Hybrid molecular graphene transistor as an operando and optoelectronic platform.

Lack of reproducibility hampers molecular devices integration into large-scale circuits. Thus, incorporating operando characterization can facilitate the understanding of multiple features producing disparities in different devices. In this work, we report the realization of hybrid molecular graphene field effect transistors (m-GFETs) based on 11-(Ferrocenyl)undecanethiol (FcC11SH) micro self-assembled monolayers (µSAMs) and high-quality graphene (Gr) in a back-gated configuration. On the one hand, Gr enables redox electron transfer, avoids molecular degradation and permits operando spectroscopy. On the other hand, molecular electrode decoration shifts the Gr Dirac point (VDP) to neutrality and generates a photocurrent in the Gr electron conduction regime. Benefitting from this heterogeneous response, the m-GFETs can implement optoelectronic AND/OR logic functions. Our approach represents a step forward in the field of molecular scale electronics with implications in sensing and computing based on sustainable chemicals.

Photodetecting Heterostructures from Graphene and Encapsulated Colloidal Quantum Dot Films.

Heterostructure devices consisting of graphene and colloidal quantum dots (QDs) have been remarkably successful as photodetectors and have opened the door to technological applications based on the combination of these low-dimensional materials. This work explores the photodetection properties of a heterostructure consisting of a graphene field effect transistor covered by a film of silica-encapsulated colloidal QDs. Defects at the surface of the silica shell trap optically excited charge carriers, which simultaneously enables photodetection via two mechanisms: photogating, resulting in a net p-doping of the device, and Coulombic scattering of charge carriers in the graphene, producing an overall decrease in the current magnitude.

Photoluminescence Activation of Organic Dyes via Optically Trapped Quantum Dots.

Laser tweezers afford quantum dot (QD) manipulation for use as localized emitters. Here, we demonstrate fluorescence by radiative energy transfer from optically trapped colloidal QDs (donors) to fluorescent dyes (acceptors). To this end, we synthesized silica-coated QDs of different compositions and triggered their luminescence by simultaneous trapping and two-photon excitation in a microfluidic chamber filled with dyes. This strategy produces a near-field light source with great spatial maneuverability, which can be exploited to scan nanostructures. In this regard, we demonstrate induced photoluminescence of dye-labeled cells via optically trapped silica-coated colloidal QDs placed at their vicinity. Allocating nanoscale donors at controlled distances from a cell is an attractive concept in fluorescence microscopy because it dramatically reduces the number of excited dyes, which improves resolution by preventing interferences from the whole sample, while prolonging dye luminescence lifetime due to the lower power absorbed from the QDs.

Unexpected Optical Blue Shift in Large Colloidal Quantum Dots by Anionic Migration and Exchange.

Compositional changes taking place during the synthesis of alloyed CdSeZnS nanocrystals (NCs) allow shifting of the optical features to higher energy as the NCs grow. Under certain synthetic conditions, the effect of those changes on the surface/interface chemistry competes with and dominates over the conventional quantum confinement effect in growing NCs. These changes, identified by means of complementary advanced spectroscopic techniques such as XPS (X-ray photoelectron spectroscopy) and XAS (X-ray absorption spectroscopy), are understood in the frame of an ion migration and exchange mechanism taking place during the synthesis. Control over the synthetic routes during NC growth represents an alternative tool to tune the optical properties of colloidal quantum dots, broadening the versatility of the wet chemical methods.

Large-Area Heterostructures from Graphene and Encapsulated Colloidal Quantum Dots via the Langmuir-Blodgett Method.

This work explores the assembly of large-area heterostructures comprised of a film of silica-encapsulated, semiconducting colloidal quantum dots, deposited via the Langmuir-Blodgett method, sandwiched between two graphene sheets. The luminescent, electrically insulating film served as a dielectric, with the top graphene sheet patterned into an electrode and successfully used as a top gate for an underlying graphene field-effect transistor. This heterostructure paves the way for developing novel hybrid optoelectronic devices through the integration of 2D and 0D materials.

Inorganically coated colloidal quantum dots in polar solvents using a microemulsion-assisted method.

The dielectric nature of organic ligands capping semiconductor colloidal nanocrystals (NCs) makes them incompatible with optoelectronic applications. For this reason, these ligands are regularly substituted through ligand-exchange processes by shorter (even atomic) or inorganic ones. In this work, an alternative path is proposed to obtain inorganically coated NCs. Differently to regular ligand exchange processes, the method reported here produces core-shell NCs and the removal of the original organic shell in a single step. This procedure leads to the formation of connected NCs resembling 1D worm-like networks with improved optical properties and polar solubility, in comparison with the initial CdSe NCs. The nature of the inorganic shell has been elucidated by X-ray Absorption Near Edge Structure (XANES), Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Photoelectron Spectroscopy (XPS). The 1D morphology along with the lack of long insulating organic ligands and the higher solubility in polar media turns these structures very attractive for their further integration into optoelectronic devices.

Protective ligand shells for luminescent SiO2-coated alloyed semiconductor nanocrystals.

SiO2 encapsulation of alloyed CdSeZnS nanocrystals (NCs) shows differences in terms of optical properties and luminescence quantum yield, depending on the surface composition, size, and ligand content. In this work, emphasis has been placed on the fine control required to obtain luminescent SiO2 encapsulated NCs by studying the role of oleic acid (OA), stearic acid (SA), and dodecanethiol (DDT) ligands on the alloyed NCs. While the use of anchored DDT molecules is essential to preserve the optical properties, intercalated OA and SA play a critical role for SiO2 nucleation, as stated by (1)H NMR (including DOSY and NOESY) spectroscopy. These results emphasize the importance of surface chemistry in NCs; it is crucial to control their reactivity, and therefore their impact, in different applications, from optics to biomedicine.

Cl-capped CdSe nanocrystals via in situ generation of chloride anions.

Halide ions cap and stabilize colloidal semiconductor nanocrystal (NC) surfaces allowing for NCs surface interactions that may improve the performance of NC thin film devices such as photo-detectors and/or solar cells. Current ways to introduce halide anions as ligands on surfaces of NCs produced by the hot injection method are based on post-synthetic treatments. In this work we explore the possibility to introduce Cl in the NC ligand shell in situ during the NCs synthesis. With this aim, the effect of 1,2-dichloroethane (DCE) in the synthesis of CdSe rod-like NCs produced under different Cd/Se precursor molar ratios has been studied. We report a double role of DCE depending on the Cd/Se precursor molar ratio (either under excess of cadmium or selenium precursor). According to mass spectrometry (ESI-TOF) and nuclear magnetic resonance ((1)H NMR), under excess of Se precursor (Se dissolved in trioctylphosphine, TOP) conditions at 265 °C ethane-1,2-diylbis(trioctylphosphonium)dichloride is released as a product of the reaction between DCE and TOP. According to XPS studies chlorine gets incorporated into the CdSe ligand shell, promoting re-shaping of rod-like NCs into pyramidal ones. In contrast, under excess Cd precursor (CdO) conditions, DCE reacts with the Cd complex releasing chlorine-containing non-active species which do not trigger NCs re-shaping. The amount of chlorine incorporated into the ligand shell can thus be controlled by properly tuning the Cd/Se precursor molar ratio.

Prácticas y percepción del riesgo en hombres con infección por el virus de la inmunodeficiencia humana que tienen sexo con otros hombres / Practices and perception of risk in human immunodeficiency virus infected males who have sex with other males

INTRODUCCIÓN: La incidencia de virus de la inmunodeficiencia humana (VIH) y otras enfermedades de transmisión sexual aumenta en hombres que tienen sexo con hombres (HSH) a pesar del conocimiento sobre cómo prevenirlas. Determinar los mecanismos que estarían motivando el fracaso de la prevención es importante para reconducir la tendencia. PACIENTES Y MÉTODOS: Con objeto de conocer las prácticas y conductas sexuales de riesgo así como las percepciones y valoraciones de los pacientes respecto a dicho riesgo, se realizaron encuestas anónimas, voluntarias y autoadministradas a HSH VIH+ que acudían a una consulta hospitalaria, que incluía 58 preguntas divididas en 10apartados para explorar conocimientos, actitudes y comportamientos frente al VIH. También se pasaron encuestas a médicos con objeto explorar sus percepciones, actitudes y opiniones respecto a la situación de la epidemia, prevención, percepción de la enfermedad y del paciente; y valores en la práctica clínica. RESULTADOS: Se analizaron 495encuestas a pacientes. El 87% dijeron conocer la manera de adquirir VIH y el 97% sabía cómo evitarlo, pero el 69% reconocía estar en situación de riesgo y el 43% se sentían poco preocupados de contraer VIH. El 65% tenían relaciones sexuales con ≥ 2 personas en un mismo día, el 47% encuentros por Internet y 26% sexo en grupo. El 65% de los encuestados consideraron que actuaban con impulsividad. Señalaron falta de información (33%), mala suerte (32%), riesgo excesivo asumido (36%) y despreocupación (25%) como motivos principales de la adquisición de la infección. Ante el diagnóstico, el 41% respondieron «nunca pensé que me pudiera pasar a mí» y el 32% respondieron «tuve mala suerte». De los 121 médicos encuestados, 24% consideraron que la infección por VIH/sida estaba fuera de control en España y el 65% respondieron que se tenía respecto a VIH/sida la imagen de enfermedad controlada y poco preocupante. El 71% de los encuestados juzgaron que el aumento de nuevas infecciones evidenciaba que no se tenía un plan preventivo adecuado. CONCLUSIONES: La gestión del riesgo de adquirir VIH se hace desde un grado de preocupación bajo, motivado por el optimismo fruto de los avances en la lucha contra la enfermedad y la dulcificación actual del discurso. La banalización del riesgo, al desvirtuar la idea de conducta arriesgada, es un determinante de actitudes que imposibilitarían adoptar un comportamiento preventivo eficaz y tomar decisiones prudentes y anticipadas

INTRODUCTION: The incidence of human immunodeficiency virus (HIV) and other sexually transmitted diseases increases in males who have sex with males (MSM), despite the knowledge on how to prevent them. To determine the mechanisms that are driving this lack of prevention is important to reverse the trend. PATIENTS AND METHODS: An anonymous, voluntary and self-reporting questionnaire was completed by HIV+ MSM patients who were seen in a hospital clinic, with the aim of finding out the sexual risk practices and behaviour, as well as their perceptions and assessment as regards this risk. The questionnaire included 58 questions, divided into 10sections, to explore the knowledge, attitudes, and behaviour as regards HIV. The questionnaires were also given to the physicians, with the aim of exploring their perceptions, attitudes and opinions as regards the situation of the epidemic, prevention, perception of the diseases and the patient, and values in clinical practice. RESULTS: A total of 495 questionnaires from the patients were analysed. Most of them (87%) said they knew how HIV was acquired, and 97% knew how to prevent it, but 69% knew they were in a risk situation, and 43% had little concern of contracting HIV. Almost two-thirds (65%) had sex with ≥2 persons on the same day, 47% met on the Internet and 26% had group sex. The same percentage of those surveyed considered that they acted impulsively. They highlighted a lack of information (33%), bad luck (32%), assumed excessive risk (36%), and lake of concern (25%), as the main reasons for acquiring the infection. When confronted with diagnosis 41% of patients answered «I never thought that it would happen to me», and 32% said «I had bad luck». Of the 121 physicians who completed the questionnaire, 24% considered that infection due to HIV/AIDS was out of control in Spain, and 65% responded that there was an image that HIV/AIDS was a controlled disease and of little concern. A large majority (71%) of those surveyed, considered that the increase in new infections showed that there was no suitable preventive plan. CONCLUSIONS: The management of the risk of acquiring HIV maintains a low level of concern, due to the optimism produced by the advances in the fight against the disease and the current toning down of the discussion. The trivialisation of the risk, on distorting the idea of risky behaviour, is a determining factor of attitudes that makes it impossible to adopt effective preventive behaviour and to take sensible and anticipated decisions

[Practices and perception of risk in human immunodeficiency virus infected males who have sex with other males]. / Prácticas y percepción del riesgo en hombres con infección por el virus de la inmunodeficiencia humana que tienen sexo con otros hombres.

INTRODUCTION: The incidence of human immunodeficiency virus (HIV) and other sexually transmitted diseases increases in males who have sex with males (MSM), despite the knowledge on how to prevent them. To determine the mechanisms that are driving this lack of prevention is important to reverse the trend. PATIENTS AND METHODS: An anonymous, voluntary and self-reporting questionnaire was completed by HIV+ MSM patients who were seen in a hospital clinic, with the aim of finding out the sexual risk practices and behaviour, as well as their perceptions and assessment as regards this risk. The questionnaire included 58questions, divided into 10sections, to explore the knowledge, attitudes, and behaviour as regards HIV. The questionnaires were also given to the physicians, with the aim of exploring their perceptions, attitudes and opinions as regards the situation of the epidemic, prevention, perception of the diseases and the patient, and values in clinical practice. RESULTS: A total of 495 questionnaires from the patients were analysed. Most of them (87%) said they knew how HIV was acquired, and 97% knew how to prevent it, but 69% knew they were in a risk situation, and 43% had little concern of contracting HIV. Almost two-thirds (65%) had sex with ≥2persons on the same day, 47% met on the Internet and 26% had group sex. The same percentage of those surveyed considered that they acted impulsively. They highlighted a lack of information (33%), bad luck (32%), assumed excessive risk (36%), and lake of concern (25%), as the main reasons for acquiring the infection. When confronted with diagnosis 41% of patients answered «I never thought that it would happen to me¼, and 32% said «I had bad luck¼. Of the 121 physicians who completed the questionnaire, 24% considered that infection due to HIV/AIDS was out of control in Spain, and 65% responded that there was an image that HIV/AIDS was a controlled disease and of little concern. A large majority (71%) of those surveyed, considered that the increase in new infections showed that there was no suitable preventive plan. CONCLUSIONS: The management of the risk of acquiring HIV maintains a low level of concern, due to the optimism produced by the advances in the fight against the disease and the current toning down of the discussion. The trivialisation of the risk, on distorting the idea of risky behaviour, is a determining factor of attitudes that makes it impossible to adopt effective preventive behaviour and to take sensible and anticipated decisions.