bluuebunny/crossref_metadata_2025 huggingface dataset:
Implementation of Mobile Entrepreneurial Learning in the Context of Flexible Integration of Traditions and Innovations
Authors: Teymurova Vusala , Abdalova Matanat , Babayeva Saida , Huseynova Vafa , Mammadov Elshan , Islamova Nurana
Published: December 2020

The study considers the issue of integrating traditions and principles of mobile learning in entrepreneurship education. The purpose of the research is to study the level of implementation of mobile learning methods in higher education through the example of the Republic of Azerbaijan. The study involves a survey of 99 teachers from 5 universities. The survey results confirmed that both external factors (primarily globalization and widespread introduction of information and communication technologies) and internal factors affect higher education. It has been shown that national traditions do not contradict the best practices of entrepreneurship education and are successfully integrated into mobile learning practices. The level of integration of advanced trends in the transformation of education in the practice of mobile learning has been highly assessed by the teachers (3.44 out of 5 points on the Likert scale). The benefit of mobile learning for implementing the identified advanced trends (3.44 - 4.84 on the Likert scale) has also been highly praised. For example, respect for elders by age, experience, rank; practical focus; comprehensive assessment; rationality; involvement of each family member in hard work are supported by advanced learning methods, including the involvement of skilled lecturers, the increased importance of practical tasks, the use of project approach and startups; the use of mobile applications to assess knowledge; personalization of classes; the introduction of distance learning, etc. Flexible integration of national traditions and innovations can become a competitive advantage of the university and the education system; it is also being successfully implemented in mobile learning. A model for the formation of entrepreneurial competence in students based on the use of mobile applications along with cloud services that takes into account the flexible integration of traditions and innovation has been developed.
The Importance of Knowledge-Based Risk Processes to Risk Analysis
Authors: Nehari-Talet Amine , Karadsheh Louay , Alhawari Samer , Hunaiti Hana
Published: December 2020

Knowledge-based risk processes are suitable key elements within organizations since they can minimize the possibility and impact of an information technology (IT) project. The aim of this paper is to explain how the alignment between knowledge-based risk processes to validate risk analysis. A questionnaire was developed and distributed to a sample of 135 respondents who were actively engaged in IT. The proposed research model explained that 50 to 62% from of the variance in knowledge-based risk processes to risk analysis. The results showed that the two selected factors (identification and sharing) have a partially mediate and significant impact on risk analysis by knowledge-based risk repository. On the other hand, the examination is not mediated and not a significant impact on risk analysis. The findings of this study imply the understanding of knowledge-based risk processes to risk analysis This study will contribute to the field by examining the effects knowledge-based risk on risk analysis for IT projects.
Baseline Total Metabolic Tumor Volume and Total Lesion Glycolysis Measured on 18F-FDG PET-CT Predict Outcomes in T-Cell Lymphoblastic Lymphoma
Authors: Feng Xiaoyan , Wen Xin , Li Ling , Sun Zhenchang , Li Xin , Zhang Lei , Wu Jingjing , Fu Xiaorui , Wang Xinhua , Yu Hui , Ma Xinran , Zhang Xudong , Xie Xinli , Han Xingmin , Zhang Mingzhi
Published: December 2020

Purpose There is no optimal prognostic model for T-cell lymphoblastic lymphoma (T-LBL). Here, we discussed the predictive value of total metabolic tumor volume (TMTV) and total lesion glycolysis (TLG) measured on 18F-fluorodeoxyglucose positron emission tomography–computed tomography (PET-CT) in T-LBL.Materials and Methods Thirty-seven treatment naïve T-LBL patients with PET-CT scans were enrolled. TMTV was obtained using the 41% maximum standardized uptake value (SUVmax) threshold method, and TLG was measured as metabolic tumor volume multiplied by the mean SUV. Progression-free survival (PFS) and overall survival (OS) were analyzed by Kaplan-Meier curves and compared by the log-rank test.Results The optimal cutoff values for SUVmax, TMTV, and TLG were 12.7, 302 cm3, and 890, respectively. A high SUVmax, TMTV, and TLG indicated a shorten PFS and OS. On multivariable analysis, TMTV ≥ 302 cm3, and central nervous system (CNS) involvement predicted inferior PFS, while high SUVmax, TLG and CNS involvement were associated with worse OS. Subsequently, we generated a risk model comprising high SUVmax, TMTV or TLG and CNS involvement, which stratified the population into three risk groups, which had significantly different median PFS of not reached, 14 months, and 7 months for low-risk group, mediate-risk group, and high-risk group, respectively (p < 0.001). Median OS were not reached, 27 months, and 13 months, respectively (p < 0.001).Conclusion Baseline SUVmax, TMTV, and TLG measured on PET-CT are strong predictors of worse outcome in T-LBL. A risk model integrating these three parameters with CNS involvement identifies patients at high risk of disease progression.
Polymorphisms in TYMS for Prediction of Capecitabine-Induced Hand-Foot Syndrome in Chinese Patients with Colorectal Cancer
Authors: Dong Si-Qi , Wang Tong-Min , Zhang Jiang-Bo , He Yong-Qiao , Xue Wen-Qiong , Wu Zi-Yi , Yang Da-Wei , Cao Lian-Jing , Huang Jing-Wen , Li Xi-Zhao , Zhang Pei-Fen , Zheng Xiao-Hui , Jia Wei-Hua
Published: December 2020

Purpose Capecitabine is an extensively used oral prodrug of 5-fluorouracil in treatment of colon cancer and is known to cause hand-foot syndrome (HFS). As the target enzyme for capecitabine, thymidylate synthase (TYMS) plays a key role for 5-fluorouracil metabolism and has been associated with some side effects caused by capecitabine. The aim of our study is to identify the possible genetic predictors of capecitabine-induced HFS (CAP-HFS) in Chinese colorectal cancer patients.Materials and Methods Whole exons of TYMS were sequenced for 288 extreme phenotype HFS patients, including 144 severe or early-onset (first 2 cycles) moderate HFS extreme cases and 144 extreme controls with no reported HFS. The associations between polymorphisms and CAP-HFS were analyzed using logistic regression under an additive model.Results We identified a novel risk mutation (c.1A>G, chr18:657743), was associated with severe HFS in an extreme case who was affected during the first cycle of treatment. Moreover, we identified three new variants, rs3786362, rs699517, rs2790, and two previously reported variants, 5’VNTR 2R/3R and 3′-untranslated region 6-bp ins-del, which were significantly associated with CAP-HFS (p < 0.05). In silico analysis revealed that the effect of these polymorphisms in the TYMS region on the development of HFS might not be restricted solely to the regulation of TYMS expression, but also the TYMS catalytic activity through the indirect effect on ENOSF1 expression.Conclusion This study identified new polymorphisms in TYMS gene significantly associated with CAP-HFS, which may serve as useful genetic predictors for CAP-HFS and help to elucidate the underlying mechanism of HFS.
Interspecific association between brown-nosed coatis and capybaras in an urban area of Brazil
Authors: Rucco Andreza Castro , Herrera Heitor Miraglia , Santos Filipe Martins , Porfirio Grasiela Edith de Oliveira
Published: December 2020

This study aimed to report an interspecific association between brown-nosed coatis (Nasua nasua) and capybaras (Hydrochoerus hydrochaeris) in an urban area of Brazil. We recorded N. nasua feeding on ectoparasites (ticks) attached to H. hydrochaeris, which in turns, did not show any reaction of discomfort with the situation. Thus, we report an unprecedented case of protocooperation between apparently unrelated species. Moreover, the interspecies interaction reveals other interesting scenarios as the inclusion of ticks in the diet of N. Nasua and the possibility of parasite transmission and adaptation to a new host species, a phenomenon known as ‘host switching’. We associate these new records as adaptations of wildlife to urbanization, and their effects should be further investigated from both wildlife conservation and ‘One Health’ approach.
A projeção mural multimédia como formação cultural e democrática no espaço público
Authors: Fernandes-Marcos Adérito , Perez Pilar , Fernandes-Marcos Adérito
Published: December 2020

A projeção mural multimédia é hoje comumente utilizada para fins puramente publicitários ou lúdicos, de entretinimento, no âmbito de eventos que convoquem grandes aglomerados de públicos, sendo menos usual os fins culturais e educacionais. Neste artigo vamos apresentar, analisar e discutir o recurso à projeção mural multimédia em espaços públicos, com objetivos educacionais, formação cultural e de interpelação artística, tomando como tema do conteúdo projetado a própria arte contemporânea e o pensamento crítico que lhe está associado. O artigo toma como base de reflexão os cenários de arte experimental do projeto "+ PROJECTION AC - Projeção da arte contemporânea no espaço público” e suas múltiplas instanciações em diversos locais onde a projeção mural multimédia foi colocada em prática.
Monthly resolved modelled oceanic emissions of carbonyl sulfide and
carbon disulfide for the period 2000–2019
Authors: Lennartz Sinikka T. , Gauss Michael , von Hobe Marc , Marandino Christa A.
Published: December 2020

Abstract. Carbonyl sulfide (OCS) is the most abundant, long-lived sulphur gas in the atmosphere and a major supplier of sulfur to the stratospheric sulfate aerosol layer. The short-lived gas carbon disulfide (CS2) is oxidized to OCS and constitutes a major indirect source to the atmospheric OCS budget. The atmospheric budget of OCS is not well constrained due to a large missing source needed to compensate for substantial evidence that was provided for significantly higher sinks. Oceanic emissions are associated with major uncertainties. Here we provide a first, monthly resolved ocean emission inventory of both gases for the period 2000–2019 (available at https://doi.org/10.5281/zenodo.4297010) (Lennartz et al., 2020a). Emissions are calculated with a numerical box model (resolution 2.8° × 2.8° at equator, T42 grid) for the surface mixed layer. We find that interannual variability in OCS emissions is smaller than seasonal variability, and is mainly driven by variations in chromophoric dissolved organic matter (CDOM), which influences both photochemical and light-independent production. A comparison with a global database of more than 2500 measurements reveals overall good agreement. Emissions of CS2 constitute a larger sulfur source to the atmosphere than OCS, and equally show interannual variability connected to variability of CDOM. The emission estimate of CS2 is associated with higher uncertainties, as process understanding of the marine cycling of CS2 is incomplete. We encourage the use of the data provided here as input for atmospheric modelling studies to further assess the atmospheric OCS budget and the role of OCS in climate.
Incorporating 15N into the outputs of SMOKE version 4.6 as the emission
input dataset for CMAQ version 5.2.1 for assessing the role emission
sources plays in controlling the isotopic composition of NOx, NOy, and atmospheric nitrate
Authors: Fang Huan , Michalski Greg
Published: December 2020

Abstract. Nitrogen oxides (NOx = nitric oxide (NO) + nitrogen dioxides (NO2)) are important trace gases that affect atmospheric chemistry, air quality and climate. Contemporary development of NOx emissions inventories is limited by understanding of the roles of vegetation (net NOx source or net sink), gasoline and diesel in vehicle emissions, and application of NOx emission control technologies. In this study, we used the nitrogen stable isotope composition of NOx (δ15N(NOx) to resolve the uncertainties in NOx emission sources, by incorporating 15N into the US EPA trace gas emission model SMOKE (Sparse Matrix Operator Kernel Emissions) and compared simulated spatiotemporal patterns in NOx isotopic composition with corresponding atmospheric measurements in West Lafayette, Indiana, USA. The results indicate potential underestimation of emissions from soil, livestock waste, off-road vehicles, and natural gas power plants and the potential overestimation of emissions from on-road vehicles and coal-fired power plants.
Thermal erosion patterns of permafrost peat plateaus in
northern Norway
Authors: Martin Léo C. P. , Nitzbon Jan , Scheer Johanna , Aas Kjetil S. , Eiken Trond , Langer Moritz , Filhol Simon , Etzelmüller Bernd , Westermann Sebastian
Published: December 2020

Abstract. Subarctic peatlands underlain by permafrost contain significant amounts of organic carbon and our ability to quantify the evolution of such permafrost landscapes in numerical models is critical to provide robust predictions of the environmental and climatic changes to come. Yet, the accuracy of large-scale predictions is so far hampered by small-scale physical processes that create a high spatial variability of surface ground thermal regime and thus of permafrost degradation patterns. In this regard, a better understanding of the small-scale interplay between microtopography and lateral fluxes of heat, water and snow can be achieved by field monitoring and process-based numerical modeling. Here, we quantify the topographic changes of the Šuoššjávri peat plateau (Northern Norway) over a three-years period using repeated drone-based high-resolution photogrammetry. Our results show that edge degradation is the main process through which thermal erosion occurs and represents about 80 % of measured subsidence, while most of the inner plateau surface exhibits no detectable subsidence. Based on detailed investigation of eight zones of the plateau edge, we show that this edge degradation corresponds to a volumetric loss of 0.13 ± 0.07 m3 yr−1 m−1 (cubic meter per year and per meter of plateau circumference). Using the CryoGrid land surface model, we show that these degradation patterns can be reproduced in a modeling framework that implements lateral redistribution of snow, subsurface water and heat, as well as ground subsidence due to melting of excess ice. We reproduce prolonged climate-driven edge degradation that is consistent with field observations and present a sensitivity test of the plateau degradation on snow depth over the plateau. Small snow depth variations (from 0 to 30 cm) result in highly different degradation behavior, from stability to fast degradation. These results represent a new step in the modeling of climate-driven landscape development and permafrost degradation in highly heterogeneous landscapes such as peat plateaus. Our approach provides a physically based quantification of permafrost thaw with a new level of realism, notably, regarding feedback mechanisms between the dynamical topography and the lateral fluxes through which a small modification of the snow depth result in dramatic modifications of the permafrost degradation intensity. In this regard, these results also highlight the major control of snow pack characteristics on the ground thermal regime and the potential improvement that accurate snow representation and prediction could bring to projections of permafrost degradation.
STUDY OF PLASMA ION NITRIDING OF AISI H13 STEEL
Authors: Souza M. C. L. , Silva G. R. da , Souza E. S. , Pinto W. C. L. , Tapanes N. C. O.
Published: December 2020

This work studied the thermochemical treatment of AISI H13 steel used for extrusion of aluminum parts, by plasma ionic nitriding, with the objective of increasing the surface hardness of the mold, by forming an external layer of stable nitrides, increasing the resistance to wear, fatigue, corrosion and thermal resistance. Because it uses ions, plasma ion nitriding is more efficient than liquid and gas nitriding. This process is widely used for ferrous materials and aluminum. The main applications are for extrusion, material injection molds, cutting tools and automotive parts. In this work, samples of the AISI H13 steel were nitrided to be used as aluminum injection molds. The treatment was carried out at 300 oC in a sodium cyanide bath, for a period of 6 h at a pressure of 15 mTorr (2 Pa). The gaseous mixture inside the nitreter consisted of 80% N2 + 20% H2. After treatment, Vickers hardness measurements reached surface values of 963 HV. The results at the end of the treatment showed a 122 µm nitrided layer.
ON THE LOCALIZED PHYSICAL EXERGY DISAGGREGATION FOR DISSIPATIVE COMPONENT ISOLATION IN THERMOECONOMICS
Authors: Santos R. G. , Faria P. R. , Belisario I. C. , Barrone M. A. , Santos J. J.C.
Published: December 2020

Thermoeconomics is a discipline that connects Thermodynamics and Economics concepts, usually used for rational cost allocation to the final products of a thermal plant, by means of a model that describes the cost formation process of the overall system. Generally, exergy or monetary costs of the external resources are distributed to the final products. Exergy is the thermodynamic magnitude used in thermoeconomics and the physical exergy disaggregation has been introduced in thermoeconomics as alternatives for the isolation of the dissipative components and residues allocation. For plants with dissipative equipment, such as condenser or valve, the productive diagram, based on total exergy (E Model), need to merge this dissipative equipment with other productive components. In order to isolate the condenser, the productive diagram must use, at least, the H&S Model and to isolate the valve, the UFS Model has to be considered.Both disaggregation models greatly increase the thermoeconomic modeling complexity. Bearing this in mind, this work aims to evaluate the advantages of combining the E Model with these other models in order to adequately isolate the dissipative equipment. The plants studied herein are two different steam turbine cogeneration systems, with dissipative components (condenser or valve). The different monetary and exergy unit costs obtained for the two final products of each plant are compared and analyzed.  The results show that localized physical exergy disaggregation for dissipative component isolation in thermoeconomics is feasible, since it reduces the complexity of the productive structure and is also consistent from the point of view of thermodynamics.
Intensive Computational Method Applied for Assessing Specialty Coffees by Trained and Untrained Consumers
Authors: Rodrigues Liska Gilberto , Alberto Beijo Luiz , Ângelo Cirillo Marcelo , Meira Borém Flávio , Silva de Menezes Fortunato
Published: December 2020

The sensory analysis of coffees assumes that a sensory panel is formed by tasters trained according to the recommendations of the American Specialty Coffee Association. However, the choice that routinely determines the preference of a coffee is made through experimentation with consumers, in which, for the most part, they have no specific ability in relation to sensory characteristics. Considering that untrained consumers or those with basic knowledge regarding the quality of specialty coffees have little ability to discriminate between different sensory attributes, it is reasonable to admit the highest score given by a taster. Given this fact, probabilistic studies considering appropriate probability distributions are necessary. To access the uncertainty inherent in the notes given by the tasters, resampling methods such as Monte Carlo’s can be considered and when there is no knowledge about the distribution of a given statistic, p-Bootstrap confidence intervals become a viable alternative. This text will bring considerations about the use of the non-parametric resampling method by Bootstrap with application in sensory analysis, using probability distributions related to the maximum scores of tasters and accessing the most frequent region (mode) through computational resampling methods.
Deep‐Blue Perovskite Single‐Mode Lasing through Efficient Vapor‐Assisted Chlorination
Authors: Pina Joao M. , Parmar Darshan H. , Bappi Golam , Zhou Chun , Choubisa Hitarth , Vafaie Maral , Najarian Amin M. , Bertens Koen , Sagar Laxmi Kishore , Dong Yitong , Gao Yuan , Hoogland Sjoerd , Saidaminov Makhsud I. , Sargent Edward H.
Published: December 2020

Metal halide perovskites have emerged as promising candidates for solution‐processed laser gain materials, with impressive performance in the green and red spectral regions. Despite exciting progress, deep‐blue—an important wavelength for laser applications—remains underexplored; indeed, cavity integration and single‐mode lasing from large‐bandgap perovskites have yet to be achieved. Here, a vapor‐assisted chlorination strategy that enables synthesis of low‐dimensional CsPbCl3 thin films exhibiting deep‐blue emission is reported. Using this approach,  high‐quality perovskite thin films having a low surface roughness (RMS ≈ 1.3 nm) and efficient charge transfer properties are achieved. These enable us to document low‐threshold amplified spontaneous emission. Levering the high quality of the gain medium,  vertical‐cavity surface‐emitting lasers with a low lasing threshold of 6.5 µJ cm−2 are fabricated. This report of deep‐blue perovskite single‐mode lasing showcases the prospect of increasing the range of deep‐blue laser sources.
Pyridine‐Catalysed Desulfonylative Addition of β‐Diketones to Arylazosulfones via Diaziridine Rearrangement
Authors: Ji Xin , Meng Ling‐Guo , Xu Hailong , Wang Lei
Published: December 2020

A pyridine‐catalysed desulfonylative addition of β‐diketones to arylazosulfones was developed to obtain diazenyl β‐dicarbonyl compounds. The aryldiazenyl group was observed in the desired product from arylazosulfones, and this diazenylation reaction was achieved via a possible rearrangement process based on diaziridine ring cleavage. The scope of the protocol was investigated and a plausible mechanism was given.

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Photoredox Fluoroalkylation of Hydrazones in Neutral and Reductive Modes
Authors: van der Worp Boris A. , Kosobokov Mikhail D. , Levin Vitalij V. , Dilman Alexander D.
Published: December 2020

Visible light promoted fluoroalkylation of hydrazones using 4‐perfluoropyridine sulfides as fluoroalkyl radical sources is described. The process can proceed in neutral and reductive modes delivering either hydrazones or hydrazines, respectively, depending on structure of starting substrates and reaction conditions. For the reductive process, ascorbic acid is used as a terminal reductant, which recycles the photocatalyst and serves as a source of hydrogen towards nitrogen‐centered radicals.

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Chemistry of Tertiary Carbon Center in the Formation of Congested C−O Ether Bonds
Authors: Hirata Goki , Takeuchi Kentarou , Shimoharai Yusuke , Sumimoto Michinori , Kaizawa Hazuki , Nokami Toshiki , Koike Takashi , Abe Manabu , Shirakawa Eiji , Nishikata Takashi
Published: December 2020

Nucleophilic substitutions, including SN1 and SN2, are classical and reliable reactions, but a serious drawback is their intolerance for both bulky nucleophiles and chiral tertiary alkyl electrophiles for the synthesis of a chiral quaternary carbon center. An SRN1 reaction via a radical species is another conventional method used to carry out substitution reactions of bulky nucleophiles and alkyl halides, but chiral tertiary alkyl electrophiles cannot be used. Therefore, a stereospecific nucleophilic substitution reaction using chiral tertiary alkyl electrophiles and bulky nucleophiles has not yet been well studied. In this paper, we describe the reaction of tertiary alkyl alcohols and non‐chiral or chiral α‐bromocarboxamides as a tertiary alkyl source for the formation of congested ether compounds possessing two different tertiary alkyl groups on the oxygen atom with stereoretention.
Probing the Consequences of Cubic Particle Shape and Applied Field on Colloidal Crystal Engineering with DNA
Authors: Urbach Zachary J. , Park Sarah S. , Weigand Steven L. , Rix James E. , Lee Byeongdu , Mirkin Chad A.
Published: December 2020

In a magnetic field, cubic Fe3O4 nanoparticles exhibit assembly behavior that is a consequence of a competition between magnetic dipole–dipole and ligand interactions. In most cases, the interactions between short hydrophobic ligands dominate and dictate assembly outcome. To better tune the face‐to‐face interactions, cubic Fe3O4 nanoparticles were functionalized with DNA. Their assembly behaviors were investigated both with and without an applied magnetic field. Upon application of a field, the tilted orientation of cubes, enabled by the flexible DNA ligand shell, led to an unexpected crystallographic alignment of the entire superlattice, as opposed to just the individual particles, along the field direction as revealed by small and wide‐angle X‐ray scattering. This observation is dependent upon DNA length and sequence and cube dimensions. Taken together, these studies show how combining physical and chemical control can expand the possibilities of crystal engineering with DNA.
Predictive Significance of Serum Interferon‐Inducible Protein Score for Response to Treatment in Systemic Sclerosis–Related Interstitial Lung Disease
Authors: Assassi Shervin , Li Ning , Volkmann Elizabeth R. , Mayes Maureen D. , Rünger Dennis , Ying Jun , Roth Michael D. , Hinchcliff Monique , Khanna Dinesh , Frech Tracy , Clements Philip J. , Furst Daniel E. , Goldin Jonathan , Bernstein Elana J. , Castelino Flavia V. , Domsic Robyn T. , Gordon Jessica K. , Hant Faye N. , Shah Ami A. , Shanmugam Victoria K. , Steen Virginia D. , Elashoff Robert M. , Tashkin Donald P.
Published: December 2020

Objective

Response to immunosuppression is highly variable in systemic sclerosis (SSc)–related interstitial lung disease (ILD). This study was undertaken to determine whether a composite serum interferon (IFN)–inducible protein score exhibits predictive significance for the response to immunosuppression in SSc‐ILD.

Methods

Serum samples collected in the Scleroderma Lung Study II, a randomized controlled trial of mycophenolate mofetil (MMF) versus cyclophosphamide (CYC), were examined. Results were validated in an independent observational cohort receiving active treatment. A composite score of 6 IFN‐inducible proteins IFNγ‐inducible 10‐kd protein, monokine induced by IFNγ, monocyte chemotactic protein 2, β2‐microglobulin, tumor necrosis factor receptor type II, and macrophage inflammatory protein 3β) was calculated, and its predictive significance for longitudinal forced vital capacity percent predicted measurements was evaluated.

Results

Higher baseline IFN‐inducible protein score predicted better response over 3 to 12 months in the MMF arm (point estimate = 0.41,P= 0.001) and CYC arm (point estimate = 0.91,P= 0.009). In contrast, higher baseline C‐reactive protein (CRP) levels were predictive of a worse ILD course in both treatment arms. The predictive significance of the IFN‐inducible protein score and CRP levels remained after adjustment for baseline demographic and clinical predictors. During the second year of treatment, in which patients in the CYC arm were switched to placebo, a higher IFN‐inducible protein score at 12 months showed a trend toward predicting a worse ILD course (point estimate = −0.61,P= 0.068), while it remained predictive of better response to active immunosuppression in the MMF arm (point estimate = 0.28,P= 0.029). The predictive significance of baseline IFN‐inducible protein score was replicated in the independent cohort (rs= 0.43,P= 0.028).

Conclusion

A higher IFN‐inducible protein score in SSc‐ILD is predictive of better response to immunosuppression and could potentially be used to identify patients who may derive the most benefit from MMF or CYC.
Ligand Induced CuII Transport Restricts Cancer and Mycobacterial Growth: Towards a Plug‐and‐Select Ion Channel Scaffold
Authors: Saha Parichita , Kumari Agarwala Prema , Dadhich Ruchika , Adhyapak Pranav , Kapoor Shobhna , Madhavan Nandita
Published: December 2020

Synthetic channels with high ion selectivity are attractive drug targets for diseases involving ion dysregulation. Achieving selective transport of divalent ions is highly challenging due their high hydration energies. A small tripeptide amphiphilic scaffold installed with a pybox ligand selectively transports CuII ions across membranes. The peptide forms stable dimeric pores in the membrane and transports ions by a Cu2+/H+ antiport mechanism. The ligand‐induced excellent CuII selectivity as well as high membrane permeability of the peptide is exploited to promote cancer cell death. The peptide's ability to restrict mycobacterial growth serves as seeds to evolve antibacterial strategies centred on selectively modulating ion homeostasis in pathogens. This simple peptide can potentially function as a universal, yet versatile, scaffold wherein the ion selectivity can be precisely controlled by modifying the ligand at the C terminus.
Benzo‐Tetrathiafulvalene‐ (BTTF‐) Annulated Expanded Porphyrins: Potential Next‐Generation Multielectron Reservoirs
Authors: Jana Atanu , Ishida Masatoshi , Furuta Hiroyuki
Published: December 2020

Two sterically crowded benzo‐tetrathiafulvalene (BTTF)‐annulated expanded porphyrins (BTTF7‐F and BTTF8) are synthesized. Detailed photophysical investigations reveal their intrinsic intramolecular charge transfer (CT) character, originated from partial electron transfer from electron‐rich TTF units to the relatively electron‐deficient macrocyclic core. This finding stands in contrast to what was observed in the previously reported Figure‐of‐eight conformer of BTTF‐annulated [28]hexaphyrin (BTTF6), in which a typical π–π* electronic transition from HOMO to LUMO was observed. However, core expansion in BTTF7‐F and BTTF8 makes the oligopyrrole macrocyclic cores relatively more electron‐deficient, facilitating the effective intramolecular CT process. Comparative electrochemical investigations reveal that the current generated at the oxidative region is directly proportional to the number of TTF units attached to the macrocyclic core. This work demonstrates the control of the intramolecular CT process through incremental addition of TTF units to the macrocyclic core. Facile multielectron electrochemical oxidations of these expanded porphyrins suggest that they behave like potential multielectron reservoirs.
Donor–Acceptor Stenhouse Adducts: Exploring the Effects of Ionic Character
Authors: Sroda Miranda M. , Stricker Friedrich , Peterson Julie A. , Bernal Alexandria , Read de Alaniz Javier
Published: December 2020

The effects of solution‐state dielectric and intermolecular interactions on the degree of charge separation provide a route to understanding the switching properties and concentration dependence of donor–acceptor Stenhouse adducts (DASAs). Through solvatochromic analysis of the open‐form DASA in conjunction with X‐ray diffraction and computational theory, we have analyzed the ionic character of a series of DASAs. First‐ and third‐generation architectures lead to a higher zwitterionic resonance contribution of the open form and a zwitterionic closed form, whereas the second‐generation architecture possesses a less charge‐separated open form and neutral closed form. This can be correlated with equilibrium control and photoswitching solvent compatibility. As a result of the high contribution of the zwitterionic resonance forms of first‐ and third‐generation DASAs, we were able to control their switching kinetics by means of ion concentration, whereas second‐generation DASAs were less affected. Importantly, these results show how the previously reported concentration dependence of DASAs is not universal, and that DASAs with a more hybrid structure in the open form can achieve photoswitching at high concentrations.
Effects of maternal and paternal postnatal depressive symptoms on infants’ parasympathetic regulation in low‐income, Mexican American families
Authors: Lin Betty , Yeo Anna J. , Luecken Linda J. , Roubinov Danielle S.
Published: December 2020

Mothers and fathers are at elevated risk for developing depression during the first postnatal year, especially among families from marginalized communities. Although a number of studies demonstrate that exposure to maternal depressive symptoms can undermine infants’ regulatory development, less is known about the extent to which paternal depressive symptoms may also contribute. The current study investigated whether maternal and paternal depressive symptoms were uniquely associated with infants’ physiological regulation, and whether associations varied depending on infant sex. Participants included 90 low‐income Mexican American families. Fathers and mothers self‐reported their depressive symptoms when infants were 15 weeks old, and infants’ resting parasympathetic activity (i.e., respiratory sinus arrhythmia [RSA]) was assessed at 6 and 24 weeks. Results indicated that, after controlling for infant 6‐week RSA and depressive symptoms in the other parent, paternal depressive symptoms were associated with lower 24‐week RSA for both girls and boys, but maternal depressive symptoms were only associated with lower 24‐week RSA for boys. Findings highlight a potential mechanism through which the consequences of parent depressive symptoms may reverberate across generations, and suggest that considerations of both infants’ and parents’ sex may lend insight into how best to intervene.
Relative impact of bleedings over ischaemic events in patients with heart failure: insights from the CARDIONOR registry
Authors: Lemesle Gilles , Ninni Sandro , de Groote Pascal , Schurtz Guillaume , Lamblin Nicolas , Bauters Christophe
Published: December 2020

Aims

Major bleeding events in heart failure (HF) patients are poorly described. We sought to investigate the importance of major bleeding and its impact on outcomes in HF patients.

Methods and results

We analysed incident bleeding and ischaemic events during a 3 year follow‐up in 2910 HF outpatients included in a prospective multicentre registry. Major bleeding was defined as a Type ≥3 bleed using the Bleeding Academic Research Consortium definition. Ischaemic event was a composite of ischaemic stroke and myocardial infarction. Events were adjudicated by a blinded committee. At inclusion, most patients (89%) received at least one antithrombotic: anticoagulation (53.9%) and/or antiplatelet therapy (46.2%). Bleeding occurred in 111 patients {3 year cumulative incidence: 3.6% [95% confidence interval (CI) 3.0–4.3]} and ischaemic events in 102 patients [3 year cumulative incidence: 3.3% (95% CI 2.7–4.0)]. Most bleedings were Bleeding Academic Research Consortium 3a (32.5%) or 3b (31.5%). Most frequent sites of bleeding were gastrointestinal (40.6%) and intracranial (27.9%). Variables associated with bleeding were atrial fibrillation [hazard ratio (HR) = 2.63 (95% CI 1.66–4.19), P < 0.0001], diabetes [HR = 1.62 (95% CI 1.11–2.38), P = 0.012], and older age [HR = 1.19 per 10 year increase (95% CI 1.00–1.41), P = 0.049]. Anticoagulation use was associated with a two‐fold increase in the bleeding risk. Bleeding events as well as ischaemic events were strongly associated with subsequent mortality [adjusted HRs: 5.67 (4.41–7.29), P < 0.0001 and 4.29 (3.18–5.78), P < 0.0001, respectively].

Conclusions

In HF outpatients, antithrombotics are widely used. Bleeding occurs at a stable rate of 1.2% annually (as frequent as ischaemic events) and is associated with a dramatic increase in mortality (at least as severe as ischaemic events). Most events occurred in patients receiving anticoagulation. Knowledge of these findings may help physicians to manage antithrombotics in HF patients.
Prevalence and determinants of systolic and diastolic cardiac dysfunction and heart failure in acute ischemic stroke patients: The SICFAIL study
Authors: Heuschmann Peter U. , Montellano Felipe A. , Ungethüm Kathrin , Rücker Viktoria , Wiedmann Silke , Mackenrodt Daniel , Quilitzsch Anika , Ludwig Timo , Kraft Peter , Albert Judith , Morbach Caroline , Frantz Stefan , Störk Stefan , Haeusler Karl Georg , Kleinschnitz Christoph
Published: December 2020

Aims

Ischaemic stroke (IS) might induce alterations of cardiac function. Prospective data on frequency of cardiac dysfunction and heart failure (HF) after IS are lacking. We assessed prevalence and determinants of diastolic dysfunction (DD), systolic dysfunction (SD), and HF in patients with acute IS.

Methods and results

The Stroke‐Induced Cardiac FAILure in mice and men (SICFAIL) study is a prospective, hospital‐based cohort study. Patients with IS underwent a comprehensive assessment of cardiac function in the acute phase (median 4 days after IS) including clinical examination, standardized transthoracic echocardiography by expert sonographers, and determination of blood‐based biomarkers. Information on demographics, lifestyle, risk factors, symptoms suggestive of HF, and medical history was collected by a standardized personal interview. Applying current guidelines, cardiac dysfunction was classified based on echocardiographic criteria into SD (left ventricular ejection fraction < 52% in men or <54% in women) and DD (≥3 signs of DD in patients without SD). Clinically overt HF was classified into HF with reduced, mid‐range, or preserved ejection fraction. Between January 2014 and February 2017, 696 IS patients were enrolled. Of them, patients with sufficient echocardiographic data on SD were included in the analyses {n = 644 patients [median age 71 years (interquartile range 60–78), 61.5% male]}. In these patients, full assessment of DD was feasible in 549 patients without SD (94%). Prevalence of cardiac dysfunction and HF was as follows: SD 9.6% [95% confidence interval (CI) 7.6–12.2%]; DD in patients without SD 23.3% (95% CI 20.0–27.0%); and clinically overt HF 5.4% (95% CI 3.9–7.5%) with subcategories of HF with preserved ejection fraction 4.35%, HF with mid‐range ejection fraction 0.31%, and HF with reduced ejection fraction 0.78%. In multivariable analysis, SD and fulfilment of HF criteria were associated with history of coronary heart disease [SD: odds ratio (OR) 3.87, 95% CI 1.93–7.75, P = 0.0001; HF: OR 2.29, 95% CI 1.04–5.05, P = 0.0406] and high‐sensitive troponin T at baseline (SD: OR 1.78, 95% CI 1.31–2.42, P = 0.0003; HF: OR 1.66, 95% CI 1.17–2.33, P = 0.004); DD was associated with older age (OR 1.08, 95% CI 1.05–1.11, P < 0.0001) and treated hypertension vs. no hypertension (OR 2.84, 95% CI 1.23–6.54, P = 0.0405).

Conclusions

A substantial proportion of the study population exhibited subclinical and clinical cardiac dysfunction. SICFAIL provides reliable data on prevalence and determinants of SD, DD, and clinically overt HF in patients with acute IS according to current guidelines, enabling further clarification of its aetiological and prognostic role.
Synthesis of Spongidepsin and Analogs
Authors: Ferrié Laurent , Picot Ondine , Guérinot Amandine , Cossy Janine
Published: December 2020

Seven syntheses of (–)‐spongidepsin, a natural product isolated from Spongia sp. with moderate antiproliferative activity, are described and the different analogs obtained during these syntheses are reported. A comparison between the different syntheses has been achieved.
Recent Developments in Deaminative Functionalization of Alkyl Amines
Authors: Li Yi‐Na , Xiao Fang , Guo Yu , Zeng Yao‐Fu
Published: December 2020

The amino group is one of the most prevalent functional groups present in a wide range of organic molecules, which has been widely applied in various organic synthesis and pharmaceuticals. Alkyl amines could be converted in a single step into Katritzky salts which could serve as alkyl radical precursors to construct C−C bonds and C−X bonds via C(sp3)−N cleavage. This deaminative functionalization could be carried out under transition‐metal catalysis, photocatalysis, carbene catalysis or promoted by base. In this paper, recent developments in the deaminative functionalization of alkyl amines were covered. This review was categorized into four parts according to the nature of the bond formation. Some representative examples and corresponding reaction mechanisms were also summarized.
Regiodivergent Synthesis of ortho‐ and para‐Cannabinoquinones
Authors: Mattoteia Daiana , Taglialatela‐Scafati Orazio , Muñoz Eduardo , de la Vega Laureano , Caprioglio Diego , Appendino Giovanni
Published: December 2020

Spurred by the remarkable biological profile of cannabinoquinoids, we have systematically investigated the periodinane oxidation of their resorcinolic precursors, discovering that the regiochemistry of oxidation, a critical maneuver for bioactivity, depends not only on the nature of the oxidant (λ3‐ vs. λ5‐iodanes), but also on post‐oxidative prototropic‐ and valence tautomeric equilibria that isomerize ortho‐quinones to para‐quinones. By complementary selection of the periodinane oxidant and by freezing prototropic equilibration with O‐methylation, isomeric ortho‐ and para‐quinones could be obtained from mono‐ and diphenolic cannabinoids, setting the stage for the exploration of novel areas of the biological space, and establishing a blueprint for the extension of this strategy to other classes of bioactive alkylresorcinols.
Organocatalytic Enantioselective Aminoalkylation of 5‐Aminopyrazole Derivatives with Cyclic Imines
Authors: Carceller‐Ferrer Laura , González del Campo Aleix , Vila Carlos , Blay Gonzalo , Muñoz M. Carmen , Pedro José R.
Published: December 2020

In this communication, an efficient asymmetric aminoalkylation of 5‐aminopyrazole derivatives with cyclic benzoxathiazine 2,2‐dioxides catalyzed by a quinine‐derived squaramide in dichloromethane has been established. This is the first example of 5‐aminopyrazole derivatives in asymmetric catalysis. A variety of chiral sulfamidates bearing an aminopyrazole moiety were obtained in good yields (up to 98 %) and moderate to excellent enantioselectivities (up to 99 %ee).
Recent Developments in C−H Functionalisation of Benzofurans and Benzothiophenes
Authors: Morgan David , Yarwood Stephen J. , Barker Graeme
Published: December 2020

Benzofurans and benzothiophenes are important pharmaceutical motifs, appearing in a broad range of small molecule therapeutic classes. Often overlooked by synthetic methodologists in favour reactions of the analogous indole bicyclic system, there is nevertheless a plurality of approaches to effecting benzofuran and benzothiophene C−H functionalisations. In this review, we summarise progress in this area over the past five years, including 1) alkylations, 2) arylations and heteroarylations, 3) carboxylations, carbamoylations, and C‐heteroatom bond formations and 4) cyclisations.
Screening and genetic studies on resistance to Soil-born Cereal Mosaic Virus (SBWMV) in rye
Authors: Schlegel R. , Eifler J. , Schmidt M. , Schmiedchen B. , Ordon F. , Kastirr U.
Published: December 2020

Due to several reasons soil-borne viruses such as the furoviruses, i. e., cereal mosaic virus (SBCMV) and wheat mosaic virus (SBWMV) as well as the bymovirus wheat spindle streak mosaic virus (WSSMV) gained importance in cereal breeding including rye. High yield losses are recorded, today. Since there is no or little resistance to these viruses in modern rye cultivars, an extended screening for resistance was initiated. In addition to earlier screenings, 37 rye genotypes were tested for resistance. Among them, three genotypes were found with persistent resistance to SBCMV. They belong to Secale montanum and S. vavilovii species, i. e., wild types of rye. One accession, PC2243 (S. montanum), was used as a resistance donor for the present genetic study. In F2 generation, it was observed that resistance to SBCMV is independently inherited from WSSMV. The evaluation of the ELISA values pointed to a 3:1 distribution assuming duplicate dominant epistasis. Molecular marker analysis supports this segregation pattern. By composite interval mapping a QTL on chromosome 2R could be detected. It can be assumed that there is a DNA region of about 13 cM on the long arm of chromosome 2R (2RL) harboring SBCMV resistance with the closest markers “C9654_1947” and “isotig11640”.
Moreover, genotypes with a yellow seed coat showed practically no infection with SBCMV. Thus, the resistance gene could be linked to the allele an1 determining non expression of anthocyanins. This locus was also mapped earlier on chromosome 2R.
Die Problematik der Implementierung von Kinästhetik in Einrichtungen der stationären Langzeitpflege – Eine Multiple Case-Study
Authors: Maurer Carola , Gattinger Heidrun , Mayer Hanna
Published: December 2020

Zusammenfassung. Hintergrund: Einrichtungen der stationären Langzeitpflege investieren seit Jahren Ressourcen in die Entwicklung der Kinästhetikkompetenz der Pflegenden. Aus aktuellen Studien geht hervor, dass die Implementierung, bzw. die nachhaltige Förderung der Kinästhetikkompetenz problematisch ist, vertiefte Erkenntnisse zu den Ursachen fehlen jedoch. Fragestellung: Welche Hemmnisse verhindern eine nachhaltige Implementierung von Kinästhetik in Einrichtungen der stationären Langzeitpflege? Methode: Es wurde eine Multiple Case-Study in drei Einrichtungen der deutschsprachigen Schweiz durchgeführt. Aus leitfadengestützten Interviews und (fallbezogener) Literatur zum externen Kontext wurden in den Within-Case-Analysen die Daten induktiv verdichtet und diese Ergebnisse in der Cross-Case-Synthese miteinander verglichen und abstrahierend zusammengeführt. Ergebnisse: Die Synthese zeigt, dass die Implementierung von Kinästhetik innerhalb der Einrichtung auf drei verschiedenen Ebenen – der Leitungs-, Pflegeteam- und Pflegeperson-Ebene – als auch durch externe Faktoren negativ beeinflusst werden kann. Schlussfolgerungen: In der Pflegepraxis und -wissenschaft sowie im Gesundheitswesen benötigt es ein grundlegendes Verständnis von Kinästhetik und wie dieses im Kontext des professionellen Pflegehandelns einzuordnen ist. Insbesondere Leitungs- und implementierungsverantwortliche Personen müssen mögliche Hemmnisse kennen, um entsprechende Strategien entwickeln zu können.
A 13‐year Trajectory‐Based Analysis of Convection‐Driven Changes in Upper Troposphere Lower Stratosphere Composition Over the United States
Authors: Tinney Emily N. , Homeyer Cameron R.
Published: December 2020

Moist convection frequently reaches the tropopause and alters the distribution and concentration of radiatively important trace gases in the upper troposphere and lower stratosphere (UTLS), but the overall impact of convection on regional and global UTLS composition remains largely unknown. To improve understanding of convection‐driven changes in water vapor (H2O), ozone (O3), and carbon monoxide (CO) in the UTLS, this study utilizes 13 years of observations of satellite‐based trace gas profiles from the Microwave Limb Sounder (MLS) aboard the Aura satellite and convection from the operational network of ground‐based weather radars in the United States. Locations with and without convection identified via radar are matched with downstream MLS observations through three‐dimensional, kinematic forward trajectories, providing two populations of trace gas observations for analysis. These populations are further classified as belonging to extratropical or tropical environments based on the tropopause pressure at the MLS profile location. Extratropical regions are further separated by tropopause type (single or double), revealing differing impacts. Results show that convection typically moistens the UT by up to 300% and the LS by up to 100%, largely reduces O3 by up to 40%, and increases CO by up to 50%. Changes in H2O and O3 are robust, with LS O3 reduced more by convection within tropical environments, where the median concentration decrease is 34% at ∼2 km above tropopause, compared to 24% in extratropical environments. Quantification of CO changes from convection is less reliable due to differences being near the MLS measurement precision and accuracy.