Data-driven design of molecular nanomagnets.

Three decades of research in molecular nanomagnets have raised their magnetic memories from liquid helium to liquid nitrogen temperature thanks to a wise choice of the magnetic ion and coordination environment. Still, serendipity and chemical intuition played a main role. In order to establish a powerful framework for statistically driven chemical design, here we collected chemical and physical data for lanthanide-based nanomagnets, catalogued over 1400 published experiments, developed an interactive dashboard (SIMDAVIS) to visualise the dataset, and applied inferential statistical analysis. Our analysis shows that the Arrhenius energy barrier correlates unexpectedly well with the magnetic memory. Furthermore, as both Orbach and Raman processes can be affected by vibronic coupling, chemical design of the coordination scheme may be used to reduce the relaxation rates. Indeed, only bis-phthalocyaninato sandwiches and metallocenes, with rigid ligands, consistently present magnetic memory up to high temperature. Analysing magnetostructural correlations, we offer promising strategies for improvement, in particular for the preparation of pentagonal bipyramids, where even softer complexes are protected against molecular vibrations.

Exchange-induced spin polarization in a single magnetic molecule junction.

Many spintronic devices rely on the presence of spin-polarized currents at zero magnetic field. This is often obtained by spin exchange-bias, where an element with long-range magnetic order creates magnetized states and displaces the hysteresis loop. Here we demonstrate that exchange-split spin states are observable and usable in the smallest conceivable unit: a single magnetic molecule. We use a redox-active porphyrin as a transport channel, coordinating a dysprosium-based single-molecule-magnet inside a graphene nano-gap. Single-molecule transport in magnetic field reveals the existence of exchange-split channels with different spin-polarizations that depend strongly on the field orientation, and comparison with the diamagnetic isostructural compound and milikelvin torque magnetometry unravels the role of the single-molecule anisotropy and the molecular orientation. These results open a path to using spin-exchange in molecular electronics, and offer a method to quantify the internal spin structure of single molecules in multiple oxidation states.

Association Between Upper Limb Strength Through 1-Repetition Maximum Test and V'O2peak in Heart Failure.

Purpose: This study aimed to evaluate whether there is a correlation between the maximum strength of upper limb when performing a multijoint exercise and peak oxygen uptake (V'O2peak) in Chronic Heart Failure (CHF) subjects. Method: This cross-sectional study involved CHF subjects with a left ventricular ejection fraction (LVEF) less than 50%, who underwent a cardiopulmonary exercise test (CPET) on a treadmill and 1-repetition maximum (1-RM) test for upper limb strength using a bench press exercise. Results: The sample consisted of 16 individuals aged 54 ± 12 years with a LVEF of 37 ± 7%. The V'O2peak was 14.98 ± 5.4 ml·min-1·kg-1 and mean maximum load in the 1-RM test was 38 ± 16 kg. There was strong correlation of V'O2peak with the load in the 1-RM test (r = 0.70; p = .037; r2 = 0.48). Conclusion: There is a strong correlation between the load in 1-RM test for upper limb with V'O2peak in CHF individuals. It is a safe, inexpensive and reproducible way to assess the muscle strength in this population.

Spin-crossover nanoparticles anchored on MoS2 layers for heterostructures with tunable strain driven by thermal or light-induced spin switching.

In the past few years, the effect of strain on the optical and electronic properties of MoS2 layers has attracted particular attention as it can improve the performance of optoelectronic and spintronic devices. Although several approaches have been explored, strain is typically externally applied on the two-dimensional material. In this work, we describe the preparation of a reversible 'self-strainable' system in which the strain is generated at the molecular level by one component of a MoS2-based composite material. Spin-crossover nanoparticles were covalently grafted onto functionalized layers of semiconducting MoS2 to form a hybrid heterostructure. Their ability to switch between two spin states on applying an external stimulus (light irradiation or temperature change) serves to generate strain over the MoS2 layer. A volume change accompanies this spin crossover, and the created strain induces a substantial and reversible change of the electrical and optical properties of the heterostructure.

Towards peptide-based tunable multistate memristive materials.

Development of new memristive hardware is a technological requirement towards widespread neuromorphic computing. Molecular spintronics seems to be a fertile field for the design and preparation of this hardware. Within molecular spintronics, recent results on metallopeptides demonstrating the interaction between paramagnetic ions and the chirality induced spin selectivity effect hold particular promise for developing fast (ns-µs) operation times. [R. Torres-Cavanillas et al., J. Am. Chem. Soc., 2020, DOI: 10.1021/jacs.0c07531]. Among the challenges in the field, a major highlight is the difficulty in modelling the spin dynamics in these complex systems, but at the same time the use of inexpensive methods has already allowed progress in that direction. Finally, we discuss the unique potential of biomolecules for the design of multistate memristors with a controlled- and indeed, programmable-nanostructure, allowing going beyond anything that is conceivable by employing conventional coordination chemistry.

Reinforced Room-Temperature Spin Filtering in Chiral Paramagnetic Metallopeptides.

Chirality-induced spin selectivity (CISS), whereby helical molecules polarize the spin of electrical current, is an intriguing effect with potential applications in nanospintronics. In this nascent field, the study of the CISS effect using paramagnetic chiral molecules, which could introduce another degree of freedom in controlling the spin transport, remains so far unexplored. To address this challenge, herein we propose the use of self-assembled monolayers (SAMs) of helical lanthanide-binding peptides. To elucidate the effect of the paramagnetic nuclei, monolayers of the peptide coordinating paramagnetic or diamagnetic ions are prepared. By means of spin-dependent electrochemistry, the CISS effect is demonstrated by cyclic voltammetry and electrochemical impedance measurements for both samples. Additionally, an implementation of the standard liquid-metal drop electron transport setup has been carried out, and this process helped to demonstrate the peptides' suitability for solid-state devices. Remarkably, the inclusion of a paramagnetic center in the peptide increases the spin polarization as was independently proved by different techniques. These findings permit the inclusion of magnetic biomolecules in the CISS field and pave the way to their implementation in a new generation of (bio)spintronic nanodevices.

Diretriz Brasileira de Reabilitação Cardiovascular ­ 2020 / Brazilian Cardiovascular Rehabilitation Guideline - 2020

INTRODUÇÃO: Está cientificamente comprovado, sendo algo incorporado ao senso comum, que ser fisicamente ativo contribui para preservar e recuperar a boa saúde do corpo e da mente. Os efeitos favoráveis da reabilitação cardiovascular (RCV) com ênfase nos exercícios físicos têm sido consistentemente documentados, inclusive em meta-análises de estudos clínicos randomizados, que demonstram significativas reduções da morbimortalidade cardiovascular e global,1 bem como da taxa de hospitalização,1,2 com expressivo ganho de qualidade de vida,1,2 justificando a sua consensual e enfática recomendação pelas principais sociedades médicas mundiais.3-6 O sedentarismo, que apresenta elevada prevalência no Brasil e no mundo, está fortemente relacionado às doenças cardiovasculares (DCV) e à mortalidade precoce.7,8 Em contrapartida, maiores volumes de atividade física são positivamente associados à melhor qualidade e à maior expectativa de vida,9-13 existindo uma forte e inversa associação dos diferentes componentes da aptidão física com a mortalidade por todas as causas e com a ocorrência de eventos cardiovasculares desfavoráveis. Ou seja, quanto menor o nível de aptidão física, maior tende ser a taxa de mortalidade.14-21 Portanto, o principal objetivo da RCV com ênfase nos exercícios físicos é propiciar uma melhora dos componentes da aptidão física, tanto aeróbico quanto não aeróbicos (força/ potência muscular, flexibilidade, equilíbrio), algo que exige a combinação de diferentes modalidades de treinamento. Assim, a RCV deve proporcionar os mais elevados níveis de aptidão física passíveis de obtenção, de modo a reduzir o risco de eventos cardiovasculares e promover todos os outros benefícios a serem auferidos pela prática regular de exercícios físicos, culminando com a redução da mortalidade geral.

Exploiting clock transitions for the chemical design of resilient molecular spin qubits.

Molecular spin qubits are chemical nanoobjects with promising applications that are so far hampered by the rapid loss of quantum information, a process known as decoherence. A strategy to improve this situation involves employing so-called Clock Transitions (CTs), which arise at anticrossings between spin energy levels. At CTs, the spin states are protected from magnetic noise and present an enhanced quantum coherence. Unfortunately, these optimal points are intrinsically hard to control since their transition energy cannot be tuned by an external magnetic field; moreover, their resilience towards geometric distortions has not yet been analyzed. Here we employ a python-based computational tool for the systematic theoretical analysis and chemical optimization of CTs. We compare three relevant case studies with increasingly complex ground states. First, we start with vanadium(iv)-based spin qubits, where the avoided crossings are controlled by hyperfine interaction and find that these S = 1/2 systems are very promising, in particular in the case of vanadyl complexes in an L-band pulsed EPR setup. Second, we proceed with a study of the effect of symmetry distortions in a holmium polyoxotungstate of formula [Ho(W5O18)2]9- where CTs had already been experimentally demonstrated. Here we determine the relative importance of the different structural distortions that causes the anticrossings. Third, we study the most complicated case, a polyoxopalladate cube [HoPd12(AsPh)8O32]5- which presents an unusually rich ground spin multiplet. This system allows us to find uniquely favorable CTs that could nevertheless be accessible with standard pulsed EPR equipment (X-band or Q-band) after a suitable chemical distortion to break the perfect cubic symmetry. Since anticrossings and CTs constitute a rich source of physical phenomena in very different kinds of quantum systems, the generalization of this study is expected to have impact not only in molecular spin science but also in other related fields such as molecular photophysics and photochemistry.

Spin-crossover iron(ii) complex showing thermal hysteresis around room temperature with symmetry breaking and an unusually high T(LIESST) of 120 K.

We report a Fe(ii) complex based on 4',4'' carboxylic acid disubstituted dipyrazolylpyridine that shows a spin-crossover close to room temperature associated to a crystallographic phase transition and the LIESST effect with a high T(LIESST) of 120 K.

Peptides as Versatile Platforms for Quantum Computing.

The pursuit of novel functional building blocks for the emerging field of quantum computing is one of the most appealing topics in the context of quantum technologies. Herein we showcase the urgency of introducing peptides as versatile platforms for quantum computing. In particular, we focus on lanthanide-binding tags, originally developed for the study of protein structure. We use pulsed electronic paramagnetic resonance to demonstrate quantum coherent oscillations in both neodymium and gadolinium peptidic qubits. Calculations based on density functional theory followed by a ligand field analysis indicate the possibility of influencing the nature of the spin qubit states by means of controlled changes in the peptidic sequence. We conclude with an overview of the challenges and opportunities opened by this interdisciplinary field.

Deciphering the Role of Dipolar Interactions in Magnetic Layered Double Hydroxides.

Layered double hydroxides (LDHs) exhibit unparalleled anion exchange properties and the ability to be exfoliated into 2D nanosheets, which can be used as a building block to fabricate a wide variety of hybrid functional nanostructured materials. Still, if one wants to use LDHs as a magnetic building blocks in the design of complex architectures, the role played by the dipolar magnetic interactions in these layered materials needs to be understood. In this work, we synthesized and characterized a five-membered CoAl-LDH series with basal spacing ranging from 7.5 to 34 Å. A detailed experimental characterization allows us to conclude that the main factor governing the dipolar interactions between magnetic layers cannot be the interlayer spacing. Supporting theoretical modeling suggests instead a relevant role for spin correlation size, which, in the limit, is related to the lateral dimension of the layer. These results highlight the importance of cation ordering in the magnetic behavior of LDHs, and underpin the differences with homometallic-layered hydroxides.

Exercise through a cardiac rehabilitation program attenuates oxidative stress in patients submitted to coronary artery bypass grafting.

BACKGROUND: Cardiovascular disease is the main cause of morbidity and mortality in the world and oxidative stress has been implicated in the pathogenesis. Cardiac rehabilitation in patients with coronary artery disease submitted to coronary artery bypass grafting may prevent cardiovascular events probably through the attenuation of oxidative stress. The aim of this study was to evaluate the benefits of a cardiac rehabilitation program in the control of the systemic oxidative stress. METHODS: The studied population consisted of 40 patients, with chronic stable coronary artery disease submitted to coronary artery bypass grafting, who attended a cardiac rehabilitation program. Biomarkers of oxidative stress were evaluated in the blood of these patients at different moments. RESULTS: After the onset of cardiac rehabilitation, there was a significant and progressive decrease in thiobarbituric acid reactive substances levels and protein carbonyls, an initial increase and subsequent decrease in superoxide dismutase, catalase and glutathione peroxidase activities. Also, a progressive increase of uric acid, while ferric reducing antioxidant power levels increased only at the end of the cardiac rehabilitation and a tendency to increase of glutathione contents. CONCLUSIONS: The results suggest that regular exercise through a cardiac rehabilitation program can attenuate oxidative stress in chronic coronary artery disease patients submitted to coronary artery bypass grafting.

Electric Field Generation and Control of Bipartite Quantum Entanglement between Electronic Spins in Mixed Valence Polyoxovanadate [GeV14O40]8.

As part of the search for systems in which control of quantum entanglement can be achieved, here we consider the paramagnetic mixed valence polyoxometalate K2Na6[GeV14O40]·10H2O in which two electrons are delocalized over the 14 vanadium ions. Applying a homogeneous electric field can induce an antiferromagnetic coupling between the two delocalized electronic spins that behave independently in the absence of the field. On the basis of the proposed theoretical model, we show that the external field can be used to generate controllable quantum entanglement between the two electronic spins traveling over a vanadium network of mixed valence polyoxoanion [GeV14O40]8-. Within a simplified two-level picture of the energy pattern of the electronic pair based on the previous ab initio analysis, we evaluate the temperature and field dependencies of concurrence and thus indicate that the entanglement can be controlled via the temperature, magnitude, and orientation of the electric field with respect to molecular axes of [GeV14O40]8-.

Clinical, scintigraphic, and angiographic predictors of oxygen pulse abnormality in patients undergoing cardiopulmonary exercise testing.

BACKGROUND: The oxygen (O2 ) pulse curve obtained at cardiopulmonary exercise testing provides information on cardiorespiratory fitness and the presence of cardiovascular disease. O2 pulse abnormalities have been attributed to myocardial ischemia, among other conditions, but the predictors of abnormal O2 pulse curves are not completely known. HYPOTHESIS: Perfusion abnormalities detected by myocardial perfusion scintigraphy (MPS) may be associated with abnormal O2 pulse curves. METHODS: Forty patients with normal left ventricular function underwent cardiopulmonary exercise testing with radiotracer injection at peak exercise, followed by MPS. The O2 pulse curves were classified as (A) normal; (B) probably normal (normal slope with lower peak value); (C) probably abnormal (flat, with low peak value); or (D) definitely abnormal (descending slope), and analyzed as A/B vs C/D. Coronary artery disease (CAD) was defined as >50% stenosis. MPS perfusion scores were calculated (summed rest score [SRS], indicating myocardial fibrosis; summed difference score, indicating ischemia). RESULTS: Comparing patients with A/B vs C/D curves, the latter were more frequently female and had higher SRS. The prevalence of ischemic MPS, of any CAD, or multivessel CAD was not significantly different among patients with A/B or C/D curve patterns. On logistic regression, female sex, body mass index, and the SRS were significantly associated with C/D curves. CONCLUSIONS: Female sex, increasing body mass index, and myocardial fibrosis were significant predictors of abnormal O2 pulse curves. Myocardial ischemia and the presence and extent of CAD were not associated with the abnormal patterns of the O2 pulse curve.

Influence of the dipolar interactions on the relative stability in spin crossover systems.

Molecules exhibiting a spin-crossover transition have been proposed for a number of applications such as molecular switches, spintronic tunable interfaces, and single molecule gates. Both the rational design of new spin-crossover systems and the improvement of the properties of the already existing ones require a theoretical understanding of the relative energy of the high (HS) and low spin state (LS) molecules in the solid-state. This has proved to be very challenging so far. Here, we shed some light on the importance of considering the symmetry and the geometry of the crystallographic cell to correctly evaluate the influence of the dipolar interactions on the relative energies of the molecular complex in both different spin states. Moreover, in the case of Fe(SCN)2 (phen)2 dipolar interactions are found to play an important role for the stabilization of the LS complex. © 2016 Wiley Periodicals, Inc.

Cardiopulmonary Exercise Test: Background, Applicability and Interpretation.

Cardiopulmonary exercise test (CPET) has been gaining importance as a method of functional assessment in Brazil and worldwide. In its most frequent applications, CPET consists in applying a gradually increasing intensity exercise until exhaustion or until the appearance of limiting symptoms and/or signs. The following parameters are measured: ventilation; oxygen consumption (VO2); carbon dioxide production (VCO2); and the other variables of conventional exercise testing. In addition, in specific situations, pulse oximetry and flow-volume loops during and after exertion are measured. The CPET provides joint data analysis that allows complete assessment of the cardiovascular, respiratory, muscular and metabolic systems during exertion, being considered gold standard for cardiorespiratory functional assessment.1-6 The CPET allows defining mechanisms related to low functional capacity that can cause symptoms, such as dyspnea, and correlate them with changes in the cardiovascular, pulmonary and skeletal muscle systems. Furthermore, it can be used to provide the prognostic assessment of patients with heart or lung diseases, and in the preoperative period, in addition to aiding in a more careful exercise prescription to healthy subjects, athletes and patients with heart or lung diseases. Similarly to CPET clinical use, its research also increases, with the publication of several scientific contributions from Brazilian researchers in high-impact journals. Therefore, this study aimed at providing a comprehensive review on the applicability of CPET to different clinical situations, in addition to serving as a practical guide for the interpretation of that test. Resumo O teste cardiopulmonar de exercício (TCPE) vem ganhando importância crescente como método de avaliação funcional tanto no Brasil quanto no Mundo. Nas suas aplicações mais frequentes, o teste consiste em submeter o indivíduo a um exercício de intensidade gradativamente crescente até a exaustão ou o surgimento de sintomas e/ou sinais limitantes. Neste exame se mensura a ventilação (VE), o consumo de oxigênio (VO2), a produção de gás carbônico (VCO2) e as demais variáveis de um teste de exercício convencional. Adicionalmente, podem ser verificadas, em situações específicas, a oximetria de pulso e as alças fluxo-volume antes, durante e após o esforço. A análise integrada dos dados permite a completa avaliação dos sistemas cardiovascular, respiratório, muscular e metabólico no esforço, sendo considerado padrão-ouro na avaliação funcional cardiorrespiratória.1-6 O TCPE permite definir mecanismos relacionados à baixa capacidade funcional, os quais podem ser causadores de sintomas como a dispneia, correlacionando-os com alterações dos sistemas cardiovascular, pulmonar e musculoesquelético. Também pode ser de grande aplicabilidade na avaliação prognóstica em cardiopatas, pneumopatas e em pré-operatório, além de auxiliar na prescrição mais criteriosa do exercício em sujeitos normais, em atletas, em cardiopatas e em pneumopatas. Assim como ocorre com o uso clínico, a pesquisa nesse campo também cresce e várias contribuições científicas de pesquisadores nacionais são publicadas em periódicos de alto fator de impacto. Sendo assim, o objetivo deste documento é fornecer uma revisão ampla da aplicabilidade do TCPE nas diferentes situações clínicas, bem como servir como guia prático na interpretação desse teste propedêutico.