bluuebunny/crossref_metadata_2025_split huggingface dataset:
Weak Interactions Initiate C−H and C−C Bond Dissociation of Ethane on Nbn+ Clusters
Authors: Gan Wen , Huang Benben , Cui Chaonan , Hansen Klavs , Luo Zhixun 
Published: February 2023

AbstractThe conversion of ethane into value‐added chemicals under ambient conditions has attracted much attention but the mechanisms remain not fully understood. Here we report a study on the reaction of ethane with thermalized Nbn+ clusters based on a multiple‐ion laminar flow tube reactor combined with a triple quadrupole mass spectrometer (MIFT‐TQMS). It is found that ethane reacts with Nbn+ clusters to form both products of dehydrogenation and methane‐removal (odd‐carbon products). Combined with density functional theory (DFT) calculations, we studied the reaction mechanisms of the C−C bond activation and C−H bond cleavage on the Nbn+ clusters. It is unveiled that hydrogen atom transfer (HAT) initiates the reaction process, giving rise to the formation of Nb−C bonds and an elongated C−C distance in the HNbn+CH2CH3 motif. Subsequent reactions allow for C−C bond activation and a competitive HAT process which is associated with CH4 removal or H2 release, resulting in the production of the observed carbides.
Time‐resolved, Gas‐phase Kinetic and Quantum Chemical Studies of the Reaction of Germylene with Hydrogen Chloride
Authors: Becerra Rosa , Cannady J. Pat , Walsh Robin 
Published: February 2023

AbstractTime‐resolved studies of germylene, GeH2, generated by laser flash photolysis of 3,4‐dimethyl‐1‐germacyclopent‐3‐ene at 193 nm and monitored by laser absorption, have been carried out to obtain rate constants for its bimolecular reaction with HCl. The reaction was studied in the gas phase, mainly at a total pressure of 10 Torr (in SF6 bath gas) at five temperatures in the range 295–558 K. Experiments at other pressures showed that these rate constants were unaffected by pressure. The second‐order rate constants at 10 Torr (SF6 bath gas) fitted the Arrhenius equation: log(k/cm3 molecule−1 s−1)=(−12.06±0.14)+(2.58±1.03 kJ mol−1)/RTln10 where the uncertainties are single standard deviations. Quantum chemical calculations at G4 level support a mechanism in which an initial weakly bound donor‐acceptor complex is formed. This can then rearrange and decompose to give H2 and HGeCl (chlorogermylene). The enthalpy barrier (36 kJ mol−1) is too high to allow rearrangement of the complex to GeH3Cl (chlorogermane).
Predicting 195Pt NMR Chemical Shifts in Water‐Soluble Inorganic/Organometallic Complexes with a Fast and Simple Protocol Combining Semiempirical Modeling and Machine Learning
Authors: Ondar Evgeniia E. , Polynski Mikhail V. , Ananikov Valentine P. 
Published: February 2023

AbstractWater‐soluble Pt complexes are the key components in medicinal chemistry and catalysis. The well‐known cisplatin family of anticancer drugs and industrial hydrosylilation catalysts are two leading examples. On the molecular level, the activity mechanisms of such complexes mostly involve changes in the Pt coordination sphere. Using 195Pt NMR spectroscopy for operando monitoring would be a valuable tool for uncovering the activity mechanisms; however, reliable approaches for the rapid correlation of Pt complex structure with 195Pt chemical shifts are very challenging and not available for everyday research practice. While NMR shielding is a response property, molecular 3D structure determines NMR spectra, as widely known, which allows us to build up 3D structure to 195Pt chemical shift correlations. Accordingly, we present a new workflow for the determination of lowest‐energy configurational/conformational isomers based on the GFN2‐xTB semiempirical method and prediction of corresponding chemical shifts with a Machine Learning (ML) model tuned for Pt complexes. The workflow was designed for the prediction of 195Pt chemical shifts of water‐soluble Pt(II) and Pt(IV) anionic, neutral, and cationic complexes with halide, NO2−, (di)amino, and (di)carboxylate ligands with chemical shift values ranging from −6293 to 7090 ppm. The model offered an accuracy (normalized root‐mean‐square deviation/RMSD) of 1.08 %/145.02 ppm on the held‐out test set.
Like‐charge attraction in one‐and two‐dimensional Coulomb systems
Authors: Téllez Gabriel 
Published: February 2023

AbstractThe bare Coulomb interaction between two like‐charges is repulsive. When these charges are immersed in an electrolyte, the thermal fluctuations of the ions turn the bare Coulomb interaction into an effective interaction between the two charges. An interesting question arises: is it possible that the effective interaction becomes attractive for like‐charges? We will show how this like‐charge attraction phenomenon is indeed predicted in some one‐and two‐dimensional models of Coulomb systems. Exact analytical results can be obtained for these Coulomb systems models due to some connections that they have with integrable field theories. We will explain the techniques that allow obtaining exact results for the correlation functions between like‐charge particles and how, under certain circumstances, the natural repulsion interaction shifts to being attractive. Although the technical details differ for 1d or 2d systems, the physical cause of this phenomenon is rooted in a three‐body interaction between the two like‐charges and an ion of the electrolyte with an opposite charge.
Control of a sulfadoxine/trimethoprim combination in the competition horse: Elimination, metabolism and detection following an intravenous administration
Authors: Schenk Ina , Broussou Diane , Roques Beatrice , Lagershausen Henrike , Machnik Marc , Röttgen Helma , Toutain Pierre‐Louis , Thevis Mario 
Published: February 2023

AbstractThe combination of sulfadoxine (SDO) with trimethoprim (TMP) is widely used in veterinarian medicine. The aim of the present study was to compare excretion profiles and detection time windows of SDO and TMP in plasma and urine by means of a validated quantitative method.Eight horses received a single intravenous (i.v.) dose of 2.7 mg TMP and 13.4 mg SDO per kg bodyweight. Plasma and urine samples were collected up to 15 and 70 days post‐administration, respectively.While urine samples underwent an enzymatic hydrolysis, plasma samples were proteolysed before further analysis. After solid‐phase extraction, samples were analysed by liquid chromatography/electrospray ionisation tandem mass spectrometry in positive ionisation mode. The applied multiple reaction monitoring (MRM) method allowed the detection of SDO and TMP with a lower limit of detection of 0.03 ng/mL in plasma and 0.2 (SDO) and 0.4 ng/mL (TMP) in urine, respectively. In the present study, detection times for SDO were 15 days in plasma and 49 days in urine, respectively. TMP was detected for up to 7 days in plasma and up to 50 days in urine, respectively. The detection via the TMP metabolite 3‐desmethyl‐trimethoprim was possible for 70 days in urine. Detection times of the other confirmed metabolites N4‐acetylated sulfadoxine, hydroxytrimethoprim, trimethoprim‐1‐oxide and trimethoprim‐3‐oxide were significantly lower.In order to postulate reasonable screening limits (SLs) to control specific withdrawal times, a Monte Carlo simulation was performed for SDO. The proposed SL of 10 ng/mL SDO in blood and 300 ng/mL urine corresponds to a detection time of 4 days.
Experimentally testing mate preference in an avian system with unidirectional bill color introgression
Authors: McDiarmid Callum S. , Finch Fiona , Peso Marianne , van Rooij Erica , Hooper Daniel M. , Rowe Melissah , Griffith Simon C. 
Published: February 2023

AbstractMating behavior can play a key role in speciation by inhibiting or facilitating gene flow between closely related taxa. Hybrid zones facilitate a direct examination of mating behavior and the traits involved in establishing species barriers. The long‐tailed finch (Poephila acuticauda) has two hybridizing subspecies that differ in bill color (red and yellow), and the yellow bill phenotype appears to have introgressed ~350 km eastward following secondary contact. To examine the role of mate choice on bill color introgression, we performed behavioral assays using natural and manipulated bill colors. We found an assortative female mating preference for males of their own subspecies when bill color was not manipulated. However, we did not find this assortative preference in trials based on artificially manipulated bill color. This could suggest that assortative preference is not fixed entirely on bill color and instead may be based on a different trait (e.g., song) or a combination of traits, or alternatively may be due to lower statistical power alongside the bill manipulations being unconvincing to the female choosers. Intriguingly, we find a bias in the inheritance of bill color in captive bred F1 hybrid females. Previous modeling suggests that assortative mate preference and this kind of partial dominance in the underlying genes may together contribute to introgression, making the genetic architecture of bill color in this system a priority for future research.
Functional assessment based on cardiopulmonary exercise testing in mild heart failure: A multicentre study
Authors: Zimerman André , da Silveira Anderson D. , Borges Marina S. , Engster Pedro H.B. , Schaan Thomas U. , de Souza Gabriel C. , de Souza Isabela P.M.A. , Ritt Luiz Eduardo F. , Stein Ricardo , Berwanger Otavio , Vaduganathan Muthiah , Rohde Luis Eduardo 
Published: February 2023

AbstractAimsIn this multicentre study, we compared cardio‐pulmonary exercise test (CPET) parameters between heart failure (HF) patients classified as New York Heart Association (NYHA) class I and II to assess NYHA performance and prognostic role in mild HF.Methods and resultsWe included consecutive HF patients in NYHA class I or II who underwent CPET in three Brazilian centres. We analysed the overlap between kernel density estimations for the per cent‐predicted peak oxygen consumption (VO2), minute ventilation/carbon dioxide production (VE/VCO2) slope, and oxygen uptake efficiency slope (OUES) by NYHA class. Area under the receiver‐operating characteristic curve (AUC) was used to assess the capacity of per cent‐predicted peak VO2 to discriminate between NYHA class I and II. For prognostication, time to all‐cause death was used to produce Kaplan–Meier estimates. Of 688 patients included in this study, 42% were classified as NYHA I and 58% as NYHA II, 55% were men, and mean age was 56 years. Median global per cent‐predicted peak VO2 was 66.8% (IQR 56–80), VE/VCO2 slope was 36.9 (31.6–43.3), and mean OUES was 1.51 (±0.59). Kernel density overlap between NYHA class I and II was 86% for per cent‐predicted peak VO2, 89% for VE/VCO2 slope, and 84% for OUES. Receiving‐operating curve analysis showed a significant, albeit limited performance of per cent‐predicted peak VO2 alone to discriminate between NYHA class I vs. II (AUC 0.55, 95% CI 0.51–0.59, P = 0.005). Model accuracy for probability of being classified as NYHA class I (vs. NYHA class II) across the spectrum of the per cent‐predicted peak VO2 was limited, with an absolute probability increment of 13% when per cent‐predicted peak VO2 increased from 50% to 100%. Overall mortality in NYHA class I and II was not significantly different (P = 0.41), whereas NYHA class III patients displayed a distinctively higher death rate (P < 0.001).ConclusionsPatients with chronic HF classified as NYHA I overlapped substantially with those classified as NYHA II in objective physiological measures and prognosis. NYHA classification may represent a poor discriminator of cardiopulmonary capacity in patients with mild HF.
Late‐Stage Functionalisation of Pyridine‐Containing Bioactive Molecules: Recent Strategies and Perspectives
Authors: Failla Mattia , Lombardo Giacomo W. , Orlando Paolo , Fiorito Daniele , Bombonato Elena , Ronchi Paolo , Passarella Daniele , Fasano Valerio 
Published: February 2023

AbstractLate‐Stage Functionalisation (LSF) is an innovative technique that has been successfully applied to the C−H diversification of pharmaceuticals. However, LSF of the pyridine ring in drug‐like molecules is often unselective. As a result, a mixture of structurally related products is obtained, thus making the purification tedious and time‐consuming. This review shines a light on recent strategies addressing the selectivity issue in the LSF of complex natural products or drugs containing the pyridine moiety. Specifically, we have reviewed the efforts reported both in academia and industries with the hope of providing a guide for the LSF of elaborated pyridines.
Catalytic Asymmetric Friedel–Crafts Alkylation of Indole via In Situ Generated Indol‐2‐one
Authors: Fei Yuanai , Hou Jun , Song Huiying , Yang Mei‐li , Lei Pan , Ge Xiayu , Wei Hongbo , Xu Yuanzhen , Xie Weiqing 
Published: February 2023

AbstractAn asymmetric Friedel–Crafts alkylation of indole with in situ generated indol‐2‐one from functionalized 3‐bromooxinidole catalyzed by chiral N,N’‐dioxide/Ni(BF4)2 has been developed. This protocol provides an efficient route to stereoselective construction of a series of 3‐substituted 3’‐indolyloxindoles bearing a quaternary carbon center in excellent yields and enantioselectivities (up to 99 % ee). In addition, the conversion of the resulted 3‐substituted 3’‐indolyloxindole to the key intermediate for the formal synthesis of (+)‐folicanthine was also demonstrated.
Statistical characterization of erosion and sediment transport mechanics in shallow tidal environments. Part 2: suspended sediment dynamics
Authors: Tognin Davide , D'Alpaos Andrea , D'Alpaos Luigi , Rinaldo Andrea , Carniello Luca 
Published: February 2023

A proper understanding of sediment transport dynamics, critically
including resuspension and deposition processes of suspended sediments,
is key to the morphodynamics of shallow tidal environments. Aiming to
account for deposition mechanics in a synthetic theoretical framework
introduced to model erosion dynamics, here we investigated suspended
sediment dynamics. A complete spatial and temporal coverage of suspended
sediment concentration (SSC) required to effectively characterize
resuspension events is hardly available through observation alone, even
combining point measurements and satellite images, but it can be
retrieved by properly calibrated and tested numerical models. We
analyzed one-year-long time series of SSC computed by a bi-dimensional,
finite-element model in six historical configurations of the Venice
Lagoon in the last four centuries. Following the peak-over-threshold
theory, we statistically characterized suspended sediment dynamics by
analyzing interarrival times, intensities and durations of
over-threshold SSC events. Our results confirm that, as for erosion
events, SSC can be modeled as a marked Poisson process in the intertidal
flats for all the considered historical configurations of the Venice
Lagoon because exponentially distributed random variables well describe
interarrival times, intensity and duration of over-threshold
events. Moreover, interarrival times, intensity and duration describing
local erosion and over-threshold SSC events are highly related, although
not identical because of the non-local dynamics of suspended sediment
transport related to advection and dispersion processes. Owing to this
statistical characterization of SSC events, it is possible to generate
synthetic, yet realistic, time series of SSC for the long-term modeling
of shallow tidal environments.
Target Lipid Model and Empirical Organic Carbon Partition Coefficients Predict Sediment Toxicity of Polychlorinated Biphenyls to Benthic Invertebrates
Authors: Fuchsman Phyllis , Fetters Kyle , O'Connor Alison 
Published: February 2023

Abstract
Quantifying causal exposure–response relationships for polychlorinated biphenyl (PCB) toxicity to benthic invertebrates can be an important component of contaminated sediment assessments, informing cleanup decisions and natural resource injury determinations. Building on prior analyses, we demonstrate that the target lipid model accurately predicts aquatic toxicity of PCBs to invertebrates, providing a means to account for effects of PCB mixture composition on the toxicity of bioavailable PCBs. We also incorporate updated data on PCB partitioning between particles and interstitial water in field-collected sediments, to better account for effects of PCB mixture composition on PCB bioavailability. To validate the resulting model, we compare its predictions with sediment toxicity data from spiked sediment toxicity tests and a variety of recent case studies from sites where PCBs are the primary sediment contaminant. The updated model should provide a useful tool for both screening-level and in-depth risk analyses for PCBs in sediment, and it should aid in diagnosing potential contributing factors at sites where sediment toxicity and benthic community impairment are observed. Environ Toxicol Chem 2023;42:1134–1151. © 2023 SETAC
Economic burden of type 2 diabetes in Iran: A cost‐of‐illness study
Authors: Jalilian Habib , Heydari Somayeh , Imani Ali , Salimi Mozhgan , Mir Nazanin , Najafipour Farzad 
Published: February 2023

AbstractBackground and AimsType 2 diabetes mellitus (T2DM) is a prevalent public health problem worldwide, and the economic burden of the disease poses one of the main challenges for health systems in low‐ and middle‐income countries. This study aimed to estimate the economic burden of T2DM in Iran, in 2018.MethodsThis was a cost‐of‐illness study. Three hundred and seventy‐five patients with T2DM who were referred to Imam Reza and Sina's educational and therapeutic centers and Asad Abadi clinic in Tabriz, Iran, in 2018 were included. A researcher‐constructed checklist was used for data collection. Data were analyzed using EXCEL and SPSS software version 22.ResultsTotal economic burden of diabetes was estimated at 152,443,862,480.3 (purchasing power parity [PPP], Current International $) (approximately 7.69% of GDP, PPP, Current International $). The mean total direct and indirect costs were 11,278.68 (PPP) (62.35% of mean total cost) and 6808.88 (PPP, Current International $) (37.64% of the total cost), respectively. The mean total direct medical cost and the direct nonmedical cost were 10,819.43 (PPP, Current International $) (59.81% of mean total cost) and 459.24 (PPP, Current International $) (2.53% of mean total cost) per patient, respectively. Besides, the mean direct medical cost was 6.18 times the total per capita expenditure on health, and the total direct medical cost was 8.9% times the total expenditure on health.ConclusionDiabetes imposes a substantial economic burden on patients, health systems, and the whole economy. Besides, since the cost of the disease in patients treated with insulin and those with diabetes complications is significantly higher, the reinforcement of self‐care measures and focusing on modifying lifestyle (dietary modification and physical activity) in patients with T2DM can significantly reduce the costs of the disease.
Frequency of respiratory symptoms among rice mill workers in Bangladesh: A cross‐sectional study
Authors: Choudhury Shah A. R. A. , Rayhan Abu , Ahmed Shamim , Chakrabortty Rajashish , Rahman Mohammed A. , Masud Abdullah A. , Paul Susanta K. , Sami Al Hasan Ahmed 
Published: February 2023

AbstractBackground and AimsRice mill workers are frequently exposed to rice dust specks containing bacteria, endotoxins, spores, and chemicals in workplaces. Consequently, they develop diverse respiratory symptoms that lead to increased disability and social burden. The present study was conducted to observe the frequency of respiratory symptoms among rice mill workers in Bangladesh.MethodsThis cross‐sectional study was conducted at different rice mills in Rangpur district of Bangladesh. Three hundred and forty‐six rice mill workers, both male and female of 18 years and above, with a job experience of at least 3 years, were selected as study subjects. An equal number of people who had never worked at rice mills were selected from the nearby locality as the nonexposed group. Enquiries were made regarding respiratory symptoms with the help of a preformed questionnaire which contained sociodemographic characteristics, occupational history, potential confounding factors, and physical parameters. A respiratory dust sampler was used to measure workplace dust concentration.ResultsThe presence of one or more respiratory symptoms was significantly higher among rice mill workers than in the nonexposed group (52.3% vs. 17.6%). Rice mill workers who worked for more than 10 h and had a working experience of more than 15 years had a higher frequency of respiratory symptoms (41.3% and 39.8%, respectively). Rice mill workers with body mass index (BMI) <18.5 also exhibited more respiratory symptoms (25.4%). All working sections had a higher‐than‐average dust concentration level, with the milling section being the dustiest (PM 2.5 492.1 µg/m3).ConclusionThis study showed an increased frequency of respiratory symptoms among rice mill workers of Bangladesh. Longer working experience and working hours, low BMI and high dust concentration levels were strongly associated with that increase in frequency.
Individual‐level determinants of COVID‐19 vaccination in pregnant people in East Tennessee
Authors: Ehrlich Samantha F. , Maples Jill , Burnette Sara , Rand Bethany , Zite Nikki , Paudel Alissa , Fortner Kimberly 
Published: February 2023

AbstractObjectiveCoronavirus disease 2019 (COVID‐19) infection during pregnancy increases the risk of severe illness and death. This study describes individual‐level determinants of COVID‐19 vaccination among pregnant people in East Tennessee.MethodsAdvertisements for the online Moms and Vaccines survey were placed in prenatal clinics in Knoxville, Tennessee. Determinants were compared between unvaccinated individuals and those partially or fully vaccinated for COVID‐19.ResultsWave 1 of the Moms and Vaccines study included 99 pregnant people: 21 (21.2%) were unvaccinated and 78 (78.8%) were partially or fully vaccinated. Compared with the unvaccinated individuals, the partially or fully vaccinated patients more often obtained information about COVID‐19 from their prenatal care provider (8 [38.1%] vs. 55 [70.5%], P = 0.006) and indicated higher levels of trust in that information (4 [19.1] vs. 69 [88.5%], P < 0.0001). Misinformation was higher in the unvaccinated group overall, although there was no difference in concern for the severity of COVID‐19 infection during pregnancy by vaccination status (1 [5.0%] of the unvaccinated vs. 16 [20.8%] of the partially or fully vaccinated, P = 0.183).ConclusionStrategies to counter misinformation are of the utmost importance, particularly pregnancy‐ and reproductive health–related misinformation, because of the increased risk of severe disease faced by unvaccinated pregnant individuals.