Spin-Phonon Coupling and Dynamic Zero-Field Splitting Contributions to Spin Conversion Processes in Iron(II) Complexes

Magnetization dynamics of transition metal complexes manifest in properties and phenomena of fundamental and applied interest [e.g., slow magnetic relaxation in single molecule magnets, quantum coherence in quantum bits (qubits), and intersystem crossing (ISC) rates in photophysics]. While spin–phonon coupling is recognized as an important determinant of these dynamics, additional fundamental studies are required to unravel the nature of the coupling and, thus, leverage it in molecular engineering approaches. To this end, we describe here a combined ligand field theory and multireference ab initio model to define spin–phonon coupling terms in S = 2 transition metal complexes and demonstrate how couplings originate from both the static and dynamic properties of ground and excited states. By extending concepts to spin conversion processes, ligand field dynamics manifest in the evolution of the excited state origins of zero-field splitting (ZFS) along specific normal mode potential energy surfaces. Dynamic ZFSs provide a powerful means to independently evaluate contributions from spin-allowed and/or spin-forbidden excited states to spin–phonon coupling terms. Furthermore, ratios between various intramolecular coupling terms for a given mode drive spin conversion processes in transition metal complexes and can be used to analyze the mechanisms of ISC. Variations in geometric structure strongly influence the relative intramolecular linear spin–phonon coupling terms and will define the overall spin state dynamics. While the findings of this study are of general importance for understanding magnetization dynamics, they also link the phenomenon of spin–phonon coupling across fields of single molecule magnetism, quantum materials/qubits, and transition metal photophysics

Average outpouring velocity and flow rate of grains discharged from a tilted quasi-2D silo

The flow of granular materials through constricted openings is important in many natural and industrial processes. These complex flows - featuring dense, dissipative flow in the bulk but low-dissipation, low density outpouring in the vicinity of the orifice - have long been characterized empirically by the Beverloo rule and, recently, modeled successfully using energy balance. The dependence of flow rate on the silo's angle with respect to gravity, however, is not captured by current models. We experimentally investigate the role of tilt angle in this work using a quasi-2D monolayer of grains in a silo. We measure mass flow rate, the average exit velocities of grains, and the packing fraction along the orifice with varying tilt angles. We propose a model that describes our results (and earlier findings with 3D systems [H. G. Sheldon and D. J. Durian, Granul. Matter 12, 579 (2010)]) by considering the dependence of outpouring speed and angle with respect to the orifice angle and, importantly, the angle of stagnant zones adjacent to the orifice. We conclude by posing questions about possible extensions of our model in order to describe spatial variations of exit velocity and density along the orifice cross section.Comment: 10 pages and 11 figure

Amino acid-dependent stability of the acyl linkage in aminoacyl-tRNA.

Aminoacyl-tRNAs are the biologically active substrates for peptide bond formation in protein synthesis. The stability of the acyl linkage in each aminoacyl-tRNA, formed through an ester bond that connects the amino acid carboxyl group with the tRNA terminal 3\u27-OH group, is thus important. While the ester linkage is the same for all aminoacyl-tRNAs, the stability of each is not well characterized, thus limiting insight into the fundamental process of peptide bond formation. Here, we show, by analysis of the half-lives of 12 of the 22 natural aminoacyl-tRNAs used in peptide bond formation, that the stability of the acyl linkage is effectively determined only by the chemical nature of the amino acid side chain. Even the chirality of the side chain exhibits little influence. Proline confers the lowest stability to the linkage, while isoleucine and valine confer the highest, whereas the nucleotide sequence in the tRNA provides negligible contribution to the stability. We find that, among the variables tested, the protein translation factor EF-Tu is the only one that can protect a weak acyl linkage from hydrolysis. These results suggest that each amino acid plays an active role in determining its own stability in the acyl linkage to tRNA, but that EF-Tu overrides this individuality and protects the acyl linkage stability for protein synthesis on the ribosome

Universal features of the stick-slip dynamics of an intruder moving through a confined granular medium

Experiments and simulations of an intruder dragged by a spring through a two-dimensional annulus of granular material exhibit robust force fluctuations. At low packing fractions ( ϕ < ϕ 0 ), the intruder clears an open channel. Above ϕ 0 , stick-slip dynamics develop, with an average energy release that is independent of the particle-particle and particle-base friction coefficients but does depend on the width W of the annulus and the diameter D of the intruder. A simple model predicts the dependence of ϕ 0 on W and D , allowing for a data collapse for the average energy release as a function of ϕ / ϕ 0 . These results pose challenges for theories of mechanical failure in amorphous materials.Fil: Pugnaloni, Luis Ariel. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Carlevaro, Carlos Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física de Líquidos y Sistemas Biológicos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física de Líquidos y Sistemas Biológicos; ArgentinaFil: Kozlowski, Ryan. Berea College; Estados UnidosFil: Zheng, Hu. Tongji University; ChinaFil: Kondic, Lou. New Jersey Institute of Technology; Estados UnidosFil: Socolar, Joshua E. S.. University of Duke; Estados Unido

Vesta:A Digital Health Analytics Platform for a Smart Home in a Box

© 2020 This paper presents Vesta, a digital health platform composed of a smart home in a box for data collection and a machine learning based analytic system for deriving health indicators using activity recognition, sleep analysis and indoor localization. This system has been deployed in the homes of 40 patients undergoing a heart valve intervention in the United Kingdom (UK) as part of the EurValve project, measuring patients health and well-being before and after their operation. In this work a cohort of 20 patients are analyzed, and 2 patients are analyzed in detail as example case studies. A quantitative evaluation of the platform is provided using patient collected data, as well as a comparison using standardized Patient Reported Outcome Measures (PROMs) which are commonly used in hospitals, and a custom survey. It is shown how the ubiquitous in-home Vesta platform can increase clinical confidence in self-reported patient feedback. Demonstrating its suitability for digital health studies, Vesta provides deeper insight into the health, well-being and recovery of patients within their home

Seven Useful Questions in Density Functional Theory

We explore a variety of unsolved problems in density functional theory, where mathematicians might prove useful. We give the background and context of the different problems, and why progress toward resolving them would help those doing computations using density functional theory. Subjects covered include the magnitude of the kinetic energy in Hartree-Fock calculations, the shape of adiabatic connection curves, using the constrained search with input densities, densities of states, the semiclassical expansion of energies, the tightness of Lieb-Oxford bounds, and how we decide the accuracy of an approximate density.Comment: 18 pages, 6 figures. Fixed typo

Dynamics of a grain-scale intruder in a two-dimensional granular medium with and without basal friction

We report on a series of experiments in which a grain-sized intruder is pushed by a spring through a two-dimensional granular material composed of photoelastic disks in a Couette geometry. We study the intruder dynamics as a function of packing fraction for two types of supporting substrates: A frictional glass plate and a layer of water for which basal friction forces are negligible. We observe two dynamical regimes: Intermittent flow, in which the intruder moves freely most of the time but occasionally gets stuck, and stick-slip dynamics, in which the intruder advances via a sequence of distinct, rapid events. When basal friction is present, we observe a smooth crossover between the two regimes as a function of packing fraction, and we find that reducing the interparticle friction coefficient causes the stick-slip regime to shift to higher packing fractions. When basal friction is eliminated, we observe intermittent flow at all accessible packing fractions. For all cases, we present results for the statistics of stick events, the intruder velocity, and the force exerted on the intruder by the grains. Our results indicate the qualitative importance of basal friction at high packing fractions and suggest a possible connection between intruder dynamics in a static material and clogging dynamics in granular flows.Fil: Kozlowski, Ryan. University of Duke; Estados UnidosFil: Carlevaro, Carlos Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física de Líquidos y Sistemas Biológicos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física de Líquidos y Sistemas Biológicos; ArgentinaFil: Daniels, Karen E.. North Carolina State University; Estados UnidosFil: Kondic, Lou. New Jersey Institute of Technology; Estados UnidosFil: Pugnaloni, Luis Ariel. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Socolar, Joshua E. S.. University of Duke; Estados UnidosFil: Zheng, Hu. University of Duke; Estados Unidos. Tongji University. College of Civil Engineering. Department of Geotechnical Engineering ; ChinaFil: Behringer, Robert P.. University of Duke; Estados Unido

SPHERE in a Box:Practical and Scalable EurValve Activity Monitoring Smart Home Kit

Non-invasive, environmental monitoring is being successfully utilised to improve health care outcomes for patients while allowing them to more safely and comfortably live in their homes instead of health care facilities. This promises to reduce costs and ease the health care burden for many countries globally. However, these systems are still in early stages of research and only highly skilled researchers and engineers can successfully deploy them. The difficulty in deploying these systems prevents their mass use and potential cost savings motivating research interest in smart homes in a box (SHiB). In this paper we present the EurValve Activity Monitoring Kit, a minimalist activity monitoring system that can be deployed in a home by the patient and still obtain valuable lifestyle and activity level information for medical clinicians. We describe the design of the system and how it is being used in the H2020 EurValve Project. The initial results show that the system is easily deployed and yet still effective for non-invasive sensing for activity classification and localisation

Clinical translation of a click-labeled 18F-octreotate radioligand for imaging neuroendocrine tumors

© 2016 by the Society of Nuclear Medicine and Molecular Imaging, Inc. We conducted the first-in-human study of 18F-fluoroethyl triazole [Tyr3] octreotate (18F-FET-βAG-TOCA) in patients with neuroendocrine tumors (NETs) to evaluate biodistribution, dosimetry, and safety. Despite advances in clinical imaging, detection and quantification of NET activity remains a challenge, with no universally accepted imaging standard. Methods: Nine patients were enrolled. Eight patients had sporadic NETs, and 1 had multiple endocrine neoplasia type 1 syndrome. Patients received 137-163 MBq (mean ± SD, 155.7 ± 8 MBq) of 18F-FET-βAG-TOCA. Safety data were obtained during and 24 h after radioligand administration. Patients underwent detailed wholebody PET/CT multibed scanning over 4 h with sampling of venous bloods for radioactivity and radioactive metabolite quantification. Regions of interest were defined to derive individual and mean organ residence times; effective dose was calculated with OLINDA 1.1. Results: All patients tolerated 18F-FET-βAG-TOCA with no adverse events. Over 60% parent radioligand was present in plasma at 60 min. High tumor (primary and metastases)-to-background contrast images were observed. Physiologic distribution was seen in the pituitary, salivary glands, thyroid, and spleen, with low background distribution in the liver, an organ in which metastases commonly occur. The organs receiving highest absorbed dose were the gallbladder, spleen, stomach, liver, kidneys, and bladder. The calculated effective dose over all subjects (mean ± SD) was 0.029 ± 0.004 mSv/MBq. Conclusion: The favorable safety, imaging, and dosimetric profile makes 18F-FET-βAGTOCA a promising candidate radioligand for staging and management of NETs. Clinical studies in an expanded cohort are ongoing to clinically qualify this agent