bluuebunny/crossref_metadata_2025 huggingface dataset:
Financial development, foreign direct investment and economic growth: Panel causality approach
Authors: Veselinović Nevena , Despotović Danijela
Published: May 2022

The examination considers the causality between banking sector depth, foreign direct investment, and economic growth in the sample of six Central and Eastern European countries in the period range between 2000 to 2018. Utilizing the Dumitrescu and Hurlin (2012) panel causality test, the results confirmed a supply-leading hypothesis, FDI-led growth hypothesis, and unidirectional causality from the banking sector depth to foreign direct investment. As the causality ranging from the depth of the banking sector to foreign direct investment and economic growth has been confirmed, the conclusion is that attention should be focused on policies that promote the development of the banking sector. In this way, a well-regulated banking sector will attract more FDI, which will lead to higher growth rates in the analyzed countries.
Sustainability in fashion: The role of a fashion designer in shaping a future that is ecologically acceptable and socially responsible
Authors: Jocić Sonja
Published: May 2022

In this paper the relationship between the current global crisis of environmental protection, the modern vision of sustainability in fashion and the creative process of realization of clothing items in the fashion industry is investigated from the aspect of fashion design. The fashion industry is expected to change the way garments are produced and designed, the way it communicates with consumers, and the way garments are handled at the end of a product's lifespan. In addition to all the usual aspects of creativity, a fashion designer nowadays and especially in the future is expected, to have an additional sort of creativity that should contribute to sustainable development by seeking and developing new creative-experimental design solutions. Different strategies are available to a designer for achieving this goal. In the process of creating a product that has aesthetic and functional values on the market and at the same time the least possible environmental impact on the planet a designer is a key factor of the fashion industry.
Arte y educación: concebir el espacio del atelier como una oportunidad de innovación didáctica
Authors: Gadea Florencia Varela , Mara Paola Marenco
Published: May 2022

Desde la Licenciatura en Educación Inicial y la Licenciatura en Artes Visuales de la Universidad Católica del Uruguay, se ha implementado un proyecto que busca nutrir a los docentes de elementos incursionar en el espacio del atelier, su diseño, y las herramientas que proporciona, para la innovación didáctica. En América Latina son escasas las formaciones específicas en la adaptación de nuevas pedagogías que involucren recursos artísticos, orientadas hacia el desarrollo de competencias relacionadas con la empatía, la comunicación, la comprensión de su contexto y el respeto por el medio ambiente. Para esta propuesta pedagógica incluimos algunas de las técncias y postulados de la cultura del atelier que se gesta en las Escuelas de Infancia en los inicios de los años 60, en el municipio italiano Reggio Emilia. Son escuelas inspiradas en el enfoque socio-constructivista del conocimiento y la valorización de una multiplicidad de lenguajes expresivos de Loris Malaguzzi (Cavallini et al., 2017). El atelier se configura como un espacio que cristaliza los aprendizajes. En palabras de Vecchi: “la percepción sensorial, el gusto de la seducción, lo que Malaguzzi llamaba la vibración estética, pueden ejercer de catalizadores de un aprendizaje, y cómo pueden apoyar y alimentar un conocimiento que no se nutre solo de información”. Para esta propuesta, nos planteamos tres objetivos específicos: 1) Sensibilizar a los participantes en la deconstrucción de la neutralidad aparente de los objetos cotidianos, para comprender las formas de percepción del sujeto; 2) Reflexionar acerca del postulado hacer es pensar, definido por el filósofo Richard Sennet como la convicción de que todas las habilidades incluso las más abstractas como pensar, deducir, etc., comienzan como prácticas corporales (2013); 3) Ejercitar un rol docente posicionado como guía y facilitador de experiencias.
Metodologias ativas: uma breve apresentação conceitual e de seus métodos
Authors: Santos Danielle Fernandes Amaro dos , Castaman Ana Sara
Published: May 2022

Este texto tem por objetivo apresentar os conceitos e princípios de seis metodologias ativas, de modo a descrever suas características e como podem ser conduzidos em sala de aula. Assim, realizou-se pesquisa bibliográfica sobre metodologia ativa em livros e produções científicas a respeito de seis métodos classificados dentro da proposta ativa. Para fins da organização do texto, as seções foram divididas da seguinte forma: a) apresentação dos procedimentos metodológicos; b) fundamentos e conceitos das metodologias ativas, bem como seus métodos; c) considerações finais. Concluiu-se que independentemente dos métodos, quando se trata de metodologias ativas, o docente necessita conhecê-los e buscar o que melhor se enquadra dentro de seu perfil, das unidades curriculares que ministra, dos estudantes que atende e dos objetivos que pretende alcançar. Além disso, ambos os atores (docente e alunos) precisam internalizar seus novos papéis, de modo a constituírem sujeitos partícipes e autônomos no seu processo de construção das aprendizagens.
Resenha do livro “Escola nova em circuito internacional: cem anos da New Education Fellowship”
Authors: Philippi Carolina Cechella
Published: May 2022

O livro “Escola Nova em circuito internacional: cem anos da New Education Fellowship” foi uma das iniciativas de publicização dos resultados investigativos do projeto temático “Saberes e práticas em fronteiras: por uma história transnacional da educação (1810-...)1”. Nessa publicação congregaram-se textos não somente da sua coordenadora, a professora Dra. Diana Gonçalves Vidal, como também dos seus integrantes em suas mais variadas etapas formativas, da iniciação científica ao pós-doutorado. Trata-se, portanto, de um livro cuja organização e composição ilustrou movimentos de pesquisa diversos em relação à mesma problemática. Ademais, ele se insere em uma perspectiva transnacional2para o entendimento da história que vem ganhando, paulatinamente, tônus conceitual, metodológico e espaço em pesquisas, ainda que não se trate de uma perspectiva recente (STRUCK; FERRIS; REVEL, 2011).
Getting Ready for Post-Quantum Cryptography: Exploring Challenges Associated with Adopting and Using Post-Quantum Cryptographic Algorithms
Authors: Barker William , Polk W. , Souppaya Murugiah
Published: May 2022

Cryptographic technologies are used throughout government and industry to authenticate the source and protect the confidentiality and integrity of information that we communicate and store. The paper describes the impact of quantum computing technology on classical cryptography, particularly on public-key cryptographic systems. This paper also introduces adoption challenges associated with post-quantum cryptography after the standardization process is completed. Planning requirements for migration to post-quantum cryptography are discussed. The paper concludes with NIST’s next steps for helping with the migration to post-quantum cryptography.
Planning for a Zero Trust Architecture
Authors: Rose Scott
Published: May 2022

NIST Special Publication 800-207 defines zero trust as a set of cybersecurity principles used when planning and implementing an enterprise architecture. These principles apply to endpoints, services, and data flows. Input and cooperation from various stakeholders in an enterprise is needed for a zero trust architecture to succeed in improving the enterprise security posture. Some of these stakeholders may not be familiar with risk analysis and management. This document provides an overview of the NIST Risk Management Framework (NIST RMF) and how the NIST RMF can be applied when developing and implementing a zero trust architecture.
Recommended Criteria for Cybersecurity Labeling for Consumer Internet of Things (IoT) Products
Authors:   National Institute of Standards and Technology
Published: May 2022

Executive Order (EO) 14028, “Improving the Nation’s Cybersecurity,” tasks the National Institute of Standards and Technology (NIST), in coordination with the Federal Trade Commission (FTC) and other agencies, to initiate pilot programs for cybersecurity labeling. These labeling programs are intended to educate the public on the security capabilities of …software development practices. To inform this effort, the EO directs NIST to “…identify secure software development practices or criteria for a consumer software labeling program….” This document seeks to fulfill this directive by detailing the following areas: 1) the role of a scheme owner in a labeling program, 2) baseline technical criteria that can inform a label, 3) labeling presentation criteria, 4) conformity assessment criteria, and 5) a detailed discussion concerning consumer education and usability.
A Taxonomic Approach to Understanding Emerging Blockchain Identity Management Systems
Authors: Lesavre Loïc , Varin Priam , Mell Peter , Davidson Michael , Shook James
Published: May 2022

Identity management systems (IDMSs) are widely used to provision user identities while managing authentication, authorization, and data sharing within organizations and on the web. Traditional identity systems typically suffer from single points of failure, lack of interoperability, and privacy issues, such as enabling mass data collection and user tracking. Blockchain technology has the potential to alleviate these concerns: it can support the ability for users to control the custody of their own identifiers and credentials, enabling novel data ownership and governance models with built-in control and consent mechanisms. Hence, blockchain-based IDMSs, which could benefit both users and businesses, are beginning to proliferate. This work categorizes these systems into a taxonomy based on differences in blockchain architectures, governance models, and other salient features. Context is provided for the taxonomy through the description of related terms, emerging standards, and use cases while highlighting relevant security and privacy considerations.
EXPLORING RELATIONSHIP POWER IN SUPPLY CHAIN SUSTAINABILITY PRACTICES: A CASE STUDY OF A SOUTH AFRICAN HOSPITAL GROUP
Authors: Schutte Carla , Niemann Wesley , Kotzé Theuns
Published: May 2022

Buyers and suppliers of healthcare products and services are more dependent on each other than ever before for the provision of scarce and unique resources, which highlights the need to implement supply chain sustainability practices. Firms controlling these resources hold excessive power over others. This study adopted resource dependence theory as a theoretical lens to explore the role of relationship power in supply chain sustainability practices between a South African private healthcare provider and its suppliers. The study employed a generic qualitative single-case study design. Semi-structured interviews were used to collect data from 12 participants at various levels of the case organisation’s hierarchy. The main findings revealed several types of environmental and social practice used in the supply chain of the private healthcare provider. Some of the environmental practices were effective waste management and recycling, while the social practices included supplier selection and periodic reviews. The healthcare provider exercised extensive power over its suppliers to implement these practices. By exploring the advantages and disadvantages of sustainability practices, the findings showed that relationship power acted as a driver of supply chain sustainability. Mutual commitment, continuous communication, and training support these practices. Healthcare managers must be aware of the importance of relationship power for supply chain sustainability practices implementation, and are advised to invest time and effort in building buyer—supplier relationships to aid sustainability. This study expands the literature on relationship power in supply chain sustainability practices in an underexplored developing country healthcare context. Keywords Sustainability; supply chain relationships; power; private hospital; single case-study
ASSESSMENT OF FORECASTING METHODS TO REDUCE THE MARGIN OF ERROR IN ELECTRONIC COMPONENT SALES
Authors: López Ricardo Daniel , Maldonado Araceli , Jasso Humberto , Huerta Gerardo , Rodríguez José Amparo
Published: May 2022

International competition in the electronic market requires that organisations use their resources not only to manufacture high quality components, but also to adopt or develop appropriate sales forecasting methods that could adapt to their needs and guarantee their economic development. From an industrial engineering perspective, keeping balanced orders and healthy safety stocks is required for such organisations. These two metrics play a significant role in their economic growth and development, because any disruption results in high costs throughout their manufacturing processes. Thus significant resources are spent by these organisations to develop information systems and logistics skills in order to implement more reliable and precise sales forecasting methods. Nevertheless, planners and forecasters constantly face different challenges such as sudden demand changes, seasonality, products with a short life cycle, a lack of historical data, and swings in the world economy. The objective of this research is to determine the most convenient demand forecasting method for the manufacturers of electronic devices that target a specific market. Twenty-seven months of sales data were analysed and different quantitative forecasting methods were tested and analysed using statistical tools. From the results obtained, the combined forecasting method appeared to be the most suitable since the least amount of forecasting error is obtained when this method is applied. The results of this research could be adopted by other companies to forecast the future sales of any items with a similar pattern to that used in our study. This has significant implications for their decision-making processes and inventory planning. Keywords Forecasting; Qualitative methods; Combined methods
RESEARCH ON MODULE PARTITION FOR REMANUFACTURING PARTS TO BE ASSEMBLED
Authors: Yin Lu , Yang Fangyan , Zhu Fuping , Qin Qin
Published: May 2022

o solve the technical, economic and environmental problems in the remanufacturing process of decommissioned machine tools, this study proposes a module partition method for remanufacturing retired machine tools. Through an analysis of the economic, accuracy, environment-friendly, and functional and physical interactivity principles, this study applies the fuzzy cluster method (FCM) to analyse the modularity of the components to be assembled. It establishes the correlation matrix between the parts, from which a module division scheme is obtained. Finally, a case study is presented to verify the feasibility of the module division method. Keywords decommissioned machine tools; remanufacturing; module partition; fuzzy clustering
MDGAs are fast-diffusing molecules that delay excitatory synapse development by altering neuroligin behavior
Authors: Toledo Andrea , Letellier Mathieu , Bimbi Giorgia , Tessier Béatrice , Daburon Sophie , Favereaux Alexandre , Chamma Ingrid , Vennekens Kristel , Vanderlinden Jeroen , Sainlos Matthieu , de Wit Joris , Choquet Daniel , Thoumine Olivier
Published: May 2022

MDGA molecules can bind neuroligins and interfere with trans-synaptic interactions to neurexins, thereby impairing synapse development. However, the subcellular localization and dynamics of MDGAs, or their specific action mode in neurons remain unclear. Here, surface immunostaining of endogenous MDGAs and single molecule tracking of recombinant MDGAs in dissociated hippocampal neurons reveal that MDGAs are homogeneously distributed and exhibit fast membrane diffusion, with a small reduction in mobility across neuronal maturation. Knocking-down/out MDGAs using shRNAs and CRISPR/Cas9 strategies increases the density of excitatory synapses, the membrane confinement of neuroligin-1, and the phosphotyrosine level of neuroligins associated with excitatory post-synaptic differentiation. Finally, MDGA silencing reduces the mobility of AMPA receptors, increases the frequency of miniature EPSCs (but not IPSCs), and selectively enhances evoked AMPA-receptor-mediated EPSCs in CA1 pyramidal neurons. Overall, our results support a mechanism by which interactions between MDGAs and neuroligin-1 delays the assembly of functional excitatory synapses containing AMPA receptors.
Flexible utilization of spatial- and motor-based codes for the storage of visuo-spatial information
Authors: Henderson Margaret M , Rademaker Rosanne L , Serences John T
Published: May 2022

Working memory provides flexible storage of information in service of upcoming behavioral goals. Some models propose specific fixed loci and mechanisms for the storage of visual information in working memory, such as sustained spiking in parietal and prefrontal cortex during working memory maintenance. An alternative view is that information can be remembered in a flexible format that best suits current behavioral goals. For example, remembered visual information might be stored in sensory areas for easier comparison to future sensory inputs, or might be re-coded into a more abstract action-oriented format and stored in motor areas. Here, we tested this hypothesis using a visuo-spatial working memory task where the required behavioral response was either known or unknown during the memory delay period. Using functional magnetic resonance imaging (fMRI) and multivariate decoding, we found that there was less information about remembered spatial position in early visual and parietal regions when the required response was known versus unknown. Furthermore, a representation of the planned motor action emerged in primary somatosensory, primary motor, and premotor cortex during the same task condition where spatial information was reduced in early visual cortex. These results suggest that the neural networks supporting working memory can be strategically reconfigured depending on specific behavioral requirements during a canonical visual working memory paradigm.
Distinct responses to rare codons in select Drosophila tissues
Authors: Allen Scott R , Stewart Rebeccah K , Rogers Michael , Ruiz Ivan Jimenez , Cohen Erez , Laederach Alain , Counter Christopher M , Sawyer Jessica K , Fox Donald T
Published: May 2022

Codon usage bias has long been appreciated to influence protein production. Yet, relatively few studies have analyzed the impacts of codon usage on tissue-specific mRNA and protein expression. Here, we use codon-modified reporters to perform an organism-wide screen in Drosophila melanogaster for distinct tissue responses to codon usage bias. These reporters reveal a cliff-like decline of protein expression near the limit of rare codon usage in endogenously expressed Drosophila genes. Near the edge of this limit, however, we find the testis and brain are uniquely capable of expressing rare codon-enriched reporters. We define a new metric of tissue-specific codon usage, the tissue-apparent Codon Adaptation Index (taCAI), to reveal a conserved enrichment for rare codon usage in the endogenously expressed genes of both Drosophila and human testis. We further demonstrate a role for rare codons in an evolutionarily young testis-specific gene, RpL10Aa. Optimizing RpL10Aa codons disrupts female fertility. Our work highlights distinct responses to rarely used codons in select tissues, revealing a critical role for codon bias in tissue biology.
COVID-19 mortality is associated with pre-existing impaired innate immunity in health conditions
Authors: Lee Matthew , Chang Yung , Ahmadinejad Navid , Johnson-Agbakwu Crista , Bailey Celeste , Liu Li
Published: May 2022

COVID-19 can be life-threatening to individuals with chronic diseases. To prevent severe outcomes, it is critical that we comprehend pre-existing molecular abnormalities found in common health conditions that predispose patients to poor prognoses. In this study, we focused on 14 pre-existing health conditions for which increased hazard ratios of COVID-19 mortality have been documented. We hypothesized that dysregulated gene expression in these pre-existing health conditions were risk factors of COVID-19 related death, and the magnitude of dysregulation (measured by fold change) were correlated with the severity of COVID-19 outcome (measured by hazard ratio). To test this hypothesis, we analyzed transcriptomics data sets archived before the pandemic in which no sample had COVID-19. For a given pre-existing health condition, we identified differentially expressed genes by comparing individuals affected by this health condition with those unaffected. Among genes differentially expressed in multiple health conditions, the fold changes of 70 upregulated genes and 181 downregulated genes were correlated with hazard ratios of COVID-19 mortality. These pre-existing dysregulations were molecular risk factors of severe COVID-19 outcomes. These genes were enriched with endoplasmic reticulum and mitochondria function, proinflammatory reaction, interferon production, and programmed cell death that participate in viral replication and innate immune responses to viral infections. Our results suggest that impaired innate immunity in pre-existing health conditions is associated with increased hazard of COVID-19 mortality. The discovered molecular risk factors are potential prognostic biomarkers and targets for therapeutic intervention.
Un estudio longitudinal de las creencias sobre el aprendizaje de la lengua española de estudiantes chinos
Authors:   Universidad de Pekín (China), Song Yang
Published: May 2022

Los resultados de un estudio longitudinal de dos años de duración de las creencias sobre el aprendizaje de una lengua a estudiantes chinos de Filología Hispánica de primer y segundo curso reflejan que se originan en su experiencia con la enseñanza de inglés durante la educación secundaria. Debido a que ambas lenguas y etapas de formación tienen objetivos educativos distintos, sus creencias se adaptan a los objetivos de la carrera.
Dispositivos ciberfeministas no Instagram: as autorias educ-ativas em contexto de Covid-19
Authors: Fernandes Terezinha , Santos Edméa de Oliveira , York Sara Wagner
Published: May 2022

A produção de mulheres na internet não é nova, mas, a partir do movimento dos feminismos plurais, principalmente mediado pelo uso das redes sociais na internet notamos a emergência de diferentes fenômenos, performances e usos, bem como o potencial dos multiletramentos críticos em Street (2014), Fernandes, Cruz e Souza (2020) mobilizados em práticas sociais na cibercultura (Santos, 2014). Durante a pandemia de COVID/19 realizamos uma etnografia na cibercultura (Pereira, 2018) a partir da qual alguns dispositivos autorais foram mapeados na plataforma Instagram, com o objetivo de compreender como dispositivos autorais educacionais foram forjados por diferentes mulheres e de que modo podem inspirar práticas pedagógicas feministas na cibercultura. Os dados produzidos foram descritos densamente e analisados buscando os sentidos e os modos de subjetivação de mulheres feministas em fenômenos emergentes como lives, ocupações, aulas públicas, pole dance e práticas de digital storytellyng, dialogando com autoras feministas como Angela Davis, Heloísa Buarque de Hollanda, bell hooks, Vilma Piedade, Djamila Ribeiro, Sara Wagner York, dentre outras. Como resultados destacamos a possibilidade de problematizar questões relacionadas à cibercultura e às práticas sociais mediadas pelo digital em rede e os sistemas estruturais como patriarcado, colonialismo e capitalismo, em intersecção com categorias importantes aos feminismos como gênero, raça e classe, sendo possível ainda, mapear o que estamos concebendo como multiletramentos críticos, ao lançar o olhar às estratégias e táticas das praticantes (Certeau, 1998) para superação e resistência aos atravessamentos e opressões sofridas historicamente e materializadas em violências como a discursiva, a política, a acadêmica, estética, entre outras.
Ideias desviantes e incertezas como elementos para pensar o futuro
Authors: Gonçalves Leonardo Conceição , Castro Luis Henrique Monteiro de , Dos Santos Rosemary
Published: May 2022

Como se já não bastasse a situação de emergência sanitária em decorrência da pandemia do novo Coronavírus no ano de 2020, com ressonância nos campos econômico, cultural dentre vários outros, a população brasileira também vivenciou inúmeros acontecimentos que ameaçaram o estado democrático de direito. Assim, diante da incerteza (MORIN, 2005) de quando efetivamente as pessoas poderiam voltar a se reunir fisicamente, seja nas tradicionais festas populares, eventos científicos ou em espetáculos de qualquer outro gênero, as atividades de toda ordem precisaram assumir formatos alternativos para (re)xistir sem colocar a vida da população em risco. Assim, este texto tem como objetivo investigar em que medida as lives musicais, cada vez mais comum entre os tantos ‘dentrofora’ das diversas redes educativas, estabeleceram relações de ‘aprenderensinar’ entre os ‘fazerespensar’ cotidianos. Em nossas pesquisas, bricolamos estudos das ‘pesquisas com os cotidianos’ (CERTEAU, 2018; ALVES, 2008), com a multirreferencialidade (ARDOINO, 1998; MACEDO, 2012) para nos inspirarmos nas criações das coisas miúdas, desviantes, muitas vezes compreendidas como irrelevantes. Dessa forma, acionamos como dispositivos de pesquisa as rodas de conversas em ambientes online para tecer criações cotidianas nas diversas redes educativas reinventadas pelos usos dos dispositivos digitais em rede. Por fim, em posse dos fragmentos das histórias e das invenções coproduzidas, apresentamos como os praticantes culturais dos cotidianos interagem com o mundo externo para além da porta da própria casa (CERTEAU, 2009), cocriando ideias desviantes e incertezas como elementos para pensar o futuro.
Supramolecular Interactions of Flexible 2D Perovskite in Microstrain Releasing and Optoelectronic Properties Recovery
Authors: Song Jinmei , Feng Xiaopeng , Wei Haotong , Yang Bai
Published: May 2022

The conductivity of 2D perovskite is mainly dominated by halide metal octahedron skeletons. However, in contrast to 3D perovskite structures, the layered inorganic skeletons are easily compressed or stretched by large organic cations, causing serious microstrain with impaired optoelectronic responses. Here, fluorination modulated supramolecular interactions in 2D fluorophenethylammonium lead iodide (FPEA2PbI4) perovskites are reported. In the double layered organic spacer, interlayer supramolecular interactions between electronegative F atoms and electron‐rich benzene rings dominate the lattice microstrain of 2D (p‐FPEA)2PbI4 perovskite, which can be released by interlayer interactions pulling during compressively bending the flexible devices. This strong electrostatic interaction can maximally release the compression to the inorganic octahedron skeleton during compressive bending, leading to a maximum degree of released microstrain with improved stability. The 60% microstrain can be released by compressive bending, and the corresponding photocurrent response is recovered by about three times in (p‐FPEA)2PbI4 perovskite film. In contrast, intralayer supramolecular interactions dominate microstrain of 2D (o‐FPEA)2PbI4 perovskites, which prevents the microstrain release during compressive bending. The strong electrostatic interaction design in the organic spacer of 2D perovskite takes an important role in releasing the microstrain and re‐bursting the device performance of flexible perovskite devices.
Metalloid‐Cluster Ligands Enabling Stable and Active FeN4‐Ten Motifs for the Oxygen Reduction Reaction
Authors: Ji Bifa , Gou Jiali , Zheng Yongping , Zhou Xiaolong , Kidkhunthod Pinit , Wang Yehai , Tang Qingyun , Tang Yongbing
Published: May 2022

In nature, the oxygen reduction reaction (ORR) is catalyzed by cytochrome P450 (CYP) enzymes containing heme iron centers with an axial thiolate ligand (FeN4‐S), which are among the most finely developed catalysts by natural selection. However, the exceptional ORR activity and selectivity of CYP enzymes originate from their non‐rigid and self‐adaptive coordination network with molecular ligands, which sacrifices the stability of the active motifs under electrochemical reaction conditions. Here, a design strategy to circumvent this dilemma by incorporating Fe‐N4 motifs into carbon matrices instead of the protein scaffold and replacing the axial molecular thiolate ligand with a stable tellurium cluster (Ten) is demonstrated. Theoretical calculations indicate a moderate interaction between Fe 3d and Te 5p orbitals once n > 2, allowing the FeTe bond to dynamically change its strength to adaptively facilitate the intermediate steps during the ORR process, which renders FeN4‐Ten active sites with superior ORR activity. This adaptive behavior mimics the conformational dynamics of an enzyme during the reaction, but retains the stability nature as a heterogeneous catalyst. The experiments validate that the as‐designed catalyst with a characterized FeN4‐Ten structure outperforms the commercial Pt/C catalyst both on activity and stability.
On the Role of Collective Electrostatic Effects in Electronic Level Pinning and Work Function Changes by Molecular Adlayers: The Case of Partially Fluorinated DNTTs Adsorbed Flat‐Lying on Various Metals and Hetero‐Structures
Authors: Dreher Maximilian , Cornil David , Tripp Matthias W. , Koert Ulrich , Cornil Jérôme , Witte Gregor
Published: May 2022

Modifying the work function of metal electrodes by monolayers of molecules with specifically tailored electronic properties is a versatile tool, but such chemical modifications often also affect the adsorption geometry and packing density, making microscopic modeling difficult. Using scanning tunneling microscopy, it is shown that the recently synthesized partially fluorinated dinaphthothienothiophenes (DNTTs) adopt the same interface structure on different metal substrates independent of the degree of fluorination. Combining Kelvin probe measurements and density functional theory (DFT) calculations, a highest occupied molecular orbital (HOMO) pinning effect for such FxDNTTs on Au(111) and Ag(111) induced by collective electrostatic interactions in the monolayer is observed. Since the adsorption of weakly interacting molecules such as the FxDNTTs is not restricted to specific surfaces as is the case with SAMs, this concept is extended to metal substrates with quite different work function values. For a low work function surface such as Cs(110), a lowest unoccupied molecular orbital (LUMO) pinning effect is predicted at the theoretical level. Since such alkali metal surfaces are not experimentally accessible, a well‐defined Cs monolayer on Cu(100) as a low work function substrate is used instead. For this substrate, however, a variation is observed in the LUMO energies and the work function as a function of the degree of fluorination. This is attributed to the formation of a second interface dipole at the buried Cs/Cu interface, which is modulated with the degree of fluorination and competes with the dipole at the outer molecule/Cs interface. Such a second internal interface dipole, which can be modified by the top layer, has to be considered when going to more complex heterointerfaces.
Transition‐Metal‐Catalyzed, Chelation‐Assisted C−H Alkenylation and Allylation of Organic Molecules with Unactivated Alkenes
Authors: Logeswaran Ravichandran , Jeganmohan Masilamani
Published: May 2022

Olefins are important building blocks and are widely utilized in synthetic organic chemistry. Owing to its omnipresence and unique reactivity, the functionalization of alkenes has become a powerful method for constructing complex organic molecules. In this context, direct chelation‐assisted C−H olefination at the inert C−H bonds represents the most straightforward synthetic method for introducing the alkenyl group into organic compounds in a highly regio‐ and stereoselective manner. Despite the remarkable advances in chelation‐assisted C−H olefination reaction, most of the successful transformations are restricted to activated or electronically biased olefins such as acrylates, styrenes, acrylamides, vinyl sulfones, and vinyl phosphonates. Literature reports on chelation‐assisted C−H olefination with unactivated or electronically unbiased alkenes are limited due to poor intrinsic reactivity and regioselectivity issues. Despite significant challenges, the past few years have witnessed tremendous growth. The present review describes the recent advances in the chelation‐assisted C−H olefination and allylation of aromatics, alkenes, and heteroaromatics with unactivated alkenes via the concerted‐metallation‐ deprotonation pathway.Transition metals such as palladium, rhodium, iridium and cobalt are widely used for these kind of transformations. The scope, mechanistic investigation, and limitation of the alkenylation and allylation reactions are discussed elaborately. The present review includes all the reported C−H olefination and allylation reactions with unactivated olefins via the base‐assisted deprotonation pathway.

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Simultaneous mixed‐integer dynamic scheduling of processes and their energy systems
Authors: Baader Florian Joseph , Bardow André , Dahmen Manuel
Published: May 2022

Increasingly volatile electricity prices make simultaneous scheduling optimization desirable for production processes and their energy systems. Simultaneous scheduling needs to account for both process dynamics and binary on/off‐decisions in the energy system leading to challenging mixed‐integer dynamic optimization problems. We propose an efficient scheduling formulation consisting of three parts: a linear scale‐bridging model for the closed‐loop process output dynamics, a data‐driven model for the process energy demand, and a mixed‐integer linear model for the energy system. Process dynamics is discretized by collocation yielding a mixed‐integer linear programming (MILP) formulation. We apply the scheduling method to three case studies: a multiproduct reactor, a single‐product reactor, and a single‐product distillation column, demonstrating the applicability to multiple input multiple output processes. For the first two case studies, we can compare our approach to nonlinear optimization and capture 82% and 95% of the improvement. The MILP formulation achieves optimization runtimes sufficiently fast for real‐time scheduling.
Odorant Metabolism in Humans
Authors: Kornbausch Nicole , Debong Marcel W. , Buettner Andrea , Heydel Jean‐Marie , Loos Helene M.
Published: May 2022

Odorants are relatively small molecules which are easily taken up and distributed in the human body. Despite their relevance in everyday life, however, only a limited amount of evidence about their metabolism, pathways, and bioactivities in the human body exists. With this Review, we aim to encourage future interdisciplinary research on the function and mechanisms of the biotransformation of odorants, involving different disciplines such as nutrition, medicine, biochemistry, chemistry, and sensory sciences. Starting with a general overview of the different ways of odorant uptake and enzymes involved in the metabolism of odorants, a more precise description of biotransformation processes and their function in the oral cavity, the nose, the lower respiratory tract (LRT), and the gastrointestinal tract (GIT) is given together with an overview of the different routes of odorant excretion. Finally, perspectives for future research are discussed.
Kinetic study of liquid lipase‐catalyzed glycerolysis of olive oil using Lipozyme TL 100L
Authors: Finco George F. , Fiametti Karina G. , Lobo Viviane da Silva , da Silva Edson A. , Palú Fernando , Wancura João H. C. , Rodrigues Maria L. F. , Valério Alexsandra , de Oliveira José Vladimir
Published: May 2022

Monoacylglycerol (MAG) and diacylglycerol (DAG) are two natural components found in most edible oils and fats. Conventional synthesis of MAG and DAG is usually conducted by glycerolysis of triacylglycerol (TAG) at high temperatures (above 200°C) in the presence of an alkaline catalyst. In this work, the synthesis of MAG and DAG using enzymatic glycerolysis of olive oil was investigated using Tween 80 as surfactant, n‐butanol as co‐surfactant and the novel lipase in free/liquid formulation Lipozyme TL 100L as catalyst. Experimental design was used to evaluate the effect of enzyme load and reaction temperature on the feedstock conversion. Enzyme load and system temperature were significant variables in the statistical design and the best condition was found at 35°C, 7.5 vol% of Lipozyme TL 100L and glycerol to oil volumetric ratio of 2:1 with conversion of TAG at approximately 98% after 2 h of process. A mathematical model based on the Ping‐Pong Bi‐Bi mechanism was used to describe the reaction kinetics. The model adequately described the behavior of the system and can be a useful tool for the design of reactors in larger scales.
Construction of a Mitochondria‐Endoplasmic Reticulum Dual‐Targeted Red‐Emitting Fluorescent Probe for Imaging Peroxynitrite in Living Cells and Zebrafish
Authors: He Lingchao , Liu Heng , Wu Jinsheng , Cheng Ziyi , Yu Fabiao
Published: May 2022

Peroxynitrite (ONOO−) is one of the important reactive oxygen species, which plays a vital role in the physiological process of intracellular redox balance. Revealing the biological functions of ONOO−will contribute to further understanding of the oxidative process of organisms. In this work, we designed and synthesized a novel red‐emitting fluorescent probe MCSA for the detection of ONOO−, which could rapidly respond to ONOO−within 250 s and exhibited high sensitivity to ONOO−with a low detection limit of 78 nM. Co‐localization experiments demonstrated MCSA had the ability to localize into the mitochondria and endoplasmic reticulum. What's more, MCSA enabled monitoring ONOO−level changes during tunicamycin‐induced endoplasmic reticulum stress. We have also successfully achieved the visual detection of exogenous and endogenous ONOO−in living cells and zebrafish. This work presented a chemical tool for imaging ONOO−in vitro and in vivo.
Separation Efficiency Measurements with Non‐Volatile Components and Elevated Feed Viscosities
Authors: Gutperl Sven , Wolke Martin , Jasch Katharina , Scholl Stephan
Published: May 2022

Common mass transfer models for multistage distillation show significant deviations between calculated and experimental height equivalent to a theoretical plate (HETP) values for viscous feed mixtures. This is due to a limited transferability of the available data which were mainly obtained from experiments with inviscid mixtures. Separation efficiency measurements at elevated viscosities can be conducted with polymer‐enhanced test mixtures and require an alternative plant setup. This contribution addresses the development of an improved plant setup suitable to conduct such separation efficiency measurements. General design considerations, simulative feasibility studies, and plant characterization experiments as well as separation efficiency measurements will be discussed.
Electrochemical Pretreatment of Solid–Electrolyte Interphase Formation for Enhanced Li4Ti5O12 Anode Performance in a Molten Li–Ca Binary Salt Hydrate Electrolyte
Authors: Kondou Shinji , Watanabe Yoshifumi , Dokko Kaoru , Watanabe Masayoshi , Ueno Kazuhide
Published: May 2022

Invited for this month's cover picture is the group of Prof. Kazuhide Ueno from Yokohama National University (Japan). The cover picture illustrates that less‐water‐soluble Ca‐based solid electrolyte interphase formed in a Li–Ca binary salt hydrate electrolyte effectively mitigates electrochemical reduction of water, leading to improvement in the cycle performance of a Li4Ti5O12 electrode. Read the full text of the Research Article at 10.1002/celc.202200061.
Molecular Bridging Enables Isolated Iron Atoms on Stereoassembled Carbon Framework To Boost Oxygen Reduction for Zinc‐Air Batteries
Authors: Wang Wenqing , Rui Kun , Wu Kaili , Wang Yisha , Ke Longwei , Wang Xin , Xu Feng , Lu Yan , Zhu Jixin
Published: May 2022

Realizing the synergy between active site regulation and rational structural engineering is essential in the electrocatalysis community but still challenging. Here, a matrix‐confined co‐pyrolysis strategy based on molecular bridging is demonstrated to realize highly dispersed Fe atoms on stereoassembled carbon framework. Both polyacrylonitrile matrix and organic linker from metal–organic frameworks (MOFs) provide sufficient N‐anchoring sites for the generation of Fe−N4 moieties. A high Fe loading of 2.9 wt.% is readily achieved based on the scalable approach without post‐treatment. Owing to the presence of highly exposed Fe−N−C sites and well‐tuned pore structures, isolated Fe atoms on porous carbon nanofiber framework (Fe−SA/NCF) exhibits decent oxygen reduction activity and stability in alkaline conditions via a near four‐electron path, demonstrating superior performance as air cathode for zinc‐air batteries (ZABs) to commercial Pt/C catalyst.
Utility of 2‐Diphenylphosphoryloxy‐1,3‐Dienes in Multicomponent Hetero‐Diels–Alder Reactions to Construct Functionalized Six‐Membered Nitrogen Heterocycles
Authors: He Qiuyu , Cao Lirong , Wei Yiran , Dake Gregory R.
Published: May 2022

The utility of 2‐diphenylphosphoryloxy‐1,3‐dienes for the construction of substituted six‐membered nitrogen heterocycles is presented. These dienes undergo boron trifluoride‐promoted aza‐Diels–Alder reactions when reacted with imines or related species formed in situ using aldehydes and amine derivatives. The stability of the dienes allows this three‐component reaction to be carried out with no special precautions to eliminate water or air. Thirty‐one examples of this process are presented. The usefulness of the enol phosphate functional group is highlighted in further reactions after the cycloaddition step to generate functionalized piperidenes or pyridines.
Construction of Hierarchical NiCo2O4@NiFe‐LDH Core‐Shell Heterostructure for High‐performance Positive Electrode for Supercapacitor
Authors: Luo Dapeng , Yong Yi , Hou Jiang , Guo Weiguang , Liu Hengbo , Zhao Xue , Xiang Jingrong , ZongZong Nima , Han Yuqi , Yan Minglei
Published: May 2022

In this work, the hierarchical NiCo2O4@NiFe‐layered double hydroxide (NiCo2O4@NiFe‐LDH) heterostructure has been successfully synthesized by sequential hydrothermal method, heat treatment and electrodeposition, which is investigated as high‐performance positive electrode for supercapacitor. In this unique structure, on the one hand, the NiCo2O4 as the scaffold provide high conductivity, which accelerates the electron transfer. On other hand, the NiFe‐LDH nanosheets increase the surface area, which offers abundant active sites for electrochemical reaction. Furthermore, the three‐dimensional (3D) hierarchical structures are beneficial to the diffusion for electrolyte ions. Hence, the synergistic effect between NiCo2O4 and NiFe‐LDH endows the optimal NiCo2O4@NiFe‐LDH‐150/CC with excellent electrochemical performance, such as high areal specific capacitance (1.09 F cm−2@1 mA cm−2), small charge‐transfer resistance (0.35 Ω) and superior cycling stability. This study demonstrates the NiCo2O4@NiFe‐LDH core‐shell heterostructures are promising positive electrode material for supercapacitors.
The Road to Bisacyldigermanes: A New Compound Class Suitable as Visible Light Photoinitiators
Authors: Wiesner Tanja , Glotz Gabriel , Wunnicke Odo , Bleger David , Knezevic Ivana , Torvisco Ana , Fischer Roland C. , Kelterer Anne‐Marie , Gescheidt Georg , Haas Michael
Published: May 2022

In this contribution we present a novel synthetic procedure towards a variety of bisacyldigermanes via the Corey‐Seebach approach. All isolated compounds were characterized by NMR spectroscopy, mass spectrometry and X‐ray crystallography. The target compounds were further analyzed via UV/Vis absorption spectroscopy and their longest wavelength absorptions were assigned by DFT calculations. Moreover, we determined the activity of our new photoinitiators by photolysis experiments (photobleaching). Additionally, CIDNP spectra confirmed the radical pathway of the investigated compounds.
Electrochemical Oxidation of HMF via Hydrogen Atom Transfer and Hydride Transfer on NiOOH and the Impact of NiOOH Composition
Authors: Bender Michael T. , Choi Kyoung‐Shin
Published: May 2022

A great deal of attention has been directed toward studying the electrochemical oxidation of 5‐hydroxymethylfurfural (HMF), a molecule that can be obtained from biomass‐derived cellulose and hemicellulose, to 2,5‐furandicarboxylic acid (FDCA), a molecule that can replace the petroleum‐derived terephthalic acid in the production of widely used polymers such as polyethylene terephthalate. NiOOH is one of the best and most well studied electrocatalysts for achieving this transformation; however, the mechanism by which it does so is still poorly understood. This study quantitatively examines how two different dehydrogenation mechanisms on NiOOH impact the oxidation of HMF and its oxidation intermediates on the way to FDCA. The first mechanism is a well‐established indirect oxidation mechanism featuring chemical hydrogen atom transfer to Ni3+ sites while the second mechanism is a newly discovered potential‐dependent (PD) oxidation mechanism involving electrochemically induced hydride transfer to Ni4+ sites. The composition of NiOOH was also tuned to shift the potential of the Ni(OH)2/NiOOH redox couple and to investigate how this affects the rates of indirect and PD oxidation as well as intermediate accumulation during a constant potential electrolysis. The new insights gained by this study will allow for the rational design of more efficient electrochemical dehydrogenation catalysts.
Through‐Space Electrostatic Effects of Positively Charged Substituents on the Hydrogen Evolution Reaction
Authors: Zhang Qingxin , Lei Haitao , Guo Hongbo , Wang Yabo , Gao Yimei , Zhang Wei , Cao Rui
Published: May 2022

Invited for this month's cover is the group of Rui Cao at Shaanxi Normal University. The image shows the effects of through‐space electrostatic interactions on the hydrogen evolution reaction. The Research Article itself is available at 10.1002/cssc.202200086.