bluuebunny/crossref_metadata_2025_split huggingface dataset:
Peroxidase‐like activity of Fe3O4 nanoparticles and Fe3O4‐graphene oxide nanohybrids: Effect of the amino‐ and carboxyl‐surface modifications on H2O2 sensing
Authors: Bilalis Panayiotis , Karagouni Evdokia , Toubanaki Dimitra K. 
Published: June 2022

Magnetic, iron oxide nanoparticles and graphene‐iron oxide nanohybrids have been introduced as artificial peroxidase‐mimics. In the present paper, the impact of coating with different functional groups on the peroxidase activity of both nanoparticles and nanohybrids was studied. Magnetite nanoparticles and graphene‐iron oxide nanohybrids, with ‐amino or ‐carboxyl terminal groups were synthesized and fully characterized by Fourier transform‐infrared, thermogravimetric analysis, transmission electron microscopy (TEM), X‐ray diffraction, vibrating sample magnetometer, and zeta potential. All particle formulations were evaluated for peroxidase activity, by studying the oxidation reaction of the peroxidase substrate 3,3,5,5‐tetramethylbenzidine (TMB) by hydrogen peroxide (H2O2). It was found that all tested formulations retained their catalytic ability (>70%) at 95 °C, at wide pH range, and were reusable with 60% of their catalytic activity after 10 uses. All nanomaterials were found to follow Michaelis–Menten kinetics and peroxidase activity varied with respect to electrostatic affinity between nanoparticles or nanohybrids and the peroxidase substrates, evidenced by differences in determined kinetic parameters. The Km values of all tested particles with H2O2 substrate were higher than those reported for horseradish peroxidase (HRP; 0.214–6.36 mM), while the calculated values of reaction rates (Vmax) for the studied nanoparticles and nanohybrids with TMB and H2O2 as substrates were comparable with those reported for HRP. Our findings confirm that iron oxide nanoparticles and graphene based metallic nanohybrids can be tailor‐made to possess improved peroxidase‐like activity. Such enhancements could further widen nanohybrids application in a wide range of biomedical applications, including H2O2 detection in a proof‐of‐concept assay, which confirmed low detection limits of the tested formulations (5.3–11.3 μM).
Efficient Imidazolium‐Biomolecule Interaction‐Assisted Amplified Quenching for Ultrasensitive Detection of Heparin
Authors: Lee Seung Yeob , Song Hyebin , Lee Sun Woo , Han Minwoo , Choi Haemin , Lee Seoung Ho 
Published: June 2022

AbstractDetection of heparin (HP) under physiological conditions is difficult due to the presence of biological obstructions including proteins and lipids. Thus, it is highly challenging to selectively detect HP and to increase its sensitivity in complex systems. Here, we report the detection of HP at nanomolar levels via efficient imidazolium‐HP interaction‐assisted fluorescence quenching amplification. The self‐assembled pyrenyl aggregates are devised as a conduit for efficient exciton transport, which induces amplified fluorescence quenching for HP detection. This amplified quenching is enhanced by introducing an imidazolium receptor designed to have a high affinity to HP via electrostatic and/or additional interactions with C2 protons, resulting in a very high Stern‐Volmer quenching constant of approximately 1.17×108 M−1.
Approaches to 1,4‐Disubstituted Cubane Derivatives as Energetic Materials: Design, Theoretical Studies and Synthesis
Authors: Lal Sohan , Bhattacharjee Argha , Chowdhury Arindrajit , Kumbhakarna Neeraj , Namboothiri Irishi N. N. 
Published: June 2022

AbstractNovel 1,4‐disubstituted cubane derivatives have been designed and selected ones have been successfully synthesized and characterized by various analytical and spectroscopic techniques, including single‐crystal X‐ray analysis. A detailed computational study at B3LYP/6‐311++G(d,p) level of theory revealed that all newly designed 1,4‐disubstituted cubane derivatives possess higher densities, higher density‐specific impulse and superior ballistic properties when compared to conventional fuels, for example, RP‐1. These compounds also exhibit acceptable kinetic and thermodynamic stabilities which were evaluated in terms of their HOMO‐LUMO energy gap and bond dissociation energies, respectively, and are superior to TEX and many other compounds containing explosophoric groups. These results provide novel insights into the possible application of cubane‐based energetic materials.
Design of a Fluorogenic Probe Based on Intramolecular Condensation for Specific Detection of HDAC3
Authors: He Huimin , Song Aiguo 
Published: June 2022

AbstractIt is crucial to develop fluorogenic probes for selective targeting of HDACs to explore the roles of HDACs in the tumor onset and progression as well as HDAC‐related drug development. However, considerable non‐specific signals were produced by spontaneous hydrolysis and undesirable intermolecular attack of the unstable caging moiety in the detection of HDACs with previous probes. To improve the detection specificity, we proposed an intramolecular condensation strategy by the replacement of the traditional acetamide moiety with a trans‐enamide unit. Upon deacetylation by HDACs, rapid intramolecular condensation reaction between newly formed terminal aldehyde and hydrazine moiety would occur to afford highly fluorescent hydrazone product. Systematic studies demonstrated that the probe exhibited an extraordinary selectivity for HDAC3 over other HDAC isoforms and interfering substances. The stability and specificity of the indicator make it a powerful tool for HDAC3 activity detection and HDAC3‐related drug development.
One‐pot synthesis of 2‐imino‐1,3,4‐thiadiazolines from acylhydrazides and isothiocyanates
Authors: Kim Su Been , Baek Sang Eun , Lim Jae Hyeok , Kim Jinho 
Published: June 2022

AbstractA one‐pot synthesis of 2‐imino‐1,3,4‐thiadiazolines was successfully achieved under mild conditions. The developed synthesis involves Fe(Pc)‐catalyzed aerobic oxidation of acylhydrazides followed by P(NMe2)3‐mediated annulation of the in situ generated N‐acyldiazene with isothiocyanates. The present annulation showed broad substrate scope with good functional group tolerance, and was effective on gram scale.
Grey matter atrophy in patients with benign multiple sclerosis
Authors: Niiranen Marja , Koikkalainen Juha , Lötjönen Jyrki , Selander Tuomas , Cajanus Antti , Hartikainen Päivi , Simula Sakari , Vanninen Ritva , Remes Anne M. 
Published: June 2022

AbstractBackgroundBrain atrophy appears during the progression of multiple sclerosis (MS) and is associated with the disability caused by the disease.MethodsWe investigated global and regional grey matter (GM) and white matter (WM) volumes, WM lesion load, and corpus callosum index (CCI), in benign relapsing‐remitting MS (BRRMS, n = 35) with and without any treatment and compared those to aggressive relapsing‐remitting MS (ARRMS, n = 46). Structures were analyzed by using an automated MRI quantification tool (cNeuro®).ResultsThe total brain and cerebral WM volumes were larger in BRRMS than in ARRMS (p = .014, p = .017 respectively). In BRRMS, total brain volumes, regional GM volumes, and CCI were found similar whether or not disease‐modifying treatment (DMT) was used. The total (p = .033), as well as subcortical (p = .046) and deep WM (p = .041) lesion load volumes were larger in BRRMS patients without DMT. Cortical GM volumes did not differ between BRRMS and ARRMS, but the volumes of total brain tissue (p = .014) and thalami (p = .003) were larger in patients with BRRMS compared to ARRMS. A positive correlation was found between CCI and whole‐brain volume in both BRRMS (r = .73, p < .001) and ARRMS (r = .80, p < .01).ConclusionsThalamic volume is the most prominent measure to differentiate BRRMS and ARRMS. Validation of automated quantification of CCI provides an additional applicable MRI biomarker to detect brain atrophy in MS.
Artificial intelligence assisted cytological detection for early esophageal squamous epithelial lesions by using low‐grade squamous intraepithelial lesion as diagnostic threshold
Authors: Yao Bin , Feng Yadong , Zhao Kai , Liang Yan , Huang Peilin , Zang Juncai , Song Jie , Li Mengjie , Wang Xiaofen , Shu Huazhong , Shi Ruihua 
Published: June 2022

AbstractBackgroundManual cytological diagnosis for early esophageal squamous cell carcinoma (early ESCC) and high‐grade intraepithelial neoplasia (HGIN) is unsatisfactory. Herein, we have introduced an artificial intelligence (AI)‐assisted cytological diagnosis for such lesions.MethodsLow‐grade squamous intraepithelial lesion or worse was set as the diagnostic threshold for AI‐assisted diagnosis. The performance of AI‐assisted diagnosis was evaluated and compared to that of manual diagnosis. Feasibility in large‐scale screening was also assessed.ResultsAI‐assisted diagnosis for abnormal cells was superior to manual reading by presenting a higher efficiency for each slide (50.9 ± 0.8 s vs 236.8 ± 3.9 s, p = 1.52 × 10−76) and a better interobserver agreement (93.27% [95% CI, 92.76%–93.74%] vs 65.29% [95% CI, 64.35%–66.22%], p = 1.03 × 10−84). AI‐assisted detection showed a higher diagnostic accuracy (96.89% [92.38%–98.57%] vs 72.54% [65.85%–78.35%], p = 1.42 × 10−14), sensitivity (99.35% [95.92%–99.97%] vs 68.39% [60.36%–75.48%], p = 7.11 × 10−15), and negative predictive value (NPV) (97.06% [82.95%–99.85%] vs 40.96% [30.46%–52.31%], p = 1.42 × 10−14). Specificity and positive predictive value (PPV) were not significantly differed. AI‐assisted diagnosis demonstrated a smaller proportion of participants of interest (3.73%, [79/2117] vs.12.84% [272/2117], p = 1.59 × 10−58), a higher consistence between cytology and endoscopy (40.51% [32/79] vs. 12.13% [33/272], p = 1.54 × 10−8), specificity (97.74% [96.98%–98.32%] vs 88.52% [87.05%–89.84%], p = 3.19 × 10−58), and PPV (40.51% [29.79%–52.15%] vs 12.13% [8.61%–16.75%], p = 1.54 × 10−8) in community‐based screening. Sensitivity and NPV were not significantly differed. AI‐assisted diagnosis as primary screening significantly reduced average cost for detecting positive cases.ConclusionOur study provides a novel cytological method for detecting and screening early ESCC and HGIN.
Utility of prehospital electrocardiogram interpretation in ST‐segment elevation myocardial infarction utilizing computer interpretation and transmission for interventional cardiologist consultation
Authors: Faour Amir , Cherrett Callum , Gibbs Oliver , Lintern Karen , Mussap Christian J. , Rajaratnam Rohan , Leung Dominic Y. , Taylor David A. , Faddy Steve C. , Lo Sidney , Juergens Craig P. , French John K. 
Published: June 2022

AbstractObjectivesWe examined the appropriateness of prehospital cardiac catheter laboratory activation (CCL‐A) in ST‐segment elevation myocardial infarction (STEMI) utilizing the University of Glasgow algorithm (UGA) and remote interventional cardiologist consultation.BackgroundThe incremental benefit of prehospital electrocardiogram (PH‐ECG) transmission on the diagnostic accuracy and appropriateness of CCL‐A has been examined in a small number of studies with conflicting results.MethodsWe identified consecutive PH‐ECG transmissions between June 2, 2010 and October 6, 2016. Blinded adjudication of ECGs, appropriateness of CCL‐A, and index diagnoses were performed using the fourth universal definition of MI. The primary outcome was the appropriate CCL‐A rate. Secondary outcomes included rates of false‐positive CCL‐A, inappropriate CCL‐A, and inappropriate CCL nonactivation.ResultsAmong 1088 PH‐ECG transmissions, there were 565 (52%) CCL‐As and 523 (48%) CCL nonactivations. The appropriate CCL‐A rate was 97% (550 of 565 CCL‐As), of which 4.9% (n = 27) were false‐positive. The inappropriate CCL‐A rate was 2.7% (15 of 565 CCL‐As) and the inappropriate CCL nonactivation rate was 3.6% (19 of 523 CCL nonactivations). Reasons for appropriate CCL nonactivation (n = 504) included nondiagnostic ST‐segment elevation (n = 128, 25%), bundle branch block (n = 132, 26%), repolarization abnormality (n = 61, 12%), artefact (n = 72, 14%), no ischemic symptoms (n = 32, 6.3%), severe comorbidities (n = 26, 5.2%), transient ST‐segment elevation (n = 20, 4.0%), and others.ConclusionsPH‐ECG interpretation utilizing UGA with interventional cardiologist consultation accurately identified STEMI with low rates of inappropriate and false‐positive CCL‐As, whereas using UGA alone would have almost doubled CCL‐As. The benefits of cardiologist consultation were identifying “masquerading” STEMI and avoiding unnecessary CCL‐As.
Influence of Chloride and Nitrate Anions on Copper Electrodeposition onto Au(111) from Deep Eutectic Solvents
Authors: Geng Tanja , Schick Benjamin W. , Uhl Matthias , Kuehne Alexander J. C. , Kibler Ludwig A. , Ceblin Maximilian U. , Jacob Timo 
Published: June 2022

AbstractCopper electrodeposition on Au(111) from deep eutectic solvents (DESs) type III was investigated employing cyclic voltammetry as well as chronoamperometry. It was further examined on Au(poly) using the electrochemical quartz crystal microbalance (EQCM). The employed DESs are mixtures of choline chloride (ChCl) or choline nitrate (ChNO3) with ethylene glycol (EG) as hydrogen bond donor (HBD), each in a molar ratio of 1 : 2. CuCl, CuCl2, or Cu(NO3)2 ⋅ 3H2O were added as copper sources. Underpotential deposition (UPD) of Cu precedes bulk deposition in chloride as well as nitrate electrolytes. Cu deposition from Cu+ in chloride media is observed as a one‐electron reaction, whereas deposition from Cu2+ occurs in two steps since Cu+ is strongly stabilized by chloride. Cu+ is less stabilized by nitrate and the beginning of bulk deposition in the nitrate‐containing DES with Cu2+ is shifted by several hundred mV to more positive potentials compared to the chloride DES. A diffusion‐controlled, three‐dimensional nucleation and growth mechanism is found by chronoamperometric measurements and analysis based on the model of Scharifker and Mostany.
Association between exposures to radon and γ‐ray radiation and histologic type of lung cancer in Eldorado uranium mining and milling workers from Canada
Authors: Zablotska Lydia B. , Lane Rachel S. D. , Randhawa Kristi 
Published: June 2022

BackgroundThe authors assessed the association between radon decay products (RDP) exposure and histologic types of incident lung cancer in a cohort of 16,752 (91.6% male) Eldorado uranium workers who were first employed from 1932 to 1980 and were followed through 1969–1999.MethodsSubstantially revised identifying information and RDP exposures were obtained on workers from the Port Radium and Beaverlodge uranium mines and from the Port Hope radium and uranium refinery and processing facility in Canada. Poisson regression was conducted using the National Research Council's Biological Effects of Ionizing Radiation (BEIR) VI–type models to estimate the risks of lung cancer by histologic type from RDP exposures and γ‐ray doses.ResultsLung cancer incidence was significantly higher in workers compared with the general Canadian male population. Radiation risks of lung cancer for all histologic types (n = 594; 34% squamous cell, 16% small cell, 17% adenocarcinoma) increased with increasing RDP exposure, with no indication of curvature in the dose response (excess relative risk per 100 working level months = 0.61; 95% confidence interval, 0.39–0.91). Radiation risks did not differ by histologic type (p = .144). The best‐fitting BEIR VI–type model included adjustments for the significant modifying effects of time since exposure, exposure rate, and attained age. The addition of γ‐ray doses to the model with RDP exposures improved the model fit, but the risk estimates remained unchanged.ConclusionsThe first analysis of radiation risks of lung cancer histologic types in the Eldorado cohort supported the use of BEIR VI–type models to predict the future risk of histologic types of lung cancer from past and current RDP exposures.Lay summary

Lung cancer survival depends strongly on the cell type of lung cancer.

The best survival rates are for patients who have the adenocarcinoma type.

This study included 16,752 Eldorado uranium workers who were exposed to radon and γ‐ray radiation during 1932–1980, were alive in 1969, and were followed for the development of new lung cancer during 1969–1999.

One third of all lung cancers were of the squamous cell type, whereas the adenocarcinoma and small cell types accounted for less than 20% each.

Radiation risks of lung cancer among men increased significantly with increasing radon exposure for all cell types, with the highest risks estimated for small cell and squamous cell lung cancers.
The brain of the tree pangolin (Manis tricuspis). X. The spinal cord
Authors: Imam Aminu , Bhagwandin Adhil , Ajao Moyosore S. , Manger Paul R. 
Published: June 2022

AbstractThe spinal cord of the tree pangolin is known to be very short compared to the overall length of the body and tail. Here, we provide a description of the tree pangolin spinal cord to determine whether the short length contributes to specific structural, and potentially functional, differences. The short spinal cord of the adult tree pangolin, at around 13 cm, terminates at the midthoracic level. Within this shortened spinal cord, we could identify six regions, which from rostral to caudal include the prebrachial, brachial, interramal, crural, postcrural, and caudal regions, with both the brachial and crural regions showing distinct swellings. The chemoarchitecture of coronal sections through these regions confirmed regional assignation, being most readily delineated by the presence of cholinergic neurons forming the intermediolateral column in the interramal region and the sacral parasympathetic nucleus in the postcrural region. The 10 laminae of Rexed were observed throughout the spinal cord and presented with an anatomical organization similar to that observed in other mammals. Despite the shortened length of the tree pangolin spinal cord, the regional and laminar anatomical organization is very similar to that observed in other mammals. This indicates that the functional aspects of the short tree pangolin spinal cord can be inferred from what is known in other mammals.
Two Novel Dinuclear Cobalt Polypyridyl Complexes in Electro‐ and Photocatalysis for Hydrogen Production: Cooperativity Increases Performance
Authors: Weder Nicola , Grundmann Nora S. , Probst Benjamin , Blacque Olivier , Ketkaew Rangsiman , Creazzo Fabrizio , Luber Sandra , Alberto Roger 
Published: June 2022

AbstractSyntheses and mechanisms of two dinuclear Co‐polypyridyl catalysts for the H2 evolution reaction (HER) were reported and compared to their mononuclear analogue (R1). In both catalysts, two di‐(2,2’‐bipyridin‐6‐yl)‐methanone units were linked by either 2,2’‐bipyridin‐6,6’‐yl or pyrazin‐2,5‐yl. Complexation with CoII gave dinuclear compounds bridged by pyrazine (C2) or bipyridine (C1). Photocatalytic HER gave turnover numbers (TONs) of up to 20000 (C2) and 7000 (C1) in water. Electrochemically, C1 was similar to the R1, whereas C2 showed electronic coupling between the two Co centers. The E(CoII/I) split by 360 mV into two separate waves. Proton reduction in DMF was investigated for R1 with [HNEt3](BF4) by simulation, foot of the wave analysis, and linear sweep voltammetry (LSV) with in‐line detection of H2. All methods agreed well with an (E)ECEC mechanism and the first protonation being rate limiting (≈104 m−1 s−1). The second reduction was more anodic than the first one. pKa values of around 10 and 7.5 were found for the two protonations. LSV analysis with H2 detection for all catalysts and acids with different pKa values [HBF4, pKa(DMF)≈3.4], intermediate {[HNEt3](BF4), pKa(DMF)≈9.2} to weak [AcOH, pKa(DMF)≈13.5] confirmed electrochemical H2 production, distinctly dependent on the pKa values. Only HBF4 protonated CoI intermediates. The two metals in the dualcore C2 cooperated with an increase in rate to a competitive 105 m−1 s−1 with [HNEt3](BF4). The overpotential decreased compared to R1 by 100 mV. Chronoamperometry established high stabilities for all catalysts with TONlim of 100 for R1 and 320 for C1 and C2.
A novel multi‐hop routing structure for throughput maximization in unmanned aerial vehicle assisted flying ad‐hoc networks
Authors: Mittal Payal , Shah Santosh , Agarwal Anirudh 
Published: June 2022

AbstractUnmanned aerial vehicle (UAV) aided wireless communication has many potential uses to improve connectivity in the harsh environments due to its high mobility and flexible deployment. To extend the coverage, multi‐hop communication with multiple UAVs as relays has become the prominent scheme in today's wireless network. In this article, we investigate the problem of generating a multi‐hop routing structure for data transmission to maximize the overall network throughput of a flying ad‐hoc network using UAVs. Specifically, we propose an optimization problem to jointly select a communication link and its transmission power so that the overall network throughput for a given total power budget is maximized. The problem is nonconvex over selected metrics, thus making it an NP‐hard problem. Without loss of generality, we consider the Dijkstra‐based shortest‐path tree as a routing structure, thereby converting the original problem into a solvable convex problem over the transmission link metric. We observe Dijkstra‐based routing is not optimal in our scenario, thus we propose a low complexity link swap approach to further improve the network throughput by exchanging appropriate child‐parent links of UAVs. Results are numerically validated, and optimal design insights are provided.
Margin requirements based on a stochastic correlation model
Authors: Szabó Dávid Zoltán , Váradi Kata 
Published: June 2022

AbstractWe demonstrate that margin requirements of central counterparties show a significantly different behavior when calculated with a portfoliowise treatment instead of taking the weighted sum of the margin requirements of the components without accounting for their correlation structures. This is shown via simulating trajectories of a joint stochastic volatility–stochastic correlation model. Results indicate that an unnecessarily large overmargin requirement is set by regulators when the applied risk measure is not calculated via a portfoliowise treatment. Finally, accounting for the correlation structure of the assets during the margining process would not lead to an overly prudent method, nor would it cause greater procyclicality.