Pyrolytic conversion of glucose into hydroxymethylfurfural and furfural: Benchmark quantum‐chemical calculations

APC[EN] Quantum chemical methods have been intensively applied to study the pyrolytic conversion of glucose into hydroxymethylfurfural (HMF) and furfural (FF). Herein, we collect the most relevant mechanistic proposals from the recent literature and orga- nize them into a single reaction network. All the transition structures (TSs) and inter- mediates are characterized using highly accurate ab initio methods and the possible reaction pathways are assessed in terms of the Gibbs energies of the TSs and inter- mediates with respect to β-glucopyranose, selecting a 2D ideal-gas standard state at 773 K to represent the pyrolysis conditions. Several pathways can lead to the forma- tion of both HMF and FF passing through rate-determining TSs that have ΔG‡ values of 49–50 kcal/mol. Both water-assisted mechanisms and nonspecific environmen- tal effects have a minor impact on the Gibbs energy profiles. We find that the HMF ! FF + CH 2O fragmentation has a small ΔrxnG value and an accessible ΔG‡ barrier. Our computational results, which are in consonance with the kinetic parame- ters derived from lumped models, the results of isotopic labeling experiments and the reported HMF/FF molecular ratios, could be useful for modeling studies including on nonequilibrium kinetic effects that may render more information about product yields and the relevance of the various pathways.SIMinisterio de Ciencia e Innovación. Gobierno de Españ

Study of the Spanish Fintech Sector and Its Use As a Financial Inclusion Tool

RESUMEN: Se ha decidido estudiar el sector Fintech español de una manera empírica, aportando datos recogidos en informes, periódicos, noticias… para ver cómo se encuentra el sector, ya sea desde una perspectiva de crecimiento, desarrollo, inversión, principales actividades que se realizan dentro de él… Además, de cómo se encuentra la regulación, ya que se trata de un sector de reciente creación, con el que se cuenta con poca experiencia y más teniendo en cuenta que las tecnologías digitales nunca llegar a ofrecer a la sociedad un 100% de seguridad. A raíz de los datos empíricos facilitados, de la importancia del cambio de época, de las nuevas tecnologías existentes, de cómo se están adaptando estas últimas tanto a la sociedad como a las finanzas y de mi propia experiencia acerca del sector Fintech, se han comentado distintas valoraciones de qué papel están jugando las Fintech y también, de cómo otros agentes externos están interviniendo, como son distintos bancos tradicionales. Ha sido importante unir los datos empíricos con lo que realmente conlleva todo este proceso de digitalización, ya que nos encontramos en una situación en la cuál el cliente habitual del sector financiero está exigiendo una mayor calidad de los servicios y productos financieros. Por una parte, las Fintech están intentando satisfacer las necesidades más cambiantes y exigentes del cliente, pero por otra, las compañías Fintech están sirviendo como una herramienta de inclusión financiera, ya que están consiguiendo reducir las exigentes medidas habituales de la banca tradicional, por lo que el sector financiero, gracias a su digitalización, se está volviendo, entre otras cosas, mucho más accesible, económico y fácil de usar. ABSTRACT: It has been decided to study the Fintech Spanish sector in an empirical way, contributing data collected in reports, newspapers, news… to see how it is the sector, either from a perspective of growth, development, investment, main activities carried out within it… Furthermore, how it is the regulation, since it is about a newly created sector which has little experience and more considering that the digital technologies can never offer to society 100% security. Following the empirical data provided, the importance of the change of era, the new existing technologies, how are these ones are adapting to society as well as to finance and from my own experience about the Fintech sector, different assessments are been commented of what role, the Fintech, is playing and also, how other external agents are intervening, such as different traditional banks. It has been important to link the empirical data with what this whole digitalization process really involves, since we are in a situation in which the habitual client of the financial sector is demanding a higher quality of financial services and products. On the one hand, Fintech are trying to gratify the most changing and demanding customer needs, but on the other hand, they are helping as a tool for financial inclusion, as they are managing to reduce the usual demanding measures of traditional banking, so that the financial sector, thanks to its digitalization, is becoming, among other things, much more accessible, economical and easy to use.Grado en Administración y Dirección de Empresa

Atoms in molecules in real space: a fertile field for chemical bonding

In this perspective, we review some recent advances in the concept of atoms-in-molecules from a real space perspective. We first introduce the general formalism of atomic weight factors that allows unifying the treatment of fuzzy and non-fuzzy decompositions under a common algebraic umbrella. We then show how the use of reduced density matrices and their cumulants allows partitioning any quantum mechanical observable into atomic or group contributions. This circumstance provides access to electron counting as well as energy partitioning, on the same footing. We focus on how the fluctuations of atomic populations, as measured by the statistical cumulants of the electron distribution functions, are related to general multi-center bonding descriptors. Then we turn our attention to the interacting quantum atom energy partitioning, which is briefly reviewed since several general accounts on it have already appeared in the literature. More attention is paid to recent applications to large systems. Finally, we consider how a common formalism to extract electron counts and energies can be used to establish an algebraic justification for the extensively used bond order-bond energy relationships. We also briefly review a path to recover one-electron functions from real space partitions. Although most of the applications considered will be restricted to real space atoms taken from the quantum theory of atoms in molecules, arguably the most successful of all the atomic partitions devised so far, all the take-home messages from this perspective are generalizable to any real space decompositionsWe acknowledge the spanish MICINN, grant PID2021-122763NB-I00 and the FICyT, grant IDI/2021/000054 for financial support. TRR gratefully acknowledges DGTIC/UNAM for computer time (LANCAD-UNAM-DGTIC 250

Aportación de la teledetección para la determinación del parámetro hidrológico del número de curva

[ES] El número de curva es uno de los parámetros más utilizados en España para estimar la infiltración en el suelo a partir de la precipitación. Uno de los problemas que presenta su estimación es que la información que para ésta se precisa no está en muchos casos actualizada. Para resolver este problema, en el presente artículo se propone utilizar la teledetección como fuente de información adicional a otras fuentes convencionales. Para evaluar su aportación, se han escogido seis cuencas experimentales pertenecientes a la base de datos del proyecto AMHY-FR1END (Ferrer y otros, 1997) y se ha analizado las diferencias que presentan los números de curva estimados a partir de diferentes fuentes de información. Los resultados muestran que dichas diferencias son importantes en cuanto a la variabilidad espacial del parámetro, pero no así en cuanto a los valores areales del mismo en la cuenca.Este trabajo se ha realizado en el marco del proyecto Estudio de las Posibilidades que ofrece la Teledetección y los Sistemas de Información Geográfica en la estimación de Parámetros Hidrológicos a escala regional (AMB95-1099) de la CICYT.Ferrer I Julià, M.; Ruiz Verdú, A.; Dimas Suárez, M.; Estrela Monreal, T. (1998). Aportación de la teledetección para la determinación del parámetro hidrológico del número de curva. Ingeniería del Agua. 5(1):35-46. https://doi.org/10.4995/ia.1998.2742SWORD354651Ardiles-López, L.; Ferrer Juliá, M..; Rodriguez Chaparro, J. (1996) The Use of GIS to estímate Hydrological Parameters in a Rainfall-Runoff Model. Proceedings of Joint European Conference and Exhibition on Geographical Information. Barcelona, March 27-29 1996, vol. 1, pp. 408-417.Arozarena, A. y Herrero, M. (1994) El Programa CORINE, Programa Land Cover. Una Metodología aplicada a las Islas Canarias En: Jornadas Técnicas sobre Sistemas de Información Geográfica y Teledetección Espacial aplicados a la Ordenación del Territorio y el Medio Ambiente. Vitoria, 21-23 Nov. 1994, pp. 87-98CEDEX (1994) Caracterización Geomorfológica de la Cuenca Alta del Río Palancia. Utilización de la Teledetección y de los Sistemas de Información Geográfica, Informe Parcial n° 3 del Proyecto I+D Modelos Hidrológicos de Previsión de Avenidas: Aplicación en Cuencas Experimentales. Centro de Estudios Hidrográficos (CEDEX).Chuvieco, E. (1996) Fundamentos de Teledetección Espacial. Editorial Rialp, 3a edición, Manuales Universitarios Rialp, 568 pp.Engman, E.T. y Gurney, R. J. (1991) Remote Sensing in Hydrology. Chapman and HallFerrer, M., Estrela, T.; Quintas, L.; Villaverde, J. (1997) Actualización de la base de datos de cuencas españolas en el proyecto Friend-Amhy. Ingeniería Civil. n° 108. pp.25-36Ferrer, M.; Rodriguez, J.; Estrela, T. (1995) Generación Automática del Número de Curva con Sistemas de Información Geográfica. Ingeniería del Agua, vol.2, n°4, pp.43-58McCuen, R.H. (1982) A Guide to Hydrologie Analysis using SCS Methods. Prentice Hall, 110 pp.McGregor (1987) Using Landsat to derive Curve number for Hydrologic Models. En:American Society for Photogrammetry and Remote Sensing and ASCM Fall Convention. Reno, NV, ASPRS Technical Papers, pp.129-135.Rango, A.; Feldman, A.; George, T. y Ragan, R. (1983) Effective Use of Landsat Data in Hydrologic Models. Water Resources Bulletin. 19 (2): 165-174Richards, J.A. (1986) Remote Sensing Digital Image Analysis. An Introduction. Springer-Verlag, 281 pp.Sharma, K.D. y Singh, S. (1992) Runoff estimation using Landsat Thematic Mapping data and the SCS model. Hydrological Sciences-Journal des Sciences Hydrologiques, 37, 1 / 2.Temez, J.R. ( 1987) Cálculo Hidrometeorológico de Caudales Máximos en Pequeñas Cuencas Naturales.MOPU, Dirección General de Carreteras, n° 12, 111 p

Measuring universal health coverage based on an index of effective coverage of health services in 204 countries and territories, 1990–2019 : A systematic analysis for the Global Burden of Disease Study 2019

Background Achieving universal health coverage (UHC) involves all people receiving the health services they need, of high quality, without experiencing financial hardship. Making progress towards UHC is a policy priority for both countries and global institutions, as highlighted by the agenda of the UN Sustainable Development Goals (SDGs) and WHO's Thirteenth General Programme of Work (GPW13). Measuring effective coverage at the health-system level is important for understanding whether health services are aligned with countries' health profiles and are of sufficient quality to produce health gains for populations of all ages. Methods Based on the Global Burden of Diseases, Injuries, and Risk Factors Study (GBD) 2019, we assessed UHC effective coverage for 204 countries and territories from 1990 to 2019. Drawing from a measurement framework developed through WHO's GPW13 consultation, we mapped 23 effective coverage indicators to a matrix representing health service types (eg, promotion, prevention, and treatment) and five population-age groups spanning from reproductive and newborn to older adults (≥65 years). Effective coverage indicators were based on intervention coverage or outcome-based measures such as mortality-to-incidence ratios to approximate access to quality care; outcome-based measures were transformed to values on a scale of 0–100 based on the 2·5th and 97·5th percentile of location-year values. We constructed the UHC effective coverage index by weighting each effective coverage indicator relative to its associated potential health gains, as measured by disability-adjusted life-years for each location-year and population-age group. For three tests of validity (content, known-groups, and convergent), UHC effective coverage index performance was generally better than that of other UHC service coverage indices from WHO (ie, the current metric for SDG indicator 3.8.1 on UHC service coverage), the World Bank, and GBD 2017. We quantified frontiers of UHC effective coverage performance on the basis of pooled health spending per capita, representing UHC effective coverage index levels achieved in 2019 relative to country-level government health spending, prepaid private expenditures, and development assistance for health. To assess current trajectories towards the GPW13 UHC billion target—1 billion more people benefiting from UHC by 2023—we estimated additional population equivalents with UHC effective coverage from 2018 to 2023. Findings Globally, performance on the UHC effective coverage index improved from 45·8 (95% uncertainty interval 44·2–47·5) in 1990 to 60·3 (58·7–61·9) in 2019, yet country-level UHC effective coverage in 2019 still spanned from 95 or higher in Japan and Iceland to lower than 25 in Somalia and the Central African Republic. Since 2010, sub-Saharan Africa showed accelerated gains on the UHC effective coverage index (at an average increase of 2·6% [1·9–3·3] per year up to 2019); by contrast, most other GBD super-regions had slowed rates of progress in 2010–2019 relative to 1990–2010. Many countries showed lagging performance on effective coverage indicators for non-communicable diseases relative to those for communicable diseases and maternal and child health, despite non-communicable diseases accounting for a greater proportion of potential health gains in 2019, suggesting that many health systems are not keeping pace with the rising non-communicable disease burden and associated population health needs. In 2019, the UHC effective coverage index was associated with pooled health spending per capita (r=0·79), although countries across the development spectrum had much lower UHC effective coverage than is potentially achievable relative to their health spending. Under maximum efficiency of translating health spending into UHC effective coverage performance, countries would need to reach $1398 pooled health spending per capita (US$ adjusted for purchasing power parity) in order to achieve 80 on the UHC effective coverage index. From 2018 to 2023, an estimated 388·9 million (358·6–421·3) more population equivalents would have UHC effective coverage, falling well short of the GPW13 target of 1 billion more people benefiting from UHC during this time. Current projections point to an estimated 3·1 billion (3·0–3·2) population equivalents still lacking UHC effective coverage in 2023, with nearly a third (968·1 million [903·5–1040·3]) residing in south Asia. Interpretation The present study demonstrates the utility of measuring effective coverage and its role in supporting improved health outcomes for all people—the ultimate goal of UHC and its achievement. Global ambitions to accelerate progress on UHC service coverage are increasingly unlikely unless concerted action on non-communicable diseases occurs and countries can better translate health spending into improved performance. Focusing on effective coverage and accounting for the world's evolving health needs lays the groundwork for better understanding how close—or how far—all populations are in benefiting from UHC

Measuring universal health coverage based on an index of effective coverage of health services in 204 countries and territories, 1990–2019: a systematic analysis for the Global Burden of Disease Study 2019

Background Achieving universal health coverage (UHC) involves all people receiving the health services they need, of high quality, without experiencing financial hardship. Making progress towards UHC is a policy priority for both countries and global institutions, as highlighted by the agenda of the UN Sustainable Development Goals (SDGs) and WHO's Thirteenth General Programme of Work (GPW13). Measuring effective coverage at the health-system level is important for understanding whether health services are aligned with countries' health profiles and are of sufficient quality to produce health gains for populations of all ages. Methods Based on the Global Burden of Diseases, Injuries, and Risk Factors Study (GBD) 2019, we assessed UHC effective coverage for 204 countries and territories from 1990 to 2019. Drawing from a measurement framework developed through WHO's GPW13 consultation, we mapped 23 effective coverage indicators to a matrix representing health service types (eg, promotion, prevention, and treatment) and five population-age groups spanning from reproductive and newborn to older adults (≥65 years). Effective coverage indicators were based on intervention coverage or outcome-based measures such as mortality-to-incidence ratios to approximate access to quality care; outcome-based measures were transformed to values on a scale of 0–100 based on the 2·5th and 97·5th percentile of location-year values. We constructed the UHC effective coverage index by weighting each effective coverage indicator relative to its associated potential health gains, as measured by disability-adjusted life-years for each location-year and population-age group. For three tests of validity (content, known-groups, and convergent), UHC effective coverage index performance was generally better than that of other UHC service coverage indices from WHO (ie, the current metric for SDG indicator 3.8.1 on UHC service coverage), the World Bank, and GBD 2017. We quantified frontiers of UHC effective coverage performance on the basis of pooled health spending per capita, representing UHC effective coverage index levels achieved in 2019 relative to country-level government health spending, prepaid private expenditures, and development assistance for health. To assess current trajectories towards the GPW13 UHC billion target—1 billion more people benefiting from UHC by 2023—we estimated additional population equivalents with UHC effective coverage from 2018 to 2023. Findings Globally, performance on the UHC effective coverage index improved from 45·8 (95% uncertainty interval 44·2–47·5) in 1990 to 60·3 (58·7–61·9) in 2019, yet country-level UHC effective coverage in 2019 still spanned from 95 or higher in Japan and Iceland to lower than 25 in Somalia and the Central African Republic. Since 2010, sub-Saharan Africa showed accelerated gains on the UHC effective coverage index (at an average increase of 2·6% [1·9–3·3] per year up to 2019); by contrast, most other GBD super-regions had slowed rates of progress in 2010–2019 relative to 1990–2010. Many countries showed lagging performance on effective coverage indicators for non-communicable diseases relative to those for communicable diseases and maternal and child health, despite non-communicable diseases accounting for a greater proportion of potential health gains in 2019, suggesting that many health systems are not keeping pace with the rising non-communicable disease burden and associated population health needs. In 2019, the UHC effective coverage index was associated with pooled health spending per capita (r=0·79), although countries across the development spectrum had much lower UHC effective coverage than is potentially achievable relative to their health spending. Under maximum efficiency of translating health spending into UHC effective coverage performance, countries would need to reach $1398 pooled health spending per capita (US$ adjusted for purchasing power parity) in order to achieve 80 on the UHC effective coverage index. From 2018 to 2023, an estimated 388·9 million (358·6–421·3) more population equivalents would have UHC effective coverage, falling well short of the GPW13 target of 1 billion more people benefiting from UHC during this time. Current projections point to an estimated 3·1 billion (3·0–3·2) population equivalents still lacking UHC effective coverage in 2023, with nearly a third (968·1 million [903·5–1040·3]) residing in south Asia. Interpretation The present study demonstrates the utility of measuring effective coverage and its role in supporting improved health outcomes for all people—the ultimate goal of UHC and its achievement. Global ambitions to accelerate progress on UHC service coverage are increasingly unlikely unless concerted action on non-communicable diseases occurs and countries can better translate health spending into improved performance. Focusing on effective coverage and accounting for the world's evolving health needs lays the groundwork for better understanding how close—or how far—all populations are in benefiting from UHC

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Pyrolytic Conversion of Glucose into Hydroxymethylfurfural and Furfural: A Survey of Mechanisms and Benchmark Quantum-Chemical Calculations

Quantum chemical methods have been intensively applied to study the pyrolytic conversion of glucose into hydroxymethylfurfural (HMF) and furfural (FF). Herein, we collect the most relevant mechanistic proposals from the recent literature and organize them into a single reaction network. The transition structures (TSs) and intermediates are characterized using high level ab initio methods that predict relative energies within chemical accuracy. The reaction pathways are assessed in terms of the Gibbs free energy differences of the TSs and intermediates with respect to β-glucopyranose, selecting a 2D ideal-gas standard state at 773K to represent the usual pyrolysis conditions. After having scored all the possible pathways throughout the network assuming reversible reaction steps, several pathways, which present various changes with respect to the former proposals, can lead to the formation of both HMF and FF passing through rate-determining TSs that have ∆G‡ values of ~ 49-50 kcal/mol. Interestingly, the catalysis by auxiliary water molecules and the non-specific environmental effects as modelled by solvent continuum methods, have only a minor impact on the Gibbs free energy profiles of the most favoured routes. Since the HMF fragmentation (HMF→FF+CH2O) is predicted to have a small ∆rxnG value and an accessible ∆G‡ barrier, the HMF/FF molecular ratio may be partly determined by equilibrium conditions. In addition, the benchmark energies and structures are employed to study the performance of density functional methodologies. Finally, we show that the computational results are in consonance with the kinetic parameters derived from lumped models, the results of isotopic labelling experiments and the reported HMF/FF molecular ratios. Eventually, they could be useful in future computational studies focused on the kinetic modelling of the pyrolysis mechanisms including non-equilibrium kinetic effects, which could render much more detailed information about product yields and the importance of the various pathways

SARS-CoV-2 Main Protease: A Molecular Dynamic Study

We provide results from a molecular dynamics simulation of the SARS-CoV-2 main protease in the monomer and dimer states of the native enzyme and also bound to a peptide substrate.<br /