Precise Fingerprint Determination of Vibrational Infrared Spectra in a Series of Co(II) Clathrochelates through Experimental and Theoretical Analyses.

The energetic demands of modern society for clean energy vectors, such as H2, have caused a surge in research associated with homogeneous and immobilized electrocatalysts that may replace Pt. In particular, clathrochelates have shown excellent electrocatalytic properties for the hydrogen evolution reaction (HER). However, the actual mechanism for the HER catalyzed by these d-metal complexes remains an open debate, which may be addressed via Operando spectroelectrochemistry. The prediction of electrochemical properties via density functional theory (DFT) needs access to thermodynamic functions, which are only available after Hessian calculations. Unfortunately, there is a notable lack in the current literature regarding the precise evaluation of vibrational spectra of such complexes, given their structural complexity and the associated tangled IR spectra. In this work, we have performed a detailed theoretical and experimental analysis in a family of Co(II) clathrochelates, in order to establish univocally their IR pattern, and also the calculation methodology that is adequate for such predictions. In summary, we have observed the presence of multiple common bands shared by this clathrochelate family, using the B3LYP functional, the LANL2DZ basis, and effective core potentials (ECP) for heavy atoms. The most important issue addressed in this article was therefore related to the detailed assignment of the fingerprint associated with cobalt(II) clathrochelates, which is a challenging endeavor due to the crowded nature of their spectra.

57Fe Mössbauer and DFT study of the electronic and spatial structures of the iron(II) (pseudo)clathrochelates: the effect of ligand field strength.

Combined experimental 57Fe Mössbauer and theoretical DFT study of a series of iron(II)-centered (pseudo)macrobicyclic analogs and homologs was performed. The field strength of the corresponding (pseudo)encapsulating ligand was found to affect both the spin state of a caged iron(II) ion and the electron density at its nucleus. In a row of the iron(II) tris-dioximates, passing from the non-macrocyclic complex to its monocapped pseudomacrobicyclic analog caused an increase both in the ligand field strength and in the electron density at the Fe2+ ion, and, therefore, a decrease in the isomer shift (IS) value (so-called "semiclathrochelate effect"). Its macrobicyclization, giving the quasiaromatic cage complex, caused a further increase in the two former parameters and a decrease in IS (so-called "macrobicyclic effect"). The trend of their IS values was successfully predicted using the performed quantum-chemical calculations and the corresponding linear correlation with the electron density at their 57Fe nuclei was plotted. A variety of different functionals can be successfully used for such excellent prediction. The slope of this correlation was found to be unaffected by the used functional. In contrast, the predictions of both the sign and the values of quadrupole splitting (QS) for them, based on the theoretical calculations of EFG tensors, were found to be a real great challenge, which could not be solved at the moment even in the case of these C3-pseudosymmetric iron(II) complexes with known XRD structures. The latter experimental data allowed us to deduce a sign of the QSs for them. The straightforwarded molecular design of a (pseudo)encapsulating ligand is proposed to control both the spin state and the redox characteristics of an encapsulated metal ion.

Design of Fluorescent Carbon Dots (CDs) for the Selective detection of Metal-Containing Ions.

The pollution caused by heavy metals (HMs) may occur through both natural processes and anthropogenic activities and is found in complex media. The purpose of this review is to summarize the state-of-art of fluorescent CDs and the sensing applications in a systematic manner. This review intends to provide clues on the origin on the observed selectivity in chemiluminiscence sensors, which was until now a stated but unaddressed question, and still remains open for debate. Indeed, it is tempting to think that CDs possessing functional groups with soft bases at the surface are able to detect soft metal acids, while the opposite is to be suspected for hard acid-base pairs. However, the literature shows several examples where this trend does not hold. We found that such observation is explained by the involvement of dynamic quenching, which does not involve the formation of a non-fluorescent complex, as in the case of static quenching. We have provided an interpretation of published data that was not provided by the original authors and offer guidelines to enable the design of CDs to target ions in solution.

Generación de conocimientos y tecnologías sanitarias: nanoonions de carbono / Generation of knowledge and health technologies: carbon nano-onions

El conocimiento posee un rol importante en los nuevos desarrollos y en especial en los relacionados con las tecnologías emergentes. Este artículo tiene como objetivo generar y gestionar el conocimiento que permita dar respuesta a las necesidades de las diferentes etapas del ciclo de vida del proyecto de I+D+i: nanoonions de carbono y, en especial, de su posible utilización en el campo de la salud. Se utilizó la metodología para la generación y gestión del conocimiento y como fuente de información la contenida en los documentos de patentes. Se muestran los resultados obtenidos al procesar la información recuperada; se observa la actividad innovadora relacionada con los nanoonions de carbono y se analizan los resultados relacionados con las tecnologías sanitarias. Los conocimientos generados en la investigación han sido decisivos para definir los objetivos específicos del proyecto. En particular se concluyó que los nanoonions, por su tamaño y su estructura, tienen una gran analogía con determinados virus, por lo que pudieran emplearse como sondas para el estudio del sistema inmune. Por otro lado, se evidenció que sus propiedades fluorescentes hacen de esta nanoestructura un candidato promisorio para su empleo en diagnosticadores in vitro para una variada gama de enfermedades(AU)

Knowledge has an important role in new developments, especially in those related to emerging technologies. This article aims at generating and managing knowledge, in order to respond to the needs that appear in the different stages of the life cycle of the project of I+D+i: carbon nano-onions, and especially its possible use in the field of health. The methodology for the generation and management of knowledge was used, together with patent documents as source of information. The results obtained from processing the retrieved information are shown, the innovative activity related to the CNOs is observed, and the results related to health technologies are analyzed. The knowledge resulting from this research has been decisive to define the specific objectives of the project. In particular, it was concluded that nano-onions, for its size and structure, have great analogy with certain viruses, so they could be used as probes to study the immune system. Furthermore, it was shown that their fluorescent properties make this nano-structure a promising candidate nanostructure to be used in in vitro diagnostic kits for a variety of diseases(AU)

Generación de conocimientos y tecnologías sanitarias: nanoonions de carbono / Generation of knowledge and health technologies: carbon nano-onions / Geração de conhecimentos e tecnologias sanitárias: nanoonions de carbono

El conocimiento posee un rol importante en los nuevos desarrollos y en especial en los relacionados con las tecnologías emergentes. Este artículo tiene como objetivo generar y gestionar el conocimiento que permita dar respuesta a las necesidades de las diferentes etapas del ciclo de vida del proyecto de I+D+i: nanoonions de carbono y, en especial, de su posible utilización en el campo de la salud. Se utilizó la metodología para la generación y gestión del conocimiento y como fuente de información la contenida en los documentos de patentes. Se muestran los resultados obtenidos al procesar la información recuperada; se observa la actividad innovadora relacionada con los nanoonions de carbono y se analizan los resultados relacionados con las tecnologías sanitarias. Los conocimientos generados en la investigación han sido decisivos para definir los objetivos específicos del proyecto. En particular se concluyó que los nanoonions, por su tamaño y su estructura, tienen una gran analogía con determinados virus, por lo que pudieran emplearse como sondas para el estudio del sistema inmune. Por otro lado, se evidenció que sus propiedades fluorescentes hacen de esta nanoestructura un candidato promisorio para su empleo en diagnosticadores in vitro para una variada gama de enfermedades.

Knowledge has an important role in new developments, especially in those related to emerging technologies. This article aims at generating and managing knowledge, in order to respond to the needs that appear in the different stages of the life cycle of the project of I+D+i: carbon nano-onions, and especially its possible use in the field of health. The methodology for the generation and management of knowledge was used, together with patent documents as source of information. The results obtained from processing the retrieved information are shown, the innovative activity related to the CNOs is observed, and the results related to health technologies are analyzed. The knowledge resulting from this research has been decisive to define the specific objectives of the project. In particular, it was concluded that nano-onions, for its size and structure, have great analogy with certain viruses, so they could be used as probes to study the immune system. Furthermore, it was shown that their fluorescent properties make this nano-structure a promising candidate nanostructure to be used in in vitro diagnostic kits for a variety of diseases.

O conhecimento possui um rol importante nos novos desenvolvimentos e em especial nos relacionados com as tecnologias emergentes. Este artigo tem como objetivo gerar e gestionar o conhecimento que permita dar resposta às necessidades das diferentes etapas do ciclo de vida do projeto de I+D+i: nanoonions de carbono e, em especial, da sua possível utilização no campo da saúde. Foi utilizada a metodologia para a generação e gestão do conhecimento e como fonte de informação a conteúda nos documentos de patentes. Amostram-se os resultados obtidos ao processar a informação recuperada; observa-se a actividade inovadora relacionada com os nanoonions de carbono e são analisados os resultados relacionados com as tecnologias sanitárias. Os conhecimentos gerados na investigação têm sido decisivos para definir os objectivos específicos do projecto. Em particular foi concluído que os nanoonions, por seu tamanho e sua estructura, têm uma grande analogia com determinados vírus, pelo que poderiam empregar-se como sondas para o estudo do sistema imune. Por outro lado, foi evidenciado que suas propriedades fluorescentes fazem desta nanoestrutura um candidato promissório para seu emprego em diagnosticadores in vitro para uma variada faixa de doenças.

¿Nuevo estándar de oro en la sensibilidad de las escalas de pesado? / New gold standard in the sensitivity of weigth scale?

En el presente trabajo se resumen los rasgos generales de la tendencia del uso de nanoresonadores mecánicos basados en nanotubos de carbono en calidad de sensores de masa atómicos. Se analizan las ventajas y obstáculos que se presentan en el camino hacia su aplicación en la espectrometría de masa, y finalmente se consideran sus posibles impactos en diferentes campos de la investigación y la tecnología.

This paper summarizes the general features of the trend of using mechanical nanoresonators based on carbon nanotubes for mass spectrometry. It discusses the advantages and obstacles that stand in the way towards its application in mass spectrometry and finally was considered possible impacts in different fields of research and technology.

Desmontaje de un irradiador autoblindado de investigación del tipo MPX--25M / Methodology for the dismantling of an investigation of irradiators type selfshielded MPX--25M

RESUMEN En el trabajo se describe el desmontaje de una instalación de irradiación gamma autoblindada de categoría I, modelo MPX--25M. Los objetivos específicos son: identificar los aspectos del aseguramiento contractual, de recursos humanos y técnicos; evaluar la situación radiológica del proceso y analizar los potenciales sucesos radiológicos extraordinarios en cada uno de los pasos del proceso, garantizando las respuestas adecuadas. La evaluación de sucesos radiológicos descritos puede servir de referencia para abordar el proceso de desmontaje de otros irradiadores similares.

ABSTRACT This paper describes the dismantling of a category I selfshielded gamma irradiation facility model MPX--25M. The following specific objectives were established: a) to identify aspects of the insurance contract, human and technical resources b) to assess the radiological situation of the process and c) to analyze the potential radiological extraordinary events in each step of the process by providing the appropriate answers. The assessment of radiological events may serve as a reference for addressing the process of dismantling other similar irradiators.