Scaling behavior in the conductivity of alkali oxide glasses

Although the frequency dependent conductivity, {sigma}({omega}), of ion-containing glasses displays power law dispersion ({sigma}({omega}) {approx} {omega}{sup n}) that can usually be described by a master curve, several findings have suggested that this scaling fails at low temperatures as indicated by a temperature dependence of the scaling exponent, n. The authors investigate this behavior in the frequency range between 1 Hz and 10{sup 6} Hz for a different materials including alkali metaphosphate glasses and a polymer. They identify two distinct regimes of conductive behavior, {sigma}{sub {vert_bar}} and {sigma}{sub {parallel}}. The first, {sigma}{sub {vert_bar}}, is strongly temperature dependent and appears to obey a master curve representation. The second, {sigma}{sub {parallel}}, exhibits only a weak temperature dependence with a roughly linear frequency dependence. A strong depression of {sigma}{sub {vert_bar}} occurs for the mixed alkali case, but {sigma}{sub {parallel}} is unaffected and occurs at roughly the same location in all the alkali compositions studied. They propose that {sigma}{sub {parallel}} does not arise from cation motion, but rather originates from a second mechanisms likely involving small distortions of the underlying glassy matrix. This assignment of {sigma}{sub {parallel}} is further supported by the roughly universal location of {sigma}{sub {parallel}}, to within an order of magnitude, of a variety of materials, including a polymer electrolyte and a doped crystal. Since {sigma}{sub {vert_bar}}(T) and {sigma}{sub {parallel}}(T {approx} const.) are viewed as separate phenomena, the temperature dependence of the scaling exponent is shown to result merely from a superposition of these two contributions and does not indicate any intrinsic failure of the scaling property of {sigma}{sub {vert_bar}}

Origin of non-exponential relaxation in a crystalline ionic conductor: a multi-dimensional 109Ag NMR study

The origin of the non-exponential relaxation of silver ions in the crystalline ion conductor Ag7P3S11 is analyzed by comparing appropriate two-time and three-time 109Ag NMR correlation functions. The non-exponentiality is due to a rate distribution, i.e., dynamic heterogeneities, rather than to an intrinsic non-exponentiality. Thus, the data give no evidence for the relevance of correlated back-and-forth jumps on the timescale of the silver relaxation.Comment: 4 pages, 3 figure

Channel diffusion of sodium in a silicate glass

We use classical molecular dynamics simulations to study the dynamics of sodium atoms in amorphous Na$_2$O-4SiO$_2$. We find that the sodium trajectories form a well connected network of pockets and channels. Inside these channels the motion of the atoms is not cooperative but rather given by independent thermally activated hops of individual atoms between the pockets. By determining the probability that an atom returns to a given starting site, we show that such events are not important for the dynamics of this system.Comment: 10 pages of Latex, 5 figures, one figure added, text expande

Hopping Transport in the Presence of Site Energy Disorder: Temperature and Concentration Scaling of Conductivity Spectra

Recent measurements on ion conducting glasses have revealed that conductivity spectra for various temperatures and ionic concentrations can be superimposed onto a common master curve by an appropriate rescaling of the conductivity and frequency. In order to understand the origin of the observed scaling behavior, we investigate by Monte Carlo simulations the diffusion of particles in a lattice with site energy disorder for a wide range of both temperatures and concentrations. While the model can account for the changes in ionic activation energies upon changing the concentration, it in general yields conductivity spectra that exhibit no scaling behavior. However, for typical concentrations and sufficiently low temperatures, a fairly good data collapse is obtained analogous to that found in experiment.Comment: 6 pages, 4 figure

Complex lithium ion dynamics in simulated LiPO3 glass studied by means of multi-time correlation functions

Molecular dynamics simulations are performed to study the lithium jumps in LiPO3 glass. In particular, we calculate higher-order correlation functions that probe the positions of single lithium ions at several times. Three-time correlation functions show that the non-exponential relaxation of the lithium ions results from both correlated back-and-forth jumps and the existence of dynamical heterogeneities, i.e., the presence of a broad distribution of jump rates. A quantitative analysis yields that the contribution of the dynamical heterogeneities to the non-exponential depopulation of the lithium sites increases upon cooling. Further, correlated back-and-forth jumps between neighboring sites are observed for the fast ions of the distribution, but not for the slow ions and, hence, the back-jump probability depends on the dynamical state. Four-time correlation functions indicate that an exchange between fast and slow ions takes place on the timescale of the jumps themselves, i.e., the dynamical heterogeneities are short-lived. Hence, sites featuring fast and slow lithium dynamics, respectively, are intimately mixed. In addition, a backward correlation beyond the first neighbor shell for highly mobile ions and the presence of long-range dynamical heterogeneities suggest that fast ion migration occurs along preferential pathways in the glassy matrix. In the melt, we find no evidence for correlated back-and-forth motions and dynamical heterogeneities on the length scale of the next-neighbor distance.Comment: 12 pages, 13 figure

Large-scale phenotyping of patients with long COVID post-hospitalization reveals mechanistic subtypes of disease

One in ten severe acute respiratory syndrome coronavirus 2 infections result in prolonged symptoms termed long coronavirus disease (COVID), yet disease phenotypes and mechanisms are poorly understood1. Here we profiled 368 plasma proteins in 657 participants ≥3 months following hospitalization. Of these, 426 had at least one long COVID symptom and 233 had fully recovered. Elevated markers of myeloid inflammation and complement activation were associated with long COVID. IL-1R2, MATN2 and COLEC12 were associated with cardiorespiratory symptoms, fatigue and anxiety/depression; MATN2, CSF3 and C1QA were elevated in gastrointestinal symptoms and C1QA was elevated in cognitive impairment. Additional markers of alterations in nerve tissue repair (SPON-1 and NFASC) were elevated in those with cognitive impairment and SCG3, suggestive of brain–gut axis disturbance, was elevated in gastrointestinal symptoms. Severe acute respiratory syndrome coronavirus 2-specific immunoglobulin G (IgG) was persistently elevated in some individuals with long COVID, but virus was not detected in sputum. Analysis of inflammatory markers in nasal fluids showed no association with symptoms. Our study aimed to understand inflammatory processes that underlie long COVID and was not designed for biomarker discovery. Our findings suggest that specific inflammatory pathways related to tissue damage are implicated in subtypes of long COVID, which might be targeted in future therapeutic trials

SARS-CoV-2-specific nasal IgA wanes 9 months after hospitalisation with COVID-19 and is not induced by subsequent vaccination

BACKGROUND: Most studies of immunity to SARS-CoV-2 focus on circulating antibody, giving limited insights into mucosal defences that prevent viral replication and onward transmission. We studied nasal and plasma antibody responses one year after hospitalisation for COVID-19, including a period when SARS-CoV-2 vaccination was introduced. METHODS: In this follow up study, plasma and nasosorption samples were prospectively collected from 446 adults hospitalised for COVID-19 between February 2020 and March 2021 via the ISARIC4C and PHOSP-COVID consortia. IgA and IgG responses to NP and S of ancestral SARS-CoV-2, Delta and Omicron (BA.1) variants were measured by electrochemiluminescence and compared with plasma neutralisation data. FINDINGS: Strong and consistent nasal anti-NP and anti-S IgA responses were demonstrated, which remained elevated for nine months (p < 0.0001). Nasal and plasma anti-S IgG remained elevated for at least 12 months (p < 0.0001) with plasma neutralising titres that were raised against all variants compared to controls (p < 0.0001). Of 323 with complete data, 307 were vaccinated between 6 and 12 months; coinciding with rises in nasal and plasma IgA and IgG anti-S titres for all SARS-CoV-2 variants, although the change in nasal IgA was minimal (1.46-fold change after 10 months, p = 0.011) and the median remained below the positive threshold determined by pre-pandemic controls. Samples 12 months after admission showed no association between nasal IgA and plasma IgG anti-S responses (R = 0.05, p = 0.18), indicating that nasal IgA responses are distinct from those in plasma and minimally boosted by vaccination. INTERPRETATION: The decline in nasal IgA responses 9 months after infection and minimal impact of subsequent vaccination may explain the lack of long-lasting nasal defence against reinfection and the limited effects of vaccination on transmission. These findings highlight the need to develop vaccines that enhance nasal immunity. FUNDING: This study has been supported by ISARIC4C and PHOSP-COVID consortia. ISARIC4C is supported by grants from the National Institute for Health and Care Research and the Medical Research Council. Liverpool Experimental Cancer Medicine Centre provided infrastructure support for this research. The PHOSP-COVD study is jointly funded by UK Research and Innovation and National Institute of Health and Care Research. The funders were not involved in the study design, interpretation of data or the writing of this manuscript