Sistemas híbridos basados en grafeno y MoS2-2D para detección óptica

Tesis Doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Física de Materiales. Fecha de Lectura: 02-12-202

Raman and Fluorescence Enhancement Approaches in Graphene-Based Platforms for Optical Sensing and Imaging

This article belongs to the Special Issue Physics and Chemistry of Graphene: From Fundamentals to Applications.The search for novel platforms and metamaterials for the enhancement of optical and particularly Raman signals is still an objective since optical techniques offer affordable, noninvasive methods with high spatial resolution and penetration depth adequate to detect and image a large variety of systems, from 2D materials to molecules in complex media and tissues. Definitely, plasmonic materials produce the most efficient enhancement through the surface-enhanced Raman scattering (SERS) process, allowing single-molecule detection, and are the most studied ones. Here we focus on less explored aspects of SERS such as the role of the inter-nanoparticle (NP) distance and the ultra-small NP size limit (down to a few nm) and on novel approaches involving graphene and graphene-related materials. The issues on reproducibility and homogeneity for the quantification of the probe molecules will also be discussed. Other light enhancement mechanisms, in particular resonant and interference Raman scatterings, as well as the platforms that allow combining several of them, are presented in this review with a special focus on the possibilities that graphene offers for the design and fabrication of novel architectures. Recent fluorescence enhancement platforms and strategies, so important for bio-detection and imaging, are reviewed as well as the relevance of graphene oxide and graphene/carbon nanodots in the field.The research leading to these results has received funding from Ministerio de Ciencia e Innovación (RTI2018-096918-B-C41). S.C. acknowledges the grant BES-2016-076440 from MINECO

Grain selective Cu oxidation and anomalous shift of graphene 2D Raman peak in the graphene-Cu system

Understanding the interaction between graphene and its supporting substrate is of paramount importance for the development of graphene based applications. In this work the interplay of the technologically relevant graphene-Cu system is investigated in detail as a function of substrate grain orientation in Cu polycrystalline foils. While (100) and (111) Cu grains show the well-known graphene-enhanced oxidation, (110) grains present a superior oxidation resistance compared to uncovered Cu and an anomalous shift of its graphene 2D Raman band which cannot be explained by the known effects of strain and doping. These results are interpreted in terms of a weak graphene-Cu coupling at the (110) grains, and show that graphene can actually be used as anticorrosion coating, contrary to previously reported. The anomalous shift is suggested to be the result of an enhanced outer Raman scattering process which surpasses the usually dominant inner process. Since Raman spectroscopy is widely used as first and main characterization tool of graphene, the existence of an anomalous shift on its 2D band not only challenges the current theory of Raman scattering in graphene, but also has profound implications from an experimental point of view

Raman amplification in the ultra-small limit of Ag nanoparticles on SiO2 and graphene: Size and inter-particle distance effects

Size, shape and hot spots are crucial to optimize Raman amplification from metallic nanoparticle (NPs). The amplification from radius = 1.8 ± 0.4 nm ultra-small silver NPs was explored. Increasing NP density redshifts and widens their plasmon that, according to simulations for NPs arrays, is originated by the reduction of the interparticle distance, d, becoming remarkable for d ≤ R. Inter-particle interaction red-shifts (>130 nm) and widens (>90 nm) the standard plasmon of non-interacting spherical particles. Graphene partly delocalizes the carriers enhancing the NIR spectral weight. Raman amplification of graphene phonons is moderate and depends smoothly on d while that of Rhodamine 6G (R6G) varies almost exponentially due to their location at hot-spots that depend strongly on d. The experimental correlation between amplification and plasmon position is well reproduced by simulations. The amplification originated by the ultra-small NPs is compared to that of larger particles, granular silver films with 7 < R < 15 nm grains, with similar extinction values. The amplification is found to be larger for the 1.8 nm NPs due to the higher surface/volume ration that allows higher density of hot spots. It is demonstrated that Raman amplification can be efficiently increased by depositing low density layers of ultra-small NPs on top of granular films.The research leading to these results has received funding from Ministerio de Ciencia, Innovación y Universidades (RTI2018-096918-B-C41). S.C. acknowledges the grant BES-2016-076440 from MINECO. L.M. acknowledges the European Union (grant number ERC-2013-SyG 610256 NANOCOSMOS)

Breast cancer biomarker detection through the photoluminescence of epitaxial monolayer MoS2 fakes

The following article appeared in Scientific Reports 10 (2020): 16039 and may be found at https://www.nature.com/articles/s41598-020-73029-9In this work we report on the characterization and biological functionalization of 2D MoS2 fakes, epitaxially grown on sapphire, to develop an optical biosensor for the breast cancer biomarker miRNA21. The MoS2 fakes were modifed with a thiolated DNA probe complementary to the target biomarker. Based on the photoluminescence of MoS2, the hybridization events were analyzed for the target (miRNA21c) and the control non-complementary sequence (miRNA21nc). A specifc redshift was observed for the hybridization with miRNA21c, but not for the control, demonstrating the biomarker recognition via PL. The homogeneity of these MoS2 platforms was verifed with microscopic maps. The detailed spectroscopic analysis of the spectra reveals changes in the trion to excitation ratio, being the redshift after the hybridization ascribed to both peaks. The results demonstrate the benefts of optical biosensors based on MoS2 monolayer for future commercial devicesThe research is supported by the MINECO (CTQ2017-84309-C2-2-R, CTQ2017-84309-C2-1-R, ELECTROBIONET, RED2018-102412-T) and Comunidad de Madrid (TRANSNANOAVANSENS, P2018/NMT4349) projects. ARC acknowledges Ramón y Cajal program (under contract number RYC-2015-18047

Machine Learning-Based Analysis in the Management of Iatrogenic Bile Duct Injury During Cholecystectomy: a Nationwide Multicenter Study

Background Iatrogenic bile duct injury (IBDI) is a challenging surgical complication. IBDI management can be guided by artificial intelligence models. Our study identified the factors associated with successful initial repair of IBDI and predicted the success of definitive repair based on patient risk levels. Methods This is a retrospective multi-institution cohort of patients with IBDI after cholecystectomy conducted between 1990 and 2020. We implemented a decision tree analysis to determine the factors that contribute to successful initial repair and developed a risk-scoring model based on the Comprehensive Complication Index. Results We analyzed 748 patients across 22 hospitals. Our decision tree model was 82.8% accurate in predicting the success of the initial repair. Non-type E (p < 0.01), treatment in specialized centers (p < 0.01), and surgical repair (p < 0.001) were associated with better prognosis. The risk-scoring model was 82.3% (79.0-85.3%, 95% confidence interval [CI]) and 71.7% (63.8-78.7%, 95% CI) accurate in predicting success in the development and validation cohorts, respectively. Surgical repair, successful initial repair, and repair between 2 and 6 weeks were associated with better outcomes. Discussion Machine learning algorithms for IBDI are a novel tool may help to improve the decision-making process and guide management of these patients

Size Effects in Single- and Few-Layer MoS2 Nanoflakes: Impact on Raman Phonons and Photoluminescence

The high optical absorption and emission of bidimensional MoS2 are fundamental properties for optoelectronic and biodetection applications and the opportunity to retain these properties in high quality nano-sized flakes would bring further possibilities. Here, a large set of single-layer and few-layer (2&ndash;3 layers) MoS2 flakes with size in the range from 10 nm to 20 &mu;m are obtained on sapphire by vapor deposition techniques and evaluated combining the information from the Raman phonons with photoluminescence (PL) and absorption bands. The flakes have triangular shape and are found to be progressively relaxed from the tensile strain imposed by the sapphire substrate as their size is reduced. An increasing hole doping as size decreases is deduced from the blue shift of the A1g phonon, related to charge transfer from adsorbed oxygen. No clear correlation is observed between defects density and size, therefore, doping would be favored by the preferential adsorption of oxygen at the edges of the flakes, being progressively more important as the edge/surface ratio is incremented. This hole doping also produces a shift of the PL band to higher energies, up to 60 meV. The PL intensity is not found to be correlated to the size but to the presence of defects. The trends with size for single-layer and for 2&ndash;3 layer samples are found to be similar and the synthesis method does not influence PL efficiency which remains high down to 40 nm being thus promising for nanoscale photonics

Supported Ultra-Thin Alumina Membranes with Graphene as Efficient Interference Enhanced Raman Scattering Platforms for Sensing

© 2020 by the authors.The detection of Raman signals from diluted molecules or biomaterials in complex media is still a challenge. Besides the widely studied Raman enhancement by nanoparticle plasmons, interference mechanisms provide an interesting option. A novel approach for amplification platforms based on supported thin alumina membranes was designed and fabricated to optimize the interference processes. The dielectric layer is the extremely thin alumina membrane itself and, its metallic aluminum support, the reflecting medium. A CVD (chemical vapor deposition) single-layer graphene is transferred on the membrane to serve as substrate to deposit the analyte. Experimental results and simulations of the interference processes were employed to determine the relevant parameters of the structure to optimize the Raman enhancement factor (E.F.). Highly homogeneous E.F. over the platform surface are obtained, typically 370 ± (5%), for membranes with ~100 nm pore depth, ~18 nm pore diameter and the complete elimination of the Al2O3 bottom barrier layer. The combined surface enhanced Raman scattering (SERS) and interference amplification is also demonstrated by depositing ultra-small silver nanoparticles. This new approach to amplify the Raman signal of analytes is easily obtained, low-cost and robust with useful enhancement factors (~400) and allows only interference or combined enhancement mechanisms, depending on the analyte requirements.The research leading to these results has received funding from Ministerio de Ciencia, Innovación y Universidades (RTI2018-096918-B-C41) and RTI2018-094040-B-I00) and by the Agency for Management of University and Research Grants (AGAUR) 2017-SGR-1527. S.C. acknowledges the grant BES-2016-076440 from MINECO.Peer reviewe