Large P-31-NMR enhancements in liquid state dynamic nuclear polarization through radical/target molecule non-covalent interaction

Dynamic nuclear polarization (DNP) is a method to enhance the low sensitivity of nuclear magnetic resonance (NMR) via spin polarization transfer from electron spins to nuclear spins. In the liquid state, this process is mediated by fast modulations of the electron-nuclear hyperfine coupling and its efficiency depends strongly on the applied magnetic field. A peculiar case study is triphenylphosphine (PPh3) dissolved in benzene and doped with BDPA radical because it gives 31P-NMR signal enhancements of two orders of magnitude up to a magnetic field of 14.1 T. Here we show that the large 31P enhancements of BDPA/PPh3 in benzene at 1.2 T (i) decrease when the moieties are dissolved in other organic solvents, (ii) are strongly reduced when using a nitroxide radical, and (iii) vanish with pentavalent 31P triphenylphosphine oxide. Those experimental observations are rationalized with numerical calculations based on density functional theory that show the tendency of BDPA and PPh3 to form a weak complex via non-covalent interaction that leads to large hyperfine couplings to 31P (ΔAiso ≥ 13 MHz). This mechanism is hampered in other investigated systems. The case study of 31P-DNP in PPh3 is an important example that extends the current understanding of DNP in the liquids state: non-covalent interactions between radical and target can be particularly effective to obtain large NMR signal enhancements

Heterogeneous nucleation and heat flux avalanches in La(Fe, Si)13 magnetocaloric compounds near the critical point

The phase transformation kinetics of LaFe11.41Mn0.30Si1.29-H1.65 magnetocaloric compound is addressed by low rate calorimetry experiments. Scans at 1 mK/s show that its first order phase transitions are made by multiple heat flux avalanches. Getting very close to the critical point, when the transition becomes of the second order type, the step-like discontinuous behaviour associated with avalanches is smoothed out and the thermal hysteresis disappears. This result is confirmed by magneto-resistivity measurements and allows to obtain accurate values of the temperature hysteresis (DThyst = 0.37 K) at zero external magnetic field and of the critical field (Hc = 1.19 T). The number and magnitude of heat flux avalanches change as the magnetic field strength is increased, showing the interplay between the intrinsic energy barrier between phases and the microstructural disorder of the sample

O-17 Hyperfine Spectroscopy Reveals Hydration Structure of Nitroxide Radicals in Aqueous Solutions

The hydrationstructureof nitroxideradicalsin aqueoussolutionsis elucidatedby advanced17Ohyperfine(hf) spectroscopywith supportof quantumchemicalcalculationsand MD simulations.A piperidineand a pyrrolidine-basednitroxideradical are comparedand show clear differencesin the preferreddirectionalityof H-bondformation.We demonstratethat thesescenariosare best representedin17O hf spectra,wherein-planecoordinationovers-type H-bondingleads tolittle spin densitytransferon the water oxygenand smallhf couplings,whereasp-type perpendicularcoordinationgeneratesmuch larger hf couplings.Quantitativeanaly-sis of the spectrabased on MD simulationsand DFTpredictedhf parametersis consistentwith a distributionof close solvatingwater molecules,in which direction-ality is influencedby subtle steric effects of the ring andthe methyl group substituents

A Geant4 simulation code for simulating optical photons in SPECT scintillation detectors

Geant4 is an object oriented toolkit created for the simulation of High-Energy Physics detectors. Geant4 allows an accurate modeling of radiation sources and detector devices, with easy configuration and friendly interface and at the same time with great accuracy in the simulation of physical processes. While most Monte Carlo codes do not allow the simulation of the transport and boundary characteristics for optical photons transport generated by scintillating crystal, Geant4 allows the simulation of the optical photons. In this paper we present an application of the Geant4 program for simulating optical photons in SPECT cameras. We aim to study the light transport within scintillators, photomultiplier tubes and coupling devices. To this end, we simulated a detector based on a scintillator, coupled to a photomultiplier tube through a glass window. We compared simulated results with experimental data and theoretical models, in order to verify the good matching with our simulations. We simulated a pencil beam of 140 keV photons impinging the crystal at different locations. For each condition, we calculated the value of the Pulse Height Centroid and the spread of the charge distribution, as read out by the anode array of the photomultiplier. Finally, the spatial and the energy resolutions of the camera have been estimated by simulated data. In all cases, we found that simulations agree very well with experimental data

19F Electron-nuclear double resonance reveals interaction between redox-active tyrosines across the α/β interface of E. coli ribonucleotide reductase

Ribonucleotide reductases (RNRs) catalyze the reduction of ribonucleotides to deoxyribonucleotides, thereby playing a key role in DNA replication and repair. Escherichia coli class Ia RNR is an α2β2 enzyme complex that uses a reversible multistep radical transfer (RT) over 32 Å across its two subunits, α and β, to initiate, using its metallo-cofactor in β2, nucleotide reduction in α2. Each step is proposed to involve a distinct proton-coupled electron-transfer (PCET) process. An unresolved step is the RT involving Y356(β) and Y731(α) across the α/β interface. Using 2,3,5-F3Y122-β2 with 3,5-F2Y731-α2, GDP (substrate) and TTP (allosteric effector), a Y356• intermediate was trapped and its identity was verified by 263 GHz electron paramagnetic resonance (EPR) and 34 GHz pulse electron–electron double resonance spectroscopies. 94 GHz 19F electron-nuclear double resonance spectroscopy allowed measuring the interspin distances between Y356• and the 19F nuclei of 3,5-F2Y731 in this RNR mutant. Similar experiments with the double mutant E52Q/F3Y122-β2 were carried out for comparison to the recently published cryo-EM structure of a holo RNR complex. For both mutant combinations, the distance measurements reveal two conformations of 3,5-F2Y731. Remarkably, one conformation is consistent with 3,5-F2Y731 within the H-bond distance to Y356•, whereas the second one is consistent with the conformation observed in the cryo-EM structure. The observations unexpectedly suggest the possibility of a colinear PCET, in which electron and proton are transferred from the same donor to the same acceptor between Y356 and Y731. The results highlight the important role of state-of-the-art EPR spectroscopy to decipher this mechanism

preliminary investigation on a rotary magnetocaloric refrigerator prototype

Abstract Environmental legislations are currently imposing important restrictions to regulate the use of refrigerant fluids in order to reduce the greenhouse gases emissions and global warming potential. To overcome these issues, a valid alternative to replace conventional refrigeration systems can be represented by magnetic refrigeration. Since magnetic refrigeration is based on the magnetocaloric effect it represents an environmental friendly technology that avoids the use of Chlorinated refrigerants. In this paper a preliminary analysis of a novel magnetocaloric refrigerator is presented. The magnetocaloric refrigeration prototype uses Gadolinium as refrigerant and water as heat exchange medium, and relies on permanent magnets as magnetic field source. The device operates according to the active regenerative principle with a rotary movement. A detailed description of the main components included in the design of the prototype device is presented along with a schematic representation of the hydraulic circuit. Focusing on the regenerators beds, some simulations have been carried out to quantify the heat energy fluxes between water and gadolinium. The results of the simulations show a decrease on gadolinium temperature distribution cycle by cycle highlighting the actual effect of the regeneration

Basic kinetic wealth-exchange models: common features and open problems

We review the basic kinetic wealth-exchange models of Angle [J. Angle, Social Forces 65 (1986) 293; J. Math. Sociol. 26 (2002) 217], Bennati [E. Bennati, Rivista Internazionale di Scienze Economiche e Commerciali 35 (1988) 735], Chakraborti and Chakrabarti [A. Chakraborti, B. K. Chakrabarti, Eur. Phys. J. B 17 (2000) 167], and of Dragulescu and Yakovenko [A. Dragulescu, V. M. Yakovenko, Eur. Phys. J. B 17 (2000) 723]. Analytical fitting forms for the equilibrium wealth distributions are proposed. The influence of heterogeneity is investigated, the appearance of the fat tail in the wealth distribution and the relaxation to equilibrium are discussed. A unified reformulation of the models considered is suggested.Comment: Updated version; 9 pages, 5 figures, 2 table

Multipurpose High Frequency Electron Spin Resonance Spectrometer for Condensed Matter Research

We describe a quasi-optical multifrequency ESR spectrometer operating in the 75-225 GHz range and optimized at 210 GHz for general use in condensed matter physics, chemistry and biology. The quasi-optical bridge detects the change of mm wave polarization at the ESR. A controllable reference arm maintains a mm wave bias at the detector. The attained sensitivity of 2x10^10 spin/G/(Hz)1/2, measured on a dilute Mn:MgO sample in a non-resonant probe head at 222.4 GHz and 300 K, is comparable to commercial high sensitive X band spectrometers. The spectrometer has a Fabry-Perot resonator based probe head to measure aqueous solutions, and a probe head to measure magnetic field angular dependence of single crystals. The spectrometer is robust and easy to use and may be operated by undergraduate students. Its performance is demonstrated by examples from various fields of condensed matter physics.Comment: submitted to Journal of Magnetic Resonanc

Hydrogeology of Stromboli volcano, Aeolian Islands (Italy) from the interpretation of resistivity tomograms, self-potential, soil temperature and soil CO2 concentration measurements

International audienceTo gain a better insight of the hydrogeology and the location of the main tectonic faults of Stromboli volcano in Italy, we collected electrical resistivity measurements, soil CO2 concentrations, temperature and self-potential measurements along two profiles. These two profiles started at the village of Ginostra in the southwest part of the island. The first profile (4.8 km in length) ended up at the village of Scari in the north east part of the volcano and the second one (3.5 km in length) at Forgia Vecchia beach, in the eastern part of the island. These data were used to provide insights regarding the position of shallow aquifers and the extension of the hydrothermal system. This large-scale study is complemented by two high-resolution studies, one at the Pizzo area (near the active vents) and one at Rina Grande where flank collapse areas can be observed. The Pizzo corresponds to one of the main degassing structure of the hydrothermal system. The main degassing area is localized along a higher permeability area corresponding to the head of the gliding plane of the Rina Grande sector collapse. We found that the self-potential data reveal the position of an aquifer above the villages of Scari and San Vincenzo. We provide an estimate of the depth of this aquifer from these data. The lateral extension of the hydrothermal system (resistivity ∼15-60 ohm m) is broader than anticipated extending in the direction of the villages of Scari and San Vincenzo (in agreement with temperature data recorded in shallow wells). The lateral extension of the hydrothermal system reaches the lower third of the Rina Grande sector collapse area in the eastern part of the island. The hydrothermal body in this area is blocked by an old collapse boundary. This position of the hydrothermal body is consistent with low values of the magnetization (<2.5 A m−1) from previously published work. The presence of the hydrothermal body below Rina Grande raises questions about the mechanical stability of this flank of the edifice