Reduced coupling of water molecules near the surface of reverse micelles

We report on vibrational dynamics of water near the surface of AOT reverse micelles studied by narrow-band excitation, mid-IR pump–probe spectroscopy. Evidence of OH-stretch frequency splitting into the symmetric and asymmetric modes is clearly observed for the interfacial H2O molecules. The polarization memory of interfacial waters is preserved over an exceptionally extended >10 ps timescale which is a factor of 100 longer than in bulk water. These observations point towards negligibly small intermolecular vibrational coupling between the water molecules as well as strongly reduced water rotational mobility within the interfacial water layer.

Ultrafast Spectroscopy with Photocurrent Detection: Watching Excitonic Optoelectronic Systems at Work.

While ultrafast spectroscopy with photocurrent detection was almost unknown before 2012, in the last 3 years, a number of research groups from different fields have independently developed ultrafast electric probe approaches and reported promising pilot studies. Here, we discuss these recent advances and provide our perspective on how photocurrent detection successfully overcomes many limitations of all-optical methods, which makes it a technique of choice when device photophysics is concerned. We also highlight compelling existing problems and research questions and suggest ways for further development, outlining the potential breakthroughs to be expected in the near future using photocurrent ultrafast optical probes.A.A.B. is currently a Royal Society University Research Fellow. A.A.B. also acknowledges a VENI grant from the NWO. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (Grant Agreement No. 639750). C.S. acknowledges funding from the Natural Science and Engineering Research Council of Canada, the Fonds de recherche du Québec–nature et technologies, the Canada Research Chair in Organic Semiconductor Materials, and the Université de Montréal Research Chair. C.S. and E.V. acknowledge collaboration with Sachetan Tuladhar, Michelle Vezie, Sheridan Few, Jenny Nelson, Hao Li, and Eric Bittner. Finally, C.S. and E.V. acknowledge essential discussions with Andy Marcus and Julia Widom for the implementation of the two-dimensional spectroscopy apparatus.This is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/acs.jpclett.5b0195

The impurity influence on the formation of oxide layers on TiAL surface

Using ab initio approach the segregation of 4d impurities to low index TiAl surfaces was studied. The site preference for all considered impurities was determined. We demonstrate that Y, Zr, Nb и Mo prefer to occupy the Ti-sublattice whereas other elements are located mainly on the Al-sublattice in case of their low concentration. The influence of impurities on oxygen adsorption on the stoichiometric γ-TiAl(100) surface is investigated. It is shown that the 4d impurities substituting for Ti result in decrease of oxygen adsorption energy whereas it increases if transition metal impurities occupy the Al-sublattice. The effect of some elements of V and VI groups on the adhesion at interfaces such as TiAl(001)Al/TiO2(001), TiAl(001)Ti/TiO2(001), TiAl(100)/TiO2(001), TiAl(110)Al/TiO2(100)O and TiAl(110)Ti/TiO2(100)O in dependence on their location in interfacial layers was also studied. Finally, we demonstrate that the 4d alloying elements with number of electrons from 2 to 5 lead to decrease of the relative stability of Al2O3 to TiO2 and to increase of the formation energy of O vacancy in TiO2. The latter is beneficial to the oxidation resistance of TiAl alloys

Ab-initio study of cation-rich InP(001) and GaP(001) surface reconstructions and iodine adsorption

Atomic and electronic structures for a number of InP and GaP (001) surface geometries were studied within the density functional theory (DFT) in order to reexamine the energy stability of surface reconstructions in the cation-rich limit. It is shown that in both cases the mixed dimer (2×4) reconstruction is the energetically favored in the cation rich limit. The ζ(4×2) reconstruction has the lowest surface energy among considered (4×2) surface structures. Comparative theoretical study of iodine adsorption on the semiconductor surface with ζ(4×2) and mixed dimer (2×4) structures was performed. It was shown that iodine prefers to be bonded with dimerized cation atoms irrespective on the surface reconstruction

HEPATORENAL SYNDROME: DIAGNOSTIC AND THERAPEUTIC MANAGEMENT

The practical guidelines on diagnosis and management of hepatorenal syndrome, which could be useful for general medical practitioners, gastroenterologists, and hepatologists, are considered in this paper. Selected recommendations are based on integrated clinical data, international recommendations and results of clinical trials. Beginning from theoretical grounds of hepatorenal syndrome (its definition, diagnostic criteria, and classification), acute kidney injury, and spontaneous bacterial peritonitis, the paper contains diagnostic algorithms (in particular, in ascites, for early revealing hepatorenal syndrome), and main approaches to therapy and prevention. The efficacy criteria and monitoring rules for the terlipressin-based therapy are listed

Materials, photophysics and device engineering of perovskite light-emitting diodes

Here we provide a comprehensive review of a newly developed lighting technology based on metal halide perovskites (i.e. perovskite light-emitting diodes) encompassing the research endeavours into materials, photophysics and device engineering. At the outset we survey the basic perovskite structures and their various dimensions (namely three-, two- and zero-dimensional perovskites), and demonstrate how the compositional engineering of these structures affects the perovskite light-emitting properties. Next, we turn to the physics underpinning photo- and electroluminescence in these materials through their connection to the fundamental excited states, energy/charge transport processes and radiative and non-radiative decay mechanisms. In the remainder of the review, we focus on the engineering of perovskite light-emitting diodes, including the history of their development as well as an extensive analysis of contemporary strategies for boosting device performance. Key concepts include balancing the electron/hole injection, suppression of parasitic carrier losses, improvement of the photoluminescence quantum yield and enhancement of the light extraction. Overall, this review reflects the current paradigm for perovskite lighting, and is intended to serve as a foundation to materials and device scientists newly working in this field

Hydrophobic Molecules Slow Down the Hydrogen-Bond Dynamics of Water

We study the spectral and orientational dynamics of HDO molecules in solutions of tertiary-butyl-alcohol (TBA), trimethyl-amine-oxide (TMAO), and tetramethylurea (TMU) in isotopically diluted water (HDO:D2O and HDO:H2O). The spectral dynamics are studied with femtosecond two-dimensional infrared spectroscopy and the orientational dynamics with femtosecond polarization-resolved vibrational pump-probe spectroscopy. We observe a strong slowing down of the spectral diffusion around the central part of the absorption line that increases with increasing solute concentration. At low concentrations, the fraction of water showing slow spectral dynamics is observed to scale with the number of methyl groups, indicating that this effect is due to slow hydrogen-bond dynamics in the hydration shell of the methyl groups of the solute molecules. The slowing down of the vibrational frequency dynamics is strongly correlated with the slowing down of the orientational mobility of the water molecules. This correlation indicates that these effects have a common origin in the effect of hydrophobic molecular groups on the hydrogen-bond dynamics of water.

Motor Cortex Hyperexcitability, Neuroplasticity, and Degeneration in Amyotrophic Lateral Sclerosis

Neuronal hyperexcitability is a well-known phenomenon in amyotrophic lateral sclerosis and other neurodegenerative diseases. The use of transcranial magnetic stimulation in clinical and research practice has recently made it possible to detect motor cortex hyperexcitability under clinical conditions. Despite numerous studies, the mechanisms and sequelae of the development of hyperexcitability still have not been completely elucidated. In this chapter, we discuss the possibilities for detecting motor cortex hyperexcitability in patients with amyotrophic lateral sclerosis using transcranial magnetic stimulation. The potential relationship between hyperexcitability and neuronal degeneration or neuroplasticity processes is discussed using the data obtained by navigated transcranial magnetic stimulation and neuroimaging data, as well as the data of experimental studies

In situ observation of picosecond polaron self-localisation in α-Fe2O3 photoelectrochemical cells

Hematite (α-Fe2O3) is the most studied artificial oxygen-evolving photo-anode and yet its efficiency limitations and their origin remain unknown. A sub-picosecond reorganisation of the hematite structure has been proposed as the mechanism which dictates carrier lifetimes, energetics and the ultimate conversion yields. However, the importance of this reorganisation for actual device performance is unclear. Here we report an in situ observation of charge carrier self-localisation in a hematite device, and demonstrate that this process affects recombination losses in photoelectrochemical cells. We apply an ultrafast, device-based optical-control method to resolve the subpicosecond formation of small polarons and estimate their reorganisation energy to be ~0.5 eV. Coherent oscillations in the photocurrent signals indicate that polaron formation may be coupled to specific phonon modes (<100 cm-1). Our results bring together spectroscopic and device characterisation approaches to reveal new photophysics of broadly-studied hematite devices

Multi-Pulse Terahertz Spectroscopy Unveils Hot Polaron Photoconductivity Dynamics in Metal-Halide Perovskites

The behavior of hot carriers in metal-halide perovskites (MHPs) present a valuable foundation for understanding the details of carrier-phonon coupling in the materials as well as the prospective development of highly efficient hot carrier and carrier multiplication solar cells. Whilst the carrier population dynamics during cooling have been intensely studied, the evolution of the hot carrier properties, namely the hot carrier mobility, remain largely unexplored. To address this, we introduce a novel ultrafast visible pump - infrared push - terahertz probe spectroscopy (PPP-THz) to monitor the real-time conductivity dynamics of cooling carriers in methylammonium lead iodide. We find a decrease in mobility upon optically depositing energy into the carriers, which is typical of band-transport. Surprisingly, the conductivity recovery dynamics are incommensurate with the intraband relaxation measured by an analogous experiment with an infrared probe (PPP- IR), and exhibit a negligible dependence on the density of hot carriers. These results and the kinetic modelling reveal the importance of highly-localized lattice heating on the mobility of the hot electronic states. This collective polaron-lattice phenomenon may contribute to the unusual photophysics observed in MHPs and should be accounted for in devices that utilize hot carriers.Comment: 28 pages, 4 figures, 77 reference