conventional glassformers is an interesting one. Recently, we have shown that a change of temperature dependence of the mean square displacement (MSD) at Tg is present in proteins solvated with bioprotectants, such as sugars or glycerol with or without the addition of water, coexisting with the dynamic transition at a higher temperature Td. The dynamical change at Tg is similar to that in conventional glassformers at sufficiently short times and low enough temperatures, where molecules are mutually caged by the intermolecular potential. This is a general and fundamental property of glassformers which is always observed at or near Tg independent of the energy resolution of the spectrometer, and is also the basis of the dynamical change of solvated proteins at Tg. When proteins are solvated with bioprotectants they show higher Tg and Td than the proteins hydrated by water alone, due to the stabilizing action of excipients, thus the observation of the change of T-dependence of the MSD at Tg is unobstructed by the methyl-group rotation contribution at lower temperatures [S. Capaccioli, K. L. Ngai, S. Ancherbak, and A. Paciaroni, J. Phys. Chem. B 116, 1745 (2012)]. On the other hand, in the case of proteins hydrated by water alone unambiguous evidence of the break at Tg is hard to find, because of their lower Tg and Td. Notwithstanding, in this paper, we provide evidence for the change at Tg of the T-dependence of proteins hydrated by pure water. This evidence turns out from (i) neutron scattering experimental investigations where the sample has been manipulated by either full or partial deuteration to suppress the methyl-group rotation contribution, and (ii) neutron scattering experimental investigations where the energy resolution is such that only motions with characteristic times shorter than 15 ps can be sensed, thus shifting the onset of both the methyl-group rotation and the dynamic transition contribution to higher temperatures. We propose that, in general, coexistence of the break of the elastic intensity or the MSD at Tg with the dynamic transition at Td in hydrated and solvated proteins. Recognition of this fact helps to remove inconsistency and conundrum encountered in interpreting data of hydrated proteins that thwart progress in understanding the origin of the dynamic transition.

Response to "Comment on 'Unified explanation of the anomalous dynamic properties of highly asymmetric polymer blends' " [J. Chem. Phys. 138, 197101 (2013)].

The Comment of Colmenero asserts no change in F(s)(Q,t) of the poly(ethylene oxide) (PEO) chains in blends with poly(methyl methacrylate) on crossing times of about 1-2 ns in data obtained by neutron scattering experiments and simulations. The assertion is opposite to that reported in the original papers where the neutron data and simulations were published. To make this point clear, we cite the data and the very statements made in the original papers concluding that indeed in the time interval from 60 ps to 1-2 ns the dynamics of PEO chain follows approximately the Rouse model, but becomes slower and departs from the Rouse model in the dependencies on time, momentum transfer, and temperature at longer times past t(c) = 1-2 ns. It is noteworthy that similar crossover of chain dynamics in entangled homopolymers at the ns time scale was found by neutron scattering.

An explanation of the differences in diffusivity of the components of the metallic glass Pd43Cu27Ni10P20.

Bartsch et al. [Phys. Rev. Lett. 104, 195901 (2010)] reported measurements of the diffusivities of different components of the multi-component bulk metallic glass Pd43Cu27Ni10P20. The diffusion of the largest Pd and the smallest P was found to be drastically different. The Stokes-Einstein relation breaks down when considering the P constituent atom, while the relation is obeyed by the Pd atom over 14 orders of magnitude of change in Pd diffusivity. This difference in behavior of Pd and P poses a problem challenging for explanation. With the assist of a recent finding in metallic glasses that the ß-relaxation and the diffusion of the smallest component are closely related processes by Yu et al. [Phys. Rev. Lett. 109, 095508 (2012)], we use the Coupling Model to explain the observed difference between P and Pd quantitatively. The same model also explains the correlation between property of the ß-relaxation with fragility found in the family of (CexLa1-x)68Al10Cu20Co2 with 0 ≤ x ≤ 1.

Unified explanation of the anomalous dynamic properties of highly asymmetric polymer blends.

In polymer blends where the glass transition temperatures of the two components differ greatly, the segmental α-relaxation and the chain dynamics of the faster component exhibit a number of anomalous properties not seen before in homopolymers, and not explainable by conventional theory of polymer dynamics. In the first part of this paper, these anomalous properties are collected altogether and made known. We show their interconnections and emphasize the necessity of explaining all of them together if the objective is to fully solve the problem. In the second part, the predictions from a single theoretical framework, namely, the coupling model, are applied to explain the anomalous properties in toto.

Cell fusion promotes chemoresistance in metastatic colon carcinoma.

Chemoresistance is an important concern in the treatment of metastatic colon cancer. It may emerge through selection of clones that are inherently resistant from the outset or through mechanisms acquired during treatment. Cell fusion represents an efficient means of rapid phenotypic evolution that make cells with new properties at a rate exceeding that achievable by random mutagenesis. Here, we first identified a number of proteins involved in cell fusion using a shotgun proteomics approach, then we investigated the role of these proteins namely tetraspanin CD81/CD9, ADAM10, GTP-binding protein α13, radixin, myosin regulatory light chain and RhoA in the regulation of colon cancer cell fusion. We also found a previously unrecognized role of ADAM10, Gα13 and RhoA in promoting cell fusion. Finally, we show that the occurrence of cell fusion in a metastatic model of colon carcinoma causes the appearance of cells resistant to both 5-fluorouracil and oxaliplatin. These findings highlight the importance of cell fusion in cancer progression and raise significant implications for overcoming chemoresistance in metastatic colon cancer.