OIST Institutional Repository
Not a member yet
2744 research outputs found
Sort by
Degradation Mechanism and Relative Stability of Methylammonium Halide Based Perovskites Analyzed on the Basis of Acid–Base Theory
Get PDFThe correct identification of all gases released during hybrid perovskite degradation is of great significance to develop strategies to extend the lifespan of any device based on this semiconductor. CH3X (X = Br/I) is a released degradation gas/low boiling point liquid arising from methylammonium (MA+) based perovskites, which has been largely overlooked in the literature focusing on stability of perovskite solar cells. Herein, we present an unambiguous identification of CH3I release using microwave (rotational) spectroscopy. An experimental back-reaction test demonstrates that the well-known CH3NH2/HX degradation route may not be the ultimate degradation pathway of MAPbX3 in thermodynamic closed systems. Meanwhile, the CH3X/NH3 route cannot back-react selectively to MAX formation as occurred for the former back-reaction. Metadynamics calculations uncover the X halide effect on energy barriers for both degradation reactions showing a better stability of Br based perovskite ascribed to two aspects: (i) lower Brönsted–Lowry acidity of HBr compared to HI and (ii) higher nucleophilic character of CH3NH2 compared to NH3. The latter property makes CH3NH2 molecules stay preferentially attached on the electrophilic perovskite surface (Pb2+) during the dynamic simulation instead of being detached as observed for the NH3 molecule.journal articl
Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions
Get PDFPolymerized ionic liquids (PILs) are a special class of polyelectrolytes with ionic liquid (IL) species being covalently attached to the repeating unit. The rheological properties of PIL in IL solutions are strongly influenced by the electrostatic screening between IL and PIL chains. However, the effect of IL electrostatic screening on the rheology of PIL in IL solutions remains elusive. To address this challenging yet important question, we conduct detailed rheological characterization of a model system containing a PIL [PC4-TFSI: poly(1-butyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide)] in a mixture of a salt-free solvent (DMF: dimethylformamide) and an IL [Bmim-TFSI: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] solution, with low to high IL concentrations, while spanning dilute and semidilute polymer regimes. We compare the specific viscosity ηsp and the longest relaxation time λ of PILs measured at various Bmim-TFSI concentrations from 0 M (pure DMF) to 3.42 M (pure Bmim-TFSI) with the scaling predictions for ordinary polyelectrolyte solutions. We find good agreement at low IL concentrations but significant deviations at higher IL concentrations. We capture this discrepancy by proposing and validating a modified scaling law accounting for the modified screening length in concentrated solutions of ordinary salts. We propose that extended PIL chains initially shrink due to the charge screening effect at low IL concentrations but revert to expanded configuration at higher IL concentrations due to the charge underscreening effect when the screening length increases with increasing IL concentrations. Our results shed new insights on the conformation of PIL in IL solutions and, for the first time, provide a valid reference for the study of general polyelectrolyte solutions at high salt concentrations, where the Debye–Hückel theory is no longer valid.journal articl
Photocarrier thermalization bottleneck in graphene
Get PDFWe present a theoretical study of photocarrier dynamics in graphene due to electron-phonon (EP) interactions. Using the relaxation-time approximation (RTA) with parameters determined from density functional theory (DFT) and a complementary explicitly solvable model, we show that the photocarrier thermalization time changes by orders of magnitude, when the excitation energy is reduced from 1 eV to the 100 meV range. In detail the ultrafast thermalization at low temperatures takes place on a femtosecond timescale via optical phonon emission, but slows down to picoseconds once excitation energies become comparable with these optical phonon energy quanta. In the latter regime thermalization times exhibit a pronounced dependence on temperature. Our DFT-based model includes all the inter- and intraband transitions due to EP scattering. Thanks to the high melting point of graphene we extend our studies up to 2000 K and show that such high temperatures reduce the photocarrier thermalization time through phonon absorption.journal articl
Self-powered RNA nanomachine driven by metastable structure
Get PDFMany non-coding and regulatory RNA elements have evolved to exploit transient or metastable structures that emerge during transcription to control complex folding pathways or to encode dynamic functions. However, efforts to engineer synthetic RNA devices have mostly focused on the thermodynamically stable structures. Consequently, significant challenges and opportunities exist in engineering functional RNAs that explicitly take advantage of cotranscriptionally generated transient or metastable structures. In this work, we designed a short RNA sequence that adopts a robust metastable structure when transcribed by an RNA polymerase. Although the metastable structure persists for hours at low temperature, it refolds almost completely into the thermodynamically stable structure upon heat denaturation followed by cooling. The synthetic RNA was also equipped with the Broccoli aptamer so that it can bind its ligand and become fluorescent only in the thermodynamically stable structure. We further demonstrated that the relaxation to the thermodynamically stable and fluorescent structure can be catalyzed by a short trigger RNA in a sequence-specific manner. Finally, the RNA architecture was redesigned to sense and respond to microRNA sequences. In summary, we designed RNA nanomachines that can detect an RNA sequence, amplify signal and produce an optical output, all encoded in a single RNA transcript, self-powered by a metastable structure.journal articl
Transcriptional Regulation of Differentiation and Functions of Effector T Regulatory Cells
Get PDFFoxp3-expressing regulatory T (Treg) cells can suppress the activity of various types of immune cells and play key roles in the maintenance of self-tolerance and in the regulation of immune responses against pathogens and tumor cells. Treg cells consist of heterogeneous subsets that have distinct phenotypes and functions. Upon antigen stimulation, naive-like thymus-derived Treg cells, which circulate in secondary lymphoid organs, can differentiate into effector Treg (eTreg) cells and migrate to and control immune homeostasis of peripheral tissues. eTreg cells are heterogeneous in terms of their ability to localize to specific tissues and suppress particular types of immune responses. Differentiation and function of diverse eTreg subsets are regulated by a variety of transcription factors that are activated by antigens and cytokines. In this article, we review the current understanding of the transcriptional regulation of differentiation and function of eTreg cells.journal articl
Polarisation control for optical nanofibres by imaging through a single lens
Get PDFWe present a simple method for controlling the polarisation state of light at the waist of a single-mode optical nanofibre. The method consists of complete polarisation compensation based on imaging scattered light from inherent inhomogeneities both on the fibre surface and in the glass material itself. In contrast to the recently reported protocol exploiting two imaging systems oriented at 45° to each other, our method requires only one lens and a video camera. It is particularly useful for nanofibre-based applications with severe geometric constraints, such as inside vacuum chambers for experiments with cold atoms. The measured fidelity of the achieved control is about 98% using lenses with moderate numerical apertures.journal articl
Adaptive, locally linear models of complex dynamics
Get PDFThe dynamics of complex systems generally include high-dimensional, nonstationary, and nonlinear behavior, all of which pose fundamental challenges to quantitative understanding. To address these difficulties, we detail an approach based on local linear models within windows determined adaptively from data. While the dynamics within each window are simple, consisting of exponential decay, growth, and oscillations, the collection of local parameters across all windows provides a principled characterization of the full time series. To explore the resulting model space, we develop a likelihood-based hierarchical clustering, and we examine the eigenvalues of the linear dynamics. We demonstrate our analysis with the Lorenz system undergoing stable spiral dynamics and in the standard chaotic regime. Applied to the posture dynamics of the nematode Caenorhabditis elegans, our approach identifies fine-grained behavioral states and model dynamics which fluctuate about an instability boundary, and we detail a bifurcation in a transition from forward to backward crawling. We analyze whole-brain imaging in C. elegans and show that global brain dynamics is damped away from the instability boundary by a decrease in oxygen concentration. We provide additional evidence for such near-critical dynamics from the analysis of electrocorticography in monkey and the imaging of a neural population from mouse visual cortex at single-cell resolution.journal articl
Nanoassemblies of ultrasmall clusters with remarkable activity in carbon dioxide conversion into C1 fuels
Get PDFCu nanoassemblies formed transiently during reaction from size-selected subnanometer Cu4 clusters supported on amorphous OH-terminated alumina convert CO2 into methanol and hydrocarbons under near-atmospheric pressure at rates considerably higher than those of individually standing Cu4 clusters. An in situ characterization reveals that the clusters self-assemble into 2D nanoassemblies at higher temperatures which then disintegrate upon cooling down to room temperature. DFT calculations postulate a formation mechanism of these nanoassemblies by hydrogen-bond bridges between the clusters and H2O molecules, which keep the building blocks together while preventing their coalescence.journal articl
Linear magnetoresistance in the low-field limit in density-wave materials
Get PDFThe magnetoresistance (MR) of a material is typically insensitive to reversing the applied field direction and varies quadratically with magnetic field in the low-field limit. Quantum effects, unusual topological band structures, and inhomogeneities that lead to wandering current paths can induce a cross-over from quadratic to linear MR with increasing magnetic field. Here we explore a series of metallic charge-and spin-density-wave systems that exhibit extremely large positive linear MR. By contrast to other linear MR mechanisms, this effect remains robust down to miniscule magnetic fields of tens of Oersted at low temperature. We frame an explanation of this phenomenon in a semiclassical narrative for a broad category of materials with partially gapped Fermi surfaces due to density waves.journal articl
Elucidating the Mechanism Involved in the Performance Improvement of Lithium‐Ion Transition Metal Oxide Battery by Conducting Polymer
Get PDFSurface treatments with conducting polymers are effective in ameliorating charge capacities and cycling performances for a wide range of lithium‐ion batteries such as Li‐layered transition metal oxide, Li‐sulfur, and Li‐air batteries. So far, however, very little is known about the key process directly involved with the improvement of cell performance and stability. The present study examines how a conducting polymer can contribute to charge capacity enhancement, employing poly(3,4‐ethylenedioxythiophene):poly(styrene‐sulfonate) coating on the lithium‐layered transition metal oxide cathode. The property of the electrode interface layer is studied on the basis of the local atomic environments. The conducting polymer not only hinders the formation of LiF, carbonates, and semicarbonates compounds but also renders the nature of the solid‐electrolyte interphase layer formed during electrochemical cycles. Furthermore, it inhibits the dissolution of the active material into the electrolyte and preserves the initial atomic states including the active material bulk. The coating enables good consistency in the local atomic environment with depth at the electrode interface, which in turn impedes the phase mismatch resulting from the surface reconstruction on the layered oxide electrode. This further mitigates the phase transformation of the active material, resulting in a lower voltage decay on charge–discharge.journal articl