bluuebunny/crossref_metadata_2025 huggingface dataset:
O Parfor como processo de formação inicial de professores para a educação básica no Brasil
Authors: Nepomuceno Frederico Batista
Published: August 2020

O artigo apresenta um estudo sobre programas fomentados pela Capes para a formação de professores, em especial o Plano Nacional de Formação de Professores da Educação Básica (Parfor), uma política pública educacional voltada para a formação inicial de professores, no período de 2007 a 2016. O objetivo foi conhecer e analisar o contexto dessa formação e compreender como ela é realizada. A partir do conceito de políticas públicas e formação de professores, embasado em Dourado (2015), Tardif (2014), Souza (2014) e Ghedin, Almeida e Leite (2008), foi feita a análise do contexto entre o que dizem os autores e o que está sendo realizado, no que tange às políticas públicas voltadas para programas de formação inicial e continuada de professores no Brasil, estando entre essas a formação inicial pelo Parfor. A metodologia da pesquisa se caracteriza como qualitativa, teve como corpus de análise documentos disponibilizados em sites oficiais e no Portal da Capes e os relatórios de prestação de contas de 16 Instituições de Ensino Superior, os quais possibilitaram conhecer os programas da Capes, suas finalidades, o público envolvido e possíveis efeitos para a Educação Básica e vislumbrar, no caso do Parfor, um panorama sobre a conexão entre teoria e prática docente, como parte de um conjunto de políticas envolvendo a formação de professores. Os principais resultados apontam para a análise dos referidos relatórios, que procurou ver como as IES organizaram os cursos e quais resultados apontaram sobre o aprimoramento da prática docente.Palavras-chave: Professores - Formação. Educação e Estado - Brasil. Educação de base.
A percepção dos gestores da unidade de controle interno em um órgão público do Rio Grande do Norte
Authors:   Universidade do Estado do Rio Grande do Norte, Silva Sérgio Luiz Pedrosa , Costa Wênyka Preston Leite Batista da ,   Universidade do Estado do Rio Grande do Norte, Silva Jandeson Dantas da , Nascimento Ítalo Carlos Soares do , Rodrigues Rafael Ramon Fonseca ,   Universidade Federal do Ceará
Published: August 2020

O objetivo desse estudo foi analisar a percepção dos gestores de um órgão público no RN no tocante ao conhecimento e procedimentos da Unidade de Controle Interno (UCI). A pesquisa classifica-se como quantitativa, possui caráter descritivo, tendo como procedimento técnico o levantamento do tipo survey. Os dados foram coletados através de questionário, estruturado com 15 perguntas diretas, atingindo 78 gestores. Os resultados evidenciaram que 80% dos gestores destacaram desconhecer as legislações internas da UCI; 75% visualizam a UCI como órgão de controle a posteriori; e 83% apontaram a falta de feedback sobre os processos. Além disso, constataram-se problemas relacionados ao modelo COSO, especialmente quanto ao ambiente de controle, informação e comunicação, e sobre as atividades de controle. Evidenciou-se ainda a necessidade de promover melhorias, principalmente no tocante a gestão da UCI. A pesquisa apresenta contribuições ao destacar a necessidade desse órgão público direcionar estratégias gerenciais para resolver os problemas apresentados em sua gestão, tendo em vista que os problemas evidenciados podem servir de direcionador para promover melhorias em outras UCI’s, as quais fazem parte das estruturas dos órgãos públicos do Brasil.
Características da informação ambiental das empresas da construção civil listadas na b3
Authors:   Centro Universitário de João Pessoa, Brito Izabelle Cris Dias de , Santos Lívia Maria da Silva ,   Universidade Federal de Rondônia
Published: August 2020

O presente estudo tem o propósito de analisar as características da informação ambiental divulgadas pelas empresas da construção civil listadas na Brasil, Bolsa, Balcão. Para a realização da pesquisa, foram analisadas as Demonstrações Financeiras Padronizadas (DFPs), os Formulários de Referência (FR), os Relatórios Anuais (RAN) e de Sustentabilidade (RS), no período de 2010 a 2016. Para analisar as características da informação ambiental foi utilizada uma estrutura dividida em nove categorias, composta por 38 itens, de acordo com o estudo de Santos (2016). A partir da análise de conteúdo, foram definidos três critérios de classificação, que compreendem a evidência (declarativa, quantitativa monetária ou quantitativa e monetária), o tipo de notícia evidenciada (boa, ruim, ou neutra) e a localização da informação (DFPs, FR, RA e RS). Os resultados obtidos na pesquisa demonstram que as empresas concentram as informações ambientais, principalmente, nos Formulários de Referência. No que se refere ao tipo de notícia, foi possível perceber que cerca de 50% das empresas optam por divulgar notícias boas. As informações ruins compreenderam seis das dezoito empresas do estudo. Constatou-se que a maioria das informações foi divulgada pelas companhias de forma declarativa. Estes resultados contribuem para o entendimento de que, conforme enunciam as Teorias da Legitimidade e dos Stakeholders, as empresas, como forma de mostrar suas ações, de modo a atender a demanda informacional das suas partes interessadas e garantir a sua legitimidade, evidenciam informações de natureza ambiental, mesmo que não sejam obrigadas por força de lei.
Tarification des risques agricoles au Sénégal
Authors: Diop Allé Nar
Published: August 2020

L’objectif de cet article est de déterminer la prime pure à payer par l’agriculteur sénégalais assuré à des risques classiques. L’utilisation du modèle linéaire général (GLM) a permis de déterminer la fréquence et la sévérité en fonction des différents types de risques auxquels sont exposés les agriculteurs. Nous avons montré que le nombre de sinistres suit une loi zéro-inflation binomial négative et le coût une distribution log-normal. Nous avons aussi montré que les risques sanitaires, les invasions acridiennes (criquets pèlerins), d’animaux et de canards et d’oiseaux sauvages, la présence de nématodes et de pourriture de collet sont les risques auxquels l’agriculture est exposée. Le modèle estime une prime plus élevée que la prime observée pour les animaux sauvages, les maladies, les oiseaux granivores et les oiseaux sauvages. En revanche, la prime calculée est inférieure à celle observée pour les canards sauvages et les criquets pèlerins. La différence entre la prime observée et celle calculée s’explique par le fait que le premier est évalué à partir de la valeur du capital assuré et non du risque auquel l’agriculteur est exposé. Pour une meilleure tarification, la compagnie d’assurance devra tenir compte du type de risque auquel chaque assuré est le plus exposé et déterminer la prime correspondante. Cette segmentation permettra de déterminer la prime adéquate.
Grounds for finding a legal entity to be the subject of criminal liability for corruption crimes
Authors: Sheirenov Zhanatbek Nurlanovich
Published: August 2020

The object of this research is the question of criminal liability of a legal entity for corruption crimes. The subject of this research is the theoretical views of the scholars upon legal nature of a legal entity, as well as the experience of foreign countries in which legal entity is a subject of criminal liability. The author explores the field experience of foreign countries, in which legislation establishes the institution of collective liability for socially dangerous acts committed by private entities. The article also analyzes different perspectives of Russian scholars upon the nature of collective institution and its vicarious liability for the acts of private entities. The scientific novelty consists in turning attention to the fundamentals of the theory and other branches of law, in which a legal entity is full subject of legal relations, and along with the rights and responsibilities, possesses a tort law’s capacity. It is concluded that legal entity has all essential characteristics of the subject of law for its recognition as a subject of criminal liability. The author also notes the effectiveness and necessity of the institution of legal liability of a legal entity in the national legislation as a productive criminal law instrument for countering corruption.  
Impact of proliferation of the new COVID-19 infection upon the changes social security legislation
Authors: Grigorev Ivan Vladimirovich
Published: August 2020

The subject of this research is the changes in the Russian social security legislation during the spread of new COVID-19 infection. The article examines the transformation of material legal relations associate with granting allowance for temporary incapacity for work, unemployment compensations, lump-sum payments and monthly payments to families with children. The author meticulously analyzes the questions of legal regulation of the additional compensations to various categories of citizens, established by the normative legal acts of the constituent entities of the Russian Federation. Special attention is paid to the implementation of distance interaction of citizens with the social security bodies of the Russian Federation, as well as the possibility to render assistance without the need to apply. The scientific novelty of this work consists in the comprehensive research of the dynamics of social security legislation aimed at neutralization of negative consequences of proliferation of the new COVID-19 infection and maintenance of the level of well-being of the citizens. The author’s special contribution lies in determination and analysis of the grounds for granting social security at the time of pandemics, as well as changes in the size of compensations. The conclusion is made on underutilization of resources of the compulsory social insurance, which led to the need for implementation of a set of new measures on social security of the citizens on the federal and regional levels.
"CULTURA DE TRABALHO NA CUBA DE HOJE: DESAFIOS E CONTRADIÇOES A SUPERAR". UMA ENTREVISTA COM O SOCIÓLOGO JOSÉ LUIS MARTÍN ROMERO.
Authors: Herrera Yeisa Sarduy
Published: August 2020

O material compara a entrevista realizada ao sociólogo cubano José Luis Martín Romero é um dos temas da cultura do trabalho no contexto cubano. O diálogo suportado, a centralidade de estudo no domínio académico, os maus tratos na realidade laboral de hoje, assim como os tópicos pendentes nas agendas investigativas relativas à temática em questão.
Fixed‐time synchronization for discontinuous delayed complex‐valued networks with semi‐Markovian switching and hybrid couplings via adaptive control
Authors: Liu Shujin , Wu Huaiqin , Cao Jinde
Published: August 2020

In this article, the global fixed‐time synchronization issue is considered for semi‐Markovian switching discontinuous complex‐valued dynamical networks (CVDNs) with hybrid couplings and time‐varying delays, in which CVDNs are not divided into two real value systems, contrary to existing literature. First, a new fixed‐time convergence principle for complex‐valued nonlinear system with semi‐Markovian switching is developed. Second, to realize the fixed‐time synchronization, the state feedback controller with integral term and adaptive controller are designed, respectively. Under the complex‐valued differential inclusions framework, by utilizing Lyapunov‐Krasovskii functional method and inequality analysis technique, the global fixed‐time synchronization conditions are addressed in terms of linear matrix inequalities. Finally, two numerical simulations are given to illustrate the validity of the presented theoretical results.
Microskeleton‐Nanofiller Composite with Mechanical Super‐Robust Superhydrophobicity against Abrasion and Impact
Authors: Qing Yongquan , Shi Songlin , Lv Cunjing , Zheng Quanshui
Published: August 2020

Superhydrophobic surfaces have promised tremendous applications in living and industrial areas for the past two decades. Real applications, however, meet challenges, with the central concern being the robustness to resist mechanical abrasions and impacts. Here, a revolutionary strategy is proposed to create a microskeleton‐nanofiller (MSNF) film with exceptionally mechanical superstable superhydrophobicity. The strategy is conceptually different from the traditional superhydrophobic 3D microskeleton, because a 3D microskeleton is used to completely fill in the infused superhydrophobic medium. The resulting MSNF film can reserve superhydrophobicity under not only continuous abrasion before the complete wearing off the film, but also Taber abrasion, knife‐scratch, and cyclic tape peels. In addition, the MSNF film enables damage resistance to heavy impact at least up to a kinetic energy of ≈40.2 J. Furthermore, the MSNF film is also superamphiphobic to prevent oil contamination and can reserve the superhydrophobicity under large bending or torsion. Together with robustness and scalability, the MSNF film will be useful in automobiles, ships, aircraft, and houses in harsh environments and the strategy can extend to various inexpensive structured materials (such as porous iron).
Superior Noise Suppression, Response Time, and Device Stability of Non‐Fullerene System over Fullerene Counterpart in Organic Photodiode
Authors: Jang Woongsik , Rasool Shafket , Kim Byung Gi , Kim Jehan , Yoon Jinhwan , Manzhos Sergei , Lee Hang Ken , Jeon Il , Wang Dong Hwan
Published: August 2020

Herein, non‐fullerene acceptor‐based organic photodiodes are compared with fullerene acceptor‐based organic photodiodes. The non‐fullerene acceptor, ethylhexyl‐rhodanine‐benzothiadiazole‐coupled indacenodithiophene (eh‐IDTBR)‐based organic photodiodes show a higher detectivity (1.61 × 1013 cm Hz1/2 W−1) and a faster response time (≈2.7 µs) than the fullerene acceptor, [6,6]‐phenyl C71 butyric acid methyl ester (PC71BM)‐based organic photodiodes (3.25 × 1012 cm Hz1/2 W−1 and ≈6.24 µs, respectively) owing to the excellent dark current suppression of the carrier injection and the low trap density of eh‐IDTBR. Moreover, the eh‐IDTBR‐based photodetector shows better operational device stability than the fullerene counterpart under electrical and thermal stress. This is corroborated by the morphology and crystallography analyses, both of which reveal that the eh‐IDTBR‐containing photo‐sensitive films remain intact after imposing an external stress. This study elucidates important key advantages of the non‐fullerene acceptor, eh‐IDTBR, and sets a milestone as it compares the non‐fullerene acceptors and fullerene acceptors in organic photodiodes for the first time. This work sets a new record for the performance and stability of solution‐processable non‐fullerene acceptor‐based organic photodiodes.
Optimizing Bifurcated Channels within an Anisotropic Scaffold for Engineering Vascularized Oriented Tissues
Authors: Fang Yongcong , Ouyang Liliang , Zhang Ting , Wang Chengjin , Lu Bingchuan , Sun Wei
Published: August 2020

Despite progress in engineering both vascularized tissues and oriented tissues, the fabrication of 3D vascularized oriented tissues remains a challenge due to an inability to successfully integrate vascular and anisotropic structures that can support mass transfer and guide cell alignment, respectively. More importantly, there is a lack of an effective approach to guiding the scaffold design bearing both structural features. Here, an approach is presented to optimize the bifurcated channels within an anisotropic scaffold based on oxygen transport simulation and biological experiments. The oxygen transport simulation is performed using the experimentally measured effective oxygen diffusion coefficient and hydraulic permeability of the anisotropic scaffolds, which are also seeded with muscle precursor cells and cultured in a custom‐made perfusion bioreactor. Symmetric bifurcation model is used as fractal unit to design the channel network based on biomimetic principles. The bifurcation level of channel network is further optimized based on the oxygen transport simulation, which is then validated by DNA quantification assay and pimonidazole immunostaining. This study provides a practical guide to optimizing bifurcated channels in anisotropic scaffolds for oriented tissue engineering.
A Review of Bioresorbable Implantable Medical Devices: Materials, Fabrication, and Implementation
Authors: Singh Rahul , Bathaei Mohammad Javad , Istif Emin , Beker Levent
Published: August 2020

Implantable medical devices (IMDs) are designed to sense specific parameters or stimulate organs and have been actively used for treatment and diagnosis of various diseases. IMDs are used for long‐term disease screening or treatments and cannot be considered for short‐term applications since patients need to go through a surgery for retrieval of the IMD. Advances in bioresorbable materials has led to the development of transient IMDs that can be resorbed by bodily fluids and disappear after a certain period. These devices are designed to be implanted in the adjacent of the targeted tissue for predetermined times with the aim of measurement of pressure, strain, or temperature, while the bioelectronic devices stimulate certain tissues. They enable opportunities for monitoring and treatment of acute diseases. To realize such transient and miniaturized devices, researchers utilize a variety of materials, novel fabrication methods, and device design strategies. This review discusses potential bioresorbable materials for each component in an IMD followed by programmable degradation and safety standards. Then, common fabrication methods for bioresorbable materials are introduced, along with challenges. The final section provides representative examples of bioresorbable IMDs for various applications with an emphasis on materials, device functionality, and fabrication methods.
Recent Advances in Radical C−H Bond Functionalization of Imidazoheterocycles
Authors: Patel Om P. S. , Nandwana Nitesh K. , Legoabe Lesetja J. , Das Bhaskar C. , Kumar Anil
Published: August 2020

Direct C−H bond functionalization through radical pathway has emerged as a powerful and ideal strategy for the synthesis of organic compounds. This review provides an overview of recent developments in radical C−H functionalization of imidazoheterocycles such as imidazo[1,2‐a]pyridine, benzo[d]imidazo[2,1‐b]thiazole, imidazo[2,1‐b]thiazole, imidazo[1,2‐a]pyrimidine, imidazo[2,1‐a]isoquinoline, imidazo[1,2‐a]pyrazine and imidazo[1,2‐a]quinoline using organic peroxides, photo/electric‐induced protocols, iodine‐based reagents, first‐row transition metal catalysts (Fe, Mn, Ni and Cu) and inorganic oxidants/or salts.

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Semiconducting Carbon Nanotubes Embedded in a Metallic Film for a Thermistor Device with an Adjustable Temperature Coefficient and Reduced Noise Source Activities
Authors: Shin Narae , Cho Youngtak , Kim Jeongsu , Hong Seunghun
Published: August 2020

Semiconducting single‐walled carbon nanotube‐Au (sSWCNT‐Au) hybrid films are prepared to build a thermistor device with an adjustable temperature coefficient and show that the embedded sSWCNTs reduce the resistivity and noise source activities in the nanoscale regions of the film. The temperature coefficient of the hybrid films can be adjusted from negative to positive values simply by increasing the deposited Au thickness. Moreover, scanning noise microscopy is utilized to map the nanoscale variation of the resistivity and noise source density on the sSWCNT‐Au hybrid films. Interestingly, the map shows that the regions with both sSWCNT and Au exhibit three times lower resistivity and 18 times smaller noise source activities than pristine Au regions, indicating that sSWCNTs embedded in metallic films can significantly reduce the resistivity and electrical noise source activities in the film.
Cotton boll distribution and yield estimation using three‐dimensional point cloud data
Authors: Dube Nothabo , Bryant Benjamin , Sari‐Sarraf Hamed , Ritchie Glen L.
Published: August 2020

Node‐by‐node boll mapping has been used to determine the effects of several environmental and management strategies, including irrigation rate and cultivar, on cotton (Gossypium hirsutum L.) boll distribution. The advent of consumer 3D digital imaging may make rapid node‐by‐node mapping of greater acreage possible in the future. Effects of irrigation rate and cultivar on boll distribution were determined from line plots of node‐specific boll distribution and boll accumulation estimate data and from vertical box and whisker plots of boll fraction using data collected by a 3D sensor system to rapidly detect open bolls before harvest over three seasons. Differences were observed between the dryland (2018 only), low irrigation, and high irrigation rates in terms of boll fraction and boll accumulation for each cultivar. The low irrigation tended to produce bolls more toward the bottom of the plant, while the high irrigation produced bolls towards the top of the plant. Yield correlation between sensor obtained and manually counted measurements was strong, with r2 values as high as 0.87. Results obtained indicated that differences among irrigation rate and cultivar were identifiable using the sensor system during the 3 yr research study. Similar systems may allow rapid, broad‐scale identification of boll distribution and yield in breeding and physiology research in the future, leading to improved identification of elite cultivars and improved management practices in cotton.
Novel progressive acrodysostosis‐like skeletal dysplasia, cerebellar atrophy, and ichthyosis
Authors: Velasco Harvy M. , Ullah Ehsan , Martin Angela M. , Hufnagel Robert B. , Prada Carlos E.
Published: August 2020

Acrodysostosis refers to a rare heterogeneous group of bone dysplasias that share skeletal features, hormone resistance, and intellectual disability. Two genes have been associated with acrodysostosis with or without hormone resistance (PRKAR1A and PDE4D). Severe intellectual disability has been reported with acrodysostosis but brain malformations and ichthyosis have not been reported in these syndromes. Here we describe a female patient with acrodysostosis, intellectual disability, cerebellar hypoplasia, and lamellar ichthyosis. The patient has an evolving distinctive facial phenotype and childhood onset ataxia. X‐rays showed generalized osteopenia, shortening of middle and distal phalanges, and abnormal distal epiphysis of the ulna and radius. Brain magnetic resonance imaging showed cerebellar atrophy without other brainstem abnormalities. Genetic workup included nondiagnostic chromosomal microarray and skeletal dysplasia molecular panels. These clinical findings are different from any recognized form of acrodysostosis syndrome. Whole exome sequencing did not identify rare or predicted pathogenic variants in genes associated with known acrodysostosis, lamellar ichthyosis, and other overlapping disorders. A broader search for rare alleles absent in healthy population databases and controls identified two heterozygous truncating alleles in FBNL7 and PPM1M genes, and one missense allele in the NPEPPS gene. Identification of additional patients is required to delineate the mechanism of this unique disorder.
A case of rare isolated agnathia and literature review
Authors: Alexander Nicole L. , Chandy Binoy , Barton Geran , Liu Yi‐Chun Carol
Published: August 2020

Agnathia is a rare congenital malformation with unknown etiology characterized by absence of the mandible, microstomia, and tongue aplasia, often found to have other anomalies including holoprosencephaly. The purpose of this paper was to describe the symptoms and imaging of a case of isolated agnathia and to conduct a comprehensive literature review of reported patients with isolated agnathia. Case reports of isolated agnathia are very rare, with most infants as stillborn. We report a child's management of isolated agnathia with microstomia and tongue aplasia. A literature review was performed with focus on diagnosis, airway, and feeding management of isolated agnathia. Polyhydramnios was a common pregnancy complication reported in 25 out of the 39 patients in the case study. Five infants were stillborn, while 23 died within the neonatal period. Of the deceased infants within the neonatal period, 19 died within minutes to hours while four died within days to weeks. There are nine patients with agnathia that survived past infancy. The results of this study suggest that isolated agnathia is a rare malformation which requires a multi‐disciplinary approach for airway and feeding management.
Das Repositorium Chemotion: Infrastruktur für nachhaltige Wissenschaft in der Chemie**
Authors: Tremouilhac Pierre , Lin Chia‐Lin , Huang Pei‐Chi , Huang Yu‐Chieh , Nguyen An , Jung Nicole , Bach Felix , Ulrich Robert , Neumair Bernhard , Streit Achim , Bräse Stefan
Published: August 2020

Chemotion, ein Repositorium für Forschungsdaten aus der Chemie, das praktikable Lösungen für die aktuellen Herausforderungen zur Speicherung von Forschungsdaten bietet, wird vorgestellt. Es ermöglicht die Erhaltung domänenspezifischer Informationen in einem maschinenlesbaren Format. Seine umfassende Funktionalität bietet Optionen zur Sammlung, Aufbereitung und Wiederverwendung von Daten mit disziplinspezifischen Methoden und Datenverarbeitungswerkzeugen. Um die Kuration der Daten zu erleichtern, wurden für ausgewählte analytische Daten automatisierte Verfahren zu deren Prüfung implementiert. Chemotion bietet Funktionen für einen einfachen Datenveröffentlichungsprozess, einschließlich automatisierter DOI‐Generierung, Peer‐Review‐Workflows für die Begutachtung der Einreichungen und das Setzen von Embargo‐Zeiten. Die beschriebenen Entwicklungen wurden genutzt, um eine Forschungsdateninfrastruktur zum Aufbau einer neuen Forschungsdateninfrastruktur für ein neues, gemeinschaftsgetriebenes Repositorium als umfassende Alternative zu kommerziellen Datenbanken aufzubauen.
Discovery and Biosynthesis of Bolagladins: Unusual Lipodepsipeptides from Burkholderia gladioli Clinical Isolates**
Authors: Dashti Yousef , Nakou Ioanna T. , Mullins Alex J. , Webster Gordon , Jian Xinyun , Mahenthiralingam Eshwar , Challis Gregory L.
Published: August 2020

Two Burkholderia gladioli strains isolated from the lungs of cystic fibrosis patients were found to produce unusual lipodepsipeptides containing a unique citrate‐derived fatty acid and a rare dehydro‐β‐alanine residue. The gene cluster responsible for their biosynthesis was identified by bioinformatics and insertional mutagenesis. In‐frame deletions and enzyme activity assays were used to investigate the functions of several proteins encoded by the biosynthetic gene cluster, which was found in the genomes of about 45 % of B. gladioli isolates, suggesting that its metabolic products play an important role in the growth and/or survival of the species. The Chrome Azurol S assay indicated that these metabolites bind ferric iron, which suppresses their production when added to the growth medium. Moreover, a gene encoding a TonB‐dependent ferric‐siderophore receptor is adjacent to the biosynthetic genes, suggesting that these metabolites may function as siderophores in B. gladioli.
[Si(O2C6F4)2]14: Selbstassemblierung eines perfluorierten makrocyclischen Wirts durch Si‐O‐Bindungsmetathese mit niedriger Barriere
Authors: Hartmann Deborah , Greb Lutz
Published: August 2020

Die dynamisch‐kovalente Selbstassemblierung von 14 Bis(perfluorocatecholato)silan‐Einheiten führt zur Bildung von [Si(O2C6F4)2]14 – dem ersten perfluorierten Riesenmakrocyclus. Der Oligomerisierungsprozess wurde spektroskopisch verfolgt und der finale Makrocyclus durch Einkristall‐Röntgenbeugung analysiert. Das Molekül bildet einen starren Hohlraum, der zwei 1,2‐Dicarbadodecaborane aufnehmen kann. Berechnungen erklären die konsistente und reproduzierbare Bildung des 14‐mers und offenbaren eine nicht‐katalysierte Si‐O/Si‐O‐σ‐Bindungsmetathese mit einer außergewöhnlich niedrigen energetischen Barriere. Erstmalig wird dabei SiO4 – der gängigste Linker unserer Geosphäre – verwendet, um ein formdefiniertes kristallines Makromolekül zu konstruieren.
Molecular Engineering of NIR‐II Fluorophores for Improved Biomedical Detection
Authors: Lei Zuhai , Zhang Fan
Published: August 2020

The development of fluorophores for the second near‐infrared window (NIR‐II, 1000–1700 nm) represents an emerging, significant, and vibrant field in analytic chemistry, chemical biology, and biomedical engineering. The wavelength, brightness, and stability are three crucial factors that determine the performance of an NIR‐II fluorophore. Up to now, significant progress has been made in the development of NIR‐II fluorescence molecular probes, including the synthesis of D‐A‐D and D‐π‐A fluorophores with improved NIR‐II fluorescence imaging performance and the construction of off–on probes and ratiometric probes via energy transfer or molecular structure modification. In this review, we summarize the most recent advances in molecular engineering design strategies of NIR‐II fluorophores and probes, then highlight a selection of bioimaging and biosensing applications. We also provide perspectives on potential challenges and opportunities in this emerging field
Serial Femtosecond Zero Dose Crystallography Captures a Water‐Free Distal Heme Site in a Dye‐Decolorising Peroxidase to Reveal a Catalytic Role for an Arginine in FeIV=O Formation
Authors: Lučić Marina , Svistunenko Dimitri A. , Wilson Michael T. , Chaplin Amanda K. , Davy Bradley , Ebrahim Ali , Axford Danny , Tosha Takehiko , Sugimoto Hiroshi , Owada Shigeki , Dworkowski Florian S. N. , Tews Ivo , Owen Robin L. , Hough Michael A. , Worrall Jonathan A. R.
Published: August 2020

Obtaining structures of intact redox states of metal centers derived from zero dose X‐ray crystallography can advance our mechanistic understanding of metalloenzymes. In dye‐decolorising heme peroxidases (DyPs), controversy exists regarding the mechanistic role of the distal heme residues aspartate and arginine in the heterolysis of peroxide to form the catalytic intermediate compound I (FeIV=O and a porphyrin cation radical). Using serial femtosecond X‐ray crystallography (SFX), we have determined the pristine structures of the FeIII and FeIV=O redox states of a B‐type DyP. These structures reveal a water‐free distal heme site that, together with the presence of an asparagine, imply the use of the distal arginine as a catalytic base. A combination of mutagenesis and kinetic studies corroborate such a role. Our SFX approach thus provides unique insight into how the distal heme site of DyPs can be tuned to select aspartate or arginine for the rate enhancement of peroxide heterolysis.
Tailoring Spectral and Photochemical Properties of Bioinspired Retinal Mimics by in Silico Engineering
Authors: El‐Tahawy Mohsen M. T. , Conti Irene , Bonfanti Matteo , Nenov Artur , Garavelli Marco
Published: August 2020

Controlling the spectral tunability and isomerization activity is currently one of the hot topics in the design of photoreversible molecular switches for application in optoelectronic devices. The present work demonstrates how to manipulate the absorption of the retinal protonated Schiff base (rPSB) chromophore over the entire visible range by targeted functionalization of the retinal backbone. Moreover, a correlation between the vertical excitation energy and the profile of the potential energy surface of the bright excited state responsible for the photoreactivity of rPSB is established. This correlation was exploited to rank the functionalized rPSBs into different classes with characteristic photoisomerization activity. Eventually, the synergic effects of functionalization and of external electric fields in the range of a few MV cm−1 were applied to achieve reversable and regioselective control of the photoisomerization propensity of selected rPBS derivatives.
Enantioselective Nickel‐Catalyzed Migratory Hydrocyanation of Nonconjugated Dienes
Authors: Yu Rongrong , Rajasekar Shanmugam , Fang Xianjie
Published: August 2020

Metal‐catalyzed chain‐walking reactions have recently emerged as a powerful strategy to functionalize remote positions in organic molecules. However, a chain‐walking protocol for nonconjugated dienes remains scarcely reported, and developments are currently ongoing. In this Communication, a nickel‐catalyzed asymmetric hydrocyanation of nonconjugated dienes involving a chain‐walking process is demonstrated. The reaction exhibits excellent regio‐ and chemoselectivity, and a wide range of substrates were tolerated, delivering the products in high yields and enantioselectivities. Deuterium‐labeling experiments support the chain‐walking process, which involves an iterative β‐H elimination and reinsertion processes. Gram‐scale synthesis, regioconvergent experiments, and downstream transformations gave further insights into the high potential of this transformation.
Posttranslationally Acting Arginases Provide a Ribosomal Route to Non‐proteinogenic Ornithine Residues in Diverse Peptide Sequences
Authors: Mordhorst Silja , Morinaka Brandon I. , Vagstad Anna L. , Piel Jörn
Published: August 2020

Ornithine is a component of many bioactive nonribosomal peptides but is challenging to incorporate into ribosomal products. We recently identified OspR, a cyanobacterial arginase‐like enzyme that installs ornithines in the antiviral ribosomally synthesised and posttranslationally modified peptide (RiPP) landornamide A. Here we report that OspR belongs to a larger family of peptide arginases from diverse organisms and RiPP types. In E. coli, seven selected enzymes converted arginine into ornithine with little preference for the leader type. A broad range of peptide sequences was modified, including polyarginine repeats. We also generated analogues of ornithine‐containing nonribosomal peptides using RiPP technology. Five pseudo‐nonribosomal products with ornithines at the correct positions were obtained, including a brevicidine analogue containing ornithine and a d‐amino acid installed by the peptide epimerase OspD. These results suggest new opportunities for peptide bioengineering.
Food‐Poisoning Bacteria Employ a Citrate Synthase and a Type II NRPS To Synthesize Bolaamphiphilic Lipopeptide Antibiotics**
Authors: Dose Benjamin , Ross Claudia , Niehs Sarah P. , Scherlach Kirstin , Bauer Johanna P. , Hertweck Christian
Published: August 2020

Mining the genome of the food‐spoiling bacterium Burkholderia gladioli pv. cocovenenans revealed five nonribosomal peptide synthetase (NRPS) gene clusters, including an orphan gene locus (bol). Gene inactivation and metabolic profiling linked the bol gene cluster to novel bolaamphiphilic lipopeptides with antimycobacterial activity. A combination of chemical analysis and bioinformatics elucidated the structures of bolagladin A and B, lipocyclopeptides featuring an unusual dehydro‐β‐alanine enamide linker fused to an unprecedented tricarboxylic fatty acid tail. Through a series of targeted gene deletions, we proved the involvement of a designated citrate synthase (CS), priming ketosynthases III (KS III), a type II NRPS, including a novel desaturase for enamide formation, and a multimodular NRPS in generating the cyclopeptide. Network analyses revealed the evolutionary origin of the CS and identified cryptic CS/NRPS gene loci in various bacterial genomes.
Tripalmitin‐Driven Crystallization of Palm Oil: The Role of Shear and Dispersed Particles
Authors: West Ryan , Rousseau Dérick
Published: August 2020

While palm oil (PO) is a reliable ingredient in formulations for biscuits, cream fillings, and compound chocolates, our understanding of its crystallization behavior and physico‐chemistry pales in comparison to many other fats and oils. Phase diagrams of triacylglycerol (TAG) mixtures may be used to elucidate fat crystal polymorphism and composition of such oils, yet conditions important to the food industry such as shear speed, relevant processing temperatures, and presence of secondary ingredients are regularly overlooked. Here, the effects of shear speed (n = 0–500 RPM), dispersion concentration (0–5 wt.%), and dispersed particle surface chemistry [silica or octadecyl‐functionalized (C18) silica] on the thermal properties of commercial PO when cooled from 60 to 20 °C at 1 °C min−1 were explored, with focus placed on PO's higher‐melting fraction. Using a series of high‐purity TAG standards, X‐ray diffraction revealed PO's higher‐melting fraction as mainly composed of tripalmitin (PPP) crystals and molecular compounds (MC) of PPP either with 1,3‐dipalmitoyl‐2‐oleoyl‐sn‐glycerol (POP) or with POP and 1,2‐dipalmitoyl‐3‐oleoyl‐rac‐glycerol (PPO) in combination, all in a double chain‐length β' (i.e., β'‐2) conformation. Shear increased the formation of lower‐melting α‐2 POP and β'‐2 MCPOP:PPO:PPP crystals while depleting the system of β'‐2 MCPOP:PPP and β'‐2 PPP crystals. This loss was further exacerbated by the addition of dispersed particles to the point where PPP was completely incorporated as MC and β'‐2 PPP crystals were eliminated. While heterogeneous nucleation tends to favor kinetic products of fat crystallization, the interactions between shear and surface chemistry varied between crystal types.
Novel Cocoa Butter Equivalent from Microalgal Butters
Authors: Ghazani Saeed M. , Marangoni Alejandro G.
Published: August 2020

An acetone solvent fractionation procedure was used to obtain two algal butter fractions, an algal stearin containing high amounts of 1,3‐stearoyl‐2‐oleoyl‐glycerol (SOS), and an algal mid‐fraction containing high amounts of 1,3‐dipalmitoyl‐2‐oleoyl‐glycerol (POP), and 1‐palmitoyl‐2‐oleoyl, 3‐stearoyl‐glycerol (POS). Algal stearin and algal mid‐fraction were blended (1:9 w/w) to yield a potential cocoa butter equivalent (CBE). The amount of POP, POS, and SOS, in algal CBE was 15.8%, 32.0%, and 24.6%, respectively, compared to 15.4%, 38.8%, and 27.7% in Cocoa butter (CB). However, a higher amount of POO and SOO in the algal CBE caused a lower solid fat content at all temperatures compared to CB. This study demonstrates the potential for producing a new algal CBE using solvent fractionation and blending techniques that can be used in chocolate and other confectionery products.
Cross‐linked poly(benzoxazole‐co‐siloxane) networks with high thermal stability and low dielectric constant based on a new ortho‐amide functional benzoxazine
Authors: Yang Rui , Hao Boran , Sun Lin , Zhang Kan
Published: August 2020

In this study, an amide functionalized bis‐benzoxazine (AI‐al) has been synthesized using allylamine, ortho‐amide functional bis‐phenol and paraformaldehyde as raw materials via Mannich condensation. This newly obtained benzoxazine has been used to react with polydimethylsiloxane (PDMS) through hydrosilylation to form poly(benzoxazine‐co‐amide‐co‐siloxane) (AI‐al‐PDMS) featuring siloxane, amide and benzoxazine as repeating units. The chemical structures of both oxazine ring‐containing monomer and copolymer are confirmed by NMR and FT‐IR spectroscopies. Besides, the thermally activated polymerization behaviors of AI‐al and AI‐al‐PDMS are investigated by DSC, and the subsequent conversion of benzoxazole formation is studied by in situ FT‐IR. Moreover, dynamic mechanical analysis and thermogravimetric analysis are used to determine the thermal properties of the cross‐linked polymers. The resulting cross‐linked poly(benzoxazole‐co‐siloxane) derived from AI‐al‐PDMS shows excellent thermal stability (no Tg can be observed before 400°C; Td5 of 393°C) and low dielectric constants (2.52–2.13 in the frequency range of 1 Hz to 1 MHz), evidencing its great potential applications in electronic packing, aerospace, and other high‐performance fields.
Movements, diving behaviour and diet of type‐C killer whales (Orcinus orca) in the Ross Sea, Antarctica
Authors: Lauriano Giancarlo , Pirotta Enrico , Joyce Trevor , Pitman Robert L. , Borrell Asunción , Panigada Simone
Published: August 2020

The fish‐eating, type‐C ecotype, killer whale is a top predator in the Ross Sea, Antarctica. Increasing knowledge of this animal's foraging habitats, diet and movement patterns is listed amongst the research priorities adopted under the framework of the Commission for the Conservation of Antarctic Marine Living Resources (CCAMLR).

To contribute to this goal, satellite transmitters were deployed on 10 type‐C killer whales and skin biopsies were obtained from seven individuals in Terra Nova Bay (Ross Sea) during austral summer (January–February) 2015. Hierarchical switching state–space models (hSSSM) were applied to Argos satellite tracking data to describe the movements of tagged whales, which were then paired with available diving data. Stable isotopes analyses were performed on the biopsy samples to describe the diet.

A total of 8,803 Argos locations were available to fit the hSSSM. All whales engaged in potential foraging activity in localized areas along the Ross Sea coastline, followed by uninterrupted travel (i.e. migration) outside Antarctic waters, with no evidence of foraging activity. The pattern of deeper dives matched the occurrence of encamped behaviour indicated by the hSSSM results. The stable isotopes analysis indicated that Antarctic toothfish comprised the largest component (35%) of the prey biomass, raising concerns since this species is targeted by commercial fishery in the Ross Sea Region.

These results provide new insights into the ecology of type‐C killer whales in the Ross Sea Region, underlining a potential threat from commercial fishing in the area. Considering the recent establishment of the Ross Sea Region Marine Protected Area, these findings will contribute to the required Research and Monitoring Programme of the Marine Protected Area and provide new empirical evidence to inform conservation measures in the existing Terra Nova Bay Antarctic Special Protected Area.
The antimalarial activity of indole alkaloids and hybrids
Authors: Li Jue‐Ying , Sun Xiao‐Feng , Li Jing‐Jing , Yu Fen , Zhang Yi , Huang Xiu‐Juan , Jiang Feng‐Xia
Published: August 2020

Malaria, caused by the genus Plasmodium, remains a global public health concern. It is estimated by the World Health Organization that over 40% of the world's population lives in areas at risk for malarial transmission, and around half a million people succumb to this infectious disease annually, which is related to the rapid spread of drug‐resistant parasite strains. Indole derivatives, which possess broad‐spectrum pharmacological properties, play a crucial role in the discovery of new drugs. Many indole derivatives exhibited potential in vitro and in vivo activity against both drug‐sensitive and drug‐resistant malaria, suggesting that the indole moiety is a useful template for the development of novel antimalarial agents. This review outlines the advances in indole alkaloids and hybrids with antimalarial potential in the recent decade.
Cell death‐inducing properties of selected dendrimers against different breast cancer and leukemia cell lines
Authors: Baecker Daniel , Kapp Timo , Schumacher Petra , Gust Ronald , Kircher Brigitte
Published: August 2020

Dendrimers represent an opportunity for targeted drug delivery into tumor cells. This is facilitated, for example, by loading of dendrimers with anticancer compounds. However, to assess the effects caused by such conjugates, knowledge of the cytotoxicity of the dendrimers themselves is necessary. The poly(amido amine)‐derived dendrimers G1(Phe)6, G1(Dan)3, and G2 were selected due to their different numbers of free amino groups and the poly(propylene imine) (PPI) dendrimer PPI‐G3 served as a reference. The compounds were evaluated for cell‐death induction using breast cancer (MCF‐7, MDA‐MB‐231) and leukemia (LAMA‐84, K562, SD‐1, SUP‐B15) cell lines. The compounds exhibited concentration‐dependent effects in the low micromolar range against the mammary carcinoma cells. A dependency on the generation, and particularly on the type of dendrimer, was deduced while the quantity of the free amino groups was subsidiary. G2 revealed to be most cytotoxic, also against all tested leukemia cell lines. The cell line SD‐1, however, was susceptible to all dendrimers. The mode of cell death was mainly determined by necrosis, especially at higher concentrations, while apoptosis played a subordinate role. The other dendrimers exerted no antimetabolic effects against LAMA‐84, K562, and SUP‐B15 cells. Therefore, these dendrimers are generally suitable as nontoxic drug carriers for leukemia cells.
Role of Substituents at 3‐position of Thienylethynyl Spacer on Electronic Properties in Diruthenium(II) Organometallic Wire‐like Complexes
Authors: Roy Sourav Saha , Chowdhury Sabyasachi Roy , Mishra Sabyashachi , Patra Sanjib K.
Published: August 2020

A series of organometallic complexes [Cl(dppe)2Ru−C≡C‐(3‐R−C4H2S)‐C≡C−Ru(dppe)2Cl] (3‐R‐C4H2S=3‐substituted thienyl moiety; R=−H, −C2H5, −C3H7, −C4H9, −C6H13, −OMe, −CN in5 a–5 grespectively) have been synthesized by systematic variation of 3‐substituents at the thienylethynyl bridging unit. The diruthenum(II) wire‐like complexes (5 a–5 g) have been achieved by the reaction of thienylethynyl bridging units, HC≡C‐(3‐R‐C4H2S)‐C≡CH (4 a–4 g) withcis‐[Ru(dppe)2Cl2]. The wire‐like diruthenium(II) complexes undergo two consecutive electrochemical oxidation processes in the potential range of 0.0 ‐ 0.8 V. Interestingly, the wave separation between the two redox waves is greatly influenced by the substituents at the 3‐position of the thienylethynyl. Thus, the substitution on 3‐position of the thienylethynyl bridging unit plays a pivotal role for tuning the electronic properties. To understand the electronic behavior, density functional theory (DFT) calculations of the selected diruthenium wire‐like complexes (5 a–5 e) with different alkyl appendages are performed. The theoretical data demonstrate that incorporation of alkyl groups to the thienylethynyl entity leaves unsymmetrical spin densities, thus affecting the electronic properties. The voltammetric features of the other two Ru(II) alkynyl complexes5 fand5 g(with −OMe and −CN group respectively) show an apparent dependence on the electronic properties. The electronic properties in the redox conjugate, (5 a+) with Kcof 3.9×106are further examined by UV‐Vis‐NIR and FTIR studies, showing optical responses in NIR region along with changes in “−Ru−C≡C−“ vibrational stretching frequency. The origin of the observed electronic transition has been assigned based on time‐dependent DFT (TDDFT) calculations.
Consistency in probability processing as a function of affective context and numeracy
Authors: Traczyk Jakub , Fulawka Kamil , Lenda Dominik , Zaleskiewicz Tomasz
Published: August 2020

Processing information about probabilities is an integral part of decision making under risk. Even when objective probabilities are explicitly provided, people tend to distort them, which is reflected by an inverted S‐shaped probability weighting function. Such distortions depend on different factors such as numeracy and affect. The present study contributes to the understanding of how people use probabilities in risky decision making by introducing the concept of consistency in probability processing―a measure of how coherent people are in using objective probabilities. We hypothesized that consistency would depend on factors similar to those that influence the shape of the probability weighting function. Moreover, we predicted that probability processing consistency would be related to better decision outcomes in an experimental betting task. In three experiments, participants were presented with the probability of a potential gain/loss and had to place a bet on a given chance to maximize their total earnings. We defined probability processing consistency as the variance of bets placed on the same probability value, with higher variance indicating lower consistency. We found that consistency in probability processing was lower in relatively affect‐rich conditions and greater for people with higher numeracy. Additionally, people who exhibited more consistent processing of probabilities gained higher earnings from the experimental task irrespective of whether their betting strategy was optimal and of their risk preference. Our findings imply that consistency in processing probabilities may be an important factor in understanding betting strategies and the quality of decisions.