Electrical sensing of the thermal and light induced spin transition in robust contactless spin-crossover/graphene hybrid devices

Hybrid devices based on spin-crossover (SCO)/2D heterostructures grant a highly sensitive platform to detect the spin transition in the molecular SCO component and tune the properties of the 2D material. However, the fragility of the SCO materials upon thermal treatment, light irradiation or contact with surfaces and the methodologies used for their processing have limited their applicability. Here, we report an easily processable and robust SCO/2D hybrid device with outstanding performance based on the sublimable SCO [Fe(Pyrz)2] molecule deposited over CVD-graphene, which is fully compatible with electronics industry protocols. Thus, a novel methodology based on growing an elusive polymorph of [Fe(Pyrz)2] (tetragonal phase) over graphene is developed that allows us to electrically detect a fast and effective light-induced spin transition in the devices (~50% yield in 5 minutes). Such performance can be enhanced even more when a flexible polymeric layer of PMMA is inserted in between the two active components in a contactless configuration, reaching a ~100 % yield in 5 minutes.Comment: 25 pages, 5 figure

Preditores de satisfação dos profissionais de saúde com a educação continuada: um estudo transversal

Objectives: to verify which organizational, methodological, and resource-related characteristics of Continuing Health Education (CHE) help to best predict the professionals´ satisfaction. Method: a cross-sectional study with multivariate logistic regressions to predict a high mean satisfaction with different dimensions of educational actions used: Overall satisfaction, Utility, Methodology, Organization and resources, and Teaching Capacity. 25,281 satisfaction questionnaires have been analysed completed by health professionals attending 1,228 training activities in Andalusia (Spain), during the period from March 2012 to April 2015. Results: the characteristics that best predict a high overall satisfaction are the following: clinical session type as opposed to the workshop (Odds Ratio [OR]=2.07, p<0.001); face-to-face attendance modality (OR=3.88, p<0.001) or semi-personal-attendance (OR=2.83, p<0.001), as opposed to e-learning; and 1-2 days in duration (OR=2.38, p<0.001) as opposed to those of between 3 and 14 days. A lower number of hours (OR=0.99, p<0.001) and a lower number of professionals (OR=0.98, p<0.05) also increase the probability. Having the educational actions accredited increases the probabilities in the following dimensions: Utility (OR=1.33, p<0.05), Methodology (OR=1.5, p<0.01) and Teaching capacity (OR=1.5, p<0.01). Conclusion: the study provides relevant information on aspects that improve professional satisfaction, such as that e-learning activities should improve their content, teaching methods, and styles, or that face-to-face clinical sessions are the type of CHE with the greatest satisfaction.Objetivo: verificar quais características organizacionais, metodológicas e relacionadas a recursos da educação continuada em saúde (ECS) ajudam a predizer melhor a satisfação dos profissionais. Método: estudo transversal com regressões logísticas multivariadas para predizer uma alta satisfação média com diferentes dimensões das ações educativas utilizadas: Satisfação Geral, Utilidade, Metodologia, Organização e Recursos, e Capacidade de Ensino. Foram analisados 25.281 questionários de satisfação preenchidos por profissionais de saúde que participaram de 1.228 atividades de treinamento na Andaluzia (Espanha), no período de março de 2012 a abril de 2015. Resultados: características que melhor predizem uma alta Satisfação Geral são as seguintes: Método de sessão clínica em oposição a workshops (Odds Ratio[OR]=2,07;p<0,001); modalidade presencial (OR=3,88;p<0,001) ou semipresencial (OR=2,83;p<0,001) em oposição a e-learning; e 1-2 dias de duração (OR=2,38;p<0,001) em oposição a 3-14 dias. Um menor número de horas (OR=0,99;p<0,001) e de profissionais (OR=0,98;p<0,05) também aumenta a probabilidade. A acreditação das ações educativas aumenta as probabilidades nas dimensões: Utilidade (OR=1,33;p<0,05), Metodologia (OR=1,5;p<0,01) e Capacidade de Ensino (OR=1,5;p<0,01). Conclusão: o estudo fornece informações relevantes sobre aspectos que melhoram a satisfação profissional, como a opinião de que atividades e-learning precisam melhorar seu conteúdo, métodos e estilos de ensino, ou de que sessões clínicas presenciais são o tipo de ECS com maior satisfação.Objetivo: verificar qué características organizativas, metodológicas y de recursos de la Educación Continua en Salud (ECS) ayudan a predecir mejor la satisfacción de los profesionales. Método: se utiliza un estudio transversal con regresiones logísticas multivariadas para predecir un alto promedio de satisfacción con los diferentes tipos de acciones educativas: Satisfacción general, Utilidad, Metodología, Organización y recursos y Capacidad docente. Se han analizado 25.281 cuestionarios de satisfacción respondidos por los profesionales de la salud que asistieron a 1228 actividades formativas, en Andalucía (España), durante el período de marzo a abril de 2012. Resultados: características que mejor predicen una alta Satisfacción general: Tipo de sesión clínica frente al taller (OddsRatio [OR]=2,07, p<0,001); modalidad de asistencia presencial (OR=3,88, p<0,001) o semipersonal (OR=2,83, p<0,001), frente al aprendizaje electrónico (e-learning); y 1-2 días de duración (OR=2,38, p<0,001) frente a 3-14 días. Una menor cantidad de horas (OR=0,99, p<0,001) y una menor cantidad de profesionales (OR=0,98, p<0,05) también aumentan la probabilidad. Acreditar las acciones educativas aumenta las probabilidades en las siguientes dimensiones: Utilidad (OR=1,33, p<0,05), Metodología (OR=1,5, p<0,01) y Capacidad docente (OR=1,5, p<0,01). Conclusión: el estudio aporta información relevante sobre aspectos que mejoran la satisfacción profesional, como que las actividades de aprendizaje electrónico deben mejorar sus contenidos, métodos y estilos de enseñanza o que las sesiones clínicas personales son el tipo de ECS con mayor satisfacción

Electrical sensing of the thermal and light induced spin transition in robust contactless spin-crossover/graphene hybrid devices

Hybrid devices based on spin-crossover (SCO)/2D heterostructures grant a highly sensitive platform to detect the spin transition in the molecular SCO component and tune the properties of the 2D material. However, the fragility of the SCO materials upon thermal treatment, light irradiation or contact with surfaces and the methodologies used for their processing have limited their applicability. Here, we report an easily processable and robust SCO/2D hybrid device with outstanding performance based on the sublimable SCO [Fe(Pyrz)2] molecule deposited over CVD-graphene, which is fully compatible with electronics industry protocols. Thus, a novel methodology based on growing an elusive polymorph of [Fe(Pyrz)2] (tetragonal phase) over graphene is developed that allows us to electrically detect a fast and effective light-induced spin transition in the devices (~50% yield in 5 minutes). Such performance can be enhanced even more when a flexible polymeric layer of PMMA is inserted in between the two active components in a contactless configuration, reaching a ~100 % yield in 5 minutes

Design and processing as ultrathin films of a sublimable Iron(II) spin crossover material exhibiting efficient and fast light-induced spin transition

Materials based on spin crossover (SCO) molecules have centred the attention in Molecular Magnetism for more than forty years as they provide unique examples of multifunctional and stimuli-responsive materials, which can be then integrated into electronic devices to exploit their molecular bistability. This process often requires the preparation of thermally stable SCO molecules that can sublime and remain intact in contact with surfaces. However, the number of robust sublimable SCO molecules is still very scarce. Here we report a novel example of this kind. It is based on a neutral iron (II) coordination complex formulated as [FeII(neoim)2], where neoimH is the ionogenic ligand 2-(1H-imidazol-2-yl)-9-methyl-1,10-phenanthroline. In the first part a comprehensive study, which covers the synthesis and magneto-structural characterization of the [FeII(neoim)2] complex as a bulk microcrystalline material, is reported. Then, in the second part we investigate the suitability of this material to form thin films through high vacuum (HV) sublimation. Finally, the retainment of all present SCO capabilities in the bulk when the material is processed is thoroughly studied by means of X-ray absorption spectroscopy. In particular, a very efficient and fast light-induced spin transition (LIESST effect) has been observed, even for ultrathin films of 15 nm.Comment: 27 pages, 2 schemes, 5 figures, 1 tabl

Bistable Hofmann-Type FeII Spin-Crossover Two-Dimensional Polymers of 4-Alkyldisulfanylpyridine for Prospective Grafting of Monolayers on Metallic Surfaces

[EN] Aiming at investigating the suitability of Hofmann-type two-dimensional ( 2D) coordination polymers {Fe-II(L-ax)(2)[M-II(CN)(4)]} to be processed as single monolayers and probed as spin crossover (SCO) junctions in spintronic devices, the synthesis and characterization of the MII derivatives (M-II = Pd and Pt) with sulfur-rich axial ligands (L-ax = 4-methyl- and 4-ethyl-disulfanylpyridine) have been conducted. The thermal dependence of the magnetic and calorimetric properties confirmed the occurrence of strong cooperative SCO behavior in the temperature interval of 100-225 K, featuring hysteresis loops 44 and 32.5 K/21 K wide for PtII-methyl and Pt-II/Pd-II- ethyl derivatives, while the Pd-II-methyl derivative undergoes a much less cooperative multistep SCO. Excluding Pt-II-methyl, the remaining compounds display light-induced excited spin-state trapping at 10 K with T-LIESST temperatures in the range of 50-70 K. Single-crystal studies performed in the temperature interval 100-250 K confirmed the layered structure and the occurrence of complete transformation between the high- and low-spin states of the Fe-II center for the four compounds. Strong positional disorder seems to be the source of elastic frustration driving the multistep SCO observed for the Pd-II-methyl derivative. It is expected that the peripheral disulfanyl groups will favor anchoring and growing of the monolayer on gold substrates and optimal electron transport in the device.This work was supported by the Spanish Ministerio de Ciencia e Innovacion (MICINN) and FEDER founds (No. PID2019-106147GB-I00), Unidad de Excelencia Maria de Maeztu (Nos. MDM2015-0538-18-2, CEX2019-000919-M) and EU Framework FET-OPEN project COSMICS (Grant Agreement No. 766726). R.T.C. and M.M.S. thank the MICINN for a predoctoral grant.Turo-Cortés, R.; Valverde-Muñoz, FJ.; Meneses-Sánchez, M.; Muñoz Roca, MDC.; Bartual-Murgui, C.; Real, JA. (2021). Bistable Hofmann-Type FeII Spin-Crossover Two-Dimensional Polymers of 4-Alkyldisulfanylpyridine for Prospective Grafting of Monolayers on Metallic Surfaces. Inorganic Chemistry. 60(12):9040-9049. https://doi.org/10.1021/acs.inorgchem.1c0101090409049601

Assessment of Maternal Effects and Genetic Variability in Resistance to Verticillium dahliae in Olive Progenies

The use of genetic resistance is likely the most efficient, economically convenient and environmentally friendly control method for plant diseases, as well as a fundamental piece in an integrated management strategy. This is particularly important for woody crops affected by diseases in which mainly horizontal resistance mechanisms are operative, such as Verticillium wilt, caused by Verticillium dahliae. In this study, we analyzed the variability in resistance to Verticillium wilt of olive trees in progenies from five crosses: ‘Picual’ × ‘Frantoio’, ‘Arbosana’ × ‘Koroneiki’, ‘Sikitita’ × ‘Arbosana’, ‘Arbosana’ × ‘Frantoio’ and ‘Arbosana’ × ‘Arbequina’ and their respective reciprocal crosses. Additionally, seedlings of ‘Picual’ and ‘Frantoio’ in open pollination were used as controls. In October 2016 and 2018, the fruits were harvested, and seeds germinated. Six-week-old seedlings were inoculated by dipping their bare roots in a conidial suspension of V. dahliae, and disease progress in terms of symptom severity and mortality was evaluated weekly. Additionally, seedling growth was evaluated every two weeks. At the end of the experiment, no significant differences were found for any of the assessed parameters when reciprocal crosses were compared. These results suggest that there is no maternal or paternal effect in regard to the heritability of resistance. In addition, this study identifies the best crosses for obtaining the highest number of resistant genotypes, highlighting the importance of the selection of specific cultivars to optimize the breeding process

Sublimable complexes with spin switching: chemical design, processing as thin films and integration in graphene-based devices

Entre los diferentes tipos de compuestos moleculares conmutables, las moléculas SCO de Fe( II ) sublimables proporcionan una plataforma adecuada para desarrollar dispositivos inteligentes que respondan a estímulos externos. En este documento, presentamos la síntesis, la estructura cristalográfica y las propiedades magnéticas de tres nuevas moléculas neutras de Fe( II ) SCO pertenecientes a la familia {Fe[H 2 B(pz) 2 ] 2 (L)} con ligandos bidentado-α-diimina L = 3-(piridin-2-il)-[1,2,3]triazolo[1,5- a ]piridina (tzpy), 5,5′,6,6′-tetrahidro-4 H ,4′ H - 2,2′-bi(1,3-tiazina) (btz) y 4,4′,5,5′-tetrahidro-2,2′-bitiazol (bt) ( 1 , 2 y 3, respectivamente), así como dos formas solvatadas de 1 y 3 . Los tres compuestos desolvatados presentan transiciones de SCO inducidas por calor y luz con diferentes grados de cooperatividad y efectividad. Además, se ha demostrado que 1 y 2 son sublimables en condiciones HV, lo que proporciona películas delgadas homogéneas de 200 nm de espesor ( TF1 y TF2) que conservan la integridad química de las moléculas originales independientemente de la superficie de depósito. El comportamiento SCO de las películas se caracteriza por la técnica XAS que revela la retención parcial de las transiciones de espín inducidas por la luz y el calor, pero pierde la cooperatividad. Finalmente, los dispositivos híbridos horizontales SCO/2D basados ​​en CVD-grafeno se producen utilizando estas películas. Siendo los primeros de este tipo utilizando moléculas de la familia {Fe[H 2 B(pz) 2 ] 2 (L)}, con L = tzpy y btz, los dispositivos han permitido la detección exitosa de la transición térmica SCO a través de la Propiedades eléctricas del CVD-grafeno.Among the different types of switchable molecular compounds, sublimable Fe(II) SCO molecules provide a suitable platform to develop smart devices that respond to external stimuli. Herein, we report the synthesis, crystallographic structure and magnetic properties of three new neutral Fe(II) SCO molecules belonging to the {Fe[H2B(pz)2]2(L)} family with bidentate-α-diimine ligands L = 3-(pyridin-2-yl)-[1,2,3]triazolo[1,5-a]pyridine (tzpy), 5,5′,6,6′-tetrahydro-4H,4′H-2,2′-bi(1,3-thiazine) (btz) and 4,4′,5,5′-tetrahydro-2,2′-bithiazole (bt) (1, 2 and 3, respectively), as well as two solvated forms of 1 and 3. All three desolvated compounds present thermal- and light-induced SCO transitions with different degrees of cooperativity and effectiveness. Furthermore, 1 and 2 are demonstrated to be sublimable under HV conditions, affording homogeneous thin films 200 nm thick (TF1 and TF2) that retain the chemical integrity of the original molecules regardless of the deposition surface. The SCO behaviour of the films is characterized by the XAS technique revealing the partial retainment of both thermal- and light-induced spin transitions, yet losing the cooperativity. Finally, SCO/2D horizontal hybrid devices based on CVD-graphene are produced using these films. Being the first ones of this type utilizing molecules of the {Fe[H2B(pz)2]2(L)} family, with L = tzpy and btz, the devices have allowed the successful detection of the thermal SCO transition through the electric properties of CVD-graphene