bluuebunny/crossref_metadata_2025 huggingface dataset:
The differential item functioning and structural equivalence of a nonverbal cognitive ability test for five language groups
Authors: Schaap Pieter
Published: October 2011

Orientation: For a number of years, eliminating a language component in testing by using nonverbal cognitive tests has been proposed as a possible solution to the effect of groups’ languages (mother tongues or first languages) on test performance. This is particularly relevant in South Africa with its 11 official languages.Research purpose: The aim of the study was to determine the differential item functioning (DIF) and structural equivalence of a nonverbal cognitive ability test (the PiB/SpEEx Observance test [401]) for five South African language groups.Motivation for study: Cultural and language group sensitive tests can lead to unfair discrimination and is a contentious workplace issue in South Africa today. Misconceptions about psychometric testing in industry can cause tests to lose credibility if industries do not use a scientifically sound test-by-test evaluation approach.Research design, approach and method: The researcher used a quasi-experimental design and factor analytic and logistic regression techniques to meet the research aims. The study used a convenience sample drawn from industry and an educational institution.Main findings: The main findings of the study show structural equivalence of the test at a holistic level and nonsignificant DIF effect sizes for most of the comparisons that the researcher made.Practical/managerial implications: This research shows that the PIB/SpEEx Observance Test (401) is not completely language insensitive. One should see it rather as a language-reduced test when people from different language groups need testing.Contribution/value-add: The findings provide supporting evidence that nonverbal cognitive tests are plausible alternatives to verbal tests when one compares people from different language groups.
Natural History of Nonmetastatic Prostate Cancer Managed With Watchful Waiting
Authors: Ventimiglia Eugenio , Gedeborg Rolf , Styrke Johan , Robinson David , Stattin Pär , Garmo Hans
Published: June 2024

Importance

It is uncertain to what extent watchful waiting (WW) in men with nonmetastatic prostate cancer (PCa) and a life expectancy of less than 10 years is associated with adverse consequences.

Objective

To report transitions to androgen deprivation therapy (ADT), castration-resistant prostate cancer (CRPC), death from PCa, or death from other causes in men treated with a WW strategy.

Design, Setting, and Participants

This nationwide, population-based cohort study included men with nonmetastatic PCa diagnosed since 2007 and registered in the National Prostate Cancer Register of Sweden with WW as the primary treatment strategy and with life expectancy less than 10 years. Life expectancy was calculated based on age, the Charlson Comorbidity Index (CCI), and a drug comorbidity index. Observed state transition models complemented observed data to extend follow-up to more than 20 years. Analyses were performed between 2022 and 2023.

Exposure

Nonmetastatic PCa.

Main Outcomes and Measures

Transitions to ADT, CRPC, death from PCa, and death from other causes were measured using state transition modeling.

Results

The sample included 5234 men (median [IQR] age at diagnosis, 81 [79-84] years). After 5 years, 954 men with low-risk PCa (66.2%) and 740 with high-risk PCa (36.1%) were still alive and not receiving ADT. At 10 years, the corresponding proportions were 25.5% (n = 367) and 10.4% (n = 213), respectively. After 10 years, 59 men with low-risk PCa (4.1%) and 221 with high-risk PCa (10.8%) had transitioned to CRPC. Ten years after diagnosis, 1330 deaths in the low-risk group (92.3%) and 1724 in the high-risk group (84.1%) were from causes other than PCa.

Conclusions and Relevance

These findings suggest that the WW management strategy is appropriate for minimizing adverse consequences of PCa in men with a baseline life expectancy of less than 10 years.
Baseline systolic blood pressure, hypertension history, and efficacy of remote ischemic conditioning
Authors: Cai Ji‐Ru , Zhang Nan‐Nan , Cui Yu , Ning Yue‐Xin , Wu Qiong , Zhang Yi‐Na , Chen Hui‐Sheng
Published: June 2024

Objective

We performed a post hoc exploratory analysis of Remote Ischemic Conditioning for Acute Moderate Ischemic Stroke (RICAMIS) to determine whether hypertension history and baseline systolic blood pressure (SBP) affect the efficacy of remote ischemic conditioning (RIC).

Methods

Based on the full analysis set of RICAMIS, patients were divided into hypertension versus non‐hypertension group, or <140 mmHg versus ≥140 mmHg group. Each group was further subdivided into RIC and control subgroups. The primary outcome was modified Rankin Scale (mRS) 0–1 at 90 days. Efficacy of RIC was compared among patients with hypertension versus nonhypertension history and SBP of <140 mmHg versus ≥140 mmHg. Furthermore, the interaction effect of treatment with hypertension and SBP was assessed.

Results

Compared with control group, RIC produced a significantly higher proportion of patients with excellent functional outcome in the nonhypertension group (RIC vs. control: 65.7% vs. 57.0%, OR 1.45, 95% CI 1.06–1.98; p = 0.02), but no significant difference was observed in the hypertension group (RIC vs. control: 69.1% vs. 65.2%, p = 0.17). Similar results were observed in SBP ≥140 mmHg group (RIC vs. control: 68.0% vs. 61.2%, p = 0.009) and SBP <140 mmHg group (RIC vs. control: 65.6% vs. 64.7%, p = 0.77). No interaction effect of RIC on primary outcome was identified.

Interpretation

Hypertension and baseline SBP did not affect the neuroprotective effect of RIC, but they were associated with higher probability of excellent functional outcome in patients with acute moderate ischemic stroke who received RIC treatment.
Adherence and Treat‐to‐Target Benchmarks in Older Adults With Gout Initiating Urate‐Lowering Therapy in Ontario, Canada: A Population‐Based Study
Authors: Kwok Timothy S. H. , Kuriya Bindee , Hawker Gillian , Eder Lihi , Li Ping , Choy Gregory , Widdifield Jessica
Published: June 2024

Objective

We sought to evaluate urate‐lowering therapy (ULT) adherence and treatment‐to‐target (T2T) serum uric acid (SUA) levels among older adults with gout starting ULT.

Methods

We performed a population‐based retrospective cohort study in Ontario, Canada in patients with gout aged ≥66 years newly dispensed ULT between 2010 and 2019. We defined successful T2T as patients having SUA levels <360 μmol/L (6 mg/dL) within 12 months after ULT dispensation. We also assessed adherence to ULT. Multilevel logistic regression clustered by ULT prescriber evaluated patient, physician, and prescription factors associated with reaching target SUA levels.

Results

Among 44,438 patients (mean ± SD age 76.0 ± 7.3 years; 64.4% male), 30,057 (67.6%) patients had ≥1 SUA test completed. Overall, 52.3% patients reached SUA target within 12 months, improving from 45.2% in 2010 to 61.2% in 2019 (P < 0.0001). ULT adherence was 55.3% overall and improved annually. Key factors associated with achieving T2T included febuxostat treatment (odds ratio [OR] 11.40, 95% confidence interval [95% CI] 5.10–25.43) (was only dispensed in 88 patients), ULT adherence (OR 5.17, 95% CI 4.89–5.47), allopurinol starting doses >50 mg (OR 2.53, 95% CI 2.14–2.99), colchicine/oral glucocorticoids co‐prescription (OR 1.24, 95% CI 1.14–1.34), and ULT prescription from a rheumatologist.

Conclusion

Only 52.3% of patients achieved an optimal SUA level within 1 year of ULT initiation. ULT adherence was suboptimal, although improving over time. ULT adherence and higher allopurinol starting doses had the strongest associations of achieving a target SUA level. This study highlights room for improvement in gout management and potential strategies to address care gaps.
Xenohormetic Phytochemicals Inhibit Neovascularization in Microphysiological Models of Vasculogenesis and Tumor Angiogenesis
Authors: Kpeli G. Wills , Conrad K. Michael , Bralower William , Byrne C. Ethan , Boue Stephen M. , Burow Matthew E. , Mondrinos Mark J.
Published: June 2024

Xenohormesis proposes that phytochemicals produced to combat stressors in the host plant exert biochemical effects in animal cells lacking cognate receptors. Xenohormetic phytochemicals such as flavonoids and phytoalexins modulate a range of human cell signaling mechanisms but functional correlations with human pathophysiology are lacking. Here, potent inhibitory effects of grapefruit‐derived Naringenin (Nar) and soybean‐derived Glyceollins (Gly) in human microphysiological models of bulk tissue vasculogenesis and tumor angiogenesis are reported. Despite this interference of vascular morphogenesis, Nar and Gly are not cytotoxic to endothelial cells and do not prevent cell cycle entry. The anti‐vasculogenic effects of Glyceollin are significantly more potent in sex‐matched female (XX) models. Nar and Gly do not decrease viability or expression of proangiogenic genes in triple negative breast cancer (TNBC) cell spheroids, suggesting that inhibition of sprouting angiogenesis by Nar and Gly in a MPS model of the (TNBC) microenvironment are mediated via direct effects in endothelial cells. The study supports further research of Naringenin and Glyceollin as health‐promoting agents with special attention to mechanisms of action in vascular endothelial cells and the role of biological sex, which can improve the understanding of dietary nutrition and the pharmacology of phytochemical preparations.
Unveiling the Links Between Microbial Alteration and Host Gene Disarray in Crohn's Disease via TAHMC
Authors: Chang Huijun , Liu Yongshuai , Wang Yue , Li Lixiang , Mu Yijun , Zheng Mengqi , Liu Junfei , Zhang Jinghui , Bai Runze , Li Yanqing , Zuo Xiuli
Published: June 2024

A compelling correlation method linking microbial communities and host gene expression in tissues is currently absent. A novel pipeline is proposed, dubbed Transcriptome Analysis of Host‐Microbiome Crosstalk (TAHMC), designed to concurrently restore both host gene expression and microbial quantification from bulk RNA‐seq data. Employing this approach, it discerned associations between the tissue microbiome and host immunity in the context of Crohn's disease (CD). Further, machine learning is utilized to separately construct networks of associations among host mRNA, long non‐coding RNA, and tissue microbes. Unique host genes and tissue microbes are extracted from these networks for potential utility in CD diagnosis. Experimental validation of the predicted host gene regulation by microbes from the association network is achieved through the co‐culturing of Faecalibacterium prausnitzii with Caco‐2 cells. Collectively, the TAHMC pipeline accurately recovers both host gene expression and microbial quantification from CD RNA‐seq data, thereby illuminating potential causal links between shifts in microbial composition as well as diversity within CD mucosal tissues and aberrant host gene expression.
Solar‐Driven Lithium Extraction by a Floating Felt
Authors: Chen Xin , Yu Wenhua , Zhang Yue , Huang Chen , Nie Lu , Yu Jiameng , Zhang Yuyao , Zhang Chang , Zhai Wenbo , Zhang Xinshui , Yu Yi , Liu Wei
Published: June 2024

Oceans/brine offers a massive supply of lithium sources that can support the renewable energy storage system. However, the current lithium extraction processes from seawater are complicated for scalable production. Here, a high‐performance solar‐driven, direct lithium‐extraction felt (DEF) is developed. DEF consists of a reasonable addition of Li1.6Mn1.6O4 particles on polypropylene/polyethylene core‐sheath fibers, which are dark‐colored and can float on top of bodies of water. Compared with the conventional method, DEF shows improved Li‐ion adsorption rate and capacity by solar‐driven. Meanwhile, the fibers’ hydrophilicity promotes spontaneous upward transport of water/ions, avoiding concentration polarization. Even for the test using simulated seawater (≈100 kg) with low Li‐ion concentration outdoors, DEF demonstrates high efficiency under natural sunlight. DEF shows good salt‐rejection performance in outdoor real‐time evaporation experiments to ensure working stability. In addition, this method saves the steps of liquid storage, liquid transportation, and pump drive. This work provides an easy, highly efficient, and low‐cost strategy to extract lithium directly from seawater/brine with the assistance of solar energy.
Synthesis and Structural Design of Graphene, Silicon and Silicon‐Based Materials Including Incorporation of Graphene as Anode to Improve Electrochemical Performance in Lithium‐Ion Batteries
Authors: Reslan Jawad , Saadaoui Mohamed , Djenizian Thierry
Published: June 2024

Silicon emerges as a candidate for advancing lithium ion batteries with important roles in various applications ranging from portable electronics to electric vehicles. However, despite its theoretical capacities silicon faces challenges such as unstable cycling and limited rate performance. This thorough review examines developments in improving the electrochemical performance of silicon and graphene within the context of lithium ion batteries. The focus lies on strategies for designing and synthesizing composite materials that incorporate silicon particularly when combined with graphene. Structural aspects like particle size, morphology and porosity are carefully optimized to harness the potential of silicon based anodes and graphene. The review highlights the effects resulting from these tailored design approaches, including key factors such as capacity retention, cycling stability and rate capability of the resulting anode materials. By exploring these design paradigms this review offers a comprehensive perspective on the transformative capabilities of silicon, graphene and silicon/graphene composites. It does not highlights recent advancements but also outlines future directions for innovation and practical applications. This compilation of progress contributes to the understanding of how silicon based anodes, in lithium ion batteries have evolved from small‐scale implementations to catalyzing advancements in energy utilization.
Gradient Dion‐Jacobson Phase Stable Quasi‐2D Perovskite@Graphene Hybrid for High Responsivity Photodetectors
Authors: Hegde Sapthami , Sridhar Varun , Chen Ruei San , Chattopadhyay Surojit
Published: June 2024

Quasi‐(2D) formamidinium lead‐iodide (FAPbI3) perovskites are winsome materials for high‐performance photodetectors (PDs). Between Ruddlesden‐Popper (RP) and Dion‐Jacobson (DJ) phases, the latter exhibits lower non‐radiative recombination and higher mobility compared to the relatively easily synthesized former. For efficient charge separation and transport, graphene‐assisted two‐terminal coplanar PD leveraging the DJ phase perovskite is proposed. Diamino octane (DAO), incorporated into 3D FAPbI3 perovskite, resulted in DJ phase [DAO(FA)n‐1PbnI3n+1], n being predefined integers 1≤ n ≤ ∞, demonstrating a vertical gradient heterostructure of n phases. Superior crystallinity and thermal stability of the quasi‐2D films are confirmed via synchrotron‐based studies. Band‐edge of the 3D film blue‐shifted consistently from 810 nm, while passing through the quasi‐2D phases, to ≈500 nm for the 2D phase. The dynamic range of photoresponsivity (R) of PDs reflected the absorption trend, with the 2D perovskite being infrared blind. Graphene's high carrier mobility coupled with the perovskite's high absorbance resulted in an unprecedented high R of ≈107 A W−1 and specific detectivity of 9.77 × 1016 Jones under 42.25 nW cm−2 of 405 nm illumination for the predefined n = 2 film. This underscores the potential of the DJ phase quasi‐2D perovskite@graphene in realizing stable, sensitive, and spectrally tunable PDs.
Inert Gas Element as Active Infrared‐Absorption Source and Donor in Silicon for Forbidden‐Wavelength Sensing
Authors: Chen Nian‐Ke , Gao Yu‐Chen , Zhao Ji‐Hong , Li Chun‐Hao , Chen Qi‐Dai , Sun Hong‐Bo , Zhang Shengbai , Li Xian‐Bin
Published: June 2024

Intrinsic silicon (Si) is forbidden for infrared (IR) sensing at the communication wavelength like 1.31 or 1.55 µm due to the well‐known bandgap limitation. In this work, an unexpected physical picture of using argon (Ar) is identified, which is usually inert to the surrounding chemical environment and used as a protective agent in semiconductor processing, to overcome the IR‐sensing‐forbidden problem in Si. Here, it is shown by an analysis of a dynamic secondary ion mass spectrometer that such a Si, when exposed to laser pulse in Ar gas, can contain a very high dose of Ar up to 1020 cm−3 even after 1300 days. First‐principles calculations, molecular dynamics, and Hall effect measurements reveal that, due to both steric and dynamic repulsions by Ar orbitals to Si dangling bonds, the Ar‐filled‐vacancy produces a much wider defect band inside the gap, which is not only responsible for strong infrared absorption, but also causes a significant increase in n‐type conductivity, both in line with experiments. The study proves that originally inert elements in fact can act as active impurities in semiconductors for advanced applications, which updates the current knowledge of defect physics.
Stereoselective Organocatalyzed Glycosylation of Glycosyl Trichloroacetimidate Donors: Thiouracil as Brønsted Acid Catalyst
Authors: Tiwari Ashwani , Khanam Ariza , Lal Mohan , Kumar Mandal Pintu
Published: June 2024

Herein, we report thiouracil‐catalyzed α‐selective O‐glycosylations employing easily accessible glycosyl trichloroacetimidate donors without using any co‐catalyst or additive. A variety of alcohol nucleophiles including saccharides, and amino acids with different protecting groups containing glycosyl trichloroacetimidate donors were successfully α‐glycosylated using an operationally simple protocol. Moreover, mechanistic investigations suggest that thiouracil functions as Brønsted acid/base catalyst in this glycosylation process.
Gold(I)−Catalyzed Synthesis of Cyclic Sulfamides via an Intramolecular Dehydrative Amination of Allylic Alcohols: A Strategy for 1,3‐Diamine Synthesis
Authors: Lee Soyun , Kim Da Mi , Ryu Jae‐Sang
Published: June 2024

A gold(I)‐catalyzed intramolecular dehydrative amination method has been developed to synthesize diverse cyclic sulfamides efficiently. Reactions proceed smoothly at room temperature using a combination of (IPr)AuCl (5 mol%) and AgBF4 (5 mol%). This method showcases a broad substrate scope, encompassing challenging seven‐membered ring structures, and exhibits functional group compatibility. Moreover, the reaction demonstrates high stereoselectivity, allowing the synthesis of enantiomerically enriched cyclic sulfamides from chiral secondary allylic alcohols. The synthesized cyclic sulfamides serve as valuable intermediates for generating 1,3‐diamines. This approach provides an improved route for cyclic sulfamide synthesis and a strategic entry point for obtaining essential 1,3‐diamine derivatives.
Bipolar Pseudohalide Ammonium Salts Bridged Perovskite Buried Interface toward Efficient Indoor Photovoltaics
Authors: Li Chen , Sun Haoxuan , Dou Da , Gan Shan , Li Liang
Published: June 2024

Due to the higher photon energy under indoor photovoltaic conditions, using perovskite materials with wider bandgaps has become a consensus. However, updating perovskite absorbers requires additional adaptations involving at least two layers of transport materials and two interfaces, increasing the development complexity. This study acknowledges that the buried interface is the primary location for the generation of photoinduced carriers, and achieving efficient carrier separation and transport at this interface will solve most of the open circuit voltage (VOC) loss issues encountered in transitioning from solar photovoltaics to indoor photovoltaics. Therefore, a class of bipolar pseudohalide ammonium salts is proposed for use as bridging agents for the buried interface to effectively resolve the issues of lattice misalignment and insufficient carrier driving force at the buried interface when broadening the perovskite bandgap, thereby reducing VOC loss in indoor photovoltaics. The optimized device exhibits an excellent photoelectric conversion efficiency (PCE) of 41.04%, with a record‐high VOC of 1.08 V. It also demonstrates impressive long‐term operational stability with a T80 lifetime of 1000 h. Substituting various non‐buried interface transport materials and different categories of wide‐bandgap perovskite absorbers does not alter the effectiveness, proving its universality.
Role of Cu Oxide and Cu Adatoms in the Reactivity of CO2 on Cu(110)
Authors: Jensen Sigmund , Cheula Raffaele , Hedevang Martin , Andersen Mie , Lauritsen Jeppe V.
Published: June 2024

We investigate the interaction of CO2 with metallic and oxidized Cu(110) surfaces using a combination of near‐ambient pressure scanning tunneling microscopy (NAP‐STM) and theoretical calculations. While the Cu(110) and full CuO films are inert, the interface between bare Cu(110) and the CuO film is observed to react instantly with CO2 at a 10 mbar pressure. The reaction is observed to proceed from the interfacial sites of CuO/Cu(110). During reaction with CO2, the CuO/Cu(110) interface releases Cu adatoms which combine with CO3 to produce a variety of added Cu−CO3 structures, whose stability depends on the gas pressure of CO2. A main implication for the reactivity of Cu(110) is that Cu adatoms and highly undercoordinated CuO segments are created on the Cu(110) surface through the interaction with CO2, which may act as reaction‐induced active sites. In the case of CO2 hydrogenation to methanol, our theoretical assessment of such sites indicates that their presence may significantly promote CH3OH formation. Our study thus implies that the CuO/Cu(110) interfacial system is highly dynamic in the presence of CO2, and it suggests a possible strong importance of reaction‐induced Cu and CuO sites for the surface chemistry of Cu(110) in CO2‐related catalysis.
Surface‐Like Diffusion of Fast Ions in Framework Energy Materials for Li‐ and Na‐Ion Batteries
Authors: Zhang Jingxi , Dong Yanhao , Wang Chang‐An
Published: June 2024

The rate performance, power density, and energy efficiency of electrochemical devices are often limited by ionic conductivities in electrolyte and electrode materials. Framework Prussian blue analogs and dense niobium oxides have been identified as high‐rate electrodes for sodium‐ and lithium‐ion batteries, respectively, yet the origin of the extremely high solid‐state Na+/Li+ transport is not fully understood. Of critical importance is the fact that their ultra‐low activation energy and anomalous pre‐exponent factor cannot be satisfactorily rationalized from conventional theory of solid‐state diffusion in the crystal lattice. Here, assisted by density‐functional‐theory calculations, we argued that the true origin is a unique surface‐like diffusion mechanism of the intercalation ions. In a surface‐like migration event, a mobile ion moves along the channel wall via a low coordination number and low migration barrier experiencing minimal steric hindrance. It is similar to surface diffusion in the conventional picture and contrasts with lattice diffusion from one interstitial/vacancy site to another one with high coordination number, crowded saddle‐point geometry and high migration barrier. We found that the shifting from solid‐state lattice diffusion to surface‐like diffusion is determined by the size difference between the mobile ion and the diffusion channel, and a lowest migration energy barrier can be reached by mediating the channel size. The analogy to gas diffusion in molecular sieves shall be discussed. Additionally, the effects of defects and crystal water in Prussian blue analogs were also discussed for better understanding their rate performances in experimental scenarios.
Efficient C(sp3)−H Bond Oxidation on Perovskite Quantum Dots Based on Ce‐Oxygen Affinity
Authors: Wang Teng , Li Yonglong , Yang Xian , Hu Yanfang , Du Xiaomeng , Zhang Maodi , Huang Zhuanzhuan , Liu Siyu , Wang Ying , Xie Wei
Published: June 2024

Perovskite quantum dots (QDs) have shown attractive prospects in the field of visible photocatalysis, especially in the synthesis of high value‐added chemicals. However, under aerobic conditions, the stable operation of QD catalysts has been limited by the reactive oxygen species (ROS) generated by photoexcitation, especially superoxide species O2⋅−. Here, we propose a strategy of Ce3+ doping in perovskite QDs to guide superoxide species for photocatalytic oxidation reactions. In C(sp3)−H bond oxidation of hydrocarbons, superoxide species were rapidly generated and efficiently utilized on the surface of perovskite QDs, which achieves the stable operation of the catalytic system and obtains a high product conversion rate (15.3 mmol/g/h for benzaldehydes). The mechanism studies show that the strong Ce‐oxygen affinity accelerates the relaxation process of photoinduced exciton transfer to superoxide species and inhibits the radiative recombination pathway. This work provides a new idea of utilizing oxygen species on perovskite surface and broadens the design strategy of high‐performance QD photocatalysts.
Interfacial Ir‐V Direct Metal Bonding Enhanced Hydrogen Evolution Activity in Vanadium Oxides Supported Catalysts
Authors: Zheng Yijuan , Geng Wei , Xiao Sutong , Ma Tian , Cheng Chong , Liao Yaozu , Zeng Zhiyuan , Li Shuang , Zhao Changsheng
Published: June 2024

Tuning the interfacial structure of metal oxide substrates is an essential strategy to induce electronic structure reconstruction of supported catalysts, which is of great importance in optimizing their catalytic activities. Herein, vanadium oxides‐supported Ir catalysts (Ir‐V2O3, Ir‐VO2, and Ir‐V2O5) with different interfacial bonding environments (Ir‐V, Ir‐Obri, and Ir‐O, respectively) were investigated for hydrogen evolution reaction (HER). The regulating mechanism of the influence of different interfacial bonding environments on HER activity was investigated by both experimental results and computational evidence. Benefiting from the unique advantages of interfacial Ir‐V direct metal bonds in Ir‐V2O3, including enhanced electron transfer and electron donation ability, an optimized HER performance can be obtained with lowest overpotentials of 16 and 26 mV at 10 mA cm−2, high mass activities of 11.24 and 6.66 A mg−1, and turnover frequency values of 11.20 and 6.63 s−1, in acidic and alkaline conditions respectively. Furthermore, the assembled Ir‐V2O3||RuO2 anion exchange membrane (AEM) electrolyzer requires only 1.92 V to achieve a high current density of 500 mA cm−2 and realizes long‐term stability. This study provides essential insights into the regulating mechanism of interfacial chemical bonding in electrocatalysts and offers a new pathway to design noble metal catalysts for different applications.
Synthesis and evaluation of oleic acid‐derived hyperbranched polyester as an efficient plasticizer for PVC
Authors: Zhang Chao , Yu Erlei , Wang Heyun , Huang Dong , Ding Guojun , Zhao Zhonghua , Wei Zhong
Published: June 2024

In response to the health and environmental concerns associated with the plasticizer dioctyl phthalate (DOP), this research explores the utilization of methyl oleate (MO) derived from plant oil, 1,2,4‐Benzeneticarboxylic anhydride (TMA) and isobutyric anhydride (IA) as a precursor for synthesizing a hyperbranched polyester named IA‐MO‐TMA. This polyester serves as an alternative plasticizer for Polyvinyl chloride (PVC). The chemical structure of IA‐MO‐TMA was thoroughly characterized using Fourier Transform Infrared Spectrometer (FTIR) and nuclear magnetic resonance hydrogen spectra, and its molecular weight was assessed. The PVC film, plasticized with IA‐MO‐TMA, underwent comprehensive testing using techniques such as differential scanning calorimetry, scanning electron microscopy, and thermogravimetric analysis. Notably, the glass transition temperature (Tg) of the plasticized PVC film exhibited a significant reduction from 75°C to −6.7°C. The plasticized film demonstrated an elongation at break of 318.1%, a tensile strength of 19.2 MPa, and a plasticizing efficiency of 109.9%. Moreover, the use of IA‐MO‐TMA as a plasticizer increased the initial decomposition temperature of PVC film from 235.6 to 264.1°C. Additionally, the extraction rate of IA‐MO‐TMA in petroleum ether was found to be 35.6% lower than that of DOP.
Universal Dimensionality of Ferroelectric Domain Walls in Ultrathin Films
Authors: Kale Somnath , Petraru Adrian , Kohlstedt Hermann , Soni Rohit
Published: June 2024

The dimensionality of dynamic interfaces—domain walls (DWs) —is greatly influenced by symmetry and physical dimensions, irrespective of the microscopic details of the system. To address this fundamental question for the ferroelectric model system, the DW scaling criticality and dimensionality is investigated in ultrathin films of varied ferroelectric materials, compositions, and electrode–ferroelectric interfaces, grown on nominally flat and vicinal substrates. In spite of significant variations among ferroelectric systems, the observed prevalence of 1D DWs is consistent with a random bond disorder, elucidated through a scenario of 2D nucleation and growth‐driven DW creep. These findings highlight the thickness size‐dominated universal behavior of ferroelectric DWs, uncovering fascinating prospects for dimensionally engineered DW‐based nanoelectronics.
Hydroxychloroquine Dose and Hospitalizations for Active Lupus
Authors: Nestor Jacquelyn , Choi Hyon , Mancini Christian , Zhou Baijun , Zhang Yuqing , Costenbader Karen H. , Jorge April
Published: June 2024

Objective

We sought to determine the impact of hydroxychloroquine (HCQ) dose on the risk of hospitalizations for systemic lupus erythematosus (SLE).

Methods

We conducted a case‐crossover study within an academic health system, including patients with SLE who used HCQ and had ≥1 hospitalization for active SLE between January 2011 and December 2021. Case periods ended in hospitalization for SLE, whereas control periods did not. The exposures were the average weight‐based HCQ dose, categorized as ≤5 or >5 mg/kg/day, and non–weight‐based HCQ dose, categorized as <400 or 400 mg/day, assessed during each six‐month case or control period. Odds ratios (ORs) were calculated using conditional logistic regression and adjusted for prior disease activity, kidney function, glucocorticoid use, and other immunosuppressant use.

Results

Of 2,974 patients with SLE who used HCQ (mean age 36.5 years; 92% female), 584 had ≥1 hospitalization with primary discharge diagnosis of SLE. Of these, 122 had ≥1 hospitalization for active SLE while using HCQ and had ≥1 control period with HCQ use during the study period. Lower HCQ weight‐based dose (≤5 vs >5 mg/kg/day) and non–weight‐based dose (<400 vs 400 mg/day) were each associated with increased hospitalizations for active SLE (adjusted OR 4.20, 95% confidence interval [CI] 1.45–12.19, and adjusted OR 3.39, 95% CI 1.31–8.81).

Conclusion

The use of lower doses of HCQ was associated with an increased risk of hospitalizations for active SLE. Although the long‐term risk of HCQ retinopathy must be acknowledged, this must be balanced with the short‐term and cumulative risks of increased SLE activity.

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Oxidative status: A general but overlooked indicator of welfare across animal species?
Authors: Beaulieu Michaël
Published: June 2024

Because of their ubiquity, plasticity, and direct effects on the nervous system, markers of oxidative status may be of great value to assess animal welfare across species and conditions in the wild. However, welfare biologists have not yet seized this opportunity, possibly because the validity of these markers as welfare indicators remains questionable. A validation process was, therefore, performed here using a meta‐analytical approach considering three conditions assumed to impair the welfare of animals. With very few exceptions, two of the four considered markers consistently varied across these negatively‐valenced conditions. By highlighting the current underrepresentation of markers of oxidative status in animal welfare studies, and by concretely illustrating that some of these markers can consistently reflect negative affective states, this article aims to encourage biologists to include these physiological markers in their toolbox to better measure, monitor, and perhaps also improve the welfare of animals in their natural habitat.
Elucidating solvent effects on lipase‐catalyzed peroxyacid synthesis through activity‐based kinetics and molecular dynamics
Authors: Brandolín Salvador E. , Scilipoti José A. , Magario Ivana
Published: June 2024

Peroxyacid synthesis is the first step in Prilezhaev epoxidation, which is an industrial method to form epoxides. Motivated by the development of a kinetic model as a tool for solvent selection, the effect of solvent type and acid chain length on the lipase‐catalyzed peroxyacid synthesis was studied. A thermodynamic activity‐based ping‐pong kinetic expression was successfully applied to predict the effect of the reagent loadings in hexane. The activity‐based reaction quotients provided a prediction of solvent‐independent equilibrium constants. However, this strategy did not achieve satisfactory estimations of initial rates in solvents of higher polarity. The lack of compliance with some assumptions of this methodology could be confirmed through molecular dynamics calculations i.e. independent solvation energies and lack of solvent interaction with the active site. A novel approach is proposed combining the activity‐based kinetic expression and the free binding energy of the solvent with the active site to predict kinetics upon solvent change. Di‐isopropyl ether generated a strong interaction with the enzyme's active site, which was detrimental to kinetics. On the other hand, toluene or limonene gave moderate interaction with the active site rendering improved catalytic yield compared with less polar solvents, a finding sharpened when peroctanoic acid was produced.
Gentle Parenting: A new parenting approach?
Authors: Walters Anne S.
Published: June 2024

Recently, the “Gentle Parenting” approach has garnered increased interest among parents. The term was first introduced by Sarah Ockwell‐Smith, a parenting expert and author of a series of books about the perspective (Ockwell‐Smith, 2023). Gentle Parenting is based on principles of attachment theory and positive discipline, advocating for understanding and meeting the child's needs rather than managing their behavior. Techniques such as active listening, validation, and problem‐solving are central to this approach. Priorities are empathy, connection, and respect for the child's autonomy. Those who advocate Gentle Parenting contrast the approach with more traditional authoritarian parenting models, which are characterized by rules, punishment, and control and are viewed as outdated and ineffective by proponents of this type of parenting practice. Parents are drawn to Gentle Parenting as an alternative that promotes cooperation and understanding rather than one based on fear or obedience.
(Ni or/and Co) Supported over Praseodymia as Oxygen Carriers for Chemical Looping Syngas Production
Authors: Santos Lucía Herráez , Caracena María Murcia , Marhuenda Daniel Sanchiz , Sigüenza María Pilar Yeste , García Avelina García
Published: June 2024

The present research describes one of the processes outlined in the literature, known as Chemical Looping Dry Reforming of Methane, which is currently to gain attraction to produce clean fuels from natural gas using a metal oxide support as a catalyst. This two‐step method offers distinct advantages by physically separating the reaction steps. This spatial separation effectively eliminates undesirable side reactions, leading to highly efficient syngas production with minimal carbon deposition. Crucial to optimizing this process is a deep understanding of the oxygen storage capacity (OSC) of the support (oxygen carrier) that will work in synergy with the supported active phase. Among the candidates, praseodymium stands out due to its favourable redox properties and exceptional OSC characteristics, making it a promising option for cleaner fuel technologies. In particular, this study emphasizes the significant influence of the nature of the active phases (Ni, Co or their bimetallic combinations), with bimetallic phases being the most promising (even without reduction, they can exhibit activity that equals or improves that of the Ru as benchmark), underscoring the fundamental role of catalyst design in achieving optimal performance. The results indicate that these compositions have high activities to generate the products, remaining close to the activity of ruthenium and generating minimal coke deposits in one reaction cycle.
Intramolecularly O,N,O‐Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation
Authors: Alnasr Hazem , Mroß David , Platzek André , Nayyar Bastian , Řičica Tomáš , Schollmeyer Dieter , Jambor Roman , Hoffmann Alexander , Jurkschat Klaus
Published: June 2024

We report the syntheses of tin(II) salts of the types [L1SnX]SnX3 [L1=2,6‐{(i‐PrO)2(O)P}2C5H3N: 1, X=Cl; 2, X=Br], [L2SnCl]SnCl3 [L2=2‐{(i‐PrO)Ph(O)P}‐6‐{(i‐PrO)2(O)P}C5H3N: 3], [L3SnX]SnX3 [L3=2,6‐{MeO(O)C}2C5H3N: 4, X=Cl; 5, X=Br], [L4SnX]SnX3 [L4=2,6‐{Et2N(O)C}2C5H3N: 6, X=Cl; 7, X=Br]. These compounds were obtained by addition of SnX2 to the corresponding ligand inducing autoionization of the respective tin(II) halide. The thermal stability of 1, 3, and 4 was elucidated, giving, under ester cleavage and cyclisation, the tin(II) derivatives 8–12. The reaction of [L1SnCl]SnCl3 (1) with W(CO)4(thf)2 afforded the tungsten tetracarbonyl complex [{L1SnCl}{SnCl3}W(CO)4] (13), representing the first example in which a tin(II) stannate anion and a tin(II) stannylium cation simultaneously coordinate to a transition metal centre. The compounds were characterized by single crystal X‐ray diffraction analyses and in part by elemental analyses, IR and NMR spectroscopy, electrospray ionization mass spectrometry. DFT calculations accompany the experimental work.
Photochemical Aerobic Upcycling of Polystyrene Plastics via Synergistic Indirect HAT Catalysis
Authors: Mountanea Olga G. , Skolia Elpida , Kokotos Christoforos G.
Published: June 2024

Plastic pollution constitutes an evergrowing urgent environmental problem, since overaccumulation of plastic waste, arising from the immense increase of the production of disposable plastic products, overcame planet's capacity to properly handle them. Chemical upcycling of polystyrene constitutes a convenient method for the conversion of plastic waste into high‐added value chemicals, suggesting an attractive perspective in dealing with the environmental crisis. We demonstrate herein a novel, easy‐to‐perform organocatalytic photoinduced aerobic protocol, which proceeds via synergistic indirect hydrogen atom transfer (HAT) catalysis under LED 390 nm Kessil lamps as the irradiation source. The developed method employs a BrCH2CN‐thioxanthone photocatalytic system and was successfully applied to a variety of everyday‐life plastic products, leading to the isolation of benzoic acid after simple base‐acid work up in yields varying from 23–49 %, while a large‐scale experiment was successfully performed, suggesting that the photocatalytic step is susceptible to industrial application.
Transition Behaviors of Isostructural Hydrogen‐Bonded Frameworks Composed of Naphthalene, Quinoxaline, and Pyrazinopyrazine Derivatives
Authors: Kubo Haruka , Konishi Shunsuke , Oketani Ryusei , Hayashi Takashi , Hisaki Ichiro
Published: June 2024

A series of isostructural reticular frameworks with systematic differences on chemical structures allows us to disclose correlations between specific structural factors and properties, providing insights for designing novel porous materials. However, even slight differences in the molecular structure often lead to non‐isostructural polymorphic frameworks particularly in the case of hydrogen‐bonded organic frameworks (HOFs) because the structures of HOFs are based on a subtle balance of reversible interactions. In this study, we found that three simple analogues of tetracarboxylic acids with naphthalene, quinoxaline, and pyrazinopyrazine cores (NT, QX, and PP, respectively) yielded isostructural solvated HOFs (NT‐1, QX‐1, and PP‐1, respectively), where hydrogen‐bonded sql‐networked sheets were slip‐stacked with closely similar manners. More importantly, these isostructural HOFs underwent structural transformations in different manners upon removal of the guest solvents. Comparison of the crystal structures of the HOFs before and after the transformation revealed that intermolecular interactions of the core significantly affected on rearrangements of hydrogen bonds in the transformation. The results suggest the potential to control the properties and functions of isostructural HOFs by elements in the core.
Chemical characterization of submicron particulate matter (PM1) and its source apportionment using positive matrix factorization
Authors: Jhamaria Charu , Sharma Shivani , Yadav Manish , Tiwari Suresh , Singh Namrata
Published: June 2024

The present study was conducted to address four key questions: (i) What are the levels of submicron particulate matter at the study area?, (ii) which are the major contributing sources of these particles?, and (iii) is there any seasonal changes in the levels of pollutants at the study site? Thus, the study was conducted at an urban residential site of Jaipur City, India, to determine the elemental and ionic composition of toxic elements associated with PM1 using inductively coupled plasma optical emission spectroscopy and ion chromatography to reveal specific sources. Monitoring was done for a period of 8 months between October 2020 and May 2021 considering three seasons: winter (December–February), pre‐monsoon (March–May), and post‐monsoon (October–November). PM1 samples were found to be highly enriched with Ag, Cd, B, Ni, and Zn. PM1 mass concentrations were observed to be greater in winter (104.13 ± 30.16 µg m−3) and lower in the pre‐monsoon season (83.62 ± 19.40 µg m−3). Ion concentrations (Cl−, NO32−, and SO42−) followed a similar pattern to PM1 concentrations. Source apportionment by positive matrix factorization at the study site revealed six major sources of pollutants (soil dust, agro‐based industry, automobile industry, salt aerosols, industrial activities, and biomass burning).
Chemical Modifications on the αvβ6 Integrin Targeting A20FMDV2 Peptide: A Review
Authors: Siow Andrew , Kowalczyk Renata , Hong Jiwon , Harris Paul W. R.
Published: June 2024

Integrin proteins have received a significant increase in attention in recent scientific endeavors. The current trend uses the pre‐established knowledge that the arginyl‐glycyl‐aspartic acid (RGD) structural motif present in the A20FMDV2 peptide is highly selective for the integrin class αvβ6 which is overexpressed in many cancer types. This review will provide an extensive overview of the existing literature research to date to the best of our knowledge, highlighting significant improvements and drawbacks of structure‐activity relationships (SAR) work undertaken, aiding future research to identify established SAR for an informed design of future A20FMDV2 mimetic inhibitors. Herein, the review aims to collate the existing structural chemical modifications present on A20FMDV2 in the literature to highlight key structural analogues that display more potent biological activity.
Glass Box and Black Box Machine Learning Approaches to Exploit Compositional Descriptors of Molecules in Drug Discovery and Aid the Medicinal Chemist
Authors: Robson Barry , Cooper Richard
Published: June 2024

The synthetic medicinal chemist plays a vital role in drug discovery. Today there are AI tools to guide next syntheses, but many are “Black Boxes” (BB). One learns little more than the prediction made. There are now also AI methods emphasizing visibility and “explainability” (thus explainable AI or XAI) that could help when “compositional data” are used, but they often still start from seemingly arbitrary learned weights and lack familiar probabilistic measures based on observation and counting from the outset. If probabilistic methods were used in a complementary way with BB methods and demonstrated comparable predictive power, they would provide guidelines about what groups to include and avoid in next syntheses and quantify the relationships in probabilistic terms. These points are demonstrated by blind test comparison of two main types of BB methods and a probabilistic “Glass Box” (GB) method new outside of medicine, but which appears well suited to the above. Because many probabilities can be involved, emphasis is on the predictive power of its simplest explanatory models. There are usually more inactive compounds by orders of magnitude, often a problem for machine learning methods. However, the approaches used here appear to work well for such “real world data”.
Innovative Approaches for Manufacturing Epoxy‐Modified Wood and Cellulose Fiber Composites: A Comparison between Injection Molding and 3D Printing
Authors: Lemos Cosse Renato , van den Berg Thijs , Voet Vincent , Folkersma Rudy , Loos Katja
Published: June 2024

The current study focused on improving the properties of polylactic acid (PLA) for wider application in load‐bearing scenarios. Various methods were explored to optimize the interaction between PLA and natural fibers, particularly wood fibers (WFs). Alkalized and epoxy‐impregnated WFs were evaluated against untreated WFs and cellulose fibers in both injection molding (IM) and fused deposition modeling (FDM). FTIR analysis revealed the removal of hemicellulose and lignin in alkalized WFs and uniform epoxy curing. Addition of fibers reduced PLA's thermal stability while acting as nucleating agents. Additionally, fibers augmented the storage modulus of biocomposites, with alkalized fibers exhibiting the highest tensile modulus in IM. FDM samples with a 0° raster angle showed superior impact resistance compared to IM counterparts. Moreover, raster angle significantly influenced FDM biocomposite properties, enhancing the tensile strength and modulus of untreated WF and cellulose fibers at 0°. Although FDM did not produce alkalized WF samples, epoxy impregnation emerged as a promising method for enhancing PLA/WF composite mechanical properties in the IM process, offering valuable insights for composite material development.
Explore new quinoxaline pharmacophore tethered sulfonamide fragments as in vitro α‐glucosidase, α‐amylase, and acetylcholinesterase inhibitors with ADMET and molecular modeling simulation
Authors: Ragab Ahmed , Salem Mohamed A. , Ammar Yousry A. , Aboulthana Wael M. , Helal Mohamed H. , Abusaif Moustafa S.
Published: June 2024

A new series of quinoxaline‐sulfonamide derivatives 3–12 were synthesized using fragment‐based drug design by reaction of quinoxaline sulfonyl chloride (QSC) with different amines and hydrazines. The quinoxaline‐sulfonamide derivatives were evaluated for antidiabetic and anti‐Alzheimer's potential against α‐glucosidase, α‐amylase, and acetylcholinesterase enzymes. These derivatives showed good to moderate potency against α‐amylase and α‐glucosidase with inhibitory percentages between 24.34 ± 0.01%–63.09 ± 0.02% and 28.95 ± 0.04%–75.36 ± 0.01%, respectively. Surprisingly, bis‐sulfonamide quinoxaline derivative 4 revealed the most potent activity with inhibitory percentages of 75.36 ± 0.01% and 63.09 ± 0.02% against α‐glucosidase and α‐amylase compared to acarbose (IP = 57.79 ± 0.01% and 67.33 ± 0.01%), respectively. Moreover, the quinoxaline derivative 3 exhibited potency as α‐glucosidase and α‐amylase inhibitory with a minute decline from compound 4 and acarbose with inhibitory percentages of 44.93 ± 0.01% and 38.95 ± 0.01%. Additionally, in vitro acetylcholinesterase inhibitory activity for designed derivatives exhibited weak to moderate activity. Still, sulfonamide‐quinoxaline derivative 3 emerged as the most active member with inhibitory percentage of 41.92 ± 0.02% compared with donepezil (IP = 67.27 ± 0.60%). The DFT calculations, docking simulation, target prediction, and ADMET analysis were performed and discussed in detail.