bluuebunny/crossref_metadata_2025_split huggingface dataset:
Silica‐Grafted Isonicotinamide to Boost Catalytic Activity of Cobalt Nanoparticles in Hydrogenation and Reductive Amination Reactions
Authors: Carmona‐Chávez Rodrigo , Pulido‐Díaz Israel T. , Rodríguez‐Nava Mota Abril , Salas‐Martin Karla P. , Portales‐Martínez Benjamín , Guerrero‐Ríos Itzel , Reina Antonio 
Published: June 2024

AbstractThe functionalization of silica supports with isonicotinamide (NIC) facilitated the stabilization of small (3.5 nm), spherical cobalt nanoparticles (CoNPs) used in catalytic hydrogenation. Various silica matrices, including amorphous, mesoporous, and non‐porous ones, were synthesized and post‐grafted with NIC to serve as ligands for stabilizing CoNPs. Comprehensive characterization techniques were employed to fully analyze the prepared materials, which were then utilized in the catalytic hydrogenation of acetophenone, serving as a benchmark reaction to assess the impact of different silica supports on catalysis. The porosity and surface nature of the silica matrices played crucial roles in anchoring the amide ligand, and the presence of the ligand was essential for stabilizing the nanoparticles. Among the catalysts tested, CoNPs@SBA‐15/NIC exhibited the highest catalytic activity and demonstrated excellent performance in the hydrogenation of alkenes, nitriles, ketones, and quinoline under relatively mild conditions. No significant alteration in catalyst morphology or leaching of metal was observed after the reaction. Notably, this catalytic system achieved turnover numbers comparable to those of homogeneous cobalt catalysts. Additionally, one‐pot tandem reductive amination reactions starting from aldehydes and involving both amines and nitrobenzene yielded secondary and tertiary amines in good yields, highlighting the robustness and versatility of the catalyst.
Effect of Varying Temperatures on the Electrochemical Performance of Lithium‐Ion Batteries Using LiNi0.3Mn0.3Co0.3Ti0.1O2 Cathode Materials
Authors: Elong Kelimah , Kasim Muhd Firdaus , Badar Nurhanna , Azahidi Azira , Osman Zurina 
Published: June 2024

AbstractLiNi1/3Mn1/3Co1/3O2 (NMC 111) materials show promise as cathodes for lithium‐ion batteries (LIBs). However, their widespread use is hampered by various technical challenges, including rapid capacity fading and voltage instability. The cathode materials synthesized using the combustion method were annealed at various temperatures ranging from 650 to 900 °C for 24 h. In this study, we identified an optimal annealing temperature of 750 °C for LiNi0.3Mn0.3Co0.3Ti0.1O2 (NMCT) materials. NMCT‐750 exhibits an initial discharge capacity of about 140.1 mAh g−1 and retains the capacity of 91 % after 30th cycles. The good performance of NMCT‐750 is directly attributed to reduced cation mixing and the establishment of a stable structure with small particle sizes. In contrast, higher annealing temperatures (850 °C) lead to a rapid increase in primary particle size and result in poor cycling stability. Therefore, NMCT‐750, annealed at 750 °C, holds great potential as a cathode material for the next generation of LIBs.
Under the Influence of Water: Molecular Recognition of Organic Hydrophilic Molecules in Water with a Prismarene Host Driven by Hydration Effects
Authors: Del Regno Rocco , Della Sala Paolo , Santonoceta Giuseppina D. G. , Neri Placido , De Rosa Margherita , Talotta Carmen , Sgarlata Carmelo , De Simone Alfonso , Gaeta Carmine 
Published: June 2024

AbstractA water‐soluble prism[5]arene host can form endo‐cavity complexes with hydrophilic organic substances in water by displacing frustrated water molecules from its deep cavity. Water molecules structured at both rims of the prismarene host can mediate hydrogen bonding interactions with the guest. Water‐mediated hydrogen bonding interactions were invoked here to elucidate the elevated binding affinities and selectivity of the prismarene host toward hydrophilic organic guests. We show that water at the interface of a host‐guest complex can act as an extension of the host structure, facilitating the accommodation of neutral guests within the binding site. This study highlights the crucial role of water in facilitating supramolecular interactions between a deep‐cavity prismarene host and organic hydrophilic guests in aqueous medium.
Effect of External Electric Field on Nitrogen Activation on a Trimetal Cluster
Authors: Zhang Song‐Yang , Ding Xun‐Lei , Qu Sheng‐Ze 
Published: June 2024

AbstractEfficient nitrogen (N2) fixation and activation under mild conditions are crucial for modern society. External electric fields (Felectric) can significantly affect N2 activation. In this work, the effect of Felectric on N2 activation by Nb3 clusters supported in a sumanene bowl was studied by density functional theory calculations. Four typical systems at different stages of N−N activation were studied, including two intermediates and two transition states. The impact of Felectric on various properties related to N2 activation was investigated, including the N−N bond length, overlap population density of states (OPDOS), total energy of the system, adsorption energy of N2, decomposition of energy changes, and electron transfer. The sumanene not only functions as a support and protective substrate, but also serves as a donor or acceptor under different Felectric conditions. Negative Felectric is beneficial to N−N bond activation because it promotes electron transfer to the N−N region and improves the d–π* orbital hybridization between metals and N2 in the activation process. Positive Felectric improves d–π* orbital hybridization only when the N−N is nearly dissociated. The microscopic mechanism of Felectric′s effects provides insight into N2 activation and theoretical guidance for the design of catalytic reaction conditions for nitrogen reduction reactions (NRR).
Validation of the Italian Version of the Telepresence in Videoconference Scale (TVS) in a Sample of Psychologists and Psychotherapists During the COVID‐19 Pandemic
Authors: Cipolletta Sabrina , Tomaino Silvia Caterina Maria , Bouchard Stéphane , Berthiaume Maxine , Manzoni Gian Mauro 
Published: June 2024

ABSTRACTObjectiveTelepresence may play a fundamental role in establishing authentic interactions and relationships in online psychological interventions and can be measured by the Telepresence in Videoconference Scale (TVS), which was validated only with patients to date. This post hoc study aimed to validate the Italian version of the TVS with mental health professionals.MethodThe Italian TVS was included in an online survey, whose primary aim was to assess the experiences of Italian psychologists and psychotherapists with online interventions during the first wave of the COVID‐19 pandemic and was filled in by 296 participants (83.4% females, mean age = 42 years old).ResultsExploratory factor analysis supported the original factor structure only partially because the scale ‘Absorption’ (i.e., the feeling of losing track of time), as it was formulated, did not measure telepresence. Correlations were also explored between the TVS scales and some survey items pertaining to intimacy and emotional closeness to patients, comfort and positive as well as negative experiences with online interventions.ConclusionThe TVS may be a useful tool to measure physical and social telepresence in online interventions, both in patients and in professionals.
Bionic Capsule Lithium‐Ion Battery Anodes for Efficiently Inhibiting Volume Expansion
Authors: Gao Zhenhai , Rao Shun , Wang Junjun , Wang Deping , Zhang Tianyao , Feng Xinbo , Liu Yuanhang , Shi Jiawei , Xue Yao , Li Weifeng , Wang Lili , Rong Changru , Chen Yupeng 
Published: June 2024

AbstractMagnetite (Fe3O4) has a large theoretical reversible capacity and rich Earth abundance, making it a promising anode material for LIBs. However, it suffers from drastic volume changes during the lithiation process, which lead to poor cycle stability and low‐rate performance. Hence, there is an urgent need for a solution to address the issue of volume expansion. Taking inspiration from how glycophyte cells mitigate excessive water uptake/loss through their cell wall to preserve the structural integrity of cells, we designed Fe3O4@PMMA multi‐core capsules by microemulsion polymerization as a kind of anode materials, also proposed a new evaluation method for real‐time repair effect of the battery capacity. The Fe3O4@PMMA anode shows a high reversible specific capacity (858.0 mAh g−1 at 0.1 C after 300 cycles) and an excellent cycle stability (450.99 mAh g−1 at 0.5 C after 450 cycles). Furthermore, the LiNi0.8Co0.1Mn0.1O2/Fe3O4@PMMA pouch cells exhibit a stable capacity (200.6 mAh) and high‐capacity retention rate (95.5 %) after 450 cycles at 0.5 C. Compared to the original battery, the capacity repair rate of this battery is as high as 93.4 %. This kind of bionic capsules provide an innovative solution for improving the electrochemical performance of Fe3O4 anodes to promote their industrial applications.
Dupilumab improves outcomes in patients with chronic rhinosinusitis with nasal polyps irrespective of gender: results from the SINUS‐52 trial
Authors: Fokkens Wytske J , Bachert Claus , Hopkins Claire , Marglani Osama , Praestgaard Amy , Nash Scott , Deniz Yamo , Rowe Paul J , Sacks Harry , Jacob‐Nara Juby A 
Published: June 2024

AbstractObjectivesThis post hoc analysis assessed disease characteristics and response to dupilumab treatment in male and female patients with severe chronic rhinosinusitis with nasal polyps (CRSwNP) (SINUS‐52 study; NCT02898454).MethodsPatients received dupilumab 300 mg or placebo every 2 weeks for 52 weeks on background intranasal corticosteroids. Efficacy was assessed through Week 52 using nasal polyp score (NPS), nasal congestion/obstruction score, loss of smell score and University of Pennsylvania Smell Identification Test score. Disease‐specific health‐related quality of life (HRQoL) was assessed using the 22‐item Sino‐Nasal Outcome Test (SNOT‐22).ResultsThe analysis included 192 male and 111 female patients. Female patients had higher mean SNOT‐22 total score (56.6 vs. 49.1, P < 0.01) and more coexisting asthma (78.4% vs. 46.4%, P < 0.0001) and non‐steroidal anti‐inflammatory drug‐exacerbated respiratory disease (NSAID‐ERD) (38.7% vs. 18.8%, P = 0.0001) than male patients, but other baseline characteristics were similar. Dupilumab significantly improved CRSwNP outcomes vs. placebo at Week 52, regardless of gender: least squares mean differences (95% confidence interval) for NPS were −2.33 (−2.80, −1.86) in male and −2.54 (−3.18, −1.90) in female patients (both P < 0.0001 vs. placebo), and for SNOT‐22 were −19.2 (−24.1, −14.2) in male and −24.4 (−31.5, −17.3) in female patients (both P < 0.0001 vs. placebo). There were no significant efficacy‐by‐gender interactions.ConclusionFemale patients had greater asthma, NSAID‐ERD and HRQoL burden at baseline than male patients. Dupilumab treatment significantly improved objective and subjective outcomes compared with placebo, irrespective of gender.
Chronostratigraphy and tectono‐sedimentary history of the Eastern South Pyrenean foreland basin (Ripoll Syncline, North‐East Spain)
Authors: Juvany Philémon , Garcés Miguel , Lopez‐Blanco Miguel , Martín Closas Carles , Beamud Amorós Elisabet , Tosquella Josep , Bekkevold Susanna Emilia 
Published: June 2024

AbstractThis paper contributes to an understanding of the tectono‐sedimentary evolution of the South Pyrenean foreland system by reviewing the chronostratigraphic framework of the basin infill in its eastern sector. Six sections are analysed and cross‐correlated to build a 6.5 km thick composite magnetostratigraphy that represents the complete record of the Cadí Nappe in the Ripoll Syncline. New and previous magnetostratigraphic sections are integrated with available biostratigraphy to provide a new age calibration of the sedimentary succession of the Cadí Nappe, encompassing from Palaeocene to Middle Lutetian age. The proposed correlation with the Geomagnetic Polarity Time Scale aims at best reconcile magnetostratigraphic data with the regional biochronology built on the marine Shallow Benthic Zonation (SBZ biozones), the continental mammalian biochronology (MP levels) and the newly collected charophyte data. A subsidence analysis was performed on the calibrated composite succession, resulting in two well‐defined intervals bounded by a hiatus. A Palaeocene to Early Eocene interval with low (11–21 cm/kyr) total subsidence rates, and an Early to Middle Eocene interval, characterised by high (70–75 cm/kyr) total subsidence rates. The detailed trends in both subsidence and sedimentation mark the development and evolution of the foreland depozones, from distal foreland depozones to foredeep and wedge‐top depozones, relative to the emplacement of the Pedraforca Nappe and Cadí Thrust Nappe. The most pronounced sedimentary shift in the Cadí Nappe occurred at 49 Ma, with the rapid drowning of the carbonate platforms and its transition into talus and deep basinal environments. Carbonate platforms collapsed and resedimented on the talus of the elongated trough, newly formed parallel to the orogenic front. This marked the onset of tectonic subsidence triggered by the submarine emplacement of the Lower Pedraforca Nappe. The emersion of the orogenic wedge drove the entry of siliciclastics, lagged by 1 Myr, into the Ripoll Trough. The foredeep filled rapidly (5.5 km thickness in less than 7 Myr) compared to other South Pyrenean regions, favoured by its semi‐enclosed palaeogeography. The emplacement of the Vallfogona Thrust as early as the Middle Lutetian (43 Ma) brought the Cadi Nappe into a wedge‐top setting. However, the Ripoll growth syncline continued acting as a temporary sink for alluvial sedimentation while a foredeep developed further south in the autochthonous Ebro Basin. The flexural response of the Iberian plate to the tectonic thickening of the Axial Zone counterbalanced for a period the local uplift of the Cadi Nappe, providing accommodation space for the top sediments filling the Ripoll Syncline.
Fasting pancreatic polypeptide predicts incident microvascular and macrovascular complications of type 2 diabetes: An observational study
Authors: Sam Amir H. , Buckley Adam J. , Lam Brian Y. H. , Bewick Gavin A. , Bech Paul R. , Meeran Karim , Barakat Maha T. , Bloom Stephen R. , Yeo Giles S. H. , Lessan Nader G. , Murphy Kevin G. 
Published: June 2024

AbstractAimsPancreatic polypeptide (PP) is elevated in people with vascular risk factors such as type 2 diabetes or increased visceral fat. We investigated potential relationships between PP and microvascular and macrovascular complications of diabetes.Materials and MethodsAnimal study: Subcutaneous PP infusion for 4 weeks in high fat diet mouse model. Retinal mRNA submitted for Ingenuity Pathway Analysis. Human study: fasting PP measured in 1478 participants and vascular complications recorded over median 5.5 (IQR 4.9–5.8) years follow‐up.ResultsAnimal study: The retinal transcriptional response to PP was indicative of cellular stress and damage, and this footprint matched responses described in previously published studies of retinal disease. Of mechanistic importance the transcriptional landscape was consistent with upregulation of folliculin, a recently identified susceptibility gene for diabetic retinopathy. Human study: Adjusting for established risk factors, PP was associated with prevalent and incident clinically significant retinopathy (odds ratio (OR) 1.289 (1.107–1.501) p = 0.001; hazard ratio (HR) 1.259 (1.035–1.531) p = 0.0213), albuminuria (OR 1.277 (1.124–1.454), p = 0.0002; HR 1.608 (1.208–2.141) p = 0.0011), and macrovascular disease (OR 1.021 (1.006–1.037) p = 0.0068; HR 1.324 (1.089–1.61), p = 0.0049), in individuals with type 2 diabetes, and progression to diabetes in non‐diabetic individuals (HR 1.402 (1.081–1.818), p = 0.0109).ConclusionsElevated fasting PP is independently associated with vascular complications of diabetes and affects retinal pathways potentially influencing retinal neuronal survival. Our results suggest possible new roles for PP‐fold peptides in the pathophysiology of diabetes complications and vascular risk stratification.
Enantioselective Synthesis of Axially Chiral Heterobiaryl N‐Cbz‐Protected Diamines via Organocatalytic Arylation of 5‐Aminoisoxazoles
Authors: Li Qian , Xu Yuan‐Yuan , Wang Tao , Wang You‐Qing 
Published: June 2024

AbstractAn enantioselective arylation of isoxazoles with N‐Cbz‐protected azonaphthalenes is disclosed, affording a range of axially chiral arylisoxazoles in good yields and excellent enantiocontrol by utilizing chiral phosphoric acid. Cbz protecting group can be readily removed, resulting in five‐six membered axially chiral heterobiaryl amines bearing free amine maintaining enantiomeric purity.
Prognostic value of preoperative mechanical hyperalgesia and neuropathic pain qualities for postoperative pain after total knee replacement
Authors: Vigotsky Andrew D. , Cong Olivia , Pinto Camila B. , Barroso Joana , Perez Jennifer , Petersen Kristian Kjaer , Arendt‐Nielsen Lars , Hardt Kevin D. , Manning David , Apkarian A. Vania , Branco Paulo 
Published: June 2024

AbstractBackgroundTotal knee replacement (TKR) is the gold standard treatment for end‐stage chronic osteoarthritis pain, yet many patients report chronic postoperative pain after TKR. The search for preoperative predictors for chronic postoperative pain following TKR has been studied with inconsistent findings.MethodsThis study investigates the predictive value of quantitative sensory testing (QST) and PainDETECT for postoperative pain 3, 6 and 12 months post‐TKR. We assessed preoperative and postoperative (3 and 6 months) QST measures in 77 patients with knee OA (KOA) and 41 healthy controls, along with neuropathic pain scores in patients (PainDETECT). QST parameters included pressure pain pressure threshold (PPT), pain tolerance threshold (PTT), conditioned pain modulation (CPM) and temporal summation (TS) using cuff algometry, alongside mechanical hyperalgesia and temporal summation to repeated pinprick stimulation.ResultsCompared to healthy controls, KOA patients at baseline demonstrated hyperalgesia to pinprick stimulation at the medial knee undergoing TKR, and cuff pressure at the calf. Lower cuff algometry PTT and mechanical pinprick hyperalgesia were associated with preoperative KOA pain intensity. Moreover, preoperative pinprick pain hyperalgesia explained 25% of variance in pain intensity 12 months post‐TKR and preoperative neuropathic pain scores also captured 30% and 20% of the variance in postoperative pain at 6 and 12 months respectively. A decrease in mechanical pinprick hyperalgesia from before surgery to 3 months after TKR was associated with lower postoperative pain at the 12 months post‐TKR follow‐up.ConclusionOur findings suggest that preoperative pinprick hyperalgesia and neuropathic‐like pain symptoms show predictive value for the development of chronic post‐TKR pain.Significance StatementThis study's findings hold significant implications for chronic pain management in knee osteoarthritis patients, particularly those undergoing total knee replacement surgery (TKR). Mechanical hyperalgesia and neuropathic pain‐like characteristics predict postoperative pain 1 year after TKR, emphasizing the importance of understanding pain phenotypes in OA for selecting appropriate pain management strategies. The normalization of hyperalgesia after surgery correlates with better long‐term outcomes, further highlighting the therapeutic potential of addressing abnormal pain processing mechanisms pre‐ and post‐TKR.
The effects of simulated monocular and binocular vision impairment on football penalty kick performance
Authors: Leivers Harrison K. , Allen Peter M. , Timmis Matthew A. , Zenk Franzi , Uppal Jaspreet , Runswick Oliver R. 
Published: June 2024

AbstractSports performance is relatively robust under high levels of binocular blur. However, the limited research studies investigating monocular impairments has shown it has a larger impact on sport performance. This research study is relevant for classification in sports for athletes with vision impairment (VI), where visual acuity (VA) from the better eye is used during classification. Across two experiments, we aimed to establish the point at which binocular and monocular impairments affected performance in a football penalty kick (PK) through simulating varying severities of degraded VA and contrast sensitivity (CS) in active football players. In experiment one, 25 footballers performed PKs as VA and CS were systematically decreased in both eyes, and in one condition, visual field (VF) was reduced. The most severe VA/CS condition and reduced VF significantly impacted outcome, ball velocity and placement (ball kicked closer to the centre of the goal) (p < 0.05). In experiment two, 29 different footballers performed PKs as VA and CS of only the dominant eye were systematically decreased and in one condition the dominant eye was occluded, and participants viewed their environment through the non‐dominant eye (monocular viewing). No differences were observed when assessing monocular impairments influence on outcome, velocity and ball placement. PKs have a high resilience to VI, but binocular impairment has a more immediate effect, suggesting binocular measures should be used in classification processes in football.
Using the reactive/transport dispersive models to simulate a monolithic anion exchanger: Experimental parameter determination, simultaneous model evaluation, and validation
Authors: Domínguez‐López Luis Gilberto , Mejía‐Manzano Luis Alberto , González‐Valdez José 
Published: June 2024

AbstractSelecting an adequate model to represent the mass transfer mechanisms occurring in a chromatographic process is generally complicated, which is one of the reasons why monolithic chromatography is scarcely simulated. In this study, the chromatographic separation of model proteins bovine serum albumin (BSA), β‐lactoglobulin‐A, and β‐lactoglobulin‐B on an anion exchange monolith was simulated based on experimental parameter determination, simultaneous model testing, and validation under three statistical criteria: retention time, dispersion accuracies, and Pearson correlation coefficient. Experimental characterization of morphologic, physicochemical, and kinetic parameters was performed through volume balances, pressure drop analysis, breakthrough curve analysis, and batch adsorptions. Free Gibbs energy indicated a spontaneous adsorption process for proteins and counterions. Dimensionless numbers were estimated based on height equivalent to a theoretical plate analysis, finding that pore diffusion controlled β‐lactoglobulin separation, whereas adsorption/desorption kinetics was the dominant mechanism for BSA. The elution profiles were modeled using the transport dispersive model and the reactive dispersive model coupled with steric mass action (SMA) isotherms because these models allowed to consider most of the mass transport mechanisms that have been described. RDM‐SMA presented the most accurate simulations at pH 6.0 and at low (250 mM) and high (400 mM) NaCl concentrations. This simulation will be used as reference to forecast the purification of these proteins from bovine whey waste and to extrapolate this methodology to other monolith‐based separations using these three statistical criteria that have not been used previously for this purpose.