Light-to-Heat Conversion of Optically Trapped Hot Brownian Particles.

Anisotropic hybrid nanostructures stand out as promising therapeutic agents in photothermal conversion-based treatments. Accordingly, understanding local heat generation mediated by light-to-heat conversion of absorbing multicomponent nanoparticles at the single-particle level has forthwith become a subject of broad and current interest. Nonetheless, evaluating reliable temperature profiles around a single trapped nanoparticle is challenging from all of the experimental, computational, and fundamental viewpoints. Committed to filling this gap, the heat generation of an anisotropic hybrid nanostructure is explored by means of two different experimental approaches from which the local temperature is measured in a direct or indirect way, all in the context of hot Brownian motion theory. The results were compared with analytical results supported by the numerical computation of the wavelength-dependent absorption efficiencies in the discrete dipole approximation for scattering calculations, which has been extended to inhomogeneous nanostructures. Overall, we provide a consistent and comprehensive view of the heat generation in optical traps of highly absorbing particles from the viewpoint of the hot Brownian motion theory.

Further extension of the Madrid-2019 force field: Parametrization of nitrate (NO3-) and ammonium (NH4+) ions.

The importance of nitrate and ammonium salts both in the environment and in biological processes cannot be questioned. In this work, using the TIP4P/2005 water model, aqueous solutions of nitrate and ammonium electrolytes are parametrized using scaled charges while keeping a rigid structure and nonpolarizable charge distributions. The models are optimized by systematically testing a set of properties for twelve electrolytes-eight nitrate and four ammonium salts-thus, enlarging the number of potential chemical species encompassed within the Madrid-2019 force field for ions. The capacity of the force field for predicting densities, ion-ion and ion-solvent structures, and transport properties of the solutions comprised by the trial batch of salts was tested and discussed. Both the dependence of the densities with the salt concentration and the solution structure were nicely reproduced by the models in the whole concentration range without any trace of precipitating events and with improved accuracy in comparison with recently reported models, while the agreement of the simulated transport properties with experimental data ranges from good to reasonable, depending on the ion/counterion pair. These scaled charge models might be considered as force fields embodying a reasonable compromise between exactness and general applicability and also as an important step in the development of accurate models for polyatomic ions.

Correlated proton dynamics in hydrogen bonding networks: the benchmark case of 3-hydroxyglutaric acid.

Proton and hydrogen-bonded networks sustain a broad range of structural and charge transfer processes in supramolecular materials. The modelling of proton dynamics is however challenging and demands insights from prototypical benchmark systems. The intramolecular H-bonding networks induced by either protonation or deprotonation of 3-hydroxyglutaric acid provide intriguing case studies of correlated proton dynamics. The vibrational signatures associated with the fluxional proton bonding and its coupling with the hydroxyglutaric backbone are investigated here with infrared action ion spectroscopy experiments and Born-Oppenheimer molecular dynamics (BOMD) computations. Despite the formally similar symmetry of protonated and deprotonated hydroxyglutaric acid, the relative proton affinities of the oxygen centers of the carboxylic and carboxylate groups with respect to that of the central hydroxyl group lead to distinct proton dynamics. In the protonated acid, a tautomeric arrangement of the type HOCO·[HOH]+·OCOH is preferred with the proton binding tighter to the central hydroxyl moiety and the electronic density being shared between the two nearly symmetric H-bonds with the carboxylic end groups. In the deprotonated acid, the asymmetric [OCO]-·HO·HOCO configuration is more stable, with a stronger H-bonding on the bare carboxylate end. Both systems display active backbone dynamics and concerted Grothuss-like proton motions, leading to diffuse band structures in their vibrational spectra. These features are accurately reproduced by the BOMD computations.

Optimization of iron oxide nanoparticles for MRI-guided magnetic hyperthermia tumor therapy: reassessing the role of shape in their magnetocaloric effect.

Superparamagnetic iron oxide nanoparticles have hogged the limelight in different fields of nanotechnology. Surprisingly, notwithstanding the prominent role played as agents in magnetic hyperthermia treatments, the effects of nanoparticle size and shape on the magnetic hyperthermia performance have not been entirely elucidated yet. Here, spherical or cubical magnetic nanoparticles synthesized by a thermal decomposition method with the same magnetic and hyperthermia properties are evaluated. Interestingly, spherical nanoparticles displayed significantly higher magnetic relaxivity than cubic nanoparticles; however, comparable differences were not observed in specific absorption rate (SAR), pointing out the need for additional research to better understand the connection between these two parameters. Additionally, the as-synthetized spherical nanoparticles showed negligible cytotoxicity and, therefore, were tested in vivo in tumor-bearing mice. Following intratumoral administration of these spherical nanoparticles and a single exposure to alternating magnetic fields (AMF) closely mimicking clinical conditions, a significant delay in tumor growth was observed. Although further in vivo experiments are warranted to optimize the magnetic hyperthermia conditions, our findings support the great potential of these nanoparticles as magnetic hyperthermia mediators for tumor therapy.

The Influence of Cultural Snapshots on Pre-service Teachers' Attitudes Towards Death Education.

Cultural snapshots may be a didactic resource that promotes the understanding of death and provides teachers with tools that can be used to work with students. This study aims to analyse pre-service teachers' attitudes towards death education. A quantitative longitudinal panel design with pre-test and post-test measures was applied, with descriptive, inferential, and predictive approaches. The sample consisted of 161 pre-service primary teachers from a Spanish university who responded to the validated questionnaire "Death Education Attitudes Scale-Teachers" (DEAS-T). The results reveal an improvement in their attitudes towards death education after implementing cultural snapshots in class, producing significant differences between the pre-test and post-test according to gender, in favour of the male participants. The variables of death anxiety and adequate training are relevant for predicting the attitudes of both genders, in addition to the motivation variable in male participants and the variable of interest towards the topic in female participants.

Digital competence of teachers in the use of ICT for research work: development of an instrument from a PLS-SEM approach.

All spheres of our life are being affected using technology, particularly its integration in the research processes carried out by teachers. The success of the integration of specific digital resources in research work can be affected by several factors, such as: digital skills for finding information, managing it, analyzing it, and communicating results; digital flow; anxiety in the use of ICT; digital ethics; quality of digital resources; and finally, the behavioral intention to integrate ICT. The purpose of this study is to examine the factors that influence the integration of ICT in the research process of the Higher Education teacher, and the relation between them. An online survey was used to collect data, and 1740 participants. This study used a causal model through partial least squares structural equations modeling (PLS-SEM). With this, the hypotheses established between the integration of ICT and its possible incident factors were verified. The findings revealed a significant influence path from factor integration to digital skills, ethics, flow digital, and behavior intention. Although, resource quality and ICT anxiety had significant effects on the causal model, they did not have a large impact on teachers' integration of digital resources. The total of these factors corresponded to 48.20% of the variance in the integration of the researcher of the specific digital resources to be used in the research process. These results confirm that this model is effective in explaining the technological integration of teachers to use ICT in research work.

Hot Brownian Motion of Thermoresponsive Microgels in Optical Tweezers Shows Discontinuous Volume Phase Transition and Bistability.

Microgels are soft microparticles that often exhibit thermoresponsiveness and feature a transformation at a critical temperature, referred to as the volume phase transition temperature. Whether this transformation occurs as a smooth or as a discontinuous one is still a matter of debate. This question can be addressed by studying individual microgels trapped in optical tweezers. For this aim, composite particles are obtained by decorating  Poly-N-isopropylacrylamide (pNIPAM) microgels with iron oxide nanocubes. These composites become self-heating when illuminated by the infrared trapping laser, performing hot Brownian motion within the trap. Above a certain laser power, a single decorated microgel features a volume phase transition that is discontinuous, while the usual continuous sigmoidal-like dependence is recovered after averaging over different microgels. The collective sigmoidal behavior enables the application of a power-to-temperature calibration and provides the effective drag coefficient of the self-heating microgels, thus establishing these composite particles as potential micro-thermometers and micro-heaters. Moreover, the self-heating microgels also exhibit an unexpected and intriguing bistability behavior above the critical temperature, probably due to partial collapses of the microgel. These results set the stage for further studies and the development of applications based on the hot Brownian motion of soft particles.

Field-Pulse-Induced Annealing of 2D Colloidal Polycrystals.

Two-dimensional colloidal crystals are of considerable fundamental and practical importance. However, their quality is often low due to the widespread presence of domain walls and defects. In this work, we explored the annealing process undergone by monolayers of superparamagnetic colloids adsorbed onto fluid interfaces in the presence of magnetic field pulses. These systems present the extraordinary peculiarity that both the extent and the character of interparticle interactions can be adjusted at will by simply varying the strength and orientation of the applied field so that the application of field pulses results in a sudden input of energy. Specifically, we have studied the effect of polycrystal size, pulse duration, slope and frequency on the efficiency of the annealing process and found that (i) this strategy is only effective when the polycrystal consists of less than approximately 10 domains; (ii) that the pulse duration should be of the order of magnitude of the time required for the outer particles to travel one diameter during the heating step; (iii) that the quality of larger polycrystals can be slightly improved by applying tilted pulses. The experimental results were corroborated by Brownian dynamics simulations.

A Dynamic Proton Bond: MH+·H2O ⇌ M·H3O+ Interconversion in Loosely Coordinated Environments.

The interaction of organic molecules with oxonium cations within their solvation shell may lead to the emergence of dynamic supramolecular structures with recurrently changing host-guest chemical identity. We illustrate this phenomenon in benchmark proton-bonded complexes of water with polyether macrocyles. Despite the smaller proton affinity of water versus the ether group, water in fact retains the proton in the form of H3O+, with increasing stability as the coordination number increases. Hindrance in many-fold coordination induces dynamic reversible (ether)·H3O+ ⇌ (etherH+)·H2O interconversion. We perform infrared action ion spectroscopy over a broad spectral range to expose the vibrational signatures of the loose proton bonding in these systems. Remarkably, characteristic bands for the two limiting proton bonding configurations are observed in the experimental vibrational spectra, superimposed onto diffuse bands associated with proton delocalization. These features cannot be described by static equilibrium structures but are accurately modeled within the framework of ab initio molecular dynamics.

Identifying predictors of digital competence of educators and their impact on online guidance.

In the current socio-health situation, new educational challenges have emerged, such as the need to implement a virtual tutorial action. Therefore, this study has three objectives: (1) to investigate the level of digital competence that early childhood and primary school teachers possess to carry out quality online tutorial actions; (2) to analyse whether there are differences in use at both education stages; and (3) to identify which variables significantly affect the development of this competence at each educational stage. For this purpose, an ex post facto design was used, based on the survey technique, by means of non-probabilistic purposive sampling. The final sample consisted of a total of 1,069 educators working at the early childhood and primary education stages, from all over Spain. The results showed acceptable digital competence, with higher scores in the primary education stage, which may be due to characteristics of the students and the education stage itself, rather than to teachers' digital competences. On the other hand, it was found that the virtual tutorial action tasks are significantly influenced in the early childhood education stage by blogs, WhatsApp, Facebook, and number of tutoring hours per month with families, while for the primary stage they are influenced by blogs, WhatsApp, Twitter, ClassDojo, Moodle, tutoring hours, number of tutoring hours per month with families, and sex. Based on these results, there is an obvious need for educational institutions to continue to develop teacher training in relation to the use of resources to carry out adequate tutoring actions and thus increase the diversification in the use of resources.

Iron-Gold Nanoflowers: A Promising Tool for Multimodal Imaging and Hyperthermia Therapy.

The development of nanoplatforms prepared to perform both multimodal imaging and combined therapies in a single entity is a fast-growing field. These systems are able to improve diagnostic accuracy and therapy success. Multicomponent Nanoparticles (MCNPs), composed of iron oxide and gold, offer new opportunities for Magnetic Resonance Imaging (MRI) and Computed Tomography (CT) diagnosis, as well as combined therapies based on Magnetic Hyperthermia (MH) and Photothermal Therapy (PT). In this work, we describe a new seed-assisted method for the synthesis of Au@Fe Nanoparticles (NPs) with a flower-like structure. For biomedical purposes, Au@Fe NPs were functionalized with a PEGylated ligand, leading to high colloidal stability. Moreover, the as-obtained Au@Fe-PEG NPs exhibited excellent features as both MRI and CT Contrast Agents (CAs), with high r2 relaxivity (60.5 mM-1⋅s-1) and X-ray attenuation properties (8.8 HU mM-1⋅HU). In addition, these nanoflowers presented considerable energy-to-heat conversion under both Alternating Magnetic Fields (AMFs) (∆T ≈ 2.5 °C) and Near-Infrared (NIR) light (∆T ≈ 17 °C). Finally, Au@Fe-PEG NPs exhibited very low cytotoxicity, confirming their potential for theranostics applications.

Inclusion complexes of the macrocycle nonactin with benchmark protonated amines: aniline and serine.

The biological activity of the macrocycle nonactin is intimately related to its ionophore properties and ability to act as a selective cation carrier. While the focus of most investigations on nonactin has been on the binding of metal cations and small molecular ions, this study pursues the characterization of its inclusion complexes with primary amines with bulky structured side groups of different polarity. To this end, the complexes of nonactin with aniline and with the amino acid L-serine, both in protonated form, are considered as case studies and their relevant coordination arrangements are assessed by means of infrared action spectroscopy, quantum chemical density functional theory and Born-Oppenheimer molecular dynamics. The study suggests that the oxygen atoms from the oxolane (tetrahydrofuran) groups of nonactin constitute the preferential docking sites of the ammonium moiety of the guest cation, although conformational constraints promote interactions with the ester carbonyl backbone groups. In the aniline complex, the benzyl side ring is oriented outwards from the cavity, whereas in the case of L-serine, the side carboxylic acid and alcohol groups participate actively in the coordination process. Interestingly, the accommodation of L-serine is favoured when nonactin adopts an enantiomeric-selective folding, that promotes the tripodal coordination of the protonated amine group with oxolane rings from three nonactinic acid blocks with enantiomeric sequence (+)-(-)-(+), which allows for a facile coordination of the serine side groups. This is recognized as a general feature associated with the alternation of chiral domains in globally achiral natural nonactin, yielding mirror-symmetric complexes with the enantiomers of chiral amines.

Proton in the ring: spectroscopy and dynamics of proton bonding in macrocycle cavities.

The proton bond is a paradigmatic quantum molecular interaction and a major driving force of supramolecular chemistry. The ring cavities of crown ethers provide an intriguing environment, promoting competitive proton sharing with multiple coordination anchors. This study shows that protons confined in crown ether cavities form dynamic bonds that migrate to varying pairs of coordinating atoms when allowed by the flexibility of the macrocycle backbone. Prototypic native crown ethers (12-crown-4, 15-crown-5 and 18-crown-6) and aza-crown ethers (cyclen, 1-aza-18-crown-6 and hexacyclen) are investigated. For each system, Infrared action spectroscopy experiments and ab initio Molecular Dynamics computations are employed to elucidate the structural effects associated with proton diffusion and its entanglement with the conformational and vibrational dynamics of the protonated host.

Temperature Effects on Optical Trapping Stability.

In recent years, optically trapped luminescent particles have emerged as a reliable probe for contactless thermal sensing because of the dependence of their luminescence on environmental conditions. Although the temperature effect in the optical trapping stability has not always been the object of study, the optical trapping of micro/nanoparticles above room temperature is hindered by disturbances caused by temperature increments of even a few degrees in the Brownian motion that may lead to the release of the particle from the trap. In this report, we summarize recent experimental results on thermal sensing experiments in which micro/nanoparticles are used as probes with the aim of providing the contemporary state of the art about temperature effects in the stability of potential trapping processes.

Infrared-Emitting Multimodal Nanostructures for Controlled In Vivo Magnetic Hyperthermia.

Deliberate and local increase of the temperature within solid tumors represents an effective therapeutic approach. Thermal therapies embrace this concept leveraging the capability of some species to convert the absorbed energy into heat. To that end, magnetic hyperthermia (MHT) uses magnetic nanoparticles (MNPs) that can effectively dissipate the energy absorbed under alternating magnetic fields. However, MNPs fail to provide real-time thermal feedback with the risk of unwanted overheating and impeding on-the-fly adjustment of the therapeutic parameters. Localization of MNPs within a tissue in an accurate, rapid, and cost-effective way represents another challenge for increasing the efficacy of MHT. In this work, MNPs are combined with state-of-the-art infrared luminescent nanothermometers (LNTh; Ag2 S nanoparticles) in a nanocapsule that simultaneously overcomes these limitations. The novel optomagnetic nanocapsule acts as multimodal contrast agents for different imaging techniques (magnetic resonance, photoacoustic and near-infrared fluorescence imaging, optical and X-ray computed tomography). Most crucially, these nanocapsules provide accurate (0.2 °C resolution) and real-time subcutaneous thermal feedback during in vivo MHT, also enabling the attainment of thermal maps of the area of interest. These findings are a milestone on the road toward controlled magnetothermal therapies with minimal side effects.

Fe3O4-Au Core-Shell Nanoparticles as a Multimodal Platform for In Vivo Imaging and Focused Photothermal Therapy.

In this study, we report the synthesis of gold-coated iron oxide nanoparticles capped with polyvinylpyrrolidone (Fe@Au NPs). The as-synthesized nanoparticles (NPs) exhibited good stability in aqueous media and excellent features as contrast agents (CA) for both magnetic resonance imaging (MRI) and X-ray computed tomography (CT). Additionally, due to the presence of the local surface plasmon resonances of gold, the NPs showed exploitable "light-to-heat" conversion ability in the near-infrared (NIR) region, a key attribute for effective photothermal therapies (PTT). In vitro experiments revealed biocompatibility as well as excellent efficiency in killing glioblastoma cells via PTT. The in vivo nontoxicity of the NPs was demonstrated using zebrafish embryos as an intermediate step between cells and rodent models. To warrant that an effective therapeutic dose was achieved inside the tumor, both intratumoral and intravenous routes were screened in rodent models by MRI and CT. The pharmacokinetics and biodistribution confirmed the multimodal imaging CA capabilities of the Fe@AuNPs and revealed constraints of the intravenous route for tumor targeting, dictating intratumoral administration for therapeutic applications. Finally, Fe@Au NPs were successfully used for an in vivo proof of concept of imaging-guided focused PTT against glioblastoma multiforme in a mouse model.

Digital competence of higher education professor according to DigCompEdu. Statistical research methods with ANOVA between fields of knowledge in different age ranges.

The tasks of the university educators must be linked to the digital demands posed by the more sophisticated professions of the twenty-first century. Faced with this panorama, the objective of this study is to examine and compare the degree of digital competence of Higher Education educators from different fields of knowledge and different age ranges according to the DigCompEdu framework. A non-probabilistic ex post facto sampling was utilized with 2180 university professors from Andalusia (Spain). The main results of the study provide evidence of an intermediate level of digital competence, for men and women. More specifically, the male professors in Architecture and Judicial & Social Sciences, younger and older than 40, possessed a higher level, as compared to the other fields. For the female professors, the highest level was found once again in Judicial and Social Sciences, in this case for both age ranges, without a clear trend found for the rest of the fields. For each dimension of the DigCompEdu instrument, the level of competence follows the same trend with respect to the overall level. More research is recommended to validate these preliminary results, as well as the development of training lines of action that are specific and adapted to each field of knowledge.

Multipodal coordination and mobility of molecular cations inside the macrocycle valinomycin.

The macrocycle valinomycin displays an outstanding ability in cation binding and carriage across hydrophobic environments (e.g., cell membranes) and constitutes a central landmark for the design of novel ionophores for the regulation of biochemical processes. Most previous investigations have focused on the capture of metal cations (primarily K+). Here, we address the versatility of valinomycin in the encapsulation of molecular ions of small and moderate size, with NH4+ and H4PO4+ as case studies. A combination of infrared action vibrational spectroscopy and quantum chemical computations of molecular structure and dynamics is employed with the two-fold aim of assessing the dominant H-bonding coordination networks in the complexes and of characterizing the positional and rotational freedom of the guest cations inside the cavity of the macrocycle. Valinomycin binds NH4+ with only moderate distortion of the C3 configuration adopted in the complexes with the metal cations. The ammonium cation occupies the center of the cavity and displays two low-energy coordination arrangements that are dynamically connected through a facile rotation of the cation. The inclusion of the bulkier phosphoric acid cation demands significant stretching of the valinomycin backbone. Interestingly, the H4PO4+ cation achieves ample positional and rotational mobility inside valinomycin. The valinomycin backbone is capable of adopting barrel-like configurations when the cation occupies a region close to the center of the cavity, and funnel-like configurations when it diffuses to positions close to the exit face. This can accommodate the cation in varying coordination arrangements, characterized by different H-bonding between the four POH arms and the ester carbonyl groups of the macrocycle.

Methodological Analysis of the Effect of an Anti-Bullying Programme in Secondary Education through Communicative Competence: A Pre-Test-Post-Test Study with a Control-Experimental Group.

The promotion of communicative competence in students play a key role in schools for the purpose of improving social, emotional and coexistence relationships in Secondary Education students. The development of said competence can represent a great strategy to improve conflicts in the classroom, notably bullying. We used a quasi-experimental pre-test and post-test control group design with a sample of 55 students from the city of Salamanca (Spain) to analyse the level of conflict and their perceptions about bullying during the 2017-2018 academic year. The anti-bullying programme called the Improvement of Coexistence and Communicative Competence (ICCC) programme used is. The behaviour of students based on their level of coexistence with the group of classmates was measured by the INSEBULL instrument (Bullying Assessment Instrument), which added one more dimension of own elaboration. The results showed that, even though the significant levels of conflict, they decreased substantially once the ICCC programme was applied. Furthermore, we found differences between the control and experimental groups which underlined the effectiveness of the program. Regarding gender, no differences were found in the experimental group. This study shows that the development of communicative competence in students has a significant impact on their level of coexistence with other classmates, although the results suggested the need for longitudinal implementation of the programme in order to improve school coexistence and social skills of students from the early stages of education.

Photochemistry of Amylene Double Bond in Clusters on Free Argon Nanoparticles.

We have investigated reactivity of double bond in 2-methyl-2-butene (also trimethylethylene or amylene) in the excited and ionized states. In a combined experimental and theoretical study, we focused on both the intermolecular and intramolecular reactions. In a molecular beam experiment, we have sequentially picked up several amylene molecules on the surface of argon nanoparticles ArM, M̅ ≈ 90, acting as a cold support. Ionization with 70 eV electrons yields mass spectra strongly dominated by amylene cluster ions Am(Am)n+. Interestingly, upon multiphoton ionization with 193 nm (6.4 eV) photons, a new strong fragment series appears in the spectra, nominally corresponding to an addition of two carbon atoms, i.e., (Am)nC2+. This difference between electron and photoionization suggests a reaction in an excited state of amylene with a neighboring amylene molecule. We used techniques of nonadiabatic molecular dynamics to study the reactivity of amylene molecules both in the excited and in ionized states. Possible reaction pathways are proposed, substantiating the observed differences between the electron ionization and photoionization mass spectra.