bluuebunny/crossref_metadata_2025_split huggingface dataset:
Determination of Pesticides in Soybean Seeds Incorrectly Discarded Near a Spring of the Paranaíba River, GO‐Brazil
Authors: Oliveira Júnior Charles I. , Cardoso Alessandra T. , Goulart Adilson C. , Oliveira Mansuêmia A. C. , Santos João Paulo V. , Goulart Simone M. 
Published: November 2021

AbstractThe objective of this research was to evaluate the contamination of pesticides of carbamate and benzimidazole classes in soil, water and soybean seeds, incorrectly discarded near a spring in the state of Goiás‐Brazil. The Solid‐Liquid and Liquid‐Liquid Extraction with Low Temperature Partition (SLE/LTP or LLE/LTP) methods were used for pesticide extraction and the analyses were performed by HPLC‐UV. A high resolution mass spectrometer was used to confirm the identity of the compounds present in the seeds. The results showed that the soybeans were treated with the pesticide carbendazim and the dosage was three times higher than established by Brazilian legislation. In the soil and water analyzed there was no presence of the pesticides researched, nor of the carbendazim detected in the seeds. Since this was an environmental crime due to incorrect disposal, it is not known how long ago it occurred. Thus, depending on how long the seeds had been exposed there, the pesticide could have leached out, and caused contamination in the spring and soil. Thus, we conclude that the incorrect disposal of seeds treated with pesticides can be a risk to the permanence of life on the site.
Non‐Heme‐Iron‐Mediated Selective Halogenation of Unactivated Carbon−Hydrogen Bonds
Authors: Bleher Katharina , Comba Peter , Faltermeier Dieter , Gupta Ashutosh , Kerscher Marion , Krieg Saskia , Martin Bodo , Velmurugan Gunasekaran , Yang Shuyi 
Published: November 2021

AbstractOxidation of the iron(II) precursor [(L1)FeIICl2], where L1 is a tetradentate bispidine, with soluble iodosylbenzene (sPhIO) leads to the extremely reactive ferryl oxidant [(L1)(Cl)FeIV=O]+ with a cis disposition of the chlorido and oxido coligands, as observed in non‐heme halogenase enzymes. Experimental data indicate that, with cyclohexane as substrate, there is selective formation of chlorocyclohexane, the halogenation being initiated by C−H abstraction and the result of a rebound of the ensuing radical to an iron‐bound Cl−. The time‐resolved formation of the halogenation product indicates that this primarily results from sPhIO oxidation of an initially formed oxido‐bridged diiron(III) resting state. The high yield of up to >70 % (stoichiometric reaction) as well as the differing reactivities of free Fe2+ and Fe3+ in comparison with [(L1)FeIICl2] indicate a high complex stability of the bispidine‐iron complexes. DFT analysis shows that, due to a large driving force and small triplet‐quintet gap, [(L1)(Cl)FeIV=O]+ is the most reactive small‐molecule halogenase model, that the FeIII/radical rebound intermediate has a relatively long lifetime (as supported by experimentally observed cage escape), and that this intermediate has, as observed experimentally, a lower energy barrier to the halogenation than the hydroxylation product; this is shown to primarily be due to steric effects.
ECD exciton chirality method today: a modern tool for determining absolute configurations
Authors: Pescitelli Gennaro 
Published: November 2021

AbstractThe application of the exciton chirality method (ECM) to interpret electronic circular dichroism (ECD) spectra is a well‐established and still popular approach to assign the absolute configuration (AC) of natural products, chiral organic compounds, and organometallic species. The method applies to compounds containing at least two chromophores with electric dipole allowed transitions (e.g., π–π* transitions). The exciton chirality rule correlates the sign of an exciton couplet (two ECD bands with opposite sign and similar intensity) with the overall molecular stereochemistry, including the AC. A correct application of the ECM requires three main prerequisites: (a) the knowledge of the molecular conformation, (b) the knowledge of the directions of the electric transition moments (TDMs), and (c) the assumption that the exciton coupling mechanism must be the major source of the observed ECD signals. All these prerequisites can be easily verified by means of quantum‐mechanical (QM) calculations. In the present review, we shortly introduce the general principles that underpin the use of the ECM for configurational assignments and survey its applications, both classic ones and some reported in the recent literature. Based on these examples, we will stress the advantages of the ECM but also the key requisites for its correct application. Additionally, we will discuss the dependence of the couplet sign on geometrical parameters (angles α,β,γ between TDMs), which can be helpful for discerning the sign of exciton chirality in ambiguous situations. Finally, we will present a molecular orbital (MO) description of the exciton coupling phenomenon.
Obstructive sleep apnea therapy for cardiovascular risk reduction—Time for a rethink?
Authors: Dissanayake Hasthi U. , Colpani Juliana T. , Sutherland Kate , Loke Weiqiang , Mohammadieh Anna , Ou Yi‐Hui , de Chazal Philip , Cistulli Peter A. , Lee Chi‐Hang 
Published: November 2021

AbstractObstructive sleep apnea (OSA) is a highly prevalent and underdiagnosed medical condition, which is associated with various cardiovascular and metabolic diseases. The current mainstay of therapy is continuous positive airway pressure (CPAP); however, CPAP is known to be poorly accepted and tolerated by patients. In randomized controlled trials evaluating CPAP in cardiovascular outcomes, the average usage was less than 3.5 hours, which is below the 4 hours per night recommended to achieve a clinical benefit. This low adherence may have resulted in poor effectiveness and failure to show cardiovascular risk reduction. The mandibular advancement device (MAD) is an intraoral device designed to advance the mandible during sleep. It functions primarily through alteration of the jaw and/or tongue position, which results in improved upper airway patency and reduced upper airway collapsibility. The MAD is an approved alternative therapy that has been consistently shown to be the preferred option by patients who are affected by OSA. Although the MAD is less efficacious than CPAP in abolishing apnea and hypopnea events in some patients, its greater usage results in comparable improvements in quality‐of‐life and cardiovascular measures, including blood pressure reduction. This review summarizes the impact of OSA on cardiovascular health, the limitations of CPAP, and the potential of OSA treatment using MADs in cardiovascular risk reduction.
Illumination estimation via random vector functional link based on improved arithmetic optimization algorithm
Authors: Liu Xiangqi , Zhou Zhiyu 
Published: November 2021

AbstractIn order to solve the problem that the existing illumination estimation methods have low accuracy in image restoration, a random vector functional link illumination estimation algorithm based on whale optimization arithmetic algorithm is proposed in this article. First, in order to improve the optimization accuracy of arithmetic optimization algorithm, the whale optimization algorithm is applied to optimize the initial population of the arithmetic optimization algorithm. Then, we utilize the improved arithmetic optimization algorithm to improve the input weight and hidden layer offset of random vector functional link, and exclude the uncertainty caused by the random generation of random vector functional link's input weight and hidden layer bias. Finally, the proposed whale arithmetic optimization algorithm‐random vector functional link model is applied to SFU lab dataset and Gehler‐Shi dataset for illumination estimation. Compared with the other earlier illumination estimation algorithms, the proposed illumination estimation model in this article has better effect and higher stability. In addition, due to the diagonal mapping method for color correction and image restoration, the proposed illumination estimation algorithm can also get better results in image restoration.
Transfer learning based recurrent neural network algorithm for linguistic analysis
Authors: Sasikala S. , Ramesh S , Gomathi S , Balambigai S , Anbumani V 
Published: November 2021

AbstractEach language is a system of understanding and skills that allow language users to work together, hypothesize, express thoughts, opinions; wishes need to be articulated. Linguistics is the research of these structures in all respects: the composition, usage, and sociology of language, in particular, are the core of linguistics. Machine learning is the research area that allows machines to learn without being specifically scheduled. In linguistics, the design of writing is understood to be a foundation for many distinct company apps and probably the most useful if incorporated with machine learning methods. Research shows that besides text tagging and algorithm training, there are major problems in the field of big data. This article provides a collaborative effort (transfer learning integrated into recurrent neural network) to analyze the distinct kinds of writing between the language's linear and noncomputational sides and to enhance granularity. In addition to this, this article creates a recurrent neural network model for learning and processing text data automatically. RNN based linguistic process is fast and cost‐effective. It analyses the text data automatically and iteratively. This is the main reason for using RNN for the linguistic process. The outcome demonstrates stronger incorporation of granularity into the language from both sides. Comparative results of machine learning algorithms are used to determine the best way to analyze and interpret the structure of the language.
Teaching Photochemistry: Experimental Approaches and Digital Media
Authors: Bohrmann‐Linde Claudia , Meuter Nico , Zeller Diana , Tausch Michael W. 
Published: November 2021

AbstractIn this paper we give an insight into results from our curricular innovation research which aims at integrating photochemistry in university and school curricula. We have been exploring experimental approaches and developing teaching materials for more than 20 years and most of our experiments and teaching materials have been digitalized and made available in German and English as open educational resources (OER) on our website. The addressed photochemical content can be connected to well‐established subject content at school and university level chemistry, but their theoretical interpretation and the understanding of their applications go well beyond this. However, primarily they should motivate learners to, even after they leave school and university, continue to work on the investigation and development of sustainable processes and materials based on the use of (solar) light.
A psychological intervention for caries active young adults, a randomized controlled trial
Authors: Hagman Jennie , Wide Ulla , Werner Helene , Hakeberg Magnus 
Published: November 2021

AbstractObjectiveThe aim of the present study was to evaluate the effect of a brief version of the behavioral intervention Acceptance and Commitment Therapy (ACT) on reducing gingivitis and plaque levels after 18 weeks.Materials and methodsOne hundred thirty‐five caries‐active young adults (18–25 years of age), recruited from two public dental clinics, participated in this parallel group randomized control trial (RCT). Participants in the intervention (n = 67) received two ACT sessions in combination with standard information on oral health, and participants allocated to the control group (n = 68) received standard information only. Gingivitis and plaque levels were recorded at baseline and at the 9‐ and 18‐week follow‐ups. The effect of the intervention versus standard information alone was analyzed by intention‐to‐treat and per protocol, applying the General Linear Model (GLM). Exploratory analyses for the intervention and control groups were conducted to evaluate the effect of gender and smoking habits on the gingivitis and plaque outcome. The CONSORT guidelines for RCT were followed.ResultsA significant decrease in gingivitis and plaque levels was observed over time, irrespective of treatment allocation. However, the ACT intervention was not significantly more effective at reducing gingivitis and plaque scores than standard information alone, even though the intervention participants had maintained their improvement to a greater extent. The exploratory analysis revealed that females improved their gingivitis and plaque levels significantly more than the males in the intervention group (p = 0.025 for gingivitis and p = 0.013 for plaque).ConclusionA brief ACT intervention was not proven to be more effective than standard information alone at improving oral health in a sample of young adults with poor oral health. However, ACT seems to have a positive effect on oral health among females. (TRN ISRCTN15009620).
Use of flow cytometry and cytology to differentiate breast implant‐associated anaplastic large cell lymphoma from reactive seromas in Brazilian patients
Authors: De Azambuja Ana Paula , Gevert Fabíola , Oliveira Raisa Merhy , Sebastião Ana Paula , Groth Anne Karoline 
Published: November 2021

AbstractIntroductionThe combination of cytology and multiparametric flow cytometry (MFC) may be useful in the diagnosis of breast implant‐associated anaplastic large cell lymphoma (BIA‐ALCL) and may be a practical way to differentiate lymphoma from benign and reactive seromas. Although the Brazilian breast implant market is the second largest in the world, with several manufacturers and the almost exclusive use of textured implants, the occurrence of BIA‐ALCL in Brazil is underreported.MethodsOne hundred seventeen sequential collections of suspicious periprosthetic fluid (PF) from 105 Brazilian patients registered between March/2018 and March/2021 were evaluated by routine cytomorphology and flow cytometry. The combination of CD30, HLA‐DR, and CD25 was used together with T and B lymphocyte and monocyte evaluation. The PF samples were divided into positive, acute reactive (neutrophilic exudate), or chronic reactive (macrophage or lymphocyte rich), and unavailable samples.ResultsNine BIA‐ALCL positive cases (7.7%) were identified, with typical morphology and increased FSC/SSC dispersion, bright expression of CD30, CD25 and HLA‐DR, and absence or weakness of T‐cell antigens (CD3, CD8, CD4, CD5, and CD7). Reactive samples were acute (n = 18, 15.4%) and chronic (n = 70, 59.8%). Twenty samples were excluded. The mean age of BIA‐ALCL patients was 50 years (31–57 years) and 35 years in reactive patients (20–69 years).ConclusionUse of MFC with a comprehensive antibody panel consisting of CD30 in conjunction with CD25 and HLA‐DR can discriminate anaplastic cells of BIA‐ALCL from lymphoid or neutrophilic reactive cells and should be considered in the initial evaluation of seroma.
1,1′‐Ferrocenylene‐Bridged Bis(N‐Heterocyclic Olefin) Derivatives
Authors: Guthardt Robin , Mellin Johanna , Bruhn Clemens , Siemeling Ulrich 
Published: November 2021

AbstractThe 1,1′‐ferrocenylene (fc)‐bridged bis(N‐heterocyclic olefin) compounds (IMes=CH)2fc (1, IMes=1,3‐dimesitylimidazolin‐2‐ylidene) and (IPr=CH)2fc (2, IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) were synthesised from (ICH2)2fc (3) and the respective N‐heterocyclic carbene IMes or IPr. Ligand substitution reactions of 1 and 2 with [BH3(THF)] afforded the complexes [1(BH3)2] and [2(BH3)2] as mixtures of the rac‐ and meso‐diastereomers. The new ferrocene derivatives 1–3 and the complexes meso‐[1(BH3)2], rac‐[1(BH3)2] and rac‐[2(BH3)2] were structurally characterised by single‐crystal X‐ray diffraction. 1 and 2 represent a new class of ferrocene‐based, and hence redox‐active, bidentate ligands. The presence of three redox‐active moieties, viz. the ferrocene unit and the two NHO units, is reflected by three consecutive oxidations according to an electrochemical investigation exemplarily performed with 2 by cyclic voltammetry.
Photochemistry at Scale: Wireless Light Emitters Drive Sustainability in Process Research & Development
Authors: Burek Bastien O. , Duong Hong Thu , Hochradel Klaus , Sutor Alexander , Rupp Matthias , Heilmann Eike K. , Lovis Kai , Bloh Jonathan Z. 
Published: November 2021

AbstractCarbon−carbon bond formation by dual Iridium‐Nickel photoredox catalysis has gained a lot of attention for late‐stage cross‐couplings of alkyls with aryls. However, the scalability of such reactions is greatly impeded by the poor light penetration depth into the strongly absorbing reaction media. Wireless internal illumination is a novel technique which circumvents the light penetration issue efficiently and therefore allows to scale photon‐driven reactions by conventional methods. Here we demonstrate that industrially relevant photoredox C−C couplings can be scaled seamlessly to different volumes, achieving qualitatively and quantitatively the same results at all scales. The use of conventional reactor types allows stirred, bubble column or fixed‐bed operation mode and is fully compatible with heterogeneous reaction mixtures. By minimizing reflection losses, we could also show a significant advantage in the reaction rate over an externally illuminated setup at the same light intensity.
Evaluation of the International League Against Epilepsy 1981, 1989, and 2017 classifications of seizure semiology and etiology in a population‐based cohort of children and adults with epilepsy
Authors: Egesa Isaac J. , Newton Charles R. J. C. , Kariuki Symon M. 
Published: November 2021

AbstractObjectiveThe International League Against Epilepsy (ILAE) has revised the classification of epilepsies and seizures on several occasions since the original classification published in 1964. It is unclear if these changes have impacted the characterization of epilepsy, including the clinical validity of seizure semiology or epilepsy outcomes in resource‐poor areas. We aim to address this important knowledge gap.MethodsWe reviewed the clinical seizure semiology and etiological data of 483 persons with epilepsy identified from a population‐based survey in rural Kenya. The seizure semiology and etiological data were classified using the 1981 (for seizures) and 1989 (for epilepsy) ILAE criteria and then reclassified according to the ILAE‐2017 criteria. Logistic regression models adjusted for potential confounders were used to measure the associations between the seizure semiology and different clinical and electroencephalographic features of epilepsy.ResultsFocal (formerly localization‐related) and generalized epilepsies were lower in ILAE‐2017 (56% and 29%) than that of ILAE‐1989 (61% and 34%), P < .001 and P < .001. Combined focal and generalized epilepsy type in ILAE‐2017 accounted for 11% of epilepsies. Individual seizure types were statistically similar in both ILAE‐1981 and 2017. New classification categories in ILAE‐2017 such as unknown seizures and epilepsies were identified, and the proportions were similar to the unclassified category in ILAE‐1989, 6% and 5%, respectively. The most common causes of epilepsy were symptomatic (76%) in the ILAE‐1989 criteria, with infectious (45%) and structural (36%) causes were highest in the ILAE‐2017 criteria.SignificanceOur study confirms that the two ILAE classification schemes are broadly consistent, but the introduction of the combined onset seizure category in ILAE‐2017 significantly reduces the proportion of mutually exclusive focal and generalized seizures. The comprehensive classification of etiology categories in ILAE‐2017 will facilitate appropriate treatment and improve prognosis.
Seasonal morphodynamics of multiple intertidal bars (MITBs) on a meso‐ to macrotidal beach
Authors: Biausque Melanie , Guisado‐Pintado Emilia , Grottoli Edoardo , Jackson Derek W. T. , Cooper J. Andrew G. 
Published: November 2021

AbstractMultiple intertidal bar (MITB) beach systems comprise a succession of subdued, shore‐parallel sandbars, developed under low‐energy conditions in meso‐ to macrotidal settings. Their relatively stable morphologies over long timescales are commonly attributed to a dynamic equilibrium, driven primarily by seasonal morphodynamics. The seasonal behaviour is, however, poorly understood. The relationship between temporal and spatial hydrodynamic forcing and morphological changes was investigated through monthly differential GPS surveys in Dundrum Bay (Northern Ireland) from April 2019 to March 2020, associated with variations in nearshore wave conditions, simulated using the SWAN wave model. During low‐energy summer conditions, southeast waves helped promote MITB stability and a slight increase in bar crest elevation, with the seaward‐most bar buffering and preserving the inner bar system through wave dissipation. In the winter, a progressive increase in wave energy, and a switch in wave direction (southwest to south), initiated the highest rates of cross‐shore bar migration and a lowering of bar crests. While the seaward‐most bar remained largely submerged, the shoreward‐most bar played a key role in protecting the upper‐beach and/or foredune. Winter conditions also forced a newly observed mesoscale longshore drift involving offshore sediment transport in the southwest and onshore transport in the northeast. Cross‐shore variability in MITB behaviour at seasonal timescales was, however, primarily driven by local hydrodynamic conditions, including variations in wave energy and direction. Conversely, alongshore variability was largely influenced by the complex nearshore bathymetry, headlands and an active ebb delta, all interacting with changing hydrodynamic forcing. These results challenge the seasonal equilibrium model for MITB systems and highlight longer‐term patterns of sediment movement.
The man in the middle—liquidity provision under central clearing in the credit default swap market: A regression discontinuity approach
Authors: Schoenemann Gregor Helmut 
Published: November 2021

AbstractIn this study, I analyze the effect of central clearing on credit default swap (CDS) market breadth, depth, and resiliency using a regression discontinuity design. I find evidence for a decrease in absolute bid–ask spreads and bid–ask spread resiliency and an increase in gross trading volume with the beginning of central clearing. However, we observe positive effects of central clearing on CDS market liquidity only for CDS contracts of high fundamental and liquidity risk. Further results indicate that lower trading frictions, that is, counterparty risk and regulatory capital charges, may explain the positive effects of central clearing on CDS market liquidity.