A nitroxide-containing cathode material for organic radical batteries studied with pulsed EPR spectroscopy

An electron spin echo in a nitroxide-containing polymer cathode film for organic radical batteries is observed for various states of charge at cryogenic temperatures. The EPR-detected state of charge (ESOC), as inferred from the number of paramagnetic centers in the film, is compared to the results of Coulomb counting based on galvanostatic charging. Spin concentration, longitudinal relaxation times T(1 )and phase memory times T-m strongly correlate with the ESOC. In the discharged film, the spin concentration reaches 5 +/- 3x10(20) cm(-3), causing a phase memory time T-m << 100 ns (shorter than the resonator ring-down time) that hinders the detection of the spin echo. In the charged film, the decreased spin concentration results in a longer T-m between 100 ns and 300 ns that enables spin-echo detection, yet limits the length of the microwave pulse sequence. The short, broad-band pulses cause instantaneous diffusion in the unoxidized domains across the oxidized film, affecting the relative peak intensities in the pulsed EPR spectrum. By simulating the spectral distortion caused by instantaneous diffusion, we obtain information on the local spin concentration, which complements the information on the 'bulk' spin concentration determined by electrochemistry and continuous-wave EPR spectroscopy

Global changes in the proteome of Cupriavidus necator H16 during poly-(3-hydroxybutyrate) synthesis from various biodiesel by-product substrates

Additional file 1: Table S1. P-scores of proteomic runs of C. necator H16 grown with different substrates

Spins at work: probing charging and discharging of organic radical batteries by electron paramagnetic resonance spectroscopy

Organic radical batteries (ORBs) are a promising class of electrochemical power sources employing organic radicals as redox-active groups. This article reports on the development of a versatile on-substrate electrode setup for spectroelectrochemical Electron Paramagnetic Resonance (EPR) measurements on redox conductive polymers for ORBs. Quantitative in operando EPR experiments performed on electrochemical cells with a di-TEMPO Ni-Salen polymer as active electrode material demonstrate a strong decrease in the number of paramagnetic centers upon oxidizing the film. The distinct EPR signatures of the TEMPO-containing polymer and its fragments in different molecular environments are used to study its degradation upon repeated cycling. A comparison between the number of EPR-active sites and the number of electrochemically active charges, as measured by cyclic voltammetry, provides information on the nature of the degradation process. Low-temperature ex situ pulse EPR measurements on the oxidized polymer film reveal the spectrum of dilute nitroxide species, which may be associated with electrochemically inactive islands. These experiments pave the way for advanced EPR techniques for accurately determining distances between adjacent paramagnetic centers and thus for identifying performance-limiting loss mechanisms, which can eventually help develop strategies for making ORBs powerful contenders on the path towards sustainable electrochemical power sources

a [Ni(Salen)]‐TEMPO redox‐conducting polymer for organic batteries

Redox-active nitroxyl-containing polymers are promising candidates as possible replacements for inorganic based energy-storage materials, due to their high energy density and fast redox kinetics. One challenge towards the implementation of such a system is the insufficient electrical conductivity, impeding the charge collection even with highly conductive additives. Herein, the first implementation of a polymeric bis(salicylideniminato) nickel (NiSalen) conductive backbone as an active charge-collecting wire is reported. NiSalen simultaneously serves as a charge collector for nitroxyl pendants and supports the redox capacity of the material. This novel polymer exhibits a specific capacity of up to 91.5 mAh g−1, retaining 87 % of its theoretical capacity at 800 C and more than 30 % at as high as 3000 C (66 % capacity retention after 2000 cycles). The properties of the new material upon operation was studied by means of operando electrochemical methods, UV-Vis, and electron paramagnetic resonance spectroscopy

Method for solvig inverse Stefan problem to control ice wall state during shaft excavation

Mathematical statement of direct and inverse problem of Stefan for horizontal layer of rock massif with homogenous and isotropic thermophysical properties is presented. It is assumed as a hypothesis that heat transfer in vertical direction is negligible compared to heat exchange in horizontal plane. At the initial moment, the rock massif has a uniform temperature and the temperature on surfaces of freezing columns was the same for all columns and constant in time. A method proposed allows getting an approximate solution of the direct Stefan problem for a single freezing column with a small consumption of computational resources. Based on a proposed method, a high-speed algorithm for solving inverse Stefan problem for the case of a single freezing column is built. An algorithm is based on the gradient descent method. The effect on the solution of different types of functions used is analyzed. Functions approximate the temperature field in a cooling zone. It is established that time dependence of the radius of a phase transition front essentially depends on the type of an approximation function. The most preferable is an integral exponential function that is a solution to the one-dimensional heat equation in cylindrical coordinates. Then, proposed technique and algorithm are considered for the case of variety of freezing columns that form circle counter and random number of control wells. Results of the calculation of inverse Stefan problem for conditions of the shaft No. 1 of the mine being under construction at the Petrikovsky ore mining and processing enterprise are presented. The calculation included well inclinometry based on geological data. It was studied how measurements of the temperature made at different wells can affect obtaining solution. Options of interpretation of inconsistency of temperatures measured in control wells are offered. Probabilistic analysis of ice wall thickness is carried out

Does Banque de France control inflation and unemployment?

We re-estimate statistical properties and predictive power of a set of Phillips curves, which are expressed as linear and lagged relationships between the rates of inflation, unemployment, and change in labour force. For France, several relationships were estimated eight years ago. The change rate of labour force was used as a driving force of inflation and unemployment within the Phillips curve framework. The set of nested models starts with a simplistic version without autoregressive terms and one lagged term of explanatory variable. The lag is determined empirically together with all coefficients. The model is estimated using the Boundary Element Method (BEM) with the least squares method applied to the integral solutions of the differential equations. All models include one structural break might be associated with revisions to definitions and measurement procedures in the 1980s and 1990s as well as with the change in monetary policy in 1994-1995. For the GDP deflator, our original model provided a root mean squared forecast error (RMSFE) of 1.0% per year at a four-year horizon for the period between 1971 and 2004. The rate of CPI inflation is predicted with RMSFE=1.5% per year. For the naive (no change) forecast, RMSFE at the same time horizon is 2.95% and 3.3% per year, respectively. Our model outperforms the naive one by a factor of 2 to 3. The relationships for inflation were successfully tested for cointegration. We have formally estimated several vector error correction (VEC) models for two measures of inflation. At a four year horizon, the estimated VECMs provide significant statistical improvements on the results obtained by the BEM: RMSFE=0.8% per year for the GDP deflator and ~1.2% per year for CPI. For a two year horizon, the VECMs improve RMSFEs by a factor of 2, with the smallest RMSFE=0.5% per year for the GDP deflator.Comment: 25 pages, 12 figure

Analysis of the African coelacanth genome sheds light on tetrapod evolution

It was a zoological sensation when a living specimen of the coelacanth was first discovered in 1938, as this lineage of lobe-finned fish was thought to have gone extinct 70 million years ago. The modern coelacanth looks remarkably similar to many of its ancient relatives, and its evolutionary proximity to our own fish ancestors provides a glimpse of the fish that first walked on land. Here we report the genome sequence of the African coelacanth, Latimeria chalumnae. Through a phylogenomic analysis, we conclude that the lungfish, and not the coelacanth, is the closest living relative of tetrapods. Coelacanth protein-coding genes are significantly more slowly evolving than those of tetrapods, unlike other genomic features . Analyses of changes in genes and regulatory elements during the vertebrate adaptation to land highlight genes involved in immunity, nitrogen excretion and the development of fins, tail, ear, eye, brain, and olfaction. Functional assays of enhancers involved in the fin-to-limb transition and in the emergence of extra-embryonic tissues demonstrate the importance of the coelacanth genome as a blueprint for understanding tetrapod evolution