Advancing the Smart Region Digital Twin: The Case of UNESCO GEOfood

Organic food waste recycling is one of the final frontiers for a sustainable food lifecycle. Digital twins may be helpful to close the loop in more advanced food supply chains, but there is a lack of guidelines on how to adopt this emerging technology in community composting. This paper presents a digital twin-driven design to address this need in a UNESCO-protected region with geological relevance (Geopark). The design science research project offers the foundations for creating intelligent composting networks supported by digital technologies. Six initial design principles are suggested for developing digital twins at a regional level. This study contributes to the deployment of layered digital twins in sustainable regional development. Moreover, our proposal assists the integration of local food producers in regional food supply chains and increases the impact of sustainability brands like GEOfood

Photocatalytic Difluoromethylation Reactions of Aromatic Compounds and Aliphatic Multiple C-C Bonds

Among the realm of visible light photocatalytic transformations, late-stagedifluoromethylation reactions (introduction of difluoromethyl groups in the last stages of syntheticprotocols) have played relevant roles as the CF2X group substitutions exert positive impacts on thephysical properties of organic compounds including solubility, metabolic stability, andlipophilicity, which are tenets of considerable importance in pharmaceutical, agrochemical, andmaterials science. Visible-light-photocatalyzed difluoromethylation reactions are shown to beaccomplished on (hetero)aromatic and carbon?carbon unsaturated aliphatic substrates under mildand environmentally benign conditions.Fil: Barata Vallejo, Sebastian. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentin

Photocatalytic fluoroalkylation reactions of organic compounds

Photocatalytic methods for fluoroalkyl-radical generation provide more convenient alternatives to the classical perfluoroalkyl-radical (Rf) production through chemical initiators, such as azo or peroxide compounds or the employment of transition metals through a thermal electron transfer (ET) initiation process. The mild photocatalytic reaction conditions tolerate a variety of functional groups and, thus, are handy to the late-stage modification of bioactive molecules. Transition metal-photocatalytic reactions for Rf radical generation profit from the redox properties of coordinatively saturated Ru or Ir organocomplexes to act as both electron donor and reductive species, thus allowing for the utilization of electron accepting and donating fluoroalkylating agents for Rf radical production. On the other hand, laboratory-available and inexpensive photoorgano catalysts (POC), in the absence of transition metals, can also act as electron exchange species upon excitation, resulting in ET reactions that produce Rf radicals. In this work, a critical account of transition metal and transition metal-free Rf radical production will be described with photoorgano catalysts, studying classical examples and the most recent investigations in the field.Fil: Barata Vallejo, Sebastian. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Bonesi, Sergio Mauricio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Bioinspired Photocatalyzed Organic Synthetic Transformations. The Use of Natural Pigments and Vitamins in Photocatalysis

Due to the necessity for more environmentally benign processes in synthetic organic chemistry, and in particular in photocatalysis, a recourse to photocatalysts that are also found in nature and mimic natural processes to accomplish organic transformations is very appealing. Synthetic useful reactions such as oxidations, reductions, carbon-oxygen, carbon-carbon and carbon-sulfur bond formation reactions, and E-to-Z geometrical isomerization reactions photocatalyzed by biological natural pigments, vitamins, cofactors, and compounds with antiviral activity will be discussed in this account. Interestingly, due to the remarkable redox properties and triplet energies of some of these catalysts that are found in nature, both electron transfer (ET)- and energy transfer (EnT)-driven photocatalytic processes can be accomplished.Fil: Barata Vallejo, Sebastian. Consiglio Nazionale delle Ricerche; Italia. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica. Cátedra de Química Orgánica I; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Yerien, Damián Emilio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica. Cátedra de Química Orgánica I; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica. Cátedra de Química Orgánica I; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Da frustração ao ódio: a construção da imagem da mulher em Hóspede, de Pardal Mallet

Este trabalho retoma o romance de estreia de Pardal Mallet, Hóspede, discutindo de que forma se constrói a imagem da mulher na narrativa, que vai da frustração ao ódio. Para tanto, discutimos a aclimatação do gênero romance, no Brasil, e a crítica que se estabeleceu sobre a estética Naturalismo. Utilizamos como referencia teórico, dentre outros autores, as obras de Telles (2000) Sade (2002) Abreu (2003), Siti (2009)

Approach to Adapt a Legacy Manufacturing System Into the IoT Paradigm

This work has been supported by Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa, by Uninova-CTS research unit and by national funds through FCT -Fundação para a Ciência e a Tecnologia within the research unit CTS - Centro de Tecnologia e Sistemas (project UID/EEA/00066/2013). The authors would like to thank all the institutions.Enterprises are adopting the Internet of Things paradigm as a strategy to improve competitiveness. But enterprises also need to rely on their legacy systems, which are of vital importance to them and normally difficult to reconfigure or modify, their mere replacement being usually not affordable. These systems constitute, therefore, barriers to agility and competitiveness, raising the need to develop cost-effective ways for IoT adaptation. An approach for adapting legacy manufacturing systems into the IoT realm is proposed in this research. The methodology is twofold: an adaptation board is firstly designed to provide IoT connectivity, allowing to remotely invoke the “legacy” functionality as services. Then, the board itself can leverage the legacy system by developing additional functionalities inside it, as the update process is usually triggered by the need of new functionality from these systems. An experiment, which consists of adapting to IoT a small distribution line that is controlled by an aged Programmable Logic Controller, is developed to illustrate how straightforward, affordable and cost effective the adaptation approach is, allowing to holistically achieve a new system with more sophisticated functionality.publishersversionpublishe

Catalytic Fluoroalkylation Reactions of Alcoxy‐subtituted (Hetero)Arenes

Electron-rich alcoxy-substituted (hetero)arenes and electrophilic fluoroalkyl moieties represent advantageous partners for substitution reactions due to their electronic match. Fluoroalkylation strategies of alcoxy-substituted (hetero)arenes are herein presented which depict photocatalytic and thermal methods. Photocatalytic methods rely on the use of diverse photocatalysts such as Ru(bpy)3Cl2, tetrabutylammonium decatungstate TBADT, N-doped carbon nanodots NCNDs, and vitamin derivatives which can partner with the Langlois reagent NaSO2CF3, CF3CO2H, and perfluoroalkyl iodides RFI as fluoroalkylating reagents. Also, electrocatalytic methods that make use of the cathodic reduction of CF3SO2Cl to generate CF3 radicals can achieve trifluoromethylation reactions of alcoxysubstituted (hetero)arenes. On the other hand, thermal methodologies comprising Pd(OAc)2 catalysis and using CF3Br as trifluoromethylating source have been implemented.Fil: Yerien, Damián Emilio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Lantaño, Beatriz. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; ArgentinaFil: Barata Vallejo, Sebastian. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consiglio Nazionale delle Ricerche; ItaliaFil: Postigo, Jose Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentin

The Role of Photocatalysts in Radical Chains of Homolytic Aromatic Substitutions, Radical Addition to Olefins, and Nucleophilic Radical Substitution Mechanisms

Photoinitiated perfluorobutylation reactions of 2-anisidine 1, propenyloxybenzene 2, and 2-mercaptoethanol 3 have been carried out employing commercially available n-C4F9I as the source of C4F9 radicals under three different photocatalysts (PCs) absorbing in the violet (Ir[dF(CF3)ppy]2(dtbbpy)+ (PC-1)), green (Rose Bengal (PC-2)) and red (zinc phthalocyanine PhZn (PC-3)) regions of the electromagnetic spectrum, in order to explore the quantum yields and radical chain lengths for each type of transformation and photoinitiated system. For substrates 1-3 and their different types of reactions, the comparative study between PCs seeks to establish the extent to which regioproducts, yields, and mechanistic proposals are influenced by the intervention of each PC. The different overall quantum yields and chain lengths obtained for each type of reaction under each PC are a direct consequence of the efficiency of the photoinitiation events, i.e., primary radical production, propagation and termination steps. This will have important implications in the understanding and representations of the mechanisms postulated, in terms of closed and open catalytic cycles. One strategy we apply to uncover radical propagating chains in our mechanisms is to explore photocatalysts that operate in oxidative and reductive quenching manners for each type of transformation.Fil: Yerien, Damián Emilio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; ArgentinaFil: Barata Vallejo, Sebastian. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Centre National de la Recherche Scientifique; FranciaFil: Mora Flores, Erwin Wilfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentin