bluuebunny/crossref_metadata_2025 huggingface dataset:
Exploiting If This Then That and Usage Control obligations for Smart Home security and management
Authors: Giorgi Giacomo , La Marra Antonio , Martinelli Fabio , Mori Paolo , Rizos Athanasios , Saracino Andrea
Published: January 2021

In this article we present an application of the Usage Control paradigm to a Smart Home infrastructure, based on a model extension and structured use of obligations. In the proposed extended model obligations are exploited to enforce two different access revocation time, namely revoke and suspend. This increases the policy expressiveness and enable to optimize the resource usage. Furthermore, obligations are exploited to send commands via IFTTT to different interconnected Smart Home devices, to impose safety‐relevant behaviors, or to act on policy attributes to implement a self‐healing paradigm for revoked sessions. The article is motivated by a parental control use case where deep learning is used in combination with Usage Control to regulate dynamically viewing rights of a smart‐TV and interactions with interconnected devices. Accuracy and performance experiments show the effectiveness and feasibility of the proposed work.
Therapeutic interventions in in‐person and remote psychotherapy: Survey with psychotherapists and patients experiencing in‐person and remote psychotherapy during COVID‐19
Authors: Probst Thomas , Haid Barbara , Schimböck Wolfgang , Reisinger Andrea , Gasser Marion , Eichberger‐Heckmann Heidrun , Stippl Peter , Jesser Andrea , Humer Elke , Korecka Nicole , Pieh Christoph
Published: January 2021

Objective

First, to investigate how psychotherapists and patients experience the change from in‐person to remote psychotherapy or vice versa during COVID‐19 regarding the therapeutic interventions used. Second, to explore the influence of therapeutic orientations on therapeutic interventions in in‐person versus remote psychotherapy.

Method

Psychotherapists (N = 217) from Austria were recruited, who in turn recruited their patients (N = 133). The therapeutic orientation of the therapists was psychodynamic (22.6%), humanistic (46.1%), systemic (20.7%) or behavioural (10.6%). All the data were collected remotely via online surveys. Therapists and patients completed two versions of the ‘Multitheoretical List of Therapeutic Interventions’ (MULTI‐30) (version 1: in‐person; version 2: remote) to investigate differences between in‐person and remote psychotherapy in the following therapeutic interventions: psychodynamic, common factors, person‐centred, process‐experiential, interpersonal, cognitive, behavioural and dialectical‐behavioural.

Results

Therapists rated all examined therapeutic interventions as more typical for in‐person than for remote psychotherapy. For patients, three therapeutic interventions (psychodynamic, process‐experiential, cognitive interventions) were more typical for in‐person than for remote psychotherapy after correcting for multiple testing. For two therapeutic interventions (behavioural, dialectical‐behavioural), differences between the four therapeutic orientations were more consistent for in‐person than for remote psychotherapy.

Conclusions

Therapeutic interventions differed between in‐person and remote psychotherapy and differences between therapeutic orientations in behavioural‐oriented interventions become indistinct in remote psychotherapy.
Inbred and hybrid sweet corn genotype performance in diverse organic environments
Authors: Zystro Jared , Peters Tessa E. , Miller Kathleen M. , Tracy William F.
Published: January 2021

The value of selection in conventional breeding trials of cultivars destined for organic systems depends on the correlation between systems and relative heritability of key traits. Genotype × environment interaction is a common phenomenon in plant breeding trials. Thus, multiple‐environment testing to identify stable genotypes is a high priority for organic systems. In addition, because organic systems have limited inputs to buffer the environment, they may have greater spatial heterogeneity, which may be better accounted for by additional spatial blocking terms beyond traditional randomized complete‐block design. Over 2 yr, we evaluated 100 hybrid and 40 inbred sweet corn (Zea mays L.) genotypes in 11 trials in organic systems across six locations and evaluated the addition of augmented incomplete block and row–column design to estimate the performance of sweet corn genotypes. Hybrids differed in their performance for all tested traits. Inbred parents differed in per se performance and general combining ability for all traits. For the hybrid entries, modeling spatial factors beyond the replicated complete blocks improved the model fit for days to anthesis, plant height, ear height, husk protection, ear width, and ear length. For inbred entries, modeling spatial factors beyond the replicated complete blocks improved ∖ model fit for plant height, ear height, tenderness, and ear width. Wricke's ecovalence (W2i) was a useful measure of stability, correlating reasonably well with two of the three stability statistics considered in this analysis. Based on Wricke's ecovalence, some inbred parents were more stable than others across tested environments in their combining ability for all traits.
Arrested development: suppression of NK cell function in the tumor microenvironment
Authors: Riggan Luke , Shah Siya , O’Sullivan Timothy E
Published: January 2021

Natural killer (NK) cells are cytotoxic innate lymphocytes that protect against viral infection and tumor metastasis. Despite their inherent ability to kill a broad range of virally infected, stressed and transformed cells, low numbers of dysfunctional NK cells are often observed in many advanced solid human cancers. Here, we review the potential mechanisms that influence suboptimal mature NK cell recruitment and function in the tumor microenvironment (TME) of solid tumors. We further highlight current immunotherapy approaches aimed to circumvent NK cell dysfunction and discuss next‐generation strategies to enhance adoptive NK cell therapy through targeting intrinsic and extrinsic checkpoints the regulate NK cell functionality in the TME. Understanding the mechanisms that drive NK cell dysfunction in the TME will lead to novel immunotherapeutic approaches in the fight against cancer.
Prognostic value of early leukocyte fluctuations for recovery from traumatic spinal cord injury
Authors: Jogia Trisha , Lübstorf Tom , Jacobson Esther , Scriven Elissa , Atresh Sridhar , Nguyen Quan H. , Liebscher Thomas , Schwab Jan M. , Kopp Marcel A. , Walsham James , Campbell Kate E. , Ruitenberg Marc J.
Published: January 2021

Background

Acute traumatic spinal cord injury (SCI) induces a systemic immune response involving circulating white blood cells (WBCs). How this response is influenced by overall trauma severity, the neurological level of injury and/or correlates with patient outcomes is poorly understood. The objective of this study was to identify relationships between early changes in circulating WBCs, injury characteristics and long‐term patient outcomes in individuals with traumatic SCI.

Methods

We retrospectively analysed data from 161 SCI patients admitted to Brisbane's Princess Alexandra Hospital (exploration cohort). Logistic regression models in conjunction with receiver operating characteristic (ROC) analyses were used to assess the strength of specific links between the WBC response, respiratory infection incidence and neurological outcomes (American Spinal Injury Association Impairment Scale (AIS) grade conversion). An independent validation cohort from the Trauma Hospital Berlin, Germany (n = 49) was then probed to assess the robustness of effects and disentangle centre effects.

Results

We find that the extent of acute neutrophilia in human SCI patients is positively correlated with New Injury Severity Scores but inversely with the neurological outcome (AIS grade). Multivariate analysis demonstrated that acute SCI‐induced neutrophilia is an independent predictor of AIS grade conversion failure, with an odds ratio (OR) of 4.16 and ROC area under curve (AUC) of 0.82 (P < 0.0001). SCI‐induced lymphopenia was separately identified as an independent predictor of better recovery (OR = 24.15; ROC AUC = 0.85, P < 0.0001). Acute neutrophilia and increased neutrophil‐lymphocyte ratios were otherwise significantly associated with respiratory infection presentation in both patient cohorts.

Conclusions

Our findings demonstrate the prognostic value of modelling early circulating neutrophil and lymphocyte counts with patient characteristics for predicting the longer term recovery after SCI.
Role of miR‐466 in mesenchymal stromal cell derived extracellular vesicles treating inoculation pneumonia caused by multidrug‐resistant Pseudomonas aeruginosa
Authors: Shi Meng‐meng , Zhu Ying‐gang , Yan Jia‐yang , Rouby Jean‐Jacques , Summah Hanssa , Monsel Antoine , Qu Jie‐ming
Published: January 2021

Rationale

The effects of mesenchymal stromal cells (MSCs) and MSC‐derived extracellular vesicles (MSC EVs) on multidrug‐resistant pseudomonas aeruginosa (MDR‐PA)‐induced pneumonia remain unclear.

Materials and methods

MicroRNA array and RT‐PCR were used to select the major microRNA in MSC EVs. Human peripheral blood monocytes were obtained and isolated from qualified patients. The crosstalk between MSCs/MSC EVs and macrophages in vitro was studied. MDR‐PA pneumonia models were further established in C57BL/6 mice and MSC EVs or miR‐466 overexpressing MSC EVs were intratracheally instilled.

Results

MiR‐466 was highly expressed in MSC EVs. MSCs and miR‐466 promoted macrophage polarization toward Type 2 phenotype through TIRAP‐MyD88‐NFκB axis. Moreover, cocultured macrophages with miR‐466 overexpressing MSCs significantly increased the phagocytosis of macrophages. MSC EVs significantly reduced mortality and decreased influx of BALF neutrophils, proinflammatory factor levels, protein, and bacterial load in murine MDR‐PA pneumonia. Administration of miR‐466 overexpressing MSC EVs further alleviated the inflammatory severity.

Conclusions

MSC‐derived EVs containing high levels of miR‐466 may partly participate in host immune responses to MDR‐PA. Both MSCs and MSC EVs have therapeutic effects in treating MDR‐PA‐induced pneumonia.
Diversity aided millimeter‐wave/free space optical cooperative relaying systems
Authors: Goel Amit , Upadhya Abhijeet , Dwivedi Vivek K.
Published: January 2021

In this paper, we investigate the performance of mixed millimeter‐wave (mmWave)/multiple input multiple output (MIMO)‐free space optics (FSO) cooperative relaying system. The mmWave link is assumed to undergo multipath fading and shadowing which has been modeled as generalized‐K distributed fading, whereas the diversity aided FSO link is considered to experience Gamma–Gamma turbulence. We consider amplify‐and‐forward (AF) relaying strategy and multiple signals arriving at the receiver are combined using equal gain combining (EGC) scheme. Analytical closed form expressions for performance metrics such as outage probability, bit error rate (BER), and the ergodic channel capacity are derived in terms of bivariate Fox's H‐function for the considered mixed mmWave/MIMO‐FSO relaying system. In order to further simplify the obtained results, we analyze the system performance for the case of high signal‐to‐noise ratio (SNR) to present the asymptotic expressions for the outage probability and BER in terms of elementary functions. To this end, we have formulated an optimum power allocation scheme which minimizes the probability of outage experienced by the end user by allocating the optimum power on the FSO link. We also analyze the proposed system for the impact of pointing errors in a separate section by deriving closed‐form expressions for the outage probability and BER. Finally, numerical results have been demonstrated the findings of the research work which have supplemented by Monte Carlo simulations.
Protection of clozapine‐induced oxidative stress and mitochondrial dysfunction by kaempferol in rat cardiomyocytes
Authors: Bakhshii Saba , Khezri Saleh , Ahangari Roya , Jahedsani Asal , Salimi Ahmad
Published: January 2021

Clozapine (CLZ) is unusually efficient in psychotic diseases. Nonetheless, its use is confined due to potentially life‐threatening adverse events, including cardiotoxicity. Since the cardiotoxicity of CLZ is mediated through the generation of active metabolites, free radical, and inflammation. Here, we tested this hypothesis that kaempferol (KP) as antioxidant and anti‐inflammatory agent could attenuate CLZ‐induced mitochondrial/lysosomal and oxidative damages in rat ventricular cardiomyocytes. Rat ventricular cardiomyocytes were isolated by collagenase perfusion. Then isolated cardiomyocytes were simultaneously treated with different concentrations of KP (10, 20, and 50 μM) and CLZ (50 μM) for 4 h at 37°C. After 4 h of incubation, using by flow cytometry and biochemical evaluations, the parameters of cellular toxicity including: cell viability, reactive oxygen species (ROS) formation, mitochondria membrane potential (ΔΨm) collapse, lysosomal membrane integrity, malondialdehyde, and oxidized/reduced glutathione were analyzed. The results showed that CLZ (50 μM) induced a significant increase in cytotoxicity, ROS formation, mitochondrial membrane potential collapse, lipid peroxidation, and oxidative stress while KP reverted the above toxic effect of CLZ on isolated cardiomyocytes. Our data suggest that KP prevents and reverses CLZ‐induced oxidative and mitochondrial/lysosomal damages in isolated cardiomyocytes, providing an experimental basis for clinical treatment on CLZ‐induced cardiotoxicity.
Early life adversity, pubertal timing, and epigenetic age acceleration in adulthood
Authors: Hamlat Elissa J. , Prather Aric A. , Horvath Steve , Belsky Jay , Epel Elissa S.
Published: January 2021

Background

Given associations linking early life adversity, pubertal timing, and biological aging, we examined the direct and indirect effects of early life trauma on adult biological aging (via age of menarche).

Methods

Participants were premenopausal women (N = 183). Path models evaluated whether early life trauma predicted early pubertal timing and thereby, adult epigenetic age acceleration (indexed via four epigenetic clocks: Horvath DNAm Age, Hannum DNAm Age, DNAm PhenoAge, and DNAm GrimAge). Secondary analyses explored the effects of type of trauma (abuse and neglect) and adult chronic stress status (caregiver of child with autism and non‐caregiver).

Results

Early life trauma and earlier age at menarche independently predicted accelerated aging based on one of the four epigenetic clocks, DNAm GrimAge, though early life trauma was not associated with age of menarche. Childhood abuse, but not neglect, predicted faster epigenetic aging; results did not differ by chronic stress status.

Conclusions

Early trauma and early menarche appear to exert independent effects on DNAm GrimAge, which has been shown to be the strongest epigenetic predictor of mortality risk. This study identifies a potential correlate or determinant of accelerated epigenetic aging—menarcheal age. Future research should address the limitations of this study by using racially diverse samples.
Recent bark beetle outbreaks influence wildfire severity in mixed‐conifer forests of the Sierra Nevada, California, USA
Authors: Wayman Rebecca B. , Safford Hugh D.
Published: January 2021

In temperate forests, elevated frequency of drought related disturbances will likely increase the incidence of interactions between disturbances such as bark beetle epidemics and wildfires. Our understanding of the influence of recent drought and insect‐induced tree mortality on wildfire severity has largely lacked information from forests adapted to frequent fire. A recent unprecedented tree mortality event in California’s Sierra Nevada provides an opportunity to examine this disturbance interaction in historically frequent‐fire forests. Using field data collected within areas of recent tree mortality that subsequently burned in wildfire, we examined whether and under what conditions wildfire severity relates to severity of prefire tree mortality in Sierra Nevada mixed‐conifer forests. We collected data on 180 plots within the 2015 Rough Fire and 2016 Cedar Fire footprints (California, USA). Our analyses identified prefire tree mortality as influential on all measures of wildfire severity (basal area killed by fire, RdNBR, and canopy torch) on the Cedar Fire, although it was less influential than fire weather (relative humidity). Prefire tree mortality was influential on two of three fire‐severity measures on the Rough Fire, and was the most important predictor of basal area killed by fire; topographic position was influential on two metrics. On the Cedar Fire, the influence of prefire mortality on basal area killed by fire was greater under milder weather conditions. All measures of fire severity increased as prefire mortality increased up to prefire mortality levels of approximately 30–40%; further increases did not result in greater fire severity. The interacting disturbances shifted a pine‐dominated system (Rough Fire) to a cedar–pine–fir system, while the pre‐disturbance fir–cedar system (Cedar Fire) saw its dominant species unchanged. Managers of historically frequent‐fire forests will benefit from utilizing this information when prioritizing fuels reduction treatments in areas of recent tree mortality, as it is the first empirical study to document a relationship between prefire mortality and subsequent wildfire severity in these systems. This study contributes to a growing body of evidence that the influence of prefire tree mortality on wildfire severity in temperate coniferous forests may depend on other conditions capable of driving extreme wildfire behavior, such as weather.
Fractal dimension of tree crowns explains species functional‐trait responses to urban environments at different scales
Authors: Arseniou Georgios , MacFarlane David W.
Published: January 2021

The evolution of form and function of trees of diverse species has taken place over hundreds of millions of years, while urban environments are relatively new on an evolutionary time scale, representing a novel set of environmental constraints for trees to respond to. It is important to understand how trees of different species, planted in these anthropogenically‐structured urban ecosystems, are responding to them. Many theories have been advanced to understand tree form and function, including several that suggest the fractal‐like geometry of trees is a direct reflection of inherent and plastic morphological and physiological traits that govern tree growth and survival. In this research, we analyzed the “fractal dimension” of thousands of tree crowns of many different tree species, growing in different urban environments across the United States, to learn more about the nature of trees and their responses to urban environments at different scales. Our results provide new insights regarding how tree crown fractal dimension relates to balances between hydraulic‐ and light‐capture‐related functions (e.g., drought and shade tolerance). Our findings indicate that trees exhibit reduced crown fractal dimension primarily to reduce water loss in hotter cities. More specifically, the intrinsic drought tolerance of the studied species arises from lower surface to volume ratios at both whole‐crown and leaf scales, preadapting them to drought stress in urban ecosystems. Needle‐leaved species showed a clear trade‐off between optimizing the fractal dimension of their crowns for drought vs. shade tolerance. Broad‐leaved species showed a fractal crown architecture that responded principally to inherent drought tolerance. Adjusting for the temperature of cities and intrinsic species effects, the fractal dimension of tree crowns was lower in more heavily urbanized areas (with greater paved area or buildings) and due to crowns conflicting with utility wires. With expectations for more urbanization and generally hotter future climates, worldwide, our results add new insights into the physiological ecology of trees in urban environments, which may help humans to provide more hospitable habitats for trees in urbanized areas and to make better decisions about tree selection in urban forest management.
Exposure to the thin beauty ideal: Are there subliminal priming effects?
Authors: Leins Judith , Waldorf Manuel , Suchan Boris , Diers Martin , Herpertz Stephan , Paslakis Georgios , Steins‐Loeber Sabine
Published: January 2021

Objective

Previous research suggested that exposure to the thin beauty ideal propagated by the media is associated with body dissatisfaction and the development of disordered eating. Given recent suggestions regarding the role of automatic processes, we aimed to enhance our understanding of automatic, unconscious responses to body pictures and the association with the internalization of the thin ideal and the severity of eating disorder symptoms.

Method

An affective priming task with body pictures of different weight as primes and a normal‐weight body picture as target, which had to be evaluated with regard to attractiveness and desirability, was administered to healthy women with either subliminal prime presentation (Experiment 1) or conscious presentation (Experiment 2).

Results

Subliminal presentation did not affect the evaluation of the normal‐weight target, although strength of evaluative shifts was significantly associated with internalization of the thin ideal. In contrast, the conscious presentation of the ultra‐thin prime decreased and of the obese prime increased desirability and attractiveness ratings of the target.

Discussion

Prevention strategies focusing on the critical evaluation of the thin ideal are important. Future studies are warranted to enhance our understanding of automatic, unconscious processes in women experiencing eating disorders.
Social predation in electric eels
Authors: Bastos Douglas A. , Zuanon Jansen , Rapp Py‐Daniel Lúcia , de Santana Carlos David
Published: January 2021

Social predation—when groups of predators coordinate actions to find and capture prey—is a common tactic among mammals but comparatively rare in fishes. We report the unexpected social predation by electric eels, an otherwise solitary predator in the Amazon rainforest. Observations made in different years and recorded on video show electric eels herding, encircling shoals of small nektonic fishes, and launching joint predatory high‐voltage strikes on the prey ball. These findings challenge the hypothesis that electric eels may have a single foraging strategy and extend our knowledge on social predation to an organism that employs high‐voltage discharge for hunting. Thereby offering a novel perspective for studies on the evolutionary interplay between predatory and escape tactics.
Why students do not turn on their video cameras during online classes and an equitable and inclusive plan to encourage them to do so
Authors: Castelli Frank R. , Sarvary Mark A.
Published: January 2021

Enrollment in courses taught remotely in higher education has been on the rise, with a recent surge in response to a global pandemic. While adapting this form of teaching, instructors familiar with traditional face‐to‐face methods are now met with a new set of challenges, including students not turning on their cameras during synchronous class meetings held via videoconferencing. After transitioning to emergency remote instruction in response to the COVID‐19 pandemic, our introductory biology course shifted all in‐person laboratory sections into synchronous class meetings held via the Zoom videoconferencing program. Out of consideration for students, we established a policy that video camera use during class was optional, but encouraged. However, by the end of the semester, several of our instructors and students reported lower than desired camera use that diminished the educational experience. We surveyed students to better understand why they did not turn on their cameras. We confirmed several predicted reasons including the most frequently reported: being concerned about personal appearance. Other reasons included being concerned about other people and the physical location being seen in the background and having a weak internet connection, all of which our exploratory analyses suggest may disproportionately influence underrepresented minorities. Additionally, some students revealed to us that social norms also play a role in camera use. This information was used to develop strategies to encourage—without requiring—camera use while promoting equity and inclusion. Broadly, these strategies are to not require camera use, explicitly encourage usage while establishing norms, address potential distractions, engage students with active learning, and understand your students’ challenges through surveys. While the demographics and needs of students vary by course and institution, our recommendations will likely be directly helpful to many instructors and also serve as a model for gathering data to develop strategies more tailored for other student populations.
Predicting seasonal movements and distribution of the sperm whale using machine learning algorithms
Authors: Chambault Philippine , Fossette Sabrina , Heide‐Jørgensen Mads Peter , Jouannet Daniel , Vély Michel
Published: January 2021

Implementation of effective conservation planning relies on a robust understanding of the spatiotemporal distribution of the target species. In the marine realm, this is even more challenging for species rarely seen at the sea surface due to their extreme diving behavior like the sperm whales. Our study aims at (a) investigating the seasonal movements, (b) predicting the potential distribution, and (c) assessing the diel vertical behavior of this species in the Mascarene Archipelago in the south‐west Indian Ocean. Using 21 satellite tracks of sperm whales and eight environmental predictors, 14 supervised machine learning algorithms were tested and compared to predict the whales' potential distribution during the wet and dry season, separately. Fourteen of the whales remained in close proximity to Mauritius, while a migratory pattern was evidenced with a synchronized departure for eight females that headed towards Rodrigues Island. The best performing algorithm was the random forest, showing a strong affinity of the whales for sea surface height during the wet season and for bottom temperature during the dry season. A more dispersed distribution was predicted during the wet season, whereas a more restricted distribution to Mauritius and Reunion waters was found during the dry season, probably related to the breeding period. A diel pattern was observed in the diving behavior, likely following the vertical migration of squids. The results of our study fill a knowledge gap regarding seasonal movements and habitat affinities of this vulnerable species, for which a regional IUCN assessment is still missing in the Indian Ocean. Our findings also confirm the great potential of machine learning algorithms in conservation planning and provide highly reproductible tools to support dynamic ocean management.
Coupled ecological and management connectivity across administrative boundaries in undeveloped landscapes
Authors: Aslan Clare E. , Brunson Mark W. , Sikes Benjamin A. , Epanchin‐Niell Rebecca S. , Veloz Samuel , Theobald David M. , Dickson Brett G.
Published: January 2021

Human‐induced ecological boundaries, or anthropogenic ecotones, may arise where administrative boundaries meet on undeveloped lands. Landscape‐level ecological processes related to factors such as fire, invasive species, grazing, resource extraction, wildlife, and water may be affected due to unique management strategies adopted by each administrative unit. Over time, different management can result in discernible ecological differences (e.g., species composition or soil characteristics). Thus, fragmentation in the management landscape can correspond to ecological fragmentation. Different ecological patterns may emerge due to an increase in the number of management units in a region, or due to an increase in the number of different types of management units in the region. Temporal effects and collaboration history can also affect the emergence of ecotones. We use conceptual models to explore the relationship between these aspects of management fragmentation and the anthropogenic ecotones between management parcels. We then use examples of different management challenges to explore how anthropogenic ecotones can disrupt ecological flows. Our models suggest that cross‐boundary collaboration that enhances management connectivity is likely essential to ecological connectivity in the face of environmental and social change.
Metal–Organic Framework‐Based Sulfur‐Loaded Materials
Authors: Du Meng , Li Qing , Zhang Guangxun , Wang Feifei , Pang Huan
Published: January 2021

Lithium‐sulfur batteries (LSBs) are considered promising new energy storage systems given their outstanding theoretical energy densities. Nevertheless, issues such as low electrical conductivity and severe volume expansion, along with the formation of polysulfides during cycling, restrict their practical applications. To overcome these issues, it is necessary to find suitable and effective sulfur host materials. Metal–organic frameworks (MOFs), which are porous crystalline materials in the bourgeoning developmental stages, have demonstrated enormous potential in LSBs owing to their high porosity and tunable porous structure. Herein, we provide a comprehensive overview of MOF‐based sulfur‐loaded materials and discuss the charge/discharge mechanisms, strategies of enhancing battery performance, sulfur loading methods, and applications in LSBs. An outlook on future directions, prospects, and possible obstacles for the development of these materials is also provided.
Characteristics, treatment, and outcomes of newly diagnosed atrial fibrillation patients with heart failure: GARFIELD‐AF
Authors: Ambrosio Giuseppe , Camm A. John , Bassand Jean‐Pierre , Corbalan Ramon , Kayani Gloria , Carluccio Erberto , Mantovani Lorenzo G. , Virdone Saverio , Kakkar Ajay K. ,   for the GARFIELD‐AF Investigators
Published: January 2021

Aims

Heart failure (HF) and atrial fibrillation (AF) may coexist and influence each other. However, characteristics, anticoagulant treatment, and outcomes of contemporary AF patients with concurrent HF are ill‐defined. This study analyses characteristics, treatment, and 2 year outcomes in newly diagnosed Global Anticoagulant Registry in the FIELD‐Atrial Fibrillation (GARFIELD‐AF) patients with vs. without HF.

Methods and results

GARFIELD‐AF is the world's largest observational AF patient study. At enrolment, 11 758 of 52 072 patients (22.6%) had HF; 76.3% were New York Heart Association class II–III. Patients with HF had comparable demographics, blood pressure, and heart rate but more likely had permanent (15.6% vs. 11.9%) or persistent AF (18.9% vs. 13.8%), acute coronary syndromes (16.7% vs. 8.9%), vascular disease (40.8% vs. 20.2%), and moderate‐to‐severe chronic kidney disease (14.6% vs. 9.0%) than those without. Anticoagulant prescription was similar between the two groups. At 2 year follow‐up, patients with HF showed a greater risk of all‐cause mortality [hazard ratio (HR), 2.06; 95% confidence interval (CI), 1.91–2.21; P < 0.0001], cardiovascular mortality (HR, 2.91; 95% CI, 2.58–3.29; P < 0.0001), acute coronary syndromes (HR, 1.25; 95% CI, 1.02–1.52; P = 0.03), and stroke/systemic embolism (HR, 1.24; 95% CI, 1.07–1.43; P = 0.0044). Major bleeding rate was comparable (adjusted HR, 1.00; 95% CI, 0.84–1.18; P = 0.968). Among patients without HF at baseline, incidence of new HF was low [0.69 (95% CI, 0.63–0.75) per 100 person‐years], whereas propensity to develop worsening HF was higher in those with HF [1.62 (95% CI, 1.45–1.80) per 100 person‐years].

Conclusions

Patients with AF and HF have a high risk of all‐cause and cardiovascular mortality and stroke/systemic embolism and may develop worsening HF.
Incremental prognostic value of cardiac metaiodobenzylguanidine imaging over the co‐morbid burden in acute decompensated heart failure
Authors: Kayama Kiyomi , Yamada Takahisa , Tamaki Shunsuke , Watanabe Tetsuya , Morita Takashi , Furukawa Yoshio , Kawasaki Masato , Kikuchi Atsushi , Kawai Tsutomu , Seo Masahiro , Nakamura Jun , Kawahira Masatsugu , Fukunami Masatake
Published: January 2021

Aims

Co‐morbidities are associated with poor clinical outcomes in patients with chronic heart failure, while cardiac iodine‐123 (I‐123) metaiodobenzylguanidine (MIBG) imaging provides prognostic information in such patients. We sought to prospectively investigate the incremental prognostic value of cardiac MIBG imaging over the co‐morbid burden, in patients admitted for acute decompensated heart failure (ADHF).

Methods and results

In 433 consecutive ADHF patients with survival to discharge, we measured the co‐morbidity using age‐adjusted Charlson co‐morbidity index (ACCI), commonly employed to evaluate a weighted and scored co‐morbid condition, adding additional points for age. In cardiac MIBG imaging, the cardiac MIBG heart‐to‐mediastinum ratio (late HMR) was measured on the delayed image. Over a follow‐up period of 2.9 ± 1.5 years, 160 patients had a cardiac event (a composite of cardiac death and unplanned hospitalization for worsening heart failure). Patients with high ACCI (≥6: median value) had a significantly greater risk of a cardiac event. In multivariate Cox analysis, the ACCI and late HMR were significantly and independently associated with a cardiac event. In both high and low ACCI subgroups (ACCI ≥ 6 and <6, respectively), patients with low late HMR had a significantly greater risk of a cardiac event (high ACCI: 51% vs. 34% P = 0.0026, adjusted HR 1.74 [1.21–2.51]; low ACCI: 34% vs. 17%, P = 0.0228, adjusted HR 2.19 [1.10–4.37]).

Conclusions

Cardiac MIBG imaging could provide additional prognostic information over ACCI, which was also promoted to be a useful risk model, in patients admitted for ADHF.
Characterization of NT‐proBNP in a large cohort of COVID‐19 patients
Authors: Caro‐Codón Juan , Rey Juan R. , Buño Antonio , Iniesta Angel M. , Rosillo Sandra O. , Castrejon‐Castrejon Sergio , Rodriguez‐Sotelo Laura , Martinez Luis A. , Marco Irene , Merino Carlos , Martin‐Polo Lorena , Garcia‐Veas Jose M. , Martinez‐Cossiani Marcel , Gonzalez‐Valle Luis , Herrero Alicia , López‐de‐Sa Esteban , Merino Jose L. ,   CARD‐COVID Investigators
Published: January 2021

Aims

Extensive research regarding the association of troponin and prognosis in coronavirus disease 2019 (COVID‐19) has been performed. However, data regarding natriuretic peptides are scarce. N‐terminal pro B‐type natriuretic peptide (NT‐proBNP) reflects haemodynamic stress and has proven useful for risk stratification in heart failure (HF) and other conditions such as pulmonary embolism and pneumonia. We aimed to adequately characterize NT‐proBNP concentrations using a large cohort of patients with COVID‐19, and to investigate its association with prognosis.

Methods and results

Consecutive patients with confirmed severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) infection and available NT‐proBNP determinations, from March 1st to April 20th, 2020 who completed at least 1‐month follow‐up or died, were studied. Of 3080 screened patients, a total of 396 (mean age 71.8 ± 14.6 years, 61.1% male) fulfilled all the selection criteria and were finally included, with a median follow‐up of 53 (18–62) days. Of those, 192 (48.5%) presented NT‐proBNP levels above the recommended cut‐off for the identification of HF. However, only 47 fulfilled the clinical criteria for the diagnosis of HF. Patients with higher NT‐proBNP during admission experienced more frequent bleeding, arrhythmias and HF decompensations. NT‐proBNP was associated with mortality both in the whole study population and after excluding patients with HF. A multivariable Cox model confirmed that NT‐proBNP was independently associated with mortality after adjusting for all relevant confounders (hazard ratio 1.28, 95% confidence interval 1.13–1.44, per logarithmic unit).

Conclusion

NT‐proBNP is frequently elevated in COVID‐19. It is strongly and independently associated with mortality after adjusting for relevant confounders, including chronic HF and acute HF. Therefore, its use may improve early prognostic stratification in this condition.
Unprecedented Catalytic Behavior of Uranyl(VI) Compounds in Chemical Reactions
Authors: Behera Nabakrushna , Sethi Sipun
Published: January 2021

Uranyl catalysis represents a progressively more significant class of current research. The key species responsible for such catalysis is UO22+ ion which is a remarkably stable molecular component possessing strongly covalent and chemically robust trans U‐oxo groups. Aside from its fundamental interest, an understanding of the chemistry of such divalent UO22+ ion is enviable due to its huge ecological importance. The unprecedented electronic non‐rigidity of uranium center with easy switching among oxidation states and kinetic lability of its coordination states are the key features to bring about a considerable development in its catalytic reactivity profiles. This review explores the topical evolutions of most promising uranyl(VI) catalytic systems appearing in the literature for the last two decades along with reports prior to 2000 incorporated where pertinent. In addition to homometallic uranyl catalysis, a succinct discussion on heterometallic uranyl catalysis is presented. Finally, some relevant comparisons have been made between the uranyl catalysis and transition metal systems.
Lattice Dynamics and Thermodynamic Properties of Bulk Phases and Monolayers of GaTe and InTe: A Comparison from First‐Principles Calculations
Authors: Bandura Andrei V. , Kovalenko Alexey V. , Kuruch Dmitry D. , Evarestov Robert A.
Published: January 2021

The hybrid density functional theory was used to study the structural, vibrational, and thermodynamic properties of stable and hypothetical bulk GaTe and InTe polymorphs, as well as their monolayer counterparts. Criteria based on the vibrational frequencies have been proposed to distinguish between different monolayer structures. Heat capacity, entropy, and Helmholtz free energy have been calculated by summing the vibrational contributions over the corresponding Brillouin zone. The relative stability of the considered systems has been estimated at different temperatures using the obtained Helmholtz free energy. Both the total energy and the Helmholtz free energy calculations confirmed that a free‐standing monolayer originated from the monoclinic GaTe phase is less stable than its hexagonal analogs. It was also found that the temperature increase favors monolayer formation in the case of GaTe, but prevents it in the case of InTe.
Seeded Growth of Au@PdAg Alloy Core‐Shell Nano‐Dendrites with Tunable Size and Composition
Authors: Zhang Gongguo , Ma Yanyun , Liu Feng , Fu Xiaowei , Luan Xiaoqian , Qu Fengli , Liu Maochang , Zheng Yiqun
Published: January 2021

We report a facile synthesis of Au@PdAg alloy core‐shell nanocrystals in dendrite form, having tunable size and composition. In particular, using spherical Au nanoparticles as seeds, the co‐reduction of Pd and Ag precursor in growth stage results in the formation of PdAg alloy shells with a dendrite shape. Their size and elemental composition can be tuned by varying the seed amount and feeding ratio in Pd and Ag precursor, respectively, illustrating the versatility of the current synthetic strategy. The size, morphology, and elemental composition of the products have been characterized using a set of techniques, including SEM, TEM, XRD, XPS, HAADF‐STEM, and EDX‐STEM mapping. When working as electrocatalysts, the current Au@PdAg alloy core‐shell nanocrystals supported by carbon black exhibit enhanced activity and excellent operation stability for electroxidation of ethanol as compared to commercial Pd/C. The current work offers a feasible strategy to preparation of multi‐metallic core‐shell dendritic nanocrystals with controllable size and composition and could find important use in fuel cells and related fields.
A New Lithium‐Rich Zeolitic 10‐MR Zincolithosilicate MZS‐1 Hydrothermally Synthesized under High Pressure and Characterized by 3D Electron Diffraction
Authors: Steciuk Gwladys , Schäf Oliver , Tortet Laurence , Pizzala Hélène , Palatinus Lukáš , Hornfeck Wolfgang , Paillaud Jean‐Louis
Published: January 2021

We report the structure of a new high lithium content zincolithosilicate (MZS‐1) obtained after hydrothermal treatment under high pressure from a glass precursor. After synthesis microcrystalline mixture of phases was obtained among which the main phase was unknown. Due to the sub micrometric size of the crystallites its structure was determined from precession‐assisted 3D electron diffraction measured at 100 K and refined using the dynamical theory of diffraction. More accurate lattice parameters are obtained from Rietveld refinement of synchrotron powder data collected at the ambient temperature. The characteristic framework is described at the ambient temperature using an average unit cell a0=8.57999(5) Å, b0=14.12332(8) Å, c0=4.96827(3) Å in the space group Ccc2. The structure of the new zeolitic 10‐membered ring zincosilicate with chemical formula per unit cell (SiO2)2Zn0.408LiO(OH)2(Li,H)2.184 (Z=4) is composed of undulated silicate layers made of fused 6‐membered rings connected via vertices of (Zn,Li)O4 tetrahedra. A weak superstructure doubling the a0 parameter is observed and is explained by a Zn/Li ordering within the (Zn,Li)O4 layers.
Oxidative Addition of α‐Glycosyl Halides to a Platinum(0) Olefin Complex: Stereochemistry of Pt−C Bond Formation
Authors: Annunziata Alfonso , Cucciolito Maria Elena , Esposito Roberto , Traboni Serena , Tuzi Angela , Budzelaar Peter H. M. , Ruffo Francesco
Published: January 2021

The oxidative addition of α‐glucosyl and α‐galactosyl halides to the platinum(0) complex [Pt(2,9‐dimethyl‐1,10‐phenanthroline)(ethene)] has been investigated. In all cases the main reaction product is the five‐coordinate Pt(II) complex containing in axial position an α‐glycosyl fragment in the unusual 1C4 conformation. In the case of glucose, a minor product could be identified as the β isomer, which retains the typical 4C1 chair. The single crystal structures of two diastereomers are compared. The outcome of the reaction does not depend on the nature of the halide and is only slightly affected by the solvent. The addition mechanism is discussed, also in the light of literature data. Experimental data, along with DFT calculations, point towards a radical chain mechanism.
Redox Instability of Copper(II) Complexes of a Triazine‐Based PNP Pincer
Authors: Mohammadnezhad Gholamhossein , Amirian Ali Mohammad , Görls Helmar , Plass Winfried , Sandleben Aaron , Schäfer Sascha , Klein Axel
Published: January 2021

The new Cu(I) complex [Cu(PNPNTPh‐Ph)Cl] (1) containing the tridentate PNP pincer ligand N,N′‐bis(diphenylphosphino)‐2,6‐diamino‐4‐phenyl‐1,3,5‐triazine was obtained from the reaction of [Cu(SMe2)Cl]n with the ligand as ether solvate 1.0.5Et2O. 1 was independently obtained from a reaction mixture containing the ligand and the Cu(II) precursor CuCl2.2H2O in 50 % yield alongside with the Cu(II) coordination polymer [Cu(O2PPh2)2]n (2). From the reaction of Cu(NO3)2 ⋅ 3H2O with PNPNTPh‐Ph in the presence of pyridine the complexes [Cu(O2PPh2)2(Py)2(H2O)] (3), [Cu(O2PPh2)(Py)2(NO3)]2 (4), and [Cu(Py)4(NO3)2].Py (5), were obtained, 2, 3, and 4 contain diphenyl‐phosphinate ligands. The underlying redox reaction of the ligand and Cu(II) yielding the oxidised ligands observed in the by‐products and the Cu(I) product complex was further studied using electrochemistry and UV‐vis spectroelectrochemistry. Attempts to synthesise the Cu(II) complex [Cu(PNPNTPh‐Ph)(NO3)2] (6) in a mechanochemical experiment gave evidence for this unprecedented species from ESI‐MS(+) and EPR spectroscopy but also revealed its very high sensitivity to air and moisture. The catalytic activity of 1 was investigated in the azide‐alkyne cycloaddition yielding various 1‐benzyl‐4‐phenyl‐1H‐1,2,3‐triazoles. The environmentally benign (“green”) and cheap EtOH/H2O solvent mixture turned out to be very suitable. Melting points, FT‐IR, and NMR spectra of the triazole products were analysed.
Oxidative Copper‐Catalyzed Regioselective Trifluoromethylation of Fused Imidazo[1,5‐a]‐N‐heteroarenes using Langlois Reagent
Authors: Sandeep Mummadi , Shantharjun Bangarigalla , Pradeep Kumar Geetala , Rajender Reddy Kallu
Published: January 2021

A simple, mild, and efficient oxidative copper‐catalyzed regioselective trifluoromethylation of imidazo[1,5‐a]‐N‐heteroarenes have been developed using Langlois, (NaSO2CF3) reagent as CF3 source. This method gives biologically relevant trifluoromethylated fused imidazoles in moderate to good yields with good functional group tolerance. The key features of the reaction are mild conditions, short reaction time, and room temperature reaction.
Metal‐Free Hydrophosphoryloxylation of Ynamides: Rapid Access to Enol Phosphates
Authors: An Dalie , Zhang Weinan , Pan Bin , Zhao Yingying
Published: January 2021

We herein report a metal‐free hydrophosphoryloxylation of ynamides with phosphoric acids, which provides an expeditious route to access useful enol phosphates. The advantages of this protocol include exclusive selectivity, short reaction time, high efficiency, and broad substrate scope. Additionally, the products can serve as good partners in Suzuki‐Miyaura cross‐coupling.
SNAr Reaction Toward the Synthesis of Fluorinated Quinolino[2,3,4‐at]porphyrins
Authors: Thuita Damaris , Guberman‐Pfeffer Matthew J. , Brückner Christian
Published: January 2021

An intramolecular SNAr displacement of one o‐fluorine atom of a meso‐pentafluorophenyl‐substituted porphyrin metal complex by a neighboring β‐amino functionality generated the corresponding meso‐fluorophenyl‐substituted metallo‐quinolino[2,3,4‐at]porphyrins that are not accessible using established quinoline‐annulation methodologies. The Cu(II), Ni(II), and Zn(II) complexes were thus prepared. The parent free base quinolino[2,3,4‐at]porphyrin is accessible only by demetallation of the copper or zinc complexes. A strong through‐space NMR‐spectroscopic coupling between the remaining o‐fluorine atoms on the annulated meso‐aryl group and the β‐hydrogen atom on the adjacent pyrrole moiety provide a clear spectroscopic signature for the annulation. Quinoline‐annulation alters the optical properties significantly. On account of the presence of the β‐amino functionality, all quinoline‐annulated porphyrins show strong halochromic responses with Brønsted acids and bases, the prerequisite for their potential use in chemosensing applications.
Synthesis and Molecular Properties of Partially Fluorinated DNTTs**
Authors: Tripp Matthias W. , Bischof Daniel , Dreher Maximilian , Witte Gregor , Koert Ulrich
Published: January 2021

1,2,3,4‐Tetrafluoro‐dinaphthothienothiophene (F4DNTT) and 1,2,3,4,8,9,10,11‐octafluoro‐dinaphthothienothiophene (F8DNTT) were synthesized via bisthiomethyl alkene intermediates which were accessible by McMurry coupling or Wittig olefination of partially fluorinated naphthalene precursors. DFT‐based electronic structure calculations, near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy, and UV/Vis measurements were used for HOMO/LUMO gap determination and to analyze the electronic structures of the partially fluorinated DNTTs. Reduced exciton binding was observed in thin films.