Optical detection and structural analysis of DNA via direct surface-enhanced Raman scattering

Un nou mètode basat en la espectroscopia Raman intensificada per superfície (SERS) és implementat en aquesta tesi per a la detecció òptica i anàlisi estructural d'àcids nucleics. Aquest mètode es basa en la utilització de partícules de plata carregades positivament, com a substrats plasmònics per a l'anàlisi d'ADN en solució per SERS. Aquesta estratègia s'ha aplicat amb èxit per a la detecció ultrasensible de mutacions puntuals en el gen K-Ras, les quals són habitualment analitzades amb objectius diagnòstics, especialment en el càncer colorectal. En paral·lel amb aquest estudi, l'impacte estructural d'aquestes partícules amb l'ADN s'analitza amb profunditat.Un nuevo método basado en la espectroscopía Raman intensificada por superficie (SERS) se implementa en esta tesis para la detección óptica y análisis estructural de ácidos nucleicos. Este método se basa en la utilización de partículas de plata cargadas positivamente, como sustratos plasmónicos para el análisis de ADN en solución por SERS. Esta estrategia se ha aplicado con éxito para la detección ultrasensible de mutaciones puntuales en el gen K-Ras, las cuales son comúnmente analizadas con objetivos diagnósticos, especialmente en el cáncer colorectal. En paralelo con este estudio, el impacto estructural de estas partículas con el ADN se analiza con profundidad.A novel approach based on surface-enhanced Raman scattering (SERS) for the label-free optical detection and structural analysis of nucleic acids is implemented in this dissertation. The method relies on the use of positively-charged silver nanoparticles as plasmonic substrates for SERS analysis of DNA in solution. This strategy is successfully applied for the sensitive detection of clinically relevant point mutations in the K-Ras gene, which are routinely screened for diagnostic purposes, especially in colorectal cancer. Along this study, the impact of the cationic nanoparticles on the structural features of the interacting DNA molecules is extensively investigated

Direct Synthesis of N,N-Disubstituted Formamides by Oxidation of Imines Using an HFIP/UHP System

The straightforward synthesis of N,N-disubstituted formamides using a combination of 1,1,1,3,3,3-hexafluoroispropanol (HFIP) and H2O2 is described. The unique features of HFIP allowed the utilization of a green oxidant such as H2O2, and the products, arising from an oxidation–rearrangement sequence, were obtained in good to high yields under smooth reaction conditions.We would like to thank the Spanish Ministerio de Economía, Industria y Competitividad (CTQ2015-66624-P and CTQ2017-88171-P), the Spanish Ministerio de Ciencia, Innovación y Universidades (PGC2018-096616-B-I00), and the University of Alicante (VIGROB-316/19, UADIF19-106) for financial support

Incidentaloma adrenal : revisión

La mayor demanda y mejor resolución de los estudios por imágenes junto con el envejecimiento progresivo de la población ha llevado al aumento en la detección de lesiones suprarrenales indeterminadas. El incidentaloma adrenal es en la actualidad uno de los dilemas diagnóstico terapéuticos más frecuentes en la endocrinología moderna, debiendo ser abordado por un equipo multidisciplinario. Conocer sus características, puede favorecer a determinar las mejores conductas ante pacientes con diagnóstico de un tumor adrenal incidental y la posibilidad de mejorar su calidad de vida.The higher demand and the better resolution of the imaging tests along with the progressive aging of the population had led to an increase of the detection of indeterminate adrenal lesions. The adrenal incidentaloma is currently one of the most common diagnostic therapeutic dilemmas in modern endocrinology, and must be treated by a multidisciplinary team. Knowing their characteristics, could improve the treatment for patients diagnosed with incidental adrenal tumor, and ensuring a better quality of life.Fil: Gisbert, Patricia. Hospital Luis Lagomaggiore (Mendoza, Argentina). Servicio de Clínica MédicaFil: Rivas, Daniela. Hospital Luis Lagomaggiore (Mendoza, Argentina). Servicio de Clínica MédicaFil: Salomón, Susana Elsa. Universidad Nacional de Cuyo. Facultad de Ciencias Médica

Temperature responsiveness of gilthead sea bream bone; an in vitro and in vivo approach

This study aimed to characterize the molecules involved in osteogenesis in seabream and establish using in vitro/in vivo approaches the responsiveness of selected key genes to temperature. The impact of a temperature drop from 23 to 13 degrees C was evaluated in juvenile fish thermally imprinted during embryogenesis. Both, in vitro/in vivo, Fib1a, appeared important in the first stages of bone formation, and Col1A1, ON and OP, in regulating matrix production and mineralization. OCN mRNA levels were up-regulated in the final larval stages when mineralization was more intense. Moreover, temperature-dependent differential gene expression was observed, with lower transcript levels in the larvae at 18 degrees C relative to those at 22 degrees C, suggesting bone formation was enhanced in the latter group. Results revealed that thermal imprinting affected the long-term regulation of osteogenesis. Specifically, juveniles under the low and low-to-high-temperature regimes had reduced levels of OCN when challenged, indicative of impaired bone development. In contrast, gene expression in fish from the high and high-to-low-temperature treatments was unchanged, suggesting imprinting may have a protective effect. Overall, the present study revealed that thermal imprinting modulates bone development in seabream larvae, and demonstrated the utility of the in vitro MSC culture as a reliable tool to investigate fish osteogenesis."Ministerio de Economia y Competitividad" (MINECO) [BES-2015-074654]; Portuguese Science Foundation (FCT) [SFRH/BPD/111512/2015, SFRH/BD/81625/2011]; MINECO, Spain [AGL2010-17324, AGL2014-57974-R]; "Generalitat de Catalunya" (XRAq); Generalitat de Catalunya [2014SGR-01371]; FCT, Portugal [CCMAR/Multi/04326/2013]; European Union [LIFECYCLE EU-FP7 222719]info:eu-repo/semantics/publishedVersio

Oxidative Coupling–Thionation of Amines Mediated by Iron-Based Imidazolium Salts for the Preparation of Thioamides

An efficient and selective multicomponent oxidative coupling, involving the use of two different amines, sodium phosphate, and elemental sulfur have been described for the preparation of thioamides, employing microwave irradiation. The use of an iron(III)-based imidazolium salt is essential as catalyst. Indeed, the iron-based catalyst is involved in the oxidative coupling of the two amines and in the subsequent C–S bond formation. The protocol is useful for a wide variety of primary benzylamines and alkylamines, as coupling partners. Thus, various electron-rich and electron-poor substituents in the aromatic rings and also fused piperidine derivatives, are suitable starting materials in this reaction. Some of the obtained products are important synthetic intermediates for natural products.This work was financially supported by the Spanish Ministry (Ministerio de Economía y Competitividad CTQ2015-66624-P) and the University of Alicante (VIGROB-285)

How ubiquitous is entanglement in quantum field theory?

It is well known that entanglement is widespread in quantum field theory, in the following sense: every Reeh-Schlieder state contains entanglement between any two spatially separated regions. This applies, in particular, to the vacuum of a non-interacting scalar theory in Minkowski spacetime. Discussions on entanglement in field theory have focused mainly on subsystems containing infinitely many degrees of freedom -- typically, the field modes that are supported within a compact region of space. In this article, we study entanglement in subsystems made of finitely many field degrees of freedom, in a free scalar theory in $D+1$-dimensional Minkowski spacetime. The focus on finitely many modes of the field is motivated by the finite capabilities of real experiments. We find that entanglement between finite-dimensional subsystems is {\em not common at all}, and that one needs to carefully select the support of modes for entanglement to show up. We also find that entanglement is increasingly sparser in higher dimensions. We conclude that entanglement in Minkowski spacetime is significantly less ubiquitous than normally thought.Comment: 25 pages, 19 figure

Is there an appropriate following up process of residents in the medical clinic field during their training?

Objetivos: Caracterizar el proceso de enseñanza, aprendizaje, evaluación y acompañamiento de los Residentes (R) en las Residencias (Re) de Clínica Médica (CM); comparar Re estatales (ReE) vs privadas (ReP) de Mendoza. Material y métodos: Estudio protocolizado, descriptivo y comparativo. Encuesta validada, autoadministrada y anónima a residentes (R) y jefe de residentes (JR) de CM de ReE y ReP. Incluyó datos sociodemográficos, formación y actividad académica, investigación y conformidad R con institución (In). Análisis estadístico: medidas de tendencia central, medidas de dispersión, test exacto de Fisher, ANOVA. Resultados: Encuestas 86. Mujeres 69%, edad 28 ±3.4, R1 39%, R2 21%, R3 19%, R4 16% y JR 6%. Comité de docencia e investigación (CODEI) 84%. Instructor residentes (IR) 95% y JR 87%. Consulta a médico clínico (MC) en guardia (G): no presencial 60.5%, presencial 26%, sin posibilidad 14%. Máximo responsable G R superior 73.5%. Comparten la G 4 R 51%. Atención pacientes ambulatorios solos y sin supervisión 64.5%. Decisiones asistenciales supervisadas por MP en CE poco frecuente 41% e internación siempre 53%. Investigación: publicación en revistas científica (PRC) 63%, presentación oral (PO) en jornadas y congresos 96.5%. Evaluación: fin rotación evaluación teórica (ET) 89% y práctica (EP) 51%, anual ET 96% y EP 70%, final Re ET 82% y EP 60%; no son evaluados 4%. Tienen programa 92%, lo conocen parcialmente 52%, se cumple satisfactoria-mente 48%. Recorridos de sala y clases teóricas diarias 93%, ateneo (At) semanal 73%, reuniones de mortalidad (RM) nunca 72%, bibliográfica semanal (BS) 63%, auditora de internación 56%, At de errores médicos nunca 47%. El 26% participa de cursos de formación continua. Evaluación Re: compromiso y dedicación MP con formación, conformes 44%, compromiso de In, conformes 52%, formación académica y capacitación conformes 50%. Análisis comparativo: ReP vs ReE: R/guardia 1.6 ±1.1 vs 3.4 ±1.1 p<0.001. Investigación: PRC 30% vs 68.5% p=0.03, PO 90% vs 97% (pNS), PI 60% vs 95% p=0.005. CODEI 80% vs 99% p=0.03, IR 70% vs 99% p=0.004, JR% 40% vs 93% p<0.001. Evaluación: Lista de procedimiento realizados (LRP) 67% vs 83% (pNS). Máximo responsable G: R superior 40% vs 75% p=0.03. BS 30% vs 67% p=0.03, RM, epicrisis y At semanal pNS. Compromiso MP en la formación conforme 80% vs 39% p=0.01. Compromiso In conforme 40% vs 53% (pNS). Conclusiones: las decisiones asistenciales en la internación son supervisadas por MP en la mitad de los casos, menos frecuente en CE. 1 de cada 3 R atiende solo y sin supervisión y solo 1 de cada 5 puede consultar. Más de la mitad han realizado publicaciones científicas. Se realizan actividades académicas en un alto porcentaje, pero el 72% no reflexiona respecto a la mortalidad de sus pacientes. La mitad nunca ha hecho un ateneo de errores médicos. Las ReP investigan menos, tienen menos CODEI y menos presencia de JR e IR. En las ReE hay menor compromiso de los MP. A pesar de esto un alto porcentaje está muy conforme con la formación académica.Objectives: to characterise the teaching and learning process, assessment, and following up process of residents (R) at residences (Re) in the field of medical clinic (MC); to compare public (PRe) vs Private ones (PriRe) in Mendoza. Materials and methods: Protocol, descriptive and comparative study. Validated, self-administrated and anonymous survey to residents and chief resident (CR) of MC in Pre and PriRe. It included socio-demographic data, training and academic activity, research and R accordance with the institution. Statistics analysis: measures of central tendency and dispersion, Fisher’s exact test and variance ANOVA test. Results: 86 Surveys. Women 69%, aged 28 ±3.4, R1 39%, R2 21%, R3 19%, R4 16% y JR 6%. Teaching and Research Committee (CODEI) 84%. Resident Instructor (IR) 95% and JR 87%. Clinician consultation (MC) on call (G): no present 60.5%, present 26%, without possibility 14%. Superior maximum responsible G R 73.5%. on-call shared G 4 R 51%. Outpatient care along and without supervision 64.5%. Caring decisions supervised by MP at CE infrequent 41% and admission 53%. Research: scientific publication journal (PRC) 63%, oral presentation (PO) at seminars and conferences 96.5%. Assessment: end-rotation theoretical examination (ET) 89% and practice (EP) 51%, annual ET 96% and EP 70%, final Re ET 82% and EP 60%; there are no evaluated 4%. Having program 92%, the program is partially known 52%, the program is satisfactory fulfilled 48%. Rounds and theorical classes on a daily basis 93%, weekly Ateneo (At) 73%, meetings about mortality (RM) never 72%, weekly bibliographic (BS) 63%, auditor of admission 56%, At of medical mistakes never 47%. 26% participates of continuous training seminars and courses. Evaluation Re: MP commitment and dedication with training, satisfied 44%, In commitment, satisfied 52%, academic training satisfied 50%. Comparative analysis: ReP vs ReE: R/on call 1.6 ±1.1 vs 3.4 ±1.1 p<0.001. Research: PRC 30% vs 68.5% p=0.03, PO 90% vs 97% (pNS), PI 60% vs 95% p=0.005. CODEI 80% vs 99% p=0.03, IR 70% vs 99% p=0.004, JR% 40% vs 93% p<0.001. Assessment: List of procedures made (LRP) 67% vs 83% (pNS). Maximum responsible G: R superior 40% vs 75% p=0.03. BS 30% vs 67% p=0.03, RM, epicrisis y At pNS weekly. MP commitment in the training, satisfied 80% vs 39% p=0.01. In commitment satisfied 40% vs 53% (pNS). Conclusion: Decisions on assistance in admission are supervised by MP in half the cases, this is less frequent at CE. 1 in 3 R sees patients alone and without supervision and only 1 in 5 can consult. More than half of them have made scientific publications. Although academic activities are made in a high percentage, 72% don’t reflect upon the mortality of their patients. Half of them have never made an Ateneo on medical mistakes. ReP do less research, they have less CODEI and less presence of JR and IR. At ReE there are less MP compromise. Despite this, a high percentage is very satisfied with academic training.Fil: Gasull, Andrea. Universidad Nacional de Cuyo. Facultad de Ciencias MédicasFil: Hoffman, María Paula. Hospital Luis Lagomaggiore (Mendoza, Argentina). Servicio de Clínica MédicaFil: Fernandez, Matías . Hospital Luis Lagomaggiore (Mendoza, Argentina). Servicio de Clínica MédicaFil: Lascano, Soledad. Hospital Luis Lagomaggiore (Mendoza, Argentina). Servicio de Clínica MédicaFil: Gisbert, Patricia. Universidad Nacional de Cuyo. Facultad de Ciencias MédicasFil: Salomón, Susana. Universidad Nacional de Cuyo. Facultad de Ciencias Médica

Cómo se muere en un servicio de medicina interna

Introducción: La muerte es un hecho biológico, con trascendencia social y cultural, que la hace particular. Conocer cómo se desarrolla es vital para entenderla y aceptarla. Objetivos: Determinar en pacientes fallecidos durante la internación las características de cómo se muere en un servicio de clínica médica: circunstancias, comorbilidad, causas de muerte, sensaciones de la familia y del equipo de salud.Introduction: Death is a biological fact, with social and cultural trascendence, which makes it particular. To know how it develops is vital to understand it and accept it. Objectives: To determine death evolution characteristics in patients who died during hospital stay in an internal medicine service: circumstances, comorbidity, death cause, family and health team‘s feelings.Fil: Rivas, Mirta Daniela. Hospital Luis Lagomaggiore (Mendoza, Argentina). Servicio de Clínica MédicaFil: Saravia, Ana. Hospital Luis Lagomaggiore (Mendoza, Argentina). Servicio de Clínica MédicaFil: Santolín, María Laura. Hospital Luis Lagomaggiore (Mendoza, Argentina). Servicio de Clínica MédicaFil: Gisbert, Patricia. Hospital Luis Lagomaggiore (Mendoza, Argentina). Servicio de Clínica MédicaFil: Salomón, Susana Elsa. Universidad Nacional de Cuyo. Facultad de Ciencias MédicasFil: Carena, José Alberto. Universidad Nacional de Cuyo. Facultad de Ciencias Médica

Comparative Study of Catalytic Systems Formed by Palladium and Acyl-Substituted Imidazolium Salts

Amino amides, which are readily accessible from amino acids, were used in the preparation of both monoamido and diamido functionalized imidazolium salts in very straightforward protocols. Different catalytic systems formed with palladium(II) acetate and acyl functionalized imidazolium salts were tested in the Matsuda-Heck reaction. The comparative study revealed that the presence of one carbamoyl moiety in the N-heterocyclic carbene precursor is more beneficial during the catalytic process. Thus, better activity was observed with the catalytic system formed using 3-benzyl-1-(N-phenylcarbamoylmethyl)imidazolium chloride in a 1:1 metal/ligand ratio. Moreover, this fact was evidenced by means of UV/vis studies.The Spanish Ministry (Ministerio de Economía y Competitividad CTQ2015-66624-P) and the University of Alicante (VIGROB-285) are gratefully acknowledged for financial support