bluuebunny/crossref_metadata_2025_split huggingface dataset:
Contrasting Photochemical and Thermal Catalysis by Ruthenium Arsine Complexes Revealed by Parahydrogen Enhanced NMR Spectroscopy
Authors: Adams Ralph W. , John Richard O. , Blazina Damir , Eguillor Beatriz , Cockett Martin C. R. , Dunne John P. , López‐Serrano Joaquín , Duckett Simon B. 
Published: December 2021

AbstractThe thermal and photochemical reactivity of Ru(CO)3(dpae) (1) and Ru(CO)2(dpae)(PPh3) (2) towards H2 and diphenylacetylene is described. These reactions are monitored by NMR spectroscopy in conjunction with the parahydrogen induced polarisation (PHIP) effect, spatially resolved chemical shift imaging and the Only Parahydrogen Spectroscopy (OPSY) signal filtering method. The results are supported by DFT. The thermal and photochemical reactions of 1 with H2 proceed by CO loss and form Ru(H)2(CO)2(dpae) (3). 1 catalyses the formation of 1,2 diphenylethane, cis‐ and trans‐stilbene, and 1,2,3,4 tetraphenylbutadiene under 325 nm irradiation at 295 K in a reaction where Ru(CO)2(dpae)(η2‐CHPh=CPhCPh=CHPh) forms. When the same reaction is monitored under thermal conditions at 333 K the η2‐diene complex is no longer detected but hydride containing Ru(CHPhCH2Ph)(H)(CO)2(dpae) and Ru(CO)2(dpae)(trans‐stilbene) are seen. For 1, the photochemical promotion of hydrogenation through 325 nm irradiation results in an approximate 5.5‐fold increase in turnover at 333 K when compared to no irradiation. In contrast, 2 reacts thermally with H2 at 295 K through PPh3 and CO loss with both Ru(H)2(CO)(dpae)(solvent) and 3 being detected. Under irradiation, CO loss dominates and two isomers of Ru(H)2(CO)(dpae)(PPh3) form. While 2 forms the same 4 organic products at 295 K and a second isomer of Ru(CHPhCH2Ph)(H)(CO)2(dpae) alongside the diene complex no photochemical promotion of hydrogenation is observed.
A Mechanistic Study on the Non‐enzymatic Hydrolysis of Kdn Glycosides
Authors: Nejatie Ali , Colombo Cinzia , Hakak‐Zargar Benyamin , Bennet Andrew J. 
Published: December 2021

AbstractSialic acids are biologically important carbohydrates that are prevalent throughout nature. We are interested in their intrinsic reactivity in aqueous solution and how such reactivity affects the design of substrates for investigation of enzymes that process these sugars. To probe the reactivity differences between two sialic acid family members N‐acetylneuraminic acid and Kdn we measured the rate constants for hydrolysis of 4‐nitrophenyl 3‐deoxy‐d‐glycero‐α‐d‐galacto‐non‐2‐ulosonide in aqueous solution. The kinetic data is consistent with glycosidic C−O bond cleavage occurring via four mechanistic pathways, and these are: (i) hydronium ion‐catalyzed hydrolysis of the neutral sugar; (ii) hydronium ion‐catalyzed hydrolysis of the glycosidic carboxylate; (iii) water‐catalyzed hydrolysis of the anionic glycoside; and (iv) base‐promoted reaction of the anionic glycoside. To study the effects of C‐5 substitution on the Kdn glycoside we made 4‐nitrophenyl 5‐O‐methyl‐α‐Kdn glycoside and determined its rate constants for hydrolysis. All hydrolytic rate constants for both Kdn glycosides were larger than those reported for the parent N‐acetyl‐α‐neuraminide. The water‐catalyzed reaction (pathway iii) exhibited a βlg value of −1.3±0.1. We conclude that the larger rate constants associated with C5‐oxygen containing sialosides results from less steric congestion at the hydrolytic transition states than for the parent C‐5 acetamido glycoside.
Recognizing a spatial extreme dependence structure: A deep learning approach
Authors: Ahmed Manaf , Maume‐Deschamps Véronique , Ribereau Pierre 
Published: December 2021

AbstractUnderstanding the behavior of extreme environmental events is crucial for evaluating economic losses, assessing risks, and providing health care, among many other related aspects. In a spatial context, relevant for environmental events, the dependence structure is extremely important, influencing joint extreme events and extrapolating on them. Thus, recognizing or at least having preliminary information on the patterns of these dependence structures is a valuable knowledge for understanding extreme events. In this study, we address the question of automatic recognition of spatial asymptotic dependence versus asymptotic independence, using a convolutional neural network (CNN). We designed a CNN architecture as an efficient classifier of a dependence structure. Extremal dependence measures are used to train the CNN. We tested our methodology on simulated and real datasets: air temperature data at 2 m over Iraq and rainfall data along the east coast of Australia.
Canadian Large Ensembles Adjusted Dataset version 1 (CanLEADv1): Multivariate bias‐corrected climate model outputs for terrestrial modelling and attribution studies in North America
Authors: Cannon Alex J. , Alford Hunter , Shrestha Rajesh R. , Kirchmeier‐Young Megan C. , Najafi Mohammad Reza 
Published: December 2021

AbstractThe Canadian Large Ensembles Adjusted Dataset version 1 (CanLEADv1) contains 50‐member ensembles of bias‐adjusted near‐surface global and regional climate model variables on a 0.5° grid over North America for historical and future scenarios (1950–2100). Canadian Earth System Model Large Ensembles (CanESM2 LE) and Canadian Regional Climate Model Large Ensemble (CanRCM4 LE) datasets are bias‐corrected using a multivariate quantile‐mapping algorithm for statistical consistency – in terms of marginal distributions and multivariate dependence structure – with two observationally constrained historical meteorological forcing datasets. For each observational dataset, bias‐adjusted variables are provided for two sets of 50‐member initial‐condition CanESM2 ensembles (historical plus RCP8.5 scenarios, 1950–2005 and 2006–2100, respectively; and historicalNAT scenario, 1950–2020, which excludes anthropogenic forcings), and one 50‐member CanRCM4 ensemble (historical plus RCP8.5). The archive includes daily minimum temperature, maximum temperature, precipitation, relative humidity, surface pressure, wind speed, incoming shortwave radiation and incoming longwave radiation. Intended uses include hydrological and land surface impact modelling, as well as related event attribution studies.
Anatomical and functional visual network patterns in progressive multiple sclerosis
Authors: Backner Yael , Zamir Sol , Petrou Panayiota , Paul Friedemann , Karussis Dimitrios , Levin Netta 
Published: December 2021

AbstractThe gradual accrual of disability over time in progressive multiple sclerosis is believed to be driven by widespread degeneration. Yet another facet of the problem may reside in the loss of the brain's ability to adapt to the damage incurred as the disease progresses. In this study, we attempted to examine whether changes associated with optic neuritis in the structural and functional visual networks can still be discerned in progressive patients even years after the acute insult. Forty‐eight progressive multiple sclerosis patients, 21 with and 27 without prior optic neuritis, underwent structural and functional MRI, including DTI and resting state fMRI. Anatomical and functional visual networks were analyzed using graph theory‐based methods. While no functional metrics were significantly different between the two groups, anatomical global efficiency and density were significantly lower in the optic neuritis group, despite no significant difference in lesion load between the groups. We conclude that long‐standing distal damage to the optic nerve causes trans‐synaptic effects and the early ability of the cortex to adapt may be altered, or possibly nullified. We suggest that this limited ability of the brain to compensate should be considered when attempting to explain the accumulation of disability in progressive multiple sclerosis patients.
Alcohol Consumption and Cardiovascular Outcomes in Patients With Nonalcoholic Fatty Liver Disease: A Population‐Based Cohort Study
Authors: Janjua Malik , Knuiman Matthew , Divitini Mark , McQuillan Brendan , Olynyk John K. , Jeffrey Gary P. , Adams Leon A. 
Published: December 2021

Low‐level alcohol consumption is associated with reduced cardiovascular disease (CVD) in the general population. It is unclear whether this association is seen in patients with nonalcoholic fatty liver disease (NAFLD) who have an increased risk of CVD. We examined the association between alcohol consumption and CVD‐related outcomes in subjects with NAFLD from a general population cohort. Subjects participating in the 1994‐1995 Busselton Health survey underwent clinical and biochemical assessment. NAFLD was identified using the Fatty Liver Index of >60, and alcohol consumption quantified using a validated questionnaire. CVD hospitalizations and death during the ensuing 20 years were ascertained using the Western Australian data linkage system. A total of 659 of 4,843 patients were diagnosed with NAFLD. The average standard drinks per week was 8.0 for men and 4.0 for women. Men consuming 8‐21 drinks per week had a 38% (hazard ratio [HR] 0.62, 95% confidence interval [CI] 0.43‐0.90) lower risk of CVD hospitalization as compared with men consuming 1‐7 drinks per week. With both men and women combined, consumption of 8‐21 drinks per week was associated with a 32% (HR 0.68, 95% CI 0.49‐0.93) reduction in CVD hospitalization in minimally adjusted and 29% (HR 0.71, 95% CI 0.51‐0.99) in fully adjusted models. No protective association was observed with binge drinking. There was no association between alcohol consumption and CVD death. Conclusion: Low to moderate alcohol consumption is associated with fewer CVD hospitalizations but not CVD death in subjects with NAFLD.
Patients' attitude towards vaccination after Guillain Barré syndrome
Authors: Holtz Ben‐Ole , Grimm Alexander , Axer Hubertus 
Published: December 2021

AbstractBackground and AimsGuillain Barré syndrome (GBS) could be triggered by an infectious disease but by vaccination as well. Thus, suffering GBS may influence patients' attitudes towards vaccination.MethodsAn anonymous questionnaire consisting of the Overall Neuropathy Limitations Score (ONLS), the short form‐36 health survey (SF‐36), and questions addressing patients' attitude towards vaccination was sent to members of a German GBS support group and to patients with GBS diagnosis who were treated at Jena University Hospital.ResultsNinety‐seven questionnaires clearly stated GBS as a diagnosis and were included in the analysis. Although 19.6% of the GBS patients reported having no disability in the long‐time follow‐up, a considerable number of patients still had persistent neurological symptoms; 74.2% of the GBS patients reported being able to walk at least 10 m independently. However, 5.2% were restricted to wheelchair. The patients reached lower scores in all domains of quality of life compared to German controls. Moreover, patients showed a more critical attitude towards vaccination compared to a German representative survey. Fewer patients (58.8%) received a vaccination after suffering from GBS than before (77.3%). Every tenth patient believed that vaccination was the trigger for the GBS. 32% of the patients did not receive a vaccination in the last 5 years mainly because of the fear of adverse effects (32%) or disadvise of the general practitioners (25.8%).DiscussionAlthough the risk of relapse following immunization may be rather low, uncertainties and fears still impair the counseling of these patients by their medical practitioner.
Numerical study of hybrid nanofluid flow and heat transfer on a stretching sheet with MHD and heat generation effects
Authors: Rajesh Vemula , Srilatha Mandava , Chamkha Ali J. 
Published: December 2021

AbstractThe key goals of this manuscript are (i) to investigate the heat transfer and unsteady flow properties of a viscous hybrid nanofluid on a stretching sheet having nonzero slot velocity, and (ii) to examine the impacts of magnetic field parameter, stretching parameter, nanoparticle volume fraction, and heat generation parameter on the Nusselt number and skin friction coefficient numerically. The Tiwari‐Das nanofluid model is used. The mathematical (PDEs) equations controlling border layer flow and heat transfer are resolved by applying a numerical finite‐difference technique in the Crank Nicolson style. For the validation process, the analytical solution is established using the Laplace transform technique and is compared with the numerical solution for a particular case and found to be in superb agreement.
Hybrid Nanostructure of Mixed Transition Metal Oxysulfides Supported by Porous PBA as Efficient Electrocatalysts for the Oxygen Evolution Reaction
Authors: Mukherjee Poulami , Sathiyan Krishnamoorthy , Vijay Aswin Kottapurath , Bar‐Ziv Ronen , Zidki Tomer 
Published: December 2021

AbstractThe construction of highly active and durable non‐noble‐metal electrocatalysts for the oxygen evolution reaction (OER) is an ongoing challenge. Here, we report the development of a hybrid nanostructure of PBA cubes wrapped with mixed W‐Co oxysulfides in a hair‐like structure through sulfurization of polyoxometalate (CoIIIW12 POM) as a bimetallic precursor. These unique heterostructures of PBA@Co−W−O−S grafted on carbon cloth afford abundant active sites and improved charge transfer kinetics that synergistically enhance the OER activity (overpotential of 250 mV at 10 mA cm−2). The synthetic approach used in this report can be extended for developing inexpensive, durable and efficient catalysts with diverse structures.
Electron Correlation: Nature's Weird and Wonderful Chemical Glue
Authors: Martin Jan M. L. 
Published: December 2021

AbstractIt can be argued that electron correlation, as a concept, deserves the same prominence in general chemistry as molecular orbital theory. We show how it acts as Nature's “chemical glue” at both the molecular and supramolecular levels. Electron correlation can be presented in a general chemistry course in an at least somewhat intuitive manner. We also propose a simple classification of correlation effects based on their length scales and the size of the orbital gap (relative to the two‐electron integrals). In the discussion, we also show how DFT can shed light on wavefunction theory, and conversely. We discuss two types of “honorary valence orbitals”, one related to small core‐valence gaps, the other to the ability of empty 3d orbitals in 2ndrow elements to act as backbonding acceptors. Finally, we show why the pursuit of absolute total energies for their own sake becomes a sterile exercise, and why atomization energies are a more realistic “fix point”.
The impact of COVID‐19 on experiences of pregnancy and/or early parenting in Chile
Authors: Olhaberry Marcia , Sieverson Catalina , Franco Pamela , Romero Macarena , Tagle Trinidad , Iribarren Daniela , Honorato Carolina , Muzard Antonia 
Published: December 2021

AbstractThe unprecedented COVID‐19 pandemic has impacted families’ mental health around the globe. In June 2020, 1163 parents of high (43%), middle (47%), and low socioeconomic status (SES) (10%) participated in an online survey developed to explore how daily life changes and restrictions that came with COVID‐19 affected the experiences of pregnancy and/or parenting children under the age of 5 in Chile.The survey's design had an exploratory and descriptive scope, with a mix of qualitative and quantitative questions. With the aim of exploring differences before and after COVID‐19, two time periods were established, and the 47‐item questionnaire covered participants’ sociodemographic information, support networks, health concerns, mood changes, self‐regulation, adult and children's perceived well‐being, parental competencies and parents’ perceptions of the unborn baby and/or their children's needs.The results relative to retrospective reporting of pre‐pandemic levels, showed an increase in children's crying and tantrums as well as in parental irritability and sadness. Additionally, decreases in the ability to calm down and sleep quality in both parents and children were identified. Finally, at a qualitative level, COVID‐19 stands out both as an opportunity to get to know their children better and as a stressor related to parental burn‐out and discomfort.
Histopathological correlation of punctate echogenic foci on ultrasonography in papillary thyroid carcinoma
Authors: Hong Min Ji , Noh Byeong‐Joo , Na Dong Gyu , Paik Wooyul 
Published: December 2021

AbstractPurposeTo investigate the pathological entities of punctate echogenic foci (PEF) by correlating PEF with histopathological features of papillary thyroid carcinoma (PTC).MethodsThis study included 121 consecutive patients who had undergone thyroidectomy for PTC. The inclusion criterion was entire tumor resection with a 3‐mm thickness for histopathological examination. We assessed the presence and number (<5 or ≥5) of PEF defined as punctate hyperechoic foci within the solid component of nodules. All surgical tumor specimens were retrospectively reviewed for the presence of microcalcifications, including the psammomatous calcification, coarse microcalcification, and micro‐ossification, and inspissated colloid.ResultsPEF were detected in 71 (58.7%) PTCs. Psammomatous calcifications, coarse microcalcifications, and inspissated colloids were more frequently found in PTCs with PEF than in those without (74.6%, 42.3%, and 46.5%, respectively, p ≤ 0.024). Any type of microcalcification was found in 90.1% of PTCs with PEF. Psammomatous calcifications, coarse microcalcifications, and inspissated colloids were independently associated with PEF (p ≤ 0.012). Psammomatous calcifications were found in all PTCs with a high number (≥5) of PEF.ConclusionMicrocalcifications were found in most PTCs with PEF and psammomatous calcification was the main pathological entity of PEF in PTC. Our study validates reliability of PEF as a predictor of microcalcifications in PTC.
Can aldehyde accumulation rates of red wines undergoing oxidation be predicted in accelerated conditions? The controverted role of aldehyde–polyphenol reactivity
Authors: Marrufo‐Curtido Almudena , Ferreira Vicente , Escudero Ana 
Published: December 2021

AbstractBACKGROUNDThe accumulation of acetaldehyde and Strecker aldehydes during wine oxidation is detrimental to quality and often determines wine shelf‐life. Knowing in advance the specific tendency of a wine to accumulate these compounds would help decision making during winemaking. An accelerated test based on a forced oxidation procedure at 45 °C (5 days) to measure aldehyde accumulation rates (AARs) is proposed and assessed by comparing results with those obtained by oxidation at 25 °C (36 days). Reactivities of aldehydes in those same wines stored in anoxia at both temperatures were also measured.RESULTSWine oxygen consumption rates at 25 °C are poorly correlated with those observed at 45 °C. By contrast, AARs of methional and of 2‐ and 3‐methylbutanals measured during wine oxidation at 25 °C are equivalent to those measured at 45 °C. AARs from isobutanal and acetaldehyde are also correlated, while AARs from phenylacetaldehyde are not. Partial least squares models explaining AARs show intriguing differences regarding the apparent limiting role played by wine anthocyanins and other polyphenols in the ability of wines to accumulate aldehydes. Measured differences in aldehyde pattern are similar to those of the other Strecker aldehydes.CONCLUSIONThe proposed assay makes it possible to obtain a reasonable estimate of a wine's tendency to accumulate aldehydes, with the exception phenylacetaldehyde, in 5 days. Neither differences in aldehyde reactivity between wines nor the change in reactivities with temperature support a major role for reactivity in differentially limiting AARs during wine oxidation. © 2021 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
Preparation and chiral resolution properties of bridged bis(cyclodextrin)s hybrid spheres for high performance liquid chromatography
Authors: Wang Litao , Lv Wenjing , Han Siqi , Yu Qinghua , Pei Dong , Xu Jian , Wang Meixia , Gao Guihua , Lv Mei 
Published: December 2021

AbstractSelenium‐bridged bis(β‐cyclodextrin)s organic–inorganic hybrid silica material with regular spherical shape as new type of chiral stationary phase was directly synthesized under the one‐pot hydrothermal synthesis method, and the chiral stationary phase was further characterized by infrared spectroscopy, scanning electron microscopy, thermogravimetry, and elemental analysis. The results of chiral separation showed that eight chiral compounds including various types of chiral alcohols and flavanone were successfully separated in the reversed‐phase separation mode by high performance liquid chromatography, which showed the better chiral resolution effect than that on the C2 position of single β‐cyclodextrin. The mechanism of chiral separation was likely due to multiple interactions such as inclusion, hydrogen bonding, electrostatic interaction, dipole–dipole interaction, and the synergistic effect of two cyclodextrins during the chiral resolution process. The synergy of the two cyclodextrins has great potential for development in chiral resolution.
HPLC‐MS/MS based comparative pharmacokinetics of 12 bioactive components in normal and osteoporosis rats after oral administration of You‐Gui‐Wan
Authors: Yin Hua , Wang Yahong , Wang Ling , Bai Xue , Zhang Jianhua 
Published: December 2021

AbstractYou‐Gui‐Wan is a traditional Chinese patent medicine that has been extensively used to treat kidney‐yang deficiency syndrome. An high‐performance liquid chromatography tandem mass spectrometry method was developed to measure contents of 12 components of You‐Gui‐Wan in rat plasma. Considering that pathological changes might directly affect the pharmacokinetic behavior of drugs, this method was further applied to compare pharmacokinetics between normal and osteoporotic animals. The results indicated that osteoporosis significantly altered the pharmacokinetic characteristics of the 12 components. Thus, the pharmacokinetics of You‐Gui‐Wan evaluated under osteoporotic conditions was much closer to clinical practice than that in normal physiological states. Thus, the optimized analytical method, along with the pharmacokinetic evaluation in the osteoporotic model may offer a more comprehensive understanding to elucidate the anti‐osteoporosis mechanism of You‐Gui‐Wan. These findings may aid in developing a more effective treatment plan for osteoporosis.
Online extraction and enrichment coupling with high‐speed counter‐current chromatography for effective and target isolation of antitumor anthraquinones from seeds of Cassia obtusifolia
Authors: Wang Fang , Cheng Li , Cao Yuanxin , Wei Qisheng , Tong Chaoying , Shi Shuyun 
Published: December 2021

AbstractTraditional bioassay‐guided investigation of bioactive compounds from natural products comprises critical steps, such as extraction, repeated column separation, and activity assay. Thus, the development of facile, rapid, and efficient technology is critically important. Here, a HepG2 cell‐based extraction method was first developed to rapidly screen potential antitumor compounds from the seeds ofCassia obtusifolia. Then, an online extraction and enrichment–high‐speed counter‐current chromatography (HSCCC) strategy was fabricated to facilely and efficiently isolate target antitumor compounds, which included direct extraction from solid C. obtusifolia, removal of polar interferences, enrichment of target compounds, and preparative isolation by HSCCC using flow rate stepwise increasing mode. After further purification by Sephadex LH‐20 column, five antitumor anthraquinones, aurantio‐obtusin, 1‐desmethylaurantio‐obtusin, chryso‐obtusin, obtusin, and questin, were obtained for structural characterization and bioassay verification. The results may not only provide new perspectives for facile and rapid investigation of bioactive compounds from complex natural products, but also offer a scientific basis for the potential applications of C. obtusifolia.