Capturing electron-driven chiral dynamics in UV-excited molecules.

Chiral molecules, used in applications such as enantioselective photocatalysis1, circularly polarized light detection2 and emission3 and molecular switches4,5, exist in two geometrical configurations that are non-superimposable mirror images of each other. These so-called (R) and (S) enantiomers exhibit different physical and chemical properties when interacting with other chiral entities. Attosecond technology might enable influence over such interactions, given that it can probe and even direct electron motion within molecules on the intrinsic electronic timescale6 and thereby control reactivity7-9. Electron currents in photoexcited chiral molecules have indeed been predicted to enable enantiosensitive molecular orientation10, but electron-driven chiral dynamics in neutral molecules have not yet been demonstrated owing to the lack of ultrashort, non-ionizing and perturbative light pulses. Here we use time-resolved photoelectron circular dichroism (TR-PECD)11-15 with an unprecedented temporal resolution of 2.9 fs to map the coherent electronic motion initiated by ultraviolet (UV) excitation of neutral chiral molecules. We find that electronic beatings between Rydberg states lead to periodic modulations of the chiroptical response on the few-femtosecond timescale, showing a sign inversion in less than 10 fs. Calculations validate this and also confirm that the combination of the photoinduced chiral current with a circularly polarized probe pulse realizes an enantioselective filter of molecular orientations following photoionization. We anticipate that our approach will enable further investigations of ultrafast electron dynamics in chiral systems and reveal a route towards enantiosensitive charge-directed reactivity.

Nursing students' internationalization: Virtual exchange and clinical simulation impact cultural intelligence.

BACKGROUND: There is a need for globally competent nurses; however, some cannot train abroad. Internationalization at home strategies seek to teach intercultural and international competencies to all students, regardless of location. PURPOSE: This study evaluated the impact of a virtual exchange and clinical simulation program on nursing students' cultural intelligence. METHODS: The Global Nursing Care (GNC) program was designed to improve nursing students' global competencies, particularly cultural intelligence. It was implemented in two universities in Spain and the USA. A quasi-experimental, analytic, and longitudinal study involved 261 nursing students, 57 from the GNC program and 204 in the control group. Sociodemographic data were collected, and the Cultural Intelligence Scale was used to measure cultural intelligence. DISCUSSION: All cultural intelligence dimensions were augmented following program participation. Moreover, students who participated in the program presented higher cultural intelligence than the control group. CONCLUSION: The results suggest that program participation was associated with a statistically significant gain in nursing students' cultural intelligence.

Ultrafast control over chiral sum-frequency generation.

We introduce an ultrafast all-optical approach for efficient chiral recognition that relies on the interference between two low-order nonlinear processes that are ubiquitous in nonlinear optics: sum-frequency generation and third-harmonic generation. In contrast to traditional sum-frequency generation, our approach encodes the medium's handedness in the intensity of the emitted harmonic signal, rather than in its phase, and it enables full control over the enantiosensitive response. We show how, by sculpting the sub-optical-cycle oscillations of the driving laser field, we can force one molecular enantiomer to emit bright light while its mirror twin remains dark, thus reaching the ultimate efficiency limit of chiral sensitivity via low-order nonlinear light-matter interactions. Our work paves the way for ultrafast and highly efficient imaging and control of the chiral electronic clouds of chiral molecules using lasers with moderate intensities, in all states of matter: from gases to liquids to solids, with molecular specificity and on ultrafast time scales.

Ultrafast chirality: the road to efficient chiral measurements.

Today we are witnessing the electric-dipole revolution in chiral measurements. Here we reflect on its lessons and outcomes, such as the perspective on chiral measurements using the complementary principles of "chiral reagent" and "chiral observer", the hierarchy of scalar, vectorial and tensorial enantio-sensitive observables, the new properties of the chiro-optical response in the ultrafast and non-linear domains, and the geometrical magnetism associated with the chiral response in photoionization. The electric-dipole revolution is a landmark event. It has opened routes to extremely efficient enantio-discrimination with a family of new methods. These methods are governed by the same principles but work in vastly different regimes - from microwaves to optical light; they address all molecular degrees of freedom - electronic, vibrational and rotational, and use flexible detection schemes, i.e. detecting photons or electrons, making them applicable to different chiral phases, from gases to liquids to amorphous solids. The electric-dipole revolution has also enabled enantio-sensitive manipulation of chiral molecules with light. This manipulation includes exciting and controlling ultrafast helical currents in vibronic states of chiral molecules, enantio-sensitive control of populations in electronic, vibronic and rotational molecular states, and opens the way to efficient enantio-separation and enantio-sensitive trapping of chiral molecules. The word "perspective" has two meanings: an "outlook" and a "point of view". In this perspective article, we have tried to cover both meanings.

Death in custody in Spain: Excited delirium syndrome. Importance of a multidisciplinary approach.

This article aims to analyse the excited delirium syndrome, especially, when Law Enforcement Officers have to make use of force and deaths in custody occur. Through a bibliographic review, inferences have been obtained to identify, in first place, what a death in custody is and the differences between positional asphyxia and excited delirium syndrome. Subsequently, we have summarized the major findings that the medical examiner should look for in order to diagnose the excited delirium syndrome from the scene examination, the autopsy and the complementary analysis. Finally, we propose some directives that may help to avoid the death of these subjects and to study them in case they occur.

New opportunities for ultrafast and highly enantio-sensitive imaging of chiral nuclear dynamics enabled by synthetic chiral light.

Synthetic chiral light [D. Ayuso et al., Nat. Photon., 2019, 13, 866-871] has opened up new opportunities for ultrafast and highly efficient imaging and control of chiral matter. Here we show that the giant enantio-sensitivity enabled by such light could be exploited to probe chiral nuclear rearrangements during chemical reactions in a highly enantio-sensitive manner. Using a state-of-the-art implementation of real-time time-dependent density functional theory, we explore how the nonlinear response of the prototypical chiral molecule H2O2 changes as a function of its dihedral angle, which defines its handedness. The macroscopic intensity emitted from randomly oriented molecules at even harmonic frequencies (of the fundamental) depends strongly on this nuclear coordinate. Because of the ultrafast nature of such nonlinear interactions, the direct mapping between the dissymmetry factor and the nuclear geometry provides a way to probe chiral nuclear dynamics at their natural time scales. Our work paves the way for ultrafast and highly efficient imaging of enantio-sensitive dynamics in more complex chiral systems, including biologically relevant molecules.

Strong chiral response in non-collinear high harmonic generation driven by purely electric-dipole interactions.

High harmonic generation (HHG) records the ultrafast electronic response of matter to light, encoding key properties of the interrogated quantum system, such as chirality. The first implementation of chiral HHG [Cireasa et al, Nat. Phys.11, 654 (2015)10.1038/nphys3369] relied on the weak electronic response of a medium of randomly oriented chiral molecules to the magnetic component of an elliptically polarized wave, yielding relatively weak chiro-optical signals. Here we apply state-of-the-art semi-analytical modelling to show that elliptically polarized light can drive a strong chiral response in chiral molecules via purely electric-dipole interactions - the magnetic component of the wave does not participate at all. This strong chiro-optical response, which remains hidden in standard HHG experiments, can be mapped into the macroscopic far-field signal using a non-collinear configuration, creating new opportunities for imaging chiral matter and chiral dynamics on ultrafast time scales.

Enantio-sensitive unidirectional light bending.

Structured light, which exhibits nontrivial intensity, phase, and polarization patterns in space, has key applications ranging from imaging and 3D micromanipulation to classical and quantum communication. However, to date, its application to molecular chirality has been limited by the weakness of magnetic interactions. Here we structure light's local handedness in space to introduce and realize an enantio-sensitive interferometer for efficient chiral recognition without magnetic interactions, which can be seen as an enantio-sensitive version of Young's double slit experiment. Upon interaction with isotropic chiral media, such chirality-structured light effectively creates chiral emitters of opposite handedness, located at different positions in space. We show that if the distribution of light's handedness breaks left-right symmetry, the interference of these chiral emitters leads to unidirectional bending of the emitted light, in opposite directions in media of opposite handedness, even if the number of the left-handed and right-handed emitters excited in the medium is exactly the same. Our work introduces the concepts of polarization of chirality and chirality-polarized light, exposes the immense potential of sculpting light's local chirality, and offers novel opportunities for efficient chiral discrimination, enantio-sensitive optical molecular fingerprinting and imaging on ultrafast time scales.

The Modification of Vital Signs According to Nursing Students' Experiences Undergoing Cardiopulmonary Resuscitation Training via High-Fidelity Simulation: Quasi-Experimental Study.

BACKGROUND: High-fidelity simulation represents a primary tool in nursing education, especially when hands-on practical training is involved. OBJECTIVE: We sought to determine the influence of high-fidelity clinical simulation, applied during cardiopulmonary resuscitation (CPR) training, on blood pressure, heart rate, stress, and anxiety levels in 2 groups of nursing students. One group had experience in health contexts, whereas the other group had none. METHODS: We performed a quasi-experimental study. Data were collected between May and June 2015 and included measurements of all the resting values, before and after participation in CPR clinical simulations regarding the 2 groups of university students (ie, with and without experience). RESULTS: An increase in vital signs was observed in students after participating in a clinical simulation scenario, especially the heart rate. In all students, increased stress and anxiety levels were observed before the first simulation case scenario. Also, in all study groups, a decrease in vital signs, stress levels, and anxiety was observed throughout the study. CONCLUSIONS: Participation in high-fidelity simulation experiences has both physiological and psychological effects on students.

Attosecond Pump-Probe Spectroscopy of Charge Dynamics in Tryptophan.

Attosecond pump-probe experiments performed in small molecules have allowed tracking charge dynamics in the natural time scale of electron motion. That this is also possible in biologically relevant molecules is still a matter of debate, because the large number of available nuclear degrees of freedom might destroy the coherent charge dynamics induced by the attosecond pulse. Here we investigate extreme ultraviolet-induced charge dynamics in the amino acid tryptophan. We find that, although nuclear motion and nonadiabatic effects introduce some decoherence in the moving electron wave packet, these do not significantly modify the coherence induced by the attosecond pulse during the early stages of the dynamics, at least for molecules in their equilibrium geometry. Our conclusions are based on elaborate theoretical calculations and the experimental observation of sub-4 fs dynamics, which can only be reasonably assigned to electronic motion. Hence, attosecond pump-probe spectroscopy appears as a promising approach to induce and image charge dynamics in complex molecules.

Prediction models of health-related quality of life in different neck pain conditions: a cross-sectional study.

PURPOSE: The main aim of the study was to predict the health-related quality of life (HRQoL) based on physical, functional, and psychological measures in patients with different types of neck pain (NP). MATERIALS AND METHODS: This cross-sectional study included 202 patients from a primary health center and the physiotherapy outpatient department of a hospital. Patients were divided into four groups according to their NP characteristics: chronic (CNP), acute whiplash (WHIP), chronic NP associated with temporomandibular dysfunction (NP-TMD), or chronic NP associated with chronic primary headache (NP-PH). The following measures were performed: Short Form-12 Health Survey (SF-12), Neck Disability Index (NDI), visual analog scale (VAS), State-Trait Anxiety Inventory (STAI), Beck Depression Inventory (BECK), and cervical range of movement (CROM). RESULTS: The regression models based on the SF-12 total HRQoL for CNP and NP-TMD groups showed that only NDI was a significant predictor of the worst HRQoL (48.9% and 48.4% of the variance, respectively). In the WHIP group, the regression model showed that BECK was the only significant predictor variable for the worst HRQoL (31.7% of the variance). Finally, in the NP-PH group, the regression showed that the BECK, STAI, and VAS model predicted the worst HRQoL (75.1% of the variance). CONCLUSION: Chronic nonspecific NP and chronic NP associated with temporomandibular dysfunction were the main predictors of neck disability. In addition, depression, anxiety, and pain were the main predictors of WHIP or primary headache associated with CNP.

Validation to Spanish of the Caring Assessment Tool (CAT-V).

OBJECTIVE: to translate and validate to Spanish the Caring Assessment Scale tool, CAT-V, by Joanne Duffy, within the framework of Jean Watson; as a secondary objective, it is proposed to evaluate its psychometric properties. There are tools designed to measure the patient's perception of provided cares, including CAT-V, the subject of our interest, in a way that it can be used in Spanish-speaking patients. METHODS: to meet the objectives, it was performed sequential translation and retro-translation of the scale to be validated, through a standardized procedure. The final version of that scale was validated in a sample of 349 patients from four public and two private hospitals in Madrid, Spain. RESULTS: The instrument was translated and validated with high internal consistency (Cronbach's alpha .953). The subsequent factor analysis revealed a three-factor structure, not coincident with the data from the US population. CONCLUSION: it is considered that the translation of CAT-V is a suitable instrument to be used in the evaluation of patient care in Ibero-american health centers whose language is Spanish.

Ultrafast charge dynamics in glycine induced by attosecond pulses.

The combination of attosecond pump-probe techniques with mass spectrometry methods has recently led to the first experimental demonstration of ultrafast charge dynamics in a biomolecule, the amino acid phenylalanine [Calegari et al., Science, 2014, 346, 336]. Using an extension of the static-exchange density functional theory (DFT) method, the observed dynamics was explained as resulting from the coherent superposition of ionic states produced by the broadband attosecond pulse. Here, we have used the static-exchange DFT method to investigate charge migration induced by attosecond pulses in the glycine molecule. We show that the observed dynamics follows patterns similar to those previously found in phenylalanine, namely that charge fluctuations occur all over the molecule and that they can be explained in terms of a few typical frequencies of the system. We have checked the validity of our approach by explicitly comparing with the photoelectron spectra obtained in synchrotron radiation experiments and with the charge dynamics that follows the removal of an electron from a given molecular orbital, for which fully correlated ab initio results are available in the literature. From this comparison, we conclude that our method provides an accurate description of both the coherent superposition of cationic states generated by the attosecond pulse and its subsequent time evolution. Hence, we expect that the static-exchange DFT method should perform equally well for other medium-size and large molecules, for which the use of fully correlated ab initio methods is not possible.

Validation to Spanish of the Caring Assessment Tool (CAT-V) / Adaptação cultural para o espanhol e consistência interna da Ferramenta de Avaliação de Cuidados, Caring Assessment Tool (CAT-V) / Validación al Español de la Herramienta de Evaluación de los Cuidados, Caring Assessment Tool (CAT-V)

Resume Objective: to translate and validate to Spanish the Caring Assessment Scale tool, CAT-V, by Joanne Duffy, within the framework of Jean Watson; as a secondary objective, it is proposed to evaluate its psychometric properties. There are tools designed to measure the patient's perception of provided cares, including CAT-V, the subject of our interest, in a way that it can be used in Spanish-speaking patients. Methods: to meet the objectives, it was performed sequential translation and retro-translation of the scale to be validated, through a standardized procedure. The final version of that scale was validated in a sample of 349 patients from four public and two private hospitals in Madrid, Spain. Results: The instrument was translated and validated with high internal consistency (Cronbach's alpha .953). The subsequent factor analysis revealed a three-factor structure, not coincident with the data from the US population. Conclusion: it is considered that the translation of CAT-V is a suitable instrument to be used in the evaluation of patient care in Ibero-american health centers whose language is Spanish.

Resume Objetivo: traduzir para castelhano e avaliar a consistência interna da escala Caring Assessment tool, CAT-V de Joanne Duffy, no marco conceitual de Jean Watson, e como objetivo secundário avaliar as suas propriedades psicométricas. Existem ferramentas desenhadas para medir a percepção do paciente sobre os cuidados dispensados, entre as quais o CAT-V, objeto de nosso interesse com o fim de poder ser aplicado aos doentes hispano falantes. Métodos: para cumprir com os objetivos serão feitas sequencialmente a tradução e retro tradução da escala a validar através de um procedimento padronizado. A versão definitiva da escala foi validada numa amostra de 349 pacientes procedente de quatro hospitais públicos e dois privados de Madrid, Espanha. Resultados: o instrumento foi traduzido e validado com uma consistência elevada (alfa de Cronbach 0,953). Conclusão: a tradução do CAT-V considera que o mesmo pode-se consistuir um instrumento adequado para a avaliação de cuidados prestados a pacientes nos centros de saúde ibero-americanos cuja língua falada seja o castelhano.

Resumen Objetivo: traducir y validar al castellano de la escala Caring Assessment tool, CAT-V, de Joanne Duffy, dentro del marco conceptual de Jean Watson, como objetivo secundario, se plantea evaluar sus propiedades psicométricas. Existen herramientas diseñadas con el fin de medir la percepción del paciente sobre los cuidados dispensados, entre ellos el CAT-V, es objeto de nuestro interés, a fin de que pueda ser utilizado en pacientes hispanohablantes. Método: para cumplir con los objetivos, se plantea, secuencialmente, la realización de la traducción y retro-traducción de la escala a validar, a través de procedimiento normalizado. La versión definitiva de esa escala se validó en una muestra de 349 pacientes procedente de cuatro hospitales públicos y dos hospitales privados en Madrid, España. Resultados: el instrumento fue traducido y validado la con una consistencia interna elevada (alfa de Cronbach .953). El análisis factorial posterior ha puesto de manifiesto una estructura de tres factores, hallazgo no coincidente con los datos procedentes de la población norteamericana. Conclusión: se considera que la traducción del CAT-V es un instrumento adecuado para su utilización en la evaluación de los cuidados a pacientes en centros sanitarios iberoamericanos cuya lengua sea el Castellano.

Decoherence, control and attosecond probing of XUV-induced charge migration in biomolecules. A theoretical outlook.

The sudden ionization of a molecule by an attosecond pulse is followed by charge redistribution on a time scale from a few femtoseconds down to hundreds of attoseconds. This ultrafast redistribution is the result of the coherent superposition of electronic continua associated with the ionization thresholds that are reached by the broadband attosecond pulse. Thus, a correct theoretical description of the time evolution of the ensuing wave packet requires the knowledge of the actual ionization amplitudes associated with all open ionization channels, a real challenge for large and medium-size molecules. Recently, the first calculation of this kind has come to light, allowing for interpretation of ultrafast electron dynamics observed in attosecond pump-probe experiments performed on the amino acid phenylalanine [Calegari et al., Science 2014, 346, 336]. However, as in most previous theoretical works, the interpretation was based on various simplifying assumptions, namely, the ionized electron was not included in the description of the cation dynamics, the nuclei were fixed at their initial position during the hole migration process, and the effect of the IR probe pulse was ignored. Here we go a step further and discuss the consequences of including these effects in the photoionization of the glycine molecule. We show that (i) the ionized electron does not affect hole dynamics beyond the first femtosecond, and (ii) nuclear dynamics has only a significant effect after approximately 8 fs, but does not destroy the coherent motion of the electronic wave packet during at least few additional tens of fs. As a first step towards understanding the role of the probe pulse, we have considered an XUV probe pulse, instead of a strong IR one, and show that such an XUV probe does not introduce significant distortions in the pump-induced dynamics, suggesting that pump-probe strategies are suitable for imaging and manipulating charge migration in complex molecules. Furthermore, we show that hole dynamics can be changed by shaping the attosecond pump pulse, thus opening the door to the control of charge dynamics in biomolecules.