MagnetoPlasmonic Waves/HOMO-LUMO Free π-Electron Transitions Coupling in Organic Macrocycles and Their Effect in Sensing Applications

Optical and magneto-optical surface plasmon resonance (MOSPR) characterization and preliminary sensing test onto single- and multi-layers of two organic macrocycles have been performed; TbPc2(OC11H21)8 phthalocyanine and CoCoPo2 porphyrin were deposited by the Langmuir-Schäfer (LS) technique onto proper Au/Co/Au magneto-optical transducers. Investigations of the MOSPR properties in Kretschmann configuration by angular modulation, gives us an indication about the potential discrimination of two organic macrocycles with absorption electronic transition in and out of the propagating plasmon energy spectral range. An improved molecular vapors sensitivity increase by the MOSPR sensing probe can be demonstrated depending on the overlap between the plasmonic probe energy and the absorption electronic transitions of the macrocycles under investigation. If the interaction between the plasmon energy and molecular HOMO-LUMO transition is preserved, a variation in the complex refractive index takes place. Under this condition, the magneto-plasmonic effect reported as 1/|MOSPR| signal allows us to increase the detection of molecules deposited onto the plasmonic transducer and their gas sensing capacity. The detection mechanism appears strongly enhanced if the Plasmon Wave/HOMO-LUMO transitions energy are in resonance. Under coupling conditions, a different volatile organic compounds (VOC) sensing capability has been demonstrated using n-butylamine as the trial molecule

Itch/β-arrestin2-dependent non-proteolytic ubiquitylation of SuFu controls Hedgehog signalling and medulloblastoma tumorigenesis

Suppressor of Fused (SuFu), a tumour suppressor mutated in medulloblastoma, is a central player of Hh signalling, a pathway crucial for development and deregulated in cancer. Although the control of Gli transcription factors by SuFu is critical in Hh signalling, our understanding of the mechanism regulating this key event remains limited. Here, we show that the Itch/β-arrestin2 complex binds SuFu and induces its Lys63-linked polyubiquitylation without affecting its stability. This process increases the association of SuFu with Gli3, promoting the conversion of Gli3 into a repressor, which keeps Hh signalling off. Activation of Hh signalling antagonises the Itch-dependent polyubiquitylation of SuFu. Notably, different SuFu mutations occurring in medulloblastoma patients are insensitive to Itch activity, thus leading to deregulated Hh signalling and enhancing medulloblastoma cell growth. Our findings uncover mechanisms controlling the tumour suppressive functions of SuFu and reveal that their alterations are implicated in medulloblastoma tumorigenesis

Itch/β-arrestin2-dependent non-proteolytic ubiquitylation of SuFu controls Hedgehog signalling and medulloblastoma tumorigenesis

Suppressor of Fused (SuFu), a tumour suppressor mutated in medulloblastoma, is a central player of Hh signalling, a pathway crucial for development and deregulated in cancer. Although the control of Gli transcription factors by SuFu is critical in Hh signalling, our understanding of the mechanism regulating this key event remains limited. Here, we show that the Itch/β-arrestin2 complex binds SuFu and induces its Lys63-linked polyubiquitylation without affecting its stability. This process increases the association of SuFu with Gli3, promoting the conversion of Gli3 into a repressor, which keeps Hh signalling off. Activation of Hh signalling antagonises the Itch-dependent polyubiquitylation of SuFu. Notably, different SuFu mutations occurring in medulloblastoma patients are insensitive to Itch activity, thus leading to deregulated Hh signalling and enhancing medulloblastoma cell growth. Our findings uncover mechanisms controlling the tumour suppressive functions of SuFu and reveal that their alterations are implicated in medulloblastoma tumorigenesis

Detección de sesgos en razón del género en decisiones judiciales utilizando PLN

Desde hace algunos años se ha instalado con fuerza la preocupación por la adopción de perspectivas de género en los operadores del Poder Judicial. Los estereotipos de género se refieren a la construcción social y cultural de hombres y mujeres, en razón de sus diferentes funciones físicas, biológicas, sexuales y sociales. Se han realizado algunos estudios que analizan de qué manera los estereotipos inciden en el razonamiento judicial. En este trabajo, a partir de un proyecto de investigación interdisciplinar, se propone utilizar técnicas de PLN para detectar estos estereotipos en decisiones judiciales de manera semi-automática. El objetivo es asistir a la revisión y análisis de resoluciones con el fin de detectar situaciones y razonamientos que evidencien discriminación en razón del género. Los resultados preliminares obtenidos hasta el momento han permitido identificar conjuntos de frases asociadas típicamente a los diferentes estereotipos.Sociedad Argentina de Informática e Investigación Operativ

Tunable Nanoplasmonic Transducers: Performance Analysis and Potential Application

Plasmonic nanostructures with tunable optical properties can have many different applications, including high-sensitivity optical sensing for biological and chemical analyses in different field such as medical, environmental and food safety. The realization of an optimized sensing platform is closely related to the ability to finely control optical properties of nanostructures, which are, in turn, intimately linked to their geometrical and compositional characteristics. In this paper, an efficient and reproducible fabrication protocol, based on nanosphere lithography, for the realization of metal nanostructures with tunable plasmonic features is presented. In particular, the relationships between the geometric characteristics of different types of nanostructures with related optical phenomena such as enhanced absorption or extraordinary transmission are investigated in detail. These properties, together with electric field enhancement and confinement, are characterized and optimized in view of the employment of the fabricated nanostructures as optical transducers in nanoplasmonic chemosensor platforms working in the UV-VIS spectral range

Peroxides and Bisphenols Detection in Extra Virgin Olive Oil (EVOO) by Plasmonic Nanodomes Transducers

Large-area nanostructured transducer for absorption opto-plasmonic measurements in the ultraviolet visible UV-VIS spectral range have been realized by colloidal lithography. The design and simulation performed guarantee the optical behaviour of the nanostructured transducers. Morphological characterization by AFM microscopy evidences the nanodome structure of the object realized in array configuration. A microfluidic device was optimized to perform measurements in real time. Qualitative evaluation of the peroxides’ and bisphenols’ concentration in extra virgin olive oil (EVOO) have been obtained by following the variation in the plasmonic resonance monitoring of a suitable array nanodome structure deposited onto a glass substrate. Comparison of the obtained results with laboratory-standard methodologies gives us guaranteed support of the potential of the realized technology

Shape Modulation of Plasmonic Nanostructures by Unconventional Lithographic Technique

Conventional nano-sphere lithography techniques have been extended to the fabrication of highly periodic arrays of sub-wavelength nanoholes in a thin metal film. By combining the dry etching processes of self-assembled monolayers of polystyrene colloids with metal physical deposition, the complete transition from increasing size triangular nanoprism to hexagonally distributed nanoholes array onto thin metal film has been gradually explored. The investigated nano-structured materials exhibit interesting plasmonic properties which can be precisely modulated in a desired optical spectral region. An interesting approach based on optical absorbance measurements has been adopted for rapid and non-invasive inspections of the nano-sphere monolayer after the ion etching process. By enabling an indirect and accurate evaluation of colloid dimensions in a large area, this approach allows the low-cost and reproducible fabrication of plasmonic materials with specifically modulated optical properties suitable for many application in biosensing devices or Raman enhanced effects

Self-Assembled Metal Nanohole Arrays with Tunable Plasmonic Properties for SERS Single-Molecule Detection

Arrays of metal nano-holes have proved to be among of the most promising structures for applications in the field of nano-photonics and optoelectronics. Supporting both localized and propagating surface plasmons resonances, they are characterized by very high versatility thanks to the tunability of these modes, by means of the change of their periodicity, the size of the holes and metal composition. The interaction between different optical features can be exploited to modulate electromagnetic field distribution leading various hot-spots excitations on the metal surfaces. In this work, long range ordered arrays of nano-holes in thin gold films, with different geometrical characteristics, were fabricated by a modified nano-sphere lithography protocol, which allows precise control on holes’ dimensions together with the preservation of the order and of the pristine periodicity of the array. An in-depth analysis of the correlation between surface plasmon modes interference and its effect on electromagnetic field distribution is proposed, both by numerical simulations and experimentally. Finally, metal nano-holes arrays are exploited for surface enhanced Raman experiments, evaluating and comparing their performances by the estimation of the enhancement factor. Values close to the single molecule detection are obtained for most of the samples, proving their potentialities in surface enhanced spectroscopy applications

Long- and Short-Range Ordered Gold Nanoholes as Large-Area Optical Transducers in Sensing Applications

Unconventional lithography (such as nanosphere lithography (NSL) and colloidal lithography (CL)) is an attractive alternative to sequential and very expensive conventional lithography for the low-cost fabrication of large-area nano-optical devices. Among these, nanohole (NH) arrays are widely studied in nanoplasmonics as transducers for sensing applications. In this work, both NSL and CL are implemented to fabricate two-dimensional distributions of gold NHs. In the case of NSL, highly ordered arrays of gold NHs distributed in a hexagonal lattice onto glass substrates were fabricated by a simple and reproducible approach based on the self-assembling of close-packed 500 nm diameter polystyrene particles at an air/water interface. After the transfer onto a solid substrate, the colloidal masks were processed to reduce the colloidal size in a controllable way. In parallel, CL was implemented with short-range ordered gold NH arrays onto glass substrates that were fabricated by electrostatically-driven self-assembly of negatively charged colloids onto a polydiallyldimethylammonium (PDDA) monolayer. These distributions were optimized as a function of the colloidal adsorption time. For both approaches, controllable and reproducible procedures are presented and discussed. The optical responses of the NH structures are related to the short-range ordering level, and their good performances as refractive index transducers are demonstrated

The RIG-I agonist M8 triggers cell death and natural killer cell activation in human papillomavirus-associated cancer and potentiates cisplatin cytotoxicity

: Although the activation of innate immunity to treat a wide variety of cancers is gaining increasing attention, it has been poorly investigated in human papillomavirus (HPV)-associated malignancies. Because these tumors harbor a severely impaired cGAS-STING axis, but they still retain a largely functional RIG-I pathway, another critical mediator of adaptive and innate immune responses, we asked whether RIG-I activation by the 5'ppp-RNA RIG-I agonist M8 would represent a therapeutically viable option to treat HPV+ cancers. Here, we show that M8 transfection of two cervical carcinoma-derived cell lines, CaSki and HeLa, both expressing a functional RIG-I, triggers intrinsic apoptotic cell death, which is significantly reduced in RIG-I KO cells. We also demonstrate that M8 stimulation potentiates cisplatin-mediated cell killing of HPV+ cells in a RIG-I dependent manner. This combination treatment is equally effective in reducing tumor growth in a syngeneic pre-clinical mouse model of HPV16-driven cancer, where enhanced expression of lymphocyte-recruiting chemokines and cytokines correlated with an increased number of activated natural killer (NK) cells in the tumor microenvironment. Consistent with a role of RIG-I signaling in immunogenic cell killing, stimulation of NK cells with conditioned medium from M8-transfected CaSki boosted NK cell proliferation, activation, and migration in a RIG-I-dependent tumor cell-intrinsic manner. Given the highly conserved molecular mechanisms of carcinogenesis and genomic features of HPV-driven cancers and the remarkably improved prognosis for HPV+ oropharyngeal cancer, targeting RIG-I may represent an effective immunotherapeutic strategy in this setting, favoring the development of de-escalating strategies