bluuebunny/crossref_metadata_2025 huggingface dataset:
Light‐Induced Redox Looping of a Rhodium/CexWO3 Photocatalyst for Highly Active and Robust Dry Reforming of Methane
Authors: Yang Yuying , Chai Zhigang , Qin Xuetao , Zhang Zhenzhen , Muhetaer Aidaer , Wang Cong , Huang Hanlin , Yang Chaoran , Ma Ding , Li Qi , Xu Dongsheng
Published: March 2022

Dry reforming of methane (DRM) has provided an effective avenue to convert two greenhouse gases, CH4 and CO2, into syngas. Here, we design a DRM photocatalyst Rh/CexWO3 that invokes both photothermal and photoelectric processes, which overcomes the thermodynamic limitation of DRM under conventional conditions. In contrast to plasmonic or UV‐response photocatalysts, our photocatalyst produces a superior light‐to‐chemical energy efficiency (LTCEE) of 4.65 % with a moderate light intensity. We propose that a light‐induced metal‐to‐metal charge transfer plays a crucial role in the DRM reaction, which induces a redox looping between Ce to W species to lower the activation energy. Quantum mechanical studies reveal that a high oxygen mobility of CexWO3, accompanied with the formation of oxo‐bridge species, results in a substantial elimination of deposited C species during the reaction. Our catalyst design strategy could offer a promising energy‐efficient industrial process for DRM.
Non‐Immunosuppressive Cyclophilin Inhibitors
Authors: Schiene‐Fischer Cordelia , Fischer Gunter , Braun Manfred
Published: March 2022

Cyclophilins, enzymes with peptidyl‐prolyl cis/trans isomerase activity, are relevant to a large variety of biological processes. The most abundant member of this enzyme family, cyclophilin A, is the cellular receptor of the immunosuppressive drug cyclosporine A (CsA). As a consequence of the pathophysiological role of cyclophilins, particularly in viral infections, there is a broad interest in cyclophilin inhibition devoid of immunosuppressive activity. This Review first gives an introduction into the physiological and pathophysiological roles of cyclophilins. The presentation of non‐immunosuppressive cyclophilin inhibitors will commence with drugs based on chemical modifications of CsA. The naturally occurring macrocyclic sanglifehrins have become other lead structures for cyclophilin‐inhibiting drugs. Finally, de novo designed compounds, whose structures are not derived from or inspired by natural products, will be presented. Relevant synthetic concepts will be discussed, but the focus will also be on biochemical studies, structure–activity relationships, and clinical studies.
Diet plasticity and links to changing foraging behaviour in the conservation of subantarctic yellow‐eyed penguins (Megadyptes antipodes)
Authors: Muller Chris G. , Chilvers B. Louise , French Rebecca K. , Battley Phil F.
Published: March 2022

Diet is a key factor affecting seabird foraging behaviour, ultimately influencing survival, breeding success and long‐term population viability. The density and distribution of prey species in the marine environment are influenced by many factors including climate effects such as El Niño southern oscillation and climate change that alter water temperature.

While poor quality diet has been implicated as a contributing factor in the decline of some mainland New Zealand yellow‐eyed penguin (Megadyptes antipodes) populations, little is known about their diet in the subantarctic where the majority of the species breeds.

Blood and feather samples (n = 63) were collected for stable isotope analysis of diet from 25 individual birds breeding on subantarctic Enderby Island, Auckland Islands, New Zealand, from 2015 to 2018.

Diet data were analysed by factors such as breeding year, sex and foraging behaviour. Stable isotope analysis demonstrated significant changes in diet during each year of the study, which included both El Niño and La Niña conditions.

Diet during El Niño conditions comprised lower trophic level prey, which were more benthic, and found closer to shore than diet during La Niña.

Coupled with the reported variable breeding success of yellow‐eyed penguins in the subantarctic, variable diet suggests prey availability is likely to be a limiting factor in some years. Prey availability is therefore expected to be a major influence on survival and breeding success of this endangered species in the future, particularly if the effects of climate change become more pronounced.

This research highlights an urgent conservation need to identify prey species utilized by the southern population, along with their distribution in time and space, and therefore also the effect of diet on long‐term population stability.
Do Glucocorticoid Injections Increase the Risk of Knee Osteoarthritis Progression Over 5 Years?
Authors: Latourte Augustin , Rat Anne‐Christine , Omorou Abdou , Ngueyon‐Sime Willy , Eymard Florent , Sellam Jérémie , Roux Christian , Ea Hang‐Korng , Cohen‐Solal Martine , Bardin Thomas , Beaudreuil Johann , Guillemin Francis , Richette Pascal
Published: March 2022

Objective

Recent findings have demonstrated that intraarticular (IA) glucocorticoid injections can be deleterious for knees with osteoarthritis (OA). This study was undertaken to assess, in a real‐life setting, the risk of knee OA progression in patients who received IA glucocorticoid injections over a 5‐year follow‐up period.

Methods

We used marginal structural modeling with inverse probability of treatment weighting to determine the causal association between IA glucocorticoid injections and the 5‐year risk of disease progression in patients with symptomatic knee OA from the Knee and Hip Osteoarthritis Long‐term Assessment cohort. OA progression was defined as an incident total knee replacement (TKR) and/or radiographic worsening (Kellgren/Lawrence [K/L] grade or joint space narrowing [JSN]). We also examined these outcomes in knees that received IA hyaluronan (IAHA) injections.

Results

Among the 564 patients with knee OA included in the study sample, 51 (9.0%) and 99 (17.5%) received IA glucocorticoid or IAHA injections, respectively, and 414 (63.1%) did not receive any injection during follow‐up. Compared to untreated knees, those treated with IA glucocorticoid injections had a similar risk of incident TKR (hazard ratio [HR] 0.92 [95% confidence interval (95% CI) 0.20, 4.14]; P = 0.91) or K/L grade worsening (HR 1.33 [95% CI 0.64, 2.79]; P = 0.44). IAHA injections had no effect on the risk of TKR (HR 0.81 [95% CI 0.14, 4.63]; P = 0.81) or K/L grade worsening (HR 1.36 [95% CI 0.85, 2.17]; P = 0.20). Similar results were obtained for JSN, and when TKR and radiographic outcomes were combined.

Conclusion

In this study, IA glucocorticoid injections for symptomatic knee OA did not significantly increase the 5‐year risk of incident TKR or radiographic worsening. These findings should be interpreted cautiously and replicated in other cohorts.
Synthesis of Highly Substituted 2‐Aminopyridines with Vinyl Azides, Isonitriles, and Ketones
Authors: Chang Wenxu , Li Zongyang , Yuan Chenhui , Liu Xinying , Feng Jiyao , Pang Sen , Duan Liusheng , Zhang Zhenhua
Published: March 2022

We developed a facile, efficient method for synthesizing highly substituted 2‐aminopyridines from unstable vinyl carbodiimides generated in situ in a one‐pot transformation. A series of novel highly substituted 3‐functionalized 2‐aminopyridines were produced in good yields. Reaction mechanism studies, which included control experiments and density‐functional theory (DFT) calculations, demonstrated that Rh and potassium carbonate played key roles in the cyclization step.
The challenges in diagnosis and management of osteitis pubis: An algorithm based on current evidence
Authors: Amer Mohammed Lotfi , Omar Kawa , Malde Sachin , Nair Rajesh , Thurairaja Ramesh , Khan Muhammad Shamim
Published: March 2022

Objective

The objective of this study is to summarise the contemporary evidence regarding the prevalence, diagnosis, and management of osteitis pubis (OP) specially from urological point of view, while proposing an algorithm for the best management based on the current evidence.

Methods

We performed a literature search using the PubMed database for the term ‘osteitis pubis’ until December 2020. We assessed pre‐clinical and clinical studies regarding the aetiology, pathophysiology, and management of OP. Case reports and case series were evaluated by study quality and patient outcomes to determine a potential clinical management algorithm.

Results

Osteitis pubis is a chronic painful condition of the symphysis pubis joint and its surrounding structures. Still, there is a paucity of data outlining the management plan and the possible triggers. The aetiology seems to be multifactorial with different proposals trying to explain the pathophysiology and correlate the findings to the outcome. The diagnosis is usually based on high suspicion index and clinical experience. The infective variant of the disease is aggressive and requires strict and active management. Universal consensus is still lacking regarding a formal algorithm of management of the condition, especially due to multiple specialities involved in the decision‐making process. Conservative management remains the cornerstone; nevertheless, surgical interventions may be needed in special settings. Hence, a multi‐disciplinary approach is of pivotal value in fashioning the plan for each case. The prognosis is usually satisfactory; however, a longstanding debilitating disease form is not uncommon.

Conclusion

OP remains a rare condition with real challenges in its diagnosis. The current management is focused on conservative management; however, surgical intervention is still needed in some difficult scenarios. Continued research into the triggers of OP, multidisciplinary approach, and standardised clinical pathways can improve the quality of care for patients suffering from this condition.
Patterns of multiple congenital anomalies in the National Birth Defect Prevention Study: Challenges and insights
Authors: Howley Meredith M. , Williford Eva , Agopian A. J. , Lin Angela E. , Botto Lorenzo D. , Cunniff Christopher M. , Romitti Paul A. , Nestoridi Eirini , Browne Marilyn L. ,   for the National Birth Defects Prevention Study
Published: March 2022

Background

About 20%–30% of children with birth defects have multiple major birth defects in more than one organ system, often referred to as multiple congenital anomalies (MCAs). Evaluating the patterns of MCAs can provide clues to the underlying causes, pathogenic mechanisms, and developmental pathways. We sought to explore selected patterns of MCAs within the National Birth Defects Prevention Study (NBDPS), a population‐based, case–control study that excluded cases attributed to known chromosomal or single‐gene abnormalities.

Methods

We defined MCAs as having two or more NBDPS‐eligible birth defects and calculated the adjusted observed‐to‐expected ratio for all observed MCA patterns using co‐occurring defect analysis.

Results

Of the 50,186 case infants eligible for NBDPS, 2,734 (3.7%) had at least two eligible birth defects. We observed 209 distinct 2‐way combinations of birth defects, 297 distinct 3‐way combinations, 179 distinct 4‐way combinations, and 69 distinct 5‐way combinations. Sacral agenesis had the largest proportion of cases with MCAs (70%), whereas gastroschisis had the lowest (3%). Among the cases with MCAs, 63% had a heart defect, 23% had an oral cleft, and 21% had anorectal atresia/stenosis. Of the patterns with adjusted observed‐to‐expected ratios in the top 20%, most were consistent with the known associations or syndromes, including VATER/VACTERL association and CHARGE syndrome.

Conclusions

Most but not all patterns that had the highest adjusted observed‐to‐expected ratios were instances of known syndromes or associations. These findings highlight the importance of considering birth defect combinations that suggest syndromic patterns in the absence of a formal syndromic diagnosis. New approaches for screening for sequences and associations, and VATER/VACTERL in particular, in surveillance systems with limited resources for manual review may be valuable for improving surveillance system quality. The observed MCA patterns within NBDPS may help focus future genetic studies by generating case groups of higher yield.
Tissue‐engineered in vitro modeling of the impact of Schwann cells in amyotrophic lateral sclerosis
Authors: Louit Aurélie , Beaudet Marie‐Josée , Gros‐Louis François , Berthod François
Published: March 2022

Amyotrophic Lateral Sclerosis (ALS) is a devastating neurodegenerative disease affecting upper and lower motor neurons (MNs). To investigate whether Schwann cells could be involved in the disease pathogenesis, we developed a tissue‐engineered three‐dimensional (3D) in vitro model that combined MNs cocultured with astrocytes and microglia seeded on top of a collagen sponge populated with epineurium fibroblasts to enable 3D axonal migration. C2C12 myoblasts were seeded underneath the sponge in the presence or absence of Schwann cells. To reproduce an ALS cellular microenvironment, MNs, astrocytes, and microglia were extracted from SOD1G93A mice recapitulating many aspects of the human disease. This 3D ALS in vitro model was compared with a 3D control made of cells isolated from SOD1WT mice. We showed that normal Schwann cells strongly enhanced MN axonal migration in the 3D control model but had no effect in the ALS model. However, ALS‐derived Schwann cells isolated from SOD1G93A mice failed to significantly improve axonal migration in both models. These results suggest that a cell therapy using healthy Schwann cells may not be effective in promoting axonal regeneration in ALS. In addition, this 3D ALS model could be used to study the impact of other cell types on ALS by various combinations of normal and diseased cells.
Design of Ru‐aqua complex possessing potential inversion behavior
Authors: Jeon Dohoon , Kang Youn K.
Published: March 2022

We attempted to design Ru‐aqua complexes that possess potential inversion behavior for sequential proton‐coupled oxidation (PCO) reactions. Standard reduction potentials for [RuIII(T)(B)(OH)]m+ + H+ + e− → [RuII(T)(B)(H2O)]m+ (E°(RuIII/II)), [RuIV(T)(B)(O)]m+ + H+ + e− → [RuIII(T)(B)(OH)]m+ (E°[RuIV/III]) reactions as well as ΔE° values (ΔE° = E°(RuIII/II) − E°(RuIV/III)) of newly designed 41 Ru‐aqua complexes along with those of previously reported 13 known ones were calculated using the DFT method with PBE1PBE/def2SVP/SDD combination. Four complexes with negative ΔE° values and nine complexes with ΔE° values smaller than 0.1 V were found by this screening work. The calculated ΔE° values had a close relationship with E°(RuIII/II). Complexes possessing large ΔE° values showed relatively small E°(RuIII/II) that gave rise to the increased gap with E°(RuIV/III). It was found that the distortion of electronic structures during progressing two PCO reactions is mostly responsible for the potential inversion.
Outcomes following radical prostatectomy or external beam radiation for veterans with Gleason 9 and 10 prostate cancer
Authors: Chao Hann‐Hsiang , Soni Payal D. , Dahman Bassam , Stilianoudakis Spiro C. , Ford Hampton , Singh Raj , Freedland Stephen J. , Moghanaki Drew , Vapiwala Neha , Chang Michael G.
Published: March 2022

Background

The optimal upfront treatment modality for patients with nonmetastatic Gleason Score 9 and 10 prostate cancer (GS 9–10 PCa) is unknown.

Methods

We conducted a retrospective cohort study of patients in the Veterans Health Administration (VHA) with GS 9–10 PCa treated with radical prostatectomy (RP) or external beam radiation therapy with androgen deprivation therapy (EBRT+ADT) from 1/2000 to 12/2010. Outcomes included overall survival (OS), distant metastasis‐free survival (DMFS), and salvage/adjuvant therapy‐free survival (SAFS), as assessed by Kaplan–Meier analysis.

Results

We identified 1220 veterans with GS 9–10 PCa; 335 were treated with RP, and 885 were treated with EBRT+ADT. With a median follow‐up of 9.9 years, propensity score‐matched analyses demonstrated that RP had superior 10‐year OS (70.8% [RP] vs. 61.2% [EBRT+ADT], p < 0.001), 10‐year DMFS rates were similar between RP (76.7%) and EBRT+ADT (81.0%), and 10‐year SAFS rates were lower for RP vs EBRT + ADT (35.2% [RP] vs. 75.2% [EBRT+ADT], p < 0.001). The receipt of salvage ADT was higher with upfront RP (51.9% vs. 26.1%, p < 0.001), despite receipt of adjuvant/salvage EBRT in 41.8% of RP patients. Among patients treated with RP, there were no differences in outcomes by race. However, higher survival rates were noted among Black patients treated with EBRT+ADT compared with White patients.

Conclusions

This analysis demonstrated higher 10‐year OS rates among men treated with upfront RP versus EBRT+ADT, though missing confounders and similar DMFS rates suggest the long‐term cause‐specific OS rates may be similar. We also highlight real‐world outcomes of a diverse patient population in the VHA and improved outcomes for Black patients receiving EBRT+ADT.
Characteristics and clinical outcomes in patients with prior chest radiation undergoing TAVR: Observations from PARTNER‐2
Authors: Mohanty Bibhu D. , Coylewright Megan , Sequeira Ashton R. , Shin Doosup , Liu Yangbo , Li Ditian , Fradley Michael , Alu Maria C. , Mack Michael J. , Kapadia Samir R. , Kodali Susheel , Thourani Vinod H. , Makkar Raj R. , Leon Martin B. , Malenka David
Published: March 2022

Objectives

The purpose of this study is to investigate the viability of transcatheter aortic valve replacement (TAVR) for severe symptomatic aortic stenosis (AS) in patients with prior chest radiation therapy (cXRT).

Background

Since patients with prior cXRT perform poorly with surgical aortic valve replacement, TAVR can be a viable alternative. However, clinical outcomes after TAVR in this patient population have not been well studied.

Methods

From the pooled registry of the placement of aortic transcatheter valves II trial, we identified patients with and without prior cXRT who underwent TAVR (n = 64 and 3923, respectively). The primary outcome was a composite of all‐cause death and any stroke at 2 years. Time to event analyses were shown as Kaplan–Meier event rates and compared by log‐rank testing. Hazard ratios (HRs) were estimated and compared by Cox proportional hazards regression model.

Results

There was no significant difference in the primary outcome between the patients with and without prior cXRT (30.7% vs. 27.0%; p = 0.75; HR, 1.08; 95% confidence interval, 0.66–1.77). Rates of myocardial infarction, vascular complications, acute kidney injury, or new pacemaker implant after TAVR were not statistically different between the two groups. The rate of immediate reintervention with a second valve for aortic regurgitation after TAVR was higher among the patients with prior cXRT. However, no further difference was observed during 2 years follow‐up after discharge from the index‐procedure hospitalization.

Conclusions

TAVR is a viable alternative for severe symptomatic AS in patients who had cXRT in the past.
Rare case of simultaneous cerebral artery and venous sinus thrombosis in the setting of elevated factor VIII and combined oral contraceptive pills
Authors: Sabry Safan Abeer , Hamid Omnia A , Al‐Mashdali Abdulrahman , AlSaud Arwa , Al‐Shokri Shaikha , Hamad Abdelrahman
Published: March 2022

We report a rare case of combined cerebral venous sinus thrombosis and ischemic stroke in a 35‐year‐old female on combined oral contraceptive pills (COCPs) with persistently elevated factor VIII, presenting with headache and sudden onset vertigo, found to have extensive cerebral venous sinus thrombosis and PICA territory ischemic infarct.
Ultrafine Pt Nanoparticles Supported on Ultrathin Nanobowl‐Shaped N‐doped Carbon for the Oxygen Reduction Reaction
Authors: Liu Hao , Hu Linyu , Cai Wenjun , Feng Xiao , Zhang Fang , Shao Ruiwen , Wang Lu , Wang Bo
Published: March 2022

To eliminate the concerns about fuel cell aroused by the scarcity of Pt and the sluggish kinetics of oxygen reduction reaction (ORR), shortening the pathway of mass transfer and optimizing the utilization of Pt are two effective ways. Herein, we report a facile strategy to efficiently anchor ultrafine Pt nanoparticles on ultrathin nanobowl‐shaped N‐doped carbon (Pt NP@BNC). Ultrathin layers of a two‐dimensional covalent organic framework (COF) were synthesized as the support via a hard‐template strategy and Pt precursors were homogeneously dispersed in the COF via a gas‐phase diffusion method. Then the composite was pyrolyzed and converted into ultrathin nanobowl‐shaped N‐doped carbon (ca. 6 nm) embedded with ultrafine Pt NPs (ca. 3.28±0.7 nm). Compared with the catalyst obtained from the bulk COF, Pt NP@BNC achieved significantly elevated activity towards ORR. This work may pave a new way for the design and synthesis of novel ORR catalysts with high efficiency.
Die komplexe Porenarchitektur des Zeoliths NaY
Authors: Lutz Wolfgang , Buhl Josef Christian
Published: March 2022

Die Zeolithe NaX und NaY besitzen ein Mikroporensystem mit Zutrittsöffnungen von 0,74 nm. In der dealuminierten Form des NaY (DAY) liegen auch Mesoporen vor. NaX und NaY dienen der Aufbereitung von Molekülgemischen, wie Trocknung von Gasen und Dämpfen und zur Stofftrennung. DAY wird als Crack‐Katalysator eingesetzt. Neben der Einlagerung passender Moleküle in die Mikro‐ und Mesoporen können aber auch größere Moleküle adsorbiert werden. Die Einlagerung erfolgt dabei jedoch nur in mikroskopische Strukturdefekte der einzelnen Kristalle und in makroskopische Hohlräume von Kristallverwachsungen.
PROTOCOL: Mobile apps to reduce depressive symptoms and alcohol use in youth: A systematic review and meta‐analysis
Authors: Magwood Olivia , Saad Ammar , Ranger Dominique , Volpini Kate , Rukikamirera Franklin , Haridas Rinila , Sayfi Shahab , Alexander Jeremie , Tan Yvonne , Petkovic Jennifer , Pottie Kevin
Published: March 2022

Background

Depressive symptoms and alcohol use in youth doubled in the first year of the COVID‐19 pandemic. The COVID‐19 pandemic has created sustained disruption in society, schools, and universities, including increasing poverty and discrimination. Public health restrictions have caused isolation and reduced social and emotional support. Together, these factors make depressive symptoms and alcohol use in youth a global public health emergency. Mobile applications (apps) have emerged as potentially scalable intervention to reduce depressive symptoms and alcohol use in youth that could meet increased demands for mental health resources. Mobile apps may potentially reduce psychological distress with accessible technology‐based mental health resources.

Objectives

This systematic review and meta‐analysis aims to assess the effect of mobile apps on depressive symptoms and alcohol use in youth.

Search Methods

We will develop a systematic search strategy in collaboration with an experienced librarian. We will search a series of databases (MEDLINE, Embase, PsycINFO, CINAHL, CENTRAL) from January 2008 to July 2021.

Selection Criteria

Following the PRISMA reporting guidelines for systematic reviews, two independent reviewers will identify eligible studies: randomized controlled trials on mobile apps for the management of depressive disorders (depression and anxiety) and alcohol use in youth aged 15–24 years of age.

Data Collection and Analysis

Eligible studies will be assessed for risk of bias, and outcomes pooled, when appropriate, for meta‐analysis. Heterogeneity, if present, will be examined for gender. ethnicity, and socioeconomic status contributions. A narrative synthesis will highlight similarities and differences between the included studies. We will report GRADE summary of finding tables.
Recent insights into the relative timing of myosin's powerstroke and release of phosphate
Authors: Debold Edward P.
Published: March 2022

Myosin is a motor enzyme that converts the chemical energy in ATP into mechanical work to drive a myriad of intracellular processes, from muscle contraction to vesicular transport. Key steps in the transduction of energy are the force‐generating powerstroke, and the release of phosphate (Pi) from the nucleotide‐binding site. Both events occur rapidly after binding to actin, making it difficult to determine which event occurs first. Early efforts suggested that these events occur simultaneously; however, recent findings indicate that they are separate and distinct events that occur at different rates. High‐resolution crystal structures of myosin captured in intermediate states of the ATPase cycle suggest that when Pi is in the active site it prevents the powerstroke from occurring, leading to the hypothesis that Pi‐release precedes the powerstroke. However, advances in functional assays, enabling sub‐millisecond temporal and nanometer spatial resolution, are challenging this hypothesis. For example, Föster Resonance Energy Transfer (FRET) based assays, as well as single molecule laser trap assays, suggest the opposite; that the powerstroke occurs prior to the release of Pi from myosin's active site. This review provides some historical context and then highlights recent reports that reveal exciting new insight into this fundamental mechanism of energy transduction by this prototypical motor enzyme.
Intelligent recommender system based on quantum clustering and matrix completion
Authors: Ouedrhiri Oumayma , Banouar Oumayma , El Hadaj Salah , Raghay Said
Published: March 2022

Faster than classical algorithms, quantum algorithms benefit from the superposition property of quantum information to offer significant speedup to complex algorithms. Therefore, quantum computing can be used to help machine learning algorithms by boosting their performance and accelerate the processing of time‐consuming ones. Clustering algorithms are very complex unsupervised learning algorithms. Indeed, the similarity calculation (distance) between input vectors is a resource‐consuming step, especially when working with large datasets. In this article, we propose a new better‐performing recommender system that operates as a combination of an adapted quantum K‐means algorithm and the singular value decomposition (SVT) algorithm. We integrate the developed quantum clustering algorithm to a prediction process of the proposed recommender system using matrix completion. To the best of our knowledge, no system with such details was proposed in the literature. The system was applied on the MovieLens dataset without a dimensionality reduction step and evaluated according to measures of information retrieval systems. The results of the quantum K‐means algorithm show that the quantum version leads to a logarithmic reduction of the time complexity compared to the classical algorithm. The proposed system has proved to be better than the previous tested ones in terms of precision and recall.
Unraveling the Origin of Symmetry Breaking in H2O@C60 Endofullerene Through Quantum Computations
Authors: Carrillo‐Bohórquez Orlando , Valdés Álvaro , Prosmiti Rita
Published: March 2022

We explore the origin of the anomalous splitting of the 101 levels reported experimentally for the H2O@C60 endofullerene, in order to give some insight about the physical interpretations of the symmetry breaking observed. We performed fully‐coupled quantum computations within the multiconfiguration time‐dependent Hartree approach employing a rigorous procedure to handle such computationally challenging problems. We introduce two competing physical models, and discuss the observed unconventional quantum patterns in terms of anisotropy in the interfullerene interactions, caused by the change in the off‐center position of the encapsulated water molecules inside the cage or the uniaxial C60‐cage distortion, arising from noncovalent bonding upon water's encapsulation, or exohedral fullerene perturbations. Our results show that both scenarios could reproduce the experimentally observed rotational degeneracy pattern, although quantitative agreement with the available experimental rotational levels splitting value has been achieved by the model that considers an uniaxial elongation of the C60‐cage. Such finding supports that the observed symmetry breaking could be mainly caused by the distortion of the fullerene cage. However, as nuclear quantum treatments rely on the underlying interactions, a decisive conclusion hinges on the availability of their improved description, taken into account both endofullerene and exohedral environments, from forthcoming highly demanding electronic structure many‐body interaction studies.
A Heuristic Approach to Linking Experimental Descriptors with Product Selectivity in Electrochemical CO2Reduction
Authors: Raman Ganesan
Published: March 2022

An important challenge in electrochemical CO2reduction (ECR) is relating experimental conditions to their consequences, particularly in terms of product selectivity. The problem lies in the lack of descriptors which adequately describe the experimental protocols and their associated results. In this study, a machine learning approach is applied to correlate the molar composition of 21 single metals and 23 bimetallic particles, as well as operating parameters, from a large collection of synthetic records compiled from the literature with product selectivity. The decision tree obtained shows the conditions that lead to high desired product selectivity and provides a heuristic insight into its electrochemistry. As such, the data does not provide details. However, machine learning algorithms are capable of identifying hidden patterns in the data, providing a deeper insight into the chemistry involved in product formation in the ECR.
Description of the cross‐cultural process adopted in the STRiDE (STrengthening Responses to dementia in DEveloping countries) program: A methodological overview
Authors: Farina Nicolas , Jacobs Roxanne , Sani Tara Puspitarini , Schneider Marguerite , Theresia Imelda , Turana Yuda , Fitri Fasihah Irfani , Albanese Emiliano , Lorenz‐Dant Klara , Docrat Sumaiyah , Toit Petra Du , Ferri Cleusa P. , Govia Ishtar , Comas‐Herrera Adelina , Ibnidris Aliaa , Knapp Martin , Banerjee Sube
Published: March 2022

Cross‐cultural adaptation is an important part of using validated questionnaires across countries and settings. Here we describe the cross‐cultural process adopted in the STRiDE (STrengthening Responses to dementia in DEveloping countries) program.

We adopted a cross‐cultural adaptation process including forward translation, back translations, and cognitive interviews of the STRiDE toolkit. In total, 50 older adults and 41 carers across sites in Indonesia and South Africa participated in cognitive interviews; field notes and verbatim quotes are reported.

We describe the cross‐cultural adaptation process of the STRiDE toolkit. During the process, issues were identified with the translated toolkit, including aspects related to cultural appropriateness, terminology equivalence, and timings.

The data demonstrate that a rigorous, yet pragmatic, cross‐cultural adaptation process can be achieved even with limited resources. Our process should help the design and conduct of future dementia research in various contexts.
Validation and measurement invariance of the Muscularity‐Oriented Eating Test among Brazilian men and women
Authors: de Carvalho Pedro Henrique Berbert , Bagolin Vitoria , Junqueira Alessandra Costa Pereira , Nagata Jason M. , Cattle Chloe J. , Murray Stuart B. , Compte Emilio J. , Costa Telma Maria Braga , Almeida Sebastião Sousa , Laus Maria Fernanda
Published: March 2022

Objective

The Muscularity‐Oriented Eating Test (MOET) is a 15‐item unidimensional scale, designed to assess eating practices that occur in the pursuit of a muscular body. The aim of the present study was to describe the translation and cultural adaptation of the MOET to Brazilian Portuguese, to explore its factor structure and measurement invariance, and to evaluate its internal consistency, three‐week test–retest reliability, and convergent validity in a community sample of Brazilian men and women.

Method

After the back‐translation procedure, the Brazilian MOET was administered online to a sample of 1246 adults (634 men and 612 women), along with measures of drive for muscularity, muscle dysmorphia symptoms, muscular/athletic‐ideal internalization, disordered eating behaviors, and exercise dependence.

Results

Findings from an exploratory factor analysis and a confirmatory factor analysis revealed a one‐factor structure and adequate internal consistency for men (ω = 0.86; α = 0.86) and women (ω = .84; α = .83). Measurement invariance across gender was supported. In addition, the scale demonstrated good three week test–retest reliability for both men (ICC = .96; p < .001) and women (ICC = .92; p < .001), and the subscales revealed moderate to large associations with drive for muscularity, muscle dysmorphia symptoms, muscular/athletic‐ideal internalization, disordered eating, and exercise dependence.

Conclusion

This study supports the validity and reliability of the MOET in a community sample of Brazilian men and women and represents an advance in measures of muscularity‐oriented disordered eating in Brazilian adults, allowing for future cross‐cultural studies in this field.

Public Significance

The Muscularity‐Oriented Eating Test (MOET) is a measure of muscularity‐oriented disordered eating, which assess strict adherence to diet rules, including the food's macronutrient content, regulation of protein intake, and eating less or more to influence muscle gain. This study evaluated the validity and reliability of the MOET in a community sample of Brazilian men and women. Our findings represent an advance in measures of muscularity‐oriented disordered eating in Brazilian adults.
Lineage diversity within a widespread endemic Australian skink to better inform conservation in response to regional‐scale disturbance
Authors: Dissanayake Duminda S. B. , Holleley Clare E. , Sumner Joanna , Melville Jane , Georges Arthur
Published: March 2022

Much attention is paid in conservation planning to the concept of a species, to ensure comparability across studies and regions when classifying taxa against criteria of endangerment and setting priorities for action. However, various jurisdictions now allow taxonomic ranks below the level of species and nontaxonomic intraspecific divisions to be factored into conservation planning—subspecies, key populations, evolutionarily significant units, or designatable units. Understanding patterns of genetic diversity and its distribution across the landscape is a key component in the identification of species boundaries and determination of substantial geographic structure within species. A total of 12,532 reliable polymorphic SNP loci were generated from 63 populations (286 individuals) covering the distribution of the Australian eastern three‐lined skink, Bassiana duperreyi, to assess genetic population structure in the form of diagnosable lineages and their distribution across the landscape, with particular reference to the recent catastrophic bushfires of eastern Australia. Five well‐supported diagnosable operational taxonomic units (OTUs) existed within B. duperreyi. Low levels of divergence of B. duperreyi between mainland Australia and Tasmania (no fixed allelic differences) support the notion of episodic exchange of alleles across Bass Strait (ca 60 m, 25 Kya) during periods of low sea level during the Upper Pleistocene rather than the much longer period of isolation (1.7 My) indicated by earlier studies using mitochondrial sequence variation. Our study provides foundational work for the detailed taxonomic re‐evaluation of this species complex and the need for biodiversity assessment to include an examination of cryptic species and/or cryptic diversity below the level of species. Such information on lineage diversity within species and its distribution in the context of disturbance at a regional scale can be factored into conservation planning regardless of whether a decision is made to formally diagnose new species taxonomically and nomenclaturally.
Type III procollagen peptide level can indicate liver dysfunction associated with volume overload in acute heart failure
Authors: Shirakabe Akihiro , Okazaki Hirotake , Matsushita Masato , Shibata Yusaku , Shigihara Shota , Nishigoori Suguru , Sawatani Tomofumi , Sasamoto Nozomi , Kiuchi Kazutaka , Atsukawa Masanori , Itokawa Norio , Arai Taeang , Kobayashi Nobuaki , Asai Kuniya
Published: March 2022

Aim

The role of serum type III procollagen peptide (P3P) level in the acute phase of acute heart failure (AHF) requires clarification. We hypothesized that serum P3P level is temporarily higher during the acute phase, reflecting liver dysfunction due to congestion.

Methods and results

A total of 800 AHF patients were screened, and data from 643 patients were analysed. Heart failure was diagnosed by the treating physician according to the European Society of Cardiology (ESC) guidelines, and included patients being treated with high‐concentration oxygen inhalation (including mechanical support) for orthopnea, inotrope administration, or mechanical support for low blood pressure, and various types of diuretics for peripheral or pulmonary oedema. In all cases, diuretics or vasodilators were administered to treat AHF. The patients were divided into three groups according to their quartile (Q) serum P3P level: low‐P3P (Q1, P3P ≤ 0.6 U/mL), mid‐P3P (Q2/Q3, 0.6 < P3P <1.2 U/mL), and high‐P3P (Q4, P3P ≥ 1.2 U/mL). The plasma volume status (PVS) was calculated using the following formula: ([actual PV − ideal PV]/ideal PV) × 100 (%). The primary endpoint was 365 day mortality. A Kaplan–Meier curve analysis showed that prognoses, including all‐cause mortality and heart failure events within 365 days, were significantly (P < 0.001) worse in the high‐P3P group when compared with the mid‐P3P and low‐P3P groups. A multivariate logistic regression analysis showed that high PVS (Q4, odds ratio [OR]: 4.702, 95% CI: 2.012–20.989, P < 0.001), high fibrosis‐4 index (Q4, OR: 2.627, 95% CI: 1.311–5.261, P = 0.006), and low estimated glomerular filtration rate per 10 mL/min/1.73 m2 decrease (OR: 1.996, 95% CI: 1.718–2.326, P < 0.001) were associated with high P3P values. The Kaplan–Meier curve analysis demonstrated a significantly lower survival rate, as well as a higher rate of heart failure events, in the high‐P3P and high‐PVS groups when compared with the other groups. A multivariate Cox regression model identified high P3P level and high PVS as an independent predictor of 365 day all‐cause mortality (hazard ratio [HR]: 2.249; 95% CI: 1.081–3.356; P = 0.026) and heart failure events (HR: 1.586, 95% CI: 1.005–2.503, P = 0.048).

Conclusion

A high P3P level during the acute phase of AHF served as a comprehensive biomarker of liver dysfunction with volume overload (i.e. liver congestion) and renal dysfunction. A high P3P level at admission may be able to predict adverse outcomes in AHF patients.
Heteroleptic Dirhodium(II) Complexes with Redox‐Active Ferrocenyl Ligands: Synthesis, Electrochemical Properties, and Redox‐Responsive Chemoselectivity in Carbene C−H Insertion
Authors: Ruzhylo Illia , Sournia‐Saquet Alix , Moreau Alain , Delord Tom , Manoury Eric , Poli Rinaldo , Labande Agnès
Published: March 2022

A series of original heteroleptic dirhodium(II) complexes (4 a–j) of formula [Rh2(OAc)3(L)], where L is a redox‐active ferrocenecarboxylate ligand, has been prepared. These dirhodium(II) complexes have been characterised by NMR, mass spectrometry and cyclic voltammetry. All complexes show a quasi‐reversible redox behaviour for the ferrocenyl unit. The latter can be selectively oxidised by [N(4‐C6H4Br)3]+BF4−. Four selected heteroleptic complexes 4 a, 4 b, 4 f and 4 i, have been evaluated as catalysts for the intramolecular decomposition of a diazo compound 5. The ratio between the aromatic substitution product 6 and the aliphatic C−H insertion product 7 increases (up to 19 % increase) when using the in situ generated oxidised form of the dirhodium(II) complexes (4 a+BF4− to 4 i+BF4−). This shows that the oxidation of the ferrocenecarboxylate ligand has an effect on the chemoselectivity of the dirhodium‐catalysed diazo decomposition, and thus that the electronic properties of a complex can be tuned without exchanging ligands.
Quinazolinone Alkaloid Febrifugine and Its Analogues To Control Phytopathogenic Diseases Caused by Oomycete Fungi
Authors: Fehr Marcus , Koch Andreas , Merget Benjamin , Winter Christian
Published: March 2022

Controlling phytopathogenic diseases caused by oomycete fungi is still a challenge in crop protection research. Studies on identifying new starting points to control phytopathogens revealed that the quinazolinone alkaloids febrifugine (1) and halofuginone (2) are efficiently inhibiting the growth of Phytophthora infestans in microtiter tests. However, despite the very good in vitro activity of 0.13 and 0.06 ppm in IC50, respectively, both compounds did not exhibit a good control of P. infestans on tomato plants. Creating a homology model of prolyl‐tRNA synthetase – the molecular target of halofuginone – helped to understand the interactions between 2 and the binding pocket and guided the synthesis of further derivatives. Ultimately, we found that deoxy‐febrifugine (14) and halofuginol (17) and its derivatives were able to control P. infestans also on the plant.
Versatile Synthesis of rac‐ and meso‐Hydroxymethyl Cyclohexenoids Containing Phenyl Groups: α‐/β‐Glucosidase Activities, Inhibition Kinetics and Molecular Docking Studies
Authors: Sevmezler Sedat , Çol Sümeyye , Emirik Mustafa , Ceylan Davut , Baran Arif
Published: March 2022

The effective strategy has been developed to synthesize a series of monophenyl and diphenyl carbasugar analogues, from the cycloadduct reaction of furan and maleic anhydride, containing halogen groups based on the conduritol scaffold. The strategy mainly consists of reduction, esterification, bromination, formation of new double bond and replacement of bromine with phenyl by Suzuki coupling reaction. New phenyl‐substituted carbasugars were obtained by cleavage of the oxo bridge and subsequent hydrolysis of the esters. The structures of the target compounds were defined using different chemical methods. In vitro inhibitory activity studies, kinetic and molecular docking studies were performed against α‐, β‐glucosidase enzymes for the final compounds.
Thermal Modeling and Analysis of an Electric Vehicle Charging System
Authors: Chea Branson , Agelin-Chaab Martin , Mastali Mehrdad , Szymczyk Rick
Published: March 2022

In this article, computational fluid dynamics is used to analyze the thermal performance of an electric vehicle charging system with lithium‐ion battery packs. In the analysis, the locations of an air conditioner, circulation fans, and safety barrier are varied to parametrically study the effectiveness of the thermal management system of the charging system. Temperature iso‐surfaces are generated and used to identify the regions within the charging system that are within normal working temperature ranges. The circulation fans greatly impact the effectiveness of the cooling system. The orientation of the fans also plays an important role in the distribution of temperatures in the battery packs. Furthermore, the individual battery improvement is quantified using the rack cooling index (RCI), where an RCI increase of up to 92.4% is reported when the circulation fans are activated. The results from this study demonstrate that a combination of circulation fans and an air conditioner can result in a simple and cost‐effective thermal management approach for a charging system, whereas an air conditioner alone cannot achieve the same cooling effectiveness.
A spatiotemporal analysis of NO2 concentrations during the Italian 2020 COVID‐19 lockdown
Authors: Fioravanti Guido , Cameletti Michela , Martino Sara , Cattani Giorgio , Pisoni Enrico
Published: March 2022

When a new environmental policy or a specific intervention is taken in order to improve air quality, it is paramount to assess and quantify—in space and time—the effectiveness of the adopted strategy. The lockdown measures taken worldwide in 2020 to reduce the spread of the SARS‐CoV‐2 virus can be envisioned as a policy intervention with an indirect effect on air quality. In this paper we propose a statistical spatiotemporal model as a tool for intervention analysis, able to take into account the effect of weather and other confounding factor, as well as the spatial and temporal correlation existing in the data. In particular, we focus here on the 2019/2020 relative change in nitrogen dioxide (NO) concentrations in the north of Italy, for the period of March and April during which the lockdown measure was in force. We found that during March and April 2020 most of the studied area is characterized by negative relative changes (median values around 25%), with the exception of the first week of March and the fourth week of April (median values around 5%). As these changes cannot be attributed to a weather effect, it is likely that they are a byproduct of the lockdown measures. There are two aspects of our research that are equally interesting. First, we provide a unique statistical perspective for calculating the relative change in the NO by jointly modeling pollutant concentrations time series. Second, as an output we provide a collection of weekly continuous maps, describing the spatial pattern of the NO 2019/2020 relative changes.
Programmed mechanisms of status epilepticus‐induced neuronal necrosis
Authors: Fujikawa Denson G.
Published: March 2022

Excitotoxicity is the underlying mechanism for all acute neuronal injury, from cerebral ischemia, status epilepticus, traumatic CNS injury, and hypoglycemia. It causes morphological neuronal necrosis, and it triggers a programmed cell death program. Excessive calcium entry through the NMDA‐receptor‐operated cation channel activates two key enzymes—calpain I and neuronal nitric oxide synthase (nNOS). Calpain I, a cytosolic enzyme, translocates to mitochondrial and lysosomal membranes, causing release of cytochrome c, endonuclease G, and apoptosis‐inducing factor (AIF) from mitochondria and DNase II and cathepsins B and D from lysosomes. These all translocate to neuronal nuclei, creating DNA damage, which activates poly(ADP) ribose polymerase‐1 (PARP‐1) to form excessive amounts of poly(ADP) ribose (PAR) polymers, which translocate to mitochondrial membranes, causing release of truncated AIF (tAIF). The free radicals that are released from mitochondria and peroxynitrite, formed from nitric oxide (NO) from nNOS catalysis of L‐arginine to L‐citrulline, damage mitochondrial and lysosomal membranes and DNA. The end result is the necrotic death of neurons. Another programmed necrotic pathway, necroptosis, occurs through a parallel pathway. As investigators of necroptosis do not recognize the excitotoxic pathway, it is unclear to what extent each contributes to programmed neuronal necrosis. We are studying the extent to which each contributes to acute neuronal necrosis and the extent of cross‐talk between these pathways.
Evaluation of annual performance for building‐integrated photovoltaics based on 2‐terminal perovskite/silicon tandem cells under realistic conditions
Authors: Nguyen Dong C. , Murata Fumihiro , Sato Kota , Hamada Masaya , Ishikawa Yasuaki
Published: March 2022

The authors optimized the thickness of the layers in the 1.67‐eV‐bandgap‐perovskite sub‐cell of a 2‐terminal perovskite/silicon monolithic tandem solar cell under standard test conditions to get the current matching between the top and the bottom sub‐cells. Based on that optimized structure of the tandem cell, we characterized, calculated, and analyzed the annual output energy and the annual efficiency of the tandem cells on the facades and the rooftop of buildings under realistic conditions composed of module temperature, realistic illumination irradiance, and incident angle directly measured in Gifu, Japan in 2015. Consequently, the obtained annual output energy is 279.52, 238.89, 129.99, and 115.21 kWh/m2with the corresponding annual efficiency of 22.42%, 19.70%, 10.50%, and 9.19% for the tandem solar cells mounted on the rooftop, the south, east, and west facades of the buildings, respectively. Thus, the rooftop and the south face of the buildings are the preferred directions for the BIPV application to gain higher energy.