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 τ α,bulk (T). Whether bulk water has the supposedly ubiquitous Johari-Goldstein (JG) β-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 τ α,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 τ α,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 τ α,bulk (T) has a small fragility index m less than 44, indicating that water is a "strong" glass-former. The existence of the JG β-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 τ conf (T). The equivalence is justified by the drastic reduction of cooperativity of the α-relaxation in nanoconfinement and rendering it to become the JG β-relaxation. Thus, the τ conf (T) from experiments can be taken as τ β,bulk (T), the JG β-relaxation time of bulk water. The ratio τ α,bulk (Tg)/τ β,bulk (Tg) is smaller than most glass-formers, and it corresponds to the Kohlrausch α-correlation function, exp[−(t/τ α,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 τ β,bulk (T), but τν(T) becomes about the same as τ β,bulk (T) at sufficiently high water content. However, τν(T) does not become shorter than τ β,bulk (T). Thus, τ β,bulk (T) is the lower bound of τν(T) for all aqueous mixtures and hydrated biomolecules. Moreover, it is τ β,bulk (T) but not τα(T) that is responsible for the dynamic transition of hydrated globular proteins.
One fundamental challenge in biophysics is to understand the connection between protein dynamics and its function. Part of the difficulty arises from the fact that proteins often present local atomic motions and collective dynamics on the same time scales, and challenge the experimental identification and quantification of different dynamic modes. Here, by taking lyophilized proteins as the example, we combined deuteration technique and neutron scattering to separate and characterize the self-motion of hydrogen and the collective interatomic motion of heavy atoms (C, O, N) in proteins on the pico-to-nanosecond time scales. We found that hydrogen atoms present an instrument-resolution-dependent onset for anharmonic motions, which can be ascribed to the thermal activation of local sidegroup motions. However, the protein heavy atoms exhibit an instrument-resolutionindependent anharmonicity around 200 K, which results from unfreezing of the relaxation of the protein structures on the laboratory equilibrium time (100−1000 s), softening of the entire bio-macromolecules.
We demonstrate a graphene–MoS2 architecture integrating multiple field-effect transistors (FETs), and we independently probe and correlate the conducting properties of van der Waals coupled graphene–MoS2 contacts with those of the MoS2 channels. Devices are fabricated starting from high-quality single-crystal monolayers grown by chemical vapor deposition. The heterojunction was investigated by scanning Raman and photoluminescence spectroscopies. Moreover, transconductance curves of MoS2 are compared with the current–voltage characteristics of graphene contact stripes, revealing a significant suppression of transport on the n-side of the transconductance curve. On the basis of ab initio modeling, the effect is understood in terms of trapping by sulfur vacancies, which counterintuitively depends on the field effect, even though the graphene contact layer is positioned between the backgate and the MoS2 channel.
Recently hBN has become an interesting platform for quantum optics due to the peculiar defect-related luminescence properties. Concomitantly, hBN was established as the ideal insulating support for realizing 2D materials device, where, on the contrary, defects can affect the device performance. In this work, we study the light emission properties of hBN flakes obtained by mechanical exfoliation with particular focus on extended defects generated in the process. In particular, we tackle different issues as the light emission in hBN flakes of different thicknesses in the range of hundreds of nanometers, revealing a higher concentration of deep level emission in thinner area of the flake. We recognize the effect of crystal deformation in some areas of the flake with an important blue-shift (130 meV) of the room temperature near band edge emission of hBN and the concurrent presence of a novel emission at 2.36 eV related to the formation of array of dislocations. We studied the light emission properties by means of cathodoluminescence and sub-bandgap excitation photoluminescence of thickness steps with different crystallographic orientations, revealing the presence of different concentration of radiative centers. CL mapping allows to detect buried thickness steps, invisible to the SEM and AFM morphological analysis.
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