Nanostructured heterogeneous catalysts for bioorthogonal reactions

Bioorthogonal chemistry has inspired a new subarea of chemistry providing a powerful tool to perform novel biocompatible chemospecific reactions in living systems. Following the premise that they do not interfere with biological functions, bioorthogonal reactions are increasingly applied in biomedical research, particularly with respect to genetic encoding systems, fluorogenic reactions for bioimaging, and cancer therapy. This Minireview compiles recent advances in the use of heterogeneous catalysts for bioorthogonal reactions. The synthetic strategies of Pd-, Au-, and Cu-based materials, their applicability in the activation of caged fluorophores and prodrugs, and the possibilities of using external stimuli to release therapeutic substances at a specific location in a diseased tissue are discussed. Finally, we highlight frontiers in the field, identifying challenges, and propose directions for future development in this emerging field.Agencia Estatal de Investigación | Ref. PID2020-113704RB-I00Xunta de Galicia | Ref. ED431C 2022/24Xunta de Galicia | Ref. ED431H 2020/08Xunta de Galicia | Ref. ED431G 2019-06Xunta de Galicia | Ref. ED481B-2019-07

Tailoring Plasmonic Bimetallic Nanocatalysts Toward Sunlight-Driven H-2 Production

Hybrid nanoparticles combining plasmonic and catalytic components have recently gained interest for their potential use in sunlight-to-chemical energy conversion. However, a deep understanding of the structure-performance that maximizes the use of the incoming energy remains elusive. Here, a suite of Au and Pd based nanostructures in core-shell and core-satellites configurations are designed and their photocatalytic activity for Hydrogen (H-2) generation under sunlight illumination is tested. Formic acid is employed as H-2 source. Core-satellite systems show a higher enhancement of the reaction upon illumination, compared to core-shell ones. Electromagnetic simulations reveal that a key difference between both configurations is the excitation of highly localized and asymmetric electric fields in the gap between both materials. In this scheme, the core Au particle acts as an antenna, efficiently capturing visible light via the excitation of localized plasmon resonances, while the surrounding Pd satellites transduce the locally-enhanced electric field into catalytic activity. These findings advance the understanding of plasmon-driven photocatalysis, and provide an important benchmark to guide the design of the next generation of plasmonic bimetallic nanostructures

The impact of physical exercise on the skeletal muscle clock genes

The most important circadian synchronizer is the central clock located in the suprachiasmatic nucleus (SCN) of the hypothalamus. The rhythmicity of all organs is achieved by molecular clock gene expression in the central clock and the pace is reached through neuronal and humoral signals to peripheral tissues. Skeletal muscle is one of the peripheral organs that express clock and clock controlled genes (CCGs) which display circadian rhythmicity. Recent studies have pointed out the role of clock genes in skeletal muscle function and metabolism. The expression of clock genes in skeletal muscle might be altered by several external stimuli and also by different diseases. Physical exercise is a nonphotic stimulus that can realign the skeletal muscle circadian system to the central clock, imposing a new rhythm at the organism level. This effect may be crucial to prevent or ameliorate diseases and disorders caused by disruptions of circadian rhythms. In this review, we discuss the role of clock genes in skeletal muscle function and the importance of physical exercise as a potent synchronizing stimulus for the skeletal muscle molecular clock

Plasmonic bimetallic two-dimensional supercrystals for H2 generation

Sunlight-driven H-2 generation is a central technology to tackle our impending carbon-based energy collapse. Colloidal photocatalysts consisting of plasmonic and catalytic nanoparticles are promising for H-2 production at solar irradiances, but their performance is hindered by absorption and multiscattering events. Here we present a two-dimensional bimetallic catalyst by incorporating platinum nanoparticles into a well-defined supercrystal of gold nanoparticles. The bimetallic supercrystal exhibited an H-2 generation rate of 139mmolg(cat)(-1)h(-1) via formic acid dehydrogenation under visible light illumination and solar irradiance. This configuration makes it possible to study the interaction between the two metallic materials and the influence of this in catalysis. We observe a correlation between the intensity of the electric field in the hotspots and the boosted catalytic activity of platinum nanoparticles, while identifying a minor role of heat and gold-to-platinum charge transfer in the enhancement. Our results demonstrate the benefits of two-dimensional configurations with optimized architecture for liquid-phase photocatalysis

A Yap-dependent mechanoregulatory program sustains cell migration for embryo axis assembly

The assembly of the embryo’s primary axis is a fundamental landmark for the establishment of the vertebrate body plan. Although the morphogenetic movements directing cell convergence towards the midline have been described extensively, little is known on how gastrulating cells interpret mechanical cues. Yap proteins are well-known transcriptional mechanotransducers, yet their role in gastrulation remains elusive. Here we show that the double knockout of yap and its paralog yap1b in medaka results in an axis assembly failure, due to reduced displacement and migratory persistence in mutant cells. Accordingly, we identified genes involved in cytoskeletal organization and cell-ECM adhesion as potentially direct Yap targets. Dynamic analysis of live sensors and downstream targets reveal that Yap is acting in migratory cells, promoting cortical actin and focal adhesions recruitment. Our results indicate that Yap coordinates a mechanoregulatory program to sustain intracellular tension and maintain the directed cell migration for embryo axis development

Impact of bimetallic interface design on heat generation in plasmonic Au/Pd nanostructures studied by single-particle thermometry

Localized surface plasmons are lossy and generate heat. However, accurate measurement of the temperature of metallic nanoparticles under illumination remains an open challenge, creating difficulties in the interpretation of results across plasmonic applications. Particularly, there is a quest for understanding the role of temperature in plasmon-assisted catalysis. Bimetallic nanoparticles combining plasmonic with catalytic metals are raising increasing interest in artificial photosynthesis and the production of solar fuels. Here, we perform single-particle thermometry measurements to investigate the link between morphology and light-to-heat conversion of colloidal Au/Pd nanoparticles with two different configurations: core–shell and core-satellite. It is observed that the inclusion of Pd as a shell strongly reduces the photothermal response in comparison to the bare cores, while the inclusion of Pd as satellites keeps photothermal properties almost unaffected. These results contribute to a better understanding of energy conversion processes in plasmon-assisted catalysis.Fil: Gargiulo, Julian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; Argentina. Universidad Nacional de San Martin. Instituto de Nanosistemas; ArgentinaFil: Herran, Matias. Ludwig Maximilians Universitat; AlemaniaFil: Violi, Ianina Lucila. Universidad Nacional de San Martin. Instituto de Nanosistemas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; ArgentinaFil: Sousa Castillo, Ana. Ludwig Maximilians Universitat; AlemaniaFil: Martínez, Luciana Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; ArgentinaFil: Ezendam, Simone. Ludwig Maximilians Universitat; AlemaniaFil: Barella, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; ArgentinaFil: Giesler, Helene. Universitat Essen; AlemaniaFil: Grzeschik, Roland. Universitat Essen; AlemaniaFil: Schlücker, Sebastian. Universitat Essen; AlemaniaFil: Maier, Stefan A.. Monash University; Australia. Imperial College London; Reino Unido. Ludwig Maximilians Universitat; AlemaniaFil: Stefani, Fernando Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; ArgentinaFil: Cortés, Emiliano. Ludwig Maximilians Universitat; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; Argentin

Mutation of vsx genes in zebrafish highlights the robustness of the retinal specification network

Genetic studies in human and mice have established a dual role for Vsx genes in retina development: an early function in progenitors' specification, and a later requirement for bipolar-cells fate determination. Despite their conserved expression patterns, it is currently unclear to which extent Vsx functions are also conserved across vertebrates, as mutant models are available only in mammals. To gain insight into vsx function in teleosts, we have generated vsx1 and vsx2 CRISPR/Cas9 double knockouts (vsxKO) in zebrafish. Our electrophysiological and histological analyses indicate severe visual impairment and bipolar cells depletion in vsxKO larvae, with retinal precursors being rerouted toward photoreceptor or Müller glia fates. Surprisingly, neural retina is properly specified and maintained in mutant embryos, which do not display microphthalmia. We show that although important cis-regulatory remodelling occurs in vsxKO retinas during early specification, this has little impact at a transcriptomic level. Our observations point to genetic redundancy as an important mechanism sustaining the integrity of the retinal specification network, and to Vsx genes regulatory weight varying substantially among vertebrate species

Tracking Surface Charge Dynamics on Single Nanoparticles

Surface charges play a fundamental role in physics and chemistry, particularly in shaping the catalytic properties of nanomaterials. Tracking nanoscale surface charge dynamics remains challenging due to the involved length and time scales. Here, we demonstrate real-time access to the nanoscale charge dynamics on dielectric nanoparticles employing reaction nanoscopy. We present a four-dimensional visualization of the non-linear charge dynamics on strong-field irradiated single SiO$_2$ nanoparticles with femtosecond-nanometer resolution and reveal how surface charges affect surface molecular bonding with quantum dynamical simulations. We performed semi-classical simulations to uncover the roles of diffusion and charge loss in the surface charge redistribution process. Understanding nanoscale surface charge dynamics and its influence on chemical bonding on a single nanoparticle level unlocks an increased ability to address global needs in renewable energy and advanced healthcare.Comment: 26 pages with (4+6(SI)) figure

Regulación de la actividad económica en el ámbito internacional y libertad de establecimiento. Cuestiones societarias, fiscales de derecho de la competencia, derecho privado y arbitraje

Ponencias presentadas al Seminario Español de Derecho Internacional Privado, que tuvo lugar en Barcelona, del 18 al 20 de octubre de 2017, Universidad Autónoma de Barcelon