bluuebunny/crossref_metadata_2025_split huggingface dataset:
Turning on Singlet Oxygen Generation by Outer‐Sphere Microenvironment Modulation in Porphyrinic Covalent Organic Frameworks for Photocatalytic Oxidation
Authors: Suleman Suleman , Zhang Yi , Qian Yunyang , Zhang Jinwei , Lin Zhongyuan , Metin Önder , Meng Zheng , Jiang Hai‐Long 
Published: November 2023

AbstractSinglet oxygen (1O2) is ubiquitously involved in various photocatalytic oxidation reactions; however, efficient and selective production of 1O2 is still challenging. Herein, we reported the synthesis of nickel porphyrin‐based covalent organic frameworks (COFs) incorporating functional groups with different electron‐donating/‐withdrawing features on their pore walls. These functional groups established a dedicated outer‐sphere microenvironment surrounding the Ni catalytic center that tunes the activity of the COFs for 1O2‐mediated thioether oxidation. With the increase of the electron‐donating ability of functional groups, the modulated outer‐sphere microenvironment turns on the catalytic activity from a yield of nearly zero by the cyano group functionalized COF to an excellent yield of 98 % by the methoxy group functionalized one. Electronic property investigation and density‐functional theory (DFT) calculations suggested that the distinct excitonic behaviors attributed to the diverse band energy levels and orbital compositions are responsible for the different activities. This study represents the first regulation of generating reactive oxygen species (ROS) based on the strategy of outer‐sphere microenvironment modulation in COFs.
A Versatile Comonomer Additive for Radically Recyclable Vinyl‐derived Polymers
Authors: Mineo Autumn M. , Katsumata Reika 
Published: November 2023

AbstractRadically‐formed, vinyl‐derived polymers account for over 30 % of polymer production. Connected through stable carbon‐carbon bonds, these materials are notoriously challenging to chemically recycle. Herein, we report universal copolymerization of a cyclic allyl sulfide (CAS) additive with multiple monomers under free‐radical conditions, to introduce main‐chain dynamic motifs. Backbone allyl sulfides undergo post‐polymerization radical rearrangement via addition‐fragmentation‐transfer (AFT) that fosters both chain scission and extension. Scission is selectively induced through allyl sulfide exchange with small molecule thiyl radicals, resulting in oligomers as low as 14 % of the initial molar mass. Crucially, oligomers retain allyl sulfide end groups, enabling their extension with monomer under radical conditions. Extended, i.e., recycled, product molar mass is tunable through the ratio of monomer to oligomer, and can surpass that of the initial copolymer. Two scission‐extension cycles are demonstrated in copolymers with methyl methacrylate and styrene without escalation in dispersity. In illustration of forming higher‐value products, i.e., upcycling, we synthesized block copolymers through the extension of oligomers with a different vinyl monomer. Collectively, our approach to chemical recycling is unparalleled in its ability to 1) function in a variety of vinyl‐derived polymers, 2) complete radical closed‐loop cycling, and 3) upcycle waste material.
Correlating Structural Disorder in Metal (Oxy)hydroxides and Catalytic Activity in Electrocatalytic Oxygen Evolution
Authors: Zuo Shouwei , Wu Zhi‐Peng , Zhang Guikai , Chen Cailing , Ren Yuanfu , Liu Qiao , Zheng Lirong , Zhang Jing , Han Yu , Zhang Huabin 
Published: December 2023

AbstractUnderstanding the correlation between the structural evolution of electrocatalysts and their catalytic activity is both essential and challenging. In this study, we investigate this correlation in the context of the oxygen evolution reaction (OER) by examining the influence of structural disorder during and after dynamic structural evolution on the OER activity of Fe−Ni (oxy)hydroxide catalysts using operando X‐ray absorption spectroscopy, alongside other experiments and theoretical calculations. The Debye–Waller factors obtained from extended X‐ray absorption fine structure analyses reflect the degree of structural disorder and exhibit a robust correlation with the intrinsic OER activities of the electrocatalysts. The enhanced OER activity of in situ‐generated metal (oxy)hydroxides derived from different pre‐catalysts is linked to increased structural disorder, offering a promising approach for designing efficient OER electrocatalysts. This strategy may inspire similar investigations in related electrocatalytic energy‐conversion systems.
Enantioselective Synthesis of Axially Chiral Diaryl Ethers via NHC Catalyzed Desymmetrization and Following Resolution
Authors: Zhou Bang‐An , Li Xue‐Ning , Zhang Chun‐Lin , Wang Zhi‐Xiang , Ye Song 
Published: November 2023

AbstractAxially chiral diaryl ethers are present in numerous natural products and bioactive molecules. However, only few catalytic enantioselective approaches have been established to access diaryl ether atropisomers. Herein, we report the N‐heterocyclic carbene‐catalyzed enantioselective synthesis of axially chiral diaryl ethers via desymmetrization of prochiral 2‐aryloxyisophthalaldehydes with aliphatic alcohols, phenol derivatives, and heteroaromatic amines. This reaction features mild reaction conditions, good functional group tolerance, broad substrate scope and excellent enantioselectivity. The utility of this methodology is illustrated by late‐stage functionalization, gram‐scale synthesis, and diverse enantioretentive transformations. Control experiments and DFT calculations support the association of NHC‐catalyzed desymmetrization with following kinetic resolution to enhance the enantioselectivity.
Synthesis and properties of a novel ionic liquid copolymer shale inhibitor
Authors: Bai Xiaodong , Chen Yu , Wu Lianci , Wang Moubo , Luo Yumei 
Published: November 2023

AbstractAs oil reserves in shallow wells continue to deplete, the drilling industry must shift its focus toward extracting oil from deeper and more complex formations. Water‐based drilling fluid inhibitors are currently limited in their ability to withstand high temperatures. In the current work, for the first time, the application of 1‐vinyl‐3‐ethylimidazolium bromide salt‐allyl alcohol polyoxyethylene ether‐2‐acrylamide‐2‐methylpropanesulfonic acid (PIAA) as the shale inhibitor is reported. The incorporation of ionic liquids has made PIAA promising to be an effective shale inhibitor for high‐temperature‐tolerant water‐based drilling fluids. The high‐temperature resistance (300°C) of PIAA was verified through thermogravimetric test. Through mud ball, shale rolling recovery, and linear swelling experiments, we found that PIAA yielded the lowest swelling rate (27.3%) in the 24‐h linear swelling rate test, as compared to HMA‐15 (46.1%) and FA‐367 (31.2%). This confirmed the superior corrosion inhibition performance of PIAA. In addition, we investigated the inhibition mechanism using Zeta potential and other tests. Bentonite inhibition can be achieved through the coating of bentonite particles by PIAA, which effectively plugs shale pores, neutralizes negative charges on the surface of bentonite particles, and adsorbs them onto particle surfaces. Overall, PIAA has excellent high‐temperature resistance and inhibition properties.
Regional outcome disparities in German head and neck cancer patients: Shorter survival in Eastern Germany
Authors: Vahl Julius M. , Nagel Gabriele , Abou Kors Tsima , Brand Matthias , von Witzleben Adrian , Sonntag Michael , Grages Ayla , Theodoraki Marie N. , Greve Jens , Denkinger Michael , Dallmeier Dhayana , Idel Christian , Stilgenbauer Stephan , Hoffmann Thomas K. , Laban Simon 
Published: December 2023

AbstractIntroductionDemographics are important prognostic factors in malignant diseases. A nationwide analysis concerning the prognostic impact of demographics in head and neck cancer (HNC) patients (HNCP) has not been performed previously.MethodsA retrospective analysis of data from the Center for Cancer Registry Data (ZfKD) and the Federal Statistical Office (Destatis) between 2002 and 2017 was performed. A total of 212′920 HNCP were included. Incidence, tumor stage, age development, sex distribution, age‐, residence‐, and diagnosis‐time‐specific survival were examined.ResultsMean age of HNCP increased more rapidly than in the general population (slope coefficient: 0.29 vs. 0.20; p < 0.0001). Higher age and male sex were associated with a worse prognosis. Whereas overall survival (OS) increased from the early to the later observation period for HNCP <70 years, no OS improvement for HNCP >70 years was found. Furthermore, an OS disadvantage was observed for East Germany compared to West Germany (median 47 vs. 60 months; p < 0.0001). This disparity was associated with a disproportionately high ratio of men in East Germany (men/women: 4.4 vs. 3.1; p < 0.0001) and a lower mean age (61 vs. 63 years; p < 0.0001). In addition to stage, age and sex, residence in East Germany were confirmed as an independent factor for OS in a multivariate analysis.ConclusionFinally, three decades after the German reunion, a survival disadvantage for patients in East Germany still exists. This discrepancy may be a result of socioeconomic disparities.
Stakeholder involvement in a Cochrane review of physical rehabilitation after stroke: Description and reflections
Authors: Brown Julie , Baer Gill , Cameron Sheila , Jackson Karl , Lamouline Carrol , Morley Richard , Ormsby Diane , Synnot Anneliese , Todhunter‐Brown Alex 
Published: December 2023

AbstractIntroductionIt is good practice to involve stakeholders in systematic reviews, but it is not clear how best to involve them.AimTo describe and reflect on the stakeholder involvement within an update of a Cochrane review of physical rehabilitation after stroke.MethodsA stakeholder group, comprising 15 stroke survivors, carers, and physiotherapists from across the United Kingdom, were recruited and contributed throughout the process of the review. A framework was used to describe when and how stakeholders were involved. Stakeholders provided feedback on their involvement after meetings. An amended version of a validated patient engagement tool was used to collect reflections on the stakeholder involvement process.ResultsFive stakeholder meetings were held throughout the review process, supplemented by additional communication. Several changes were made to the review structure, analyses, and wording as a direct result of the stakeholder involvement. Stakeholders and researchers agreed that stakeholders' contributions were taken seriously and influenced the review. Stakeholders felt that they were given the chance to share their views and that information was shared well before, during, and after each meeting to help them to contribute knowledgeably in the process. Stakeholder reflections highlighted a number of key lessons relating to stakeholder involvement, including process of reflection and feedback, use of remote/virtual meetings, need for adequate time and funding, tensions experienced by clinicians, and recruitment considerations.ConclusionsWe describe and reflect on stakeholder involvement in a systematic review and explores practical ways to support meaningful engagement during systematic review production. Our experience supports the view that coproducing reviews with stakeholders can make systematic reviews more relevant and meaningful. Our approach and experiences can be used to inform future review coproduction, supporting development of useful reviews that will improve clinical practice.
Optimization study of obstacles in T–T mixing channel at low Reynolds numbers
Authors: Rampalli Shasidhar , Raju V. R. K. 
Published: November 2023

AbstractIn this study, numerical simulations were conducted to optimize obstacle geometry for improving mixing in T–T mixers at low Reynolds numbers (2 < Re < 100). The study considered obstacles of cylindrical and prismatic shapes and optimized their pitch and geometrical parameters for enhanced mixing. For cylindrical obstacles, the optimized configuration resulted in symmetrical recirculation zones at Re > 30, which led to larger mixing qualities of 80% and 85% for Re values above 30 and 50, respectively. However, the pressure drop increased in the optimized T–T mixer due to the larger size of the obstacles. On the other hand, in the case of prismatic obstacles, the mixing qualities of 80% and 85% were achieved only at relatively higher Re values of 70 and 90, respectively. The recirculation zone formed behind the obstacle was asymmetric due to the asymmetrical shape of the optimized prism. At higher Re, the optimized cylindrical obstacle configuration resulted in better mixing than the prismatic configuration. However, the choking effect in the former increased the pressure drop.
Should patients with hormone receptor–positive, HER2–negative breast cancer and one or two positive sentinel nodes undergo axillary dissection to determine candidacy for adjuvant abemaciclib?
Authors: Williams Austin D. , Ruth Karen , Shaikh Saba S. , Vasigh Mahtab , Pronovost Mary T. , Aggon Allison A. , Porpiglia Andrea S. , Bleicher Richard J. 
Published: November 2023

AbstractBackgroundThe monarchE trial demonstrated improved outcomes with the use of adjuvant abemaciclib in patients with high‐risk hormone receptor–positive, HER2–negative (HR+/HER2–) breast cancer defined as ≥4 positive lymph nodes (+LNs) or one to three +LNs with one or more additional high‐risk features (HRFs). The proportion of patients with one or two positive sentinel lymph nodes (+SLNs) without HRFs who had ≥4 +LNs at the time of completion axillary lymph node dissection (cALND), and who therefore qualified for receipt of abemaciclib, was investigated.MethodsFemales with pathologically node‐positive nonmetastatic HR+/HER2– breast cancer stratified by the number of +SLNs and +LNs and the presence of one or more HRFs were identified from the National Cancer Database (2018–2019). The proportion of patients meeting the criteria for abemaciclib both before and after ALND was assessed.ResultsOf the 22,048 patients identified, 1578 patients underwent upfront surgery, had one or two +SLNs without HRFs, and went on to cALND. Only 213 (13%) of these patients had ≥4 +LNs; thus, cALND performed solely to determine abemaciclib candidacy would have constituted surgical overtreatment in 1365 patients (87%). When stratified by the number of +SLNs, only 10% of those with one +SLN and 24% of those with two +SLNs had ≥4 +LNs after cALND, which meets the criteria for abemaciclib.ConclusionsPatients with one +SLN without HRFs are unlikely to have ≥4 +LNs and should not be subjected to the morbidity of ALND in order to inform candidacy for abemaciclib. An individualized multidisciplinary discussion should be undertaken about the risk:benefit ratio of ALND and abemaciclib for those with two +SLNs.
Cerebral hypometabolism mediates the effect of stroke volume on cognitive impairment in heart failure patients
Authors: Zheng Chong , Cui Yadong , Gu Shanshan , Yan Shaozhen , Cui Bixiao , Song Tianbin , Li Jing , Si Jin , Xiao Keling , Ge Qi , Yang Yang , Zhou Yun , Li Jing , Li Xiang , Lu Jie 
Published: December 2023

AbstractAimsThe present study aimed to phenotype the cerebral structural and glucose metabolic alterations in patients with heart failure (HF) using simultaneous positron emission tomography (PET)/magnetic resonance (MR) and to investigate their relationship to cardiac biomarkers and cognitive performance.Methods and resultsForty‐two HF patients caused by ischaemic heart disease (mean age 67.2 ± 10.4, 32 males) and 32 age‐ and sex‐matched healthy volunteers (mean age 61.3 ± 4.8, 18 males) were included in this study. Participants underwent simultaneous cerebral fluorine‐18 (18F) fluorodeoxyglucose PET/MR followed by cardiac MR scan, and neuropsychological scores were obtained to assess cognitive performance. The grey matter volume (GMV) and standardized uptake value ratio (SUVR) were calculated to examine cerebral structural and metabolic alterations. Cardiac biomarkers included cardiac MR parameters and cardiac serum laboratory tests. Mediation analysis was performed to explore the associations among cerebral alterations, cardiac biomarkers, and cognitive performance. HF patients demonstrated notable cognitive impairment compared with normal controls (P < 0.001). Furthermore, HF patients exhibited regional brain hypometabolism in the bilateral calcarine cortex, caudate nucleus, thalamus, hippocampus, precuneus, posterior cingulate cortex, lingual and olfactory cortex, and GMV reduction in bilateral thalamus and hippocampus (cluster level at P < 0.05, Gaussian random field correction). The SUVR of the hypometabolic brain regions was correlated with the Montreal Cognitive Assessment (MoCA) scores (r = 0.55, P = 0.038) and cardiac stroke volume (r = 0.49, P = 0.002). Cerebral hypometabolism played a key role in the relationship between the decreased stroke volume and MoCA scores, with a mediation effect of 33.2%.ConclusionsHF patients suffered cerebral metabolic and structural alterations in regions associated with cognition. The observed correlation between cardiac stroke volume and cognitive impairment underscored the potential influence of cerebral hypometabolism, suggesting that cerebral hypometabolism due to chronic systemic hypoperfusion may significantly contribute to cognitive impairment in HF patients.
PERPRISE: A prospective non‐interventional study of PERampanel as only adjunctive treatment in patients with PRImary or SEcondarily generalized tonic–clonic seizures: First interim analysis
Authors: Steinhoff Bernhard J , Goldmann Tobias , Kockelmann Edgar , Winter Yaroslav ,   for the PERPRISE Study Group
Published: November 2023

AbstractObjectiveTo report the interim results of the PERPRISE study (Study 509; NCT04202159), which is evaluating perampanel as the only adjunctive anti‐seizure medication (ASM) in adults with focal to bilateral tonic–clonic seizures (FBTCS) or primary generalized tonic–clonic seizures (GTCS).MethodsPERPRISE is an ongoing 12‐month multicenter, prospective, observational, non‐interventional study of perampanel in a real‐world setting in Germany. Patients are aged ≥18 years with FBTCS or GTCS due to focal or idiopathic generalized epilepsy. Perampanel, as an adjunctive therapy to ASM monotherapy (‘add‐on therapy’) or as a substitute for one ASM in dual therapy (‘substitution therapy’), is prescribed in line with its SmPC. The Interim Analysis Set comprises the first 100 patients who received ≥1 dose of perampanel and attended or discontinued prior to the ~6‐month visit. Interim endpoints include retention rate, measures of effects on seizure frequency, and treatment‐emergent adverse events (TEAEs).ResultsOne hundred patients were included in the Interim Analysis Set (add‐on, n = 43 [43.0%]; substitution, n = 55 [55.0%]; unknown, n = 2). The 6‐month retention rate was 78.0% (add‐on, 83.7%; substitution, 72.7%). For the overall population with GTCS and/or FBTCS, seizure‐freedom rate at 6 months was 58.8% (add‐on, 72.2%; substitution, 47.9%) and 50% responder rate at 6 months was 82.6% (add‐on, 89.2%; substitution, 76.6%). Retention rates and seizure outcomes were better with perampanel as an early‐line treatment than as a late‐line treatment. TEAEs were reported by 48 patients (48.0%), most commonly dizziness (n = 9), fatigue (n = 7), and irritability (n = 7). Sixteen patients (16.0%) withdrew from perampanel treatment due to TEAEs.SignificanceThe interim analysis of PERPRISE offers insight into the real‐world use of perampanel in Germany, including for the first time, clinical practice data from patients with GTCS and switching ASMs within a dual therapy. Further data from PERPRISE will be of value to inform clinical decision‐making in this patient cohort.Plain Language SummaryPatients with epilepsy often take more than one medication for seizure control. This 12month study looked at patients in Germany receiving perampanel as only add‐on medication. The interim analysis shows, that at 6 months, over 70% of the 100 patients continued to use perampanel; 59% experienced no seizures during treatment with perampanel, and in 83%, seizure frequency was reduced by half. Side effects occurred in 48% of patients (most commonly dizziness, fatigue, and irritability) and caused 16% to withdraw from the study. Overall, perampanel was a suitable as only add‐on medication for patients with epilepsy.
Identification of metabolic biomarkers of chronic vagus nerve stimulation (VNS) in subjects with drug‐resistant epilepsy (DRE)
Authors: Manca Claudia , Coa Roberta , Murru Elisabetta , Carta Gianfranca , Pinna Giovanni , Sanfilippo Roberto , Polizzi Lorenzo , Pistis Marco , Follesa Paolo , Puligheddu Monica , Banni Sebastiano 
Published: November 2023

AbstractNeuromodulation by means of vagus nerve stimulation (VNS) therapy, reduces seizure frequency and improves quality of life in subjects with drug‐resistant epilepsy (DRE), yet its molecular mechanism remains unclear. This study investigates the impact of chronic VNS on lipid bioactive metabolites and fatty acids (FA) in the plasma and red blood cells of seven subjects with DRE. By measuring expression levels of peroxisome proliferator‐activated receptor α (PPARα) and sirtuin1 (SIRT1) genes—key regulators in energy and lipid metabolism—and lipid profiles before and after various stages of VNS, this study identifies potential mechanisms by which VNS may reduce seizure frequency. Blood samples collected before VNS device implantation, after acute VNS stimulus, and following gradual intensity increments up to therapeutic levels revealed that VNS increases SIRT1 and PPARα expression and erythrocyte concentrations of PPARα ligands. Additionally, we observe reduced de novo lipogenesis biomarkers in erythrocytes, indicating that VNS may influence systemic lipid and energy metabolism. Our findings suggest that VNS could enhance neuronal function by modulating energy metabolism, thus potentially reducing seizure frequency in subjects with DRE. Future research targeting SIRT1 and PPARα may provide innovative therapeutic strategies for managing DRE.Plain Language Summary: The exact mechanism of VNS is still unknown. This study investigated the effects of VNS Therapy on energetic metabolism, suggesting possible novel biomarkers for DRE subjects and neuromodulation therapies.
A new application of hydrocolloids from Echinops setifer (Shekartighal): Mayonnaise‐type sauces
Authors: Nemati Narges , Hesarinejad Mohammad Ali 
Published: December 2023

AbstractDue to the importance of the production of functional and nutraceutical foods with high added value, Shekartighal was used to develop ready‐made functional mayonnaise‐type sauces and evaluate their physicochemical, sensory, and antioxidant properties over 60 days of storage. Shekartighal had, on average, 76.85% carbohydrate, 9.24% protein, 4.91% fat, 1.74% ash, 7.26% moisture, 20.38 mgGAE/g total phenol content, 14.31 μM ferrous sulphate/g, and 145.12 μg/mL antioxidant activity. The results indicated that Shekartighal had high water absorption capacity (408.01%) and emulsion stability (91.83%). Following the textural and sensorial study, the product that stood out as the best performer was the sauce containing 3% Shekartighal. Consequently, this product was selected for further evaluation, where its physicochemical and antioxidant properties were assessed for a 60‐day duration under refrigerated storage (4°C). The formulation with 3% Shekartighal presented significantly more phenolic content and antioxidant properties than the control. During the 60‐day refrigerated storage (4°C) period, the physicochemical and antioxidant parameters of the enriched sauce remained stable. The addition of Shekartighal to the sauce significantly improved its nutritional quality, and the sauce enriched with 3% Shekartighal demonstrated the most favorable characteristics among the different concentrations tested. Overall, these findings suggest that Shekartighal could be utilized as a natural ingredient to create a functional sauce with notable antioxidant and nutritional properties.