bluuebunny/crossref_metadata_2025 huggingface dataset:
Solid‐Phase‐Supported Chemoenzymatic Synthesis and Analysis of Chondroitin Sulfate Proteoglycan Glycopeptides
Authors: Lin Po‐han , Xu Yongmei , Bali Semiha Kevser , Kim Jandi , Gimeno Ana , Roberts Elijah T. , James Deepak , Almeida Nuno M. S. , Loganathan Narasimhan , Fan Fei , Wilson Angela K. , Jonathan Amster I. , Moremen Kelley W. , Liu Jian , Jiménez‐Barbero Jesús , Huang Xuefei
Published: May 2024

Proteoglycans (PGs), consisting of glycosaminoglycans (GAGs) linked with the core protein through a tetrasaccharide linkage region, play roles in many important biological events. The chemical synthesis of PG glycopeptides is extremely challenging. In this work, the enzymes required for synthesis of chondroitin sulfate (CS) PG (CSPG) have been expressed and the suitable sequence of enzymatic reactions has been established. To expedite CSPG synthesis, the peptide acceptor was immobilized on solid phase and the glycan units were directly installed enzymatically onto the peptide. Subsequent enzymatic chain elongation and sulfation led to the successful synthesis of CSPG glycopeptides. The CS dodecasaccharide glycopeptide was the longest homogeneous CS glycopeptide synthesized to date. The enzymatic synthesis was much more efficient than the chemical synthesis of the corresponding CS glycopeptides, which could reduce the total number of synthetic steps by 80 %. The structures of the CS glycopeptides were confirmed by mass spectrometry analysis and NMR studies. In addition, the interactions between the CS glycopeptides and cathepsin G were studied. The sulfation of glycan chain was found to be important for binding with cathepsin G. This efficient chemoenzymatic strategy opens new avenues to investigate the structures and functions of PGs.
Trigonal Planar [PN3]4− Anion in the Nitridophosphate Oxide Ba3[PN3]O
Authors: Pritzl Reinhard M. , Witthaut Kristian , Dialer Marwin , Buda Amalina T. , Milman Victor , Bayarjargal Lkhamsuren , Winkler Björn , Schnick Wolfgang
Published: May 2024

Nitridophosphates, with their primary structural motif of isolated or condensed PN4 tetrahedra, meet many requirements for high performance materials. Their properties are associated with their structural diversity, which is mainly limited by this specific building block. Herein, we present the alkaline earth metal nitridophosphate oxide Ba3[PN3]O featuring a trigonal planar [PN3]4− anion. Ba3[PN3]O was obtained using a hot isostatic press by medium‐pressure high‐temperature synthesis (MP/HT) at 200 MPa and 880 °C. The crystal structure was solved and refined from single‐crystal X‐ray diffraction data in space group R
c (no. 167) and confirmed by SEM‐EDX, magic angle spinning (MAS) NMR, vibrational spectroscopy (Raman, IR) and low‐cost crystallographic calculations (LCC). MP/HT synthesis reveals great potential by extending the structural chemistry of P to include trigonal planar [PN3]4− motifs.
Ultra‐High Proportion of Grain Boundaries in Zinc Metal Anode Spontaneously Inhibiting Dendrites Growth
Authors: Lian Sitian , Cai Zhijun , Yan Mengyu , Sun Congli , Chai Nianyao , Zhang Bomian , Yu Kesong , Xu Ming , Zhu Jiexin , Pan Xuelei , Dai Yuhang , Huang Jiazhao , Mai Bo , Qin Ling , Shi Wenchao , Xin Qiqi , Chen Xiangyu , Fu Kai , An Qinyou , Yu Qiang , Zhou Liang , Luo Wen , Zhao Kangning , Wang Xuewen , Mai Liqiang
Published: May 2024

Aqueous Zn‐ion batteries are an attractive electrochemical energy storage solution for their budget and safe properties. However, dendrites and uncontrolled side reactions in anodes detract the cycle life and energy density of the batteries. Grain boundaries in metals are generally considered as the source of the above problems but we present a diverse result. This study introduces an ultra‐high proportion of grain boundaries on zinc electrodes through femtosecond laser bombardment to enhance stability of zinc metal/electrolyte interface. The ultra‐high proportion of grain boundaries promotes the homogenization of zinc growth potential, to achieve uniform nucleation and growth, thereby suppressing dendrite formation. Additionally, the abundant active sites mitigate the side reactions during the electrochemical process. Consequently, the 15 μm Fs−Zn||MnO2 pouch cell achieves an energy density of 249.4 Wh kg−1 and operates for over 60 cycles at a depth‐of‐discharge of 23 %. The recognition of the favorable influence exerted by UP‐GBs paves a new way for other metal batteries.
Time‐Resolved Mechanistic Depiction of Photoinduced CO2 Reduction Catalysis on a Urea‐Modified Iron Porphyrin
Authors: Cruz Neto Daniel H. , Pugliese Eva , Gotico Philipp , Quaranta Annamaria , Leibl Winfried , Steenkeste Karine , Peláez Daniel , Pino Thomas , Halime Zakaria , Ha‐Thi Minh‐Huong
Published: May 2024

The development of functional artificial photosynthetic devices relies on the understanding of mechanistic aspects involved in specialized photocatalysts. Modified iron porphyrins have long been explored as efficient catalysts for the light‐induced reduction of carbon dioxide (CO2) towards solar fuels. In spite of the advancements in homogeneous catalysis, the development of the next generation of catalysts requires a complete understanding of the fundamental photoinduced processes taking place prior to and after activation of the substrate by the catalyst. In this work, we employ a state‐of‐the‐art nanosecond optical transient absorption spectroscopic setup with a double excitation capability to induce charge accumulation and trigger the reduction of CO2 to carbon monoxide (CO). Our biomimetic system is composed of a urea‐modified iron(III) tetraphenylporphyrin (UrFeIII) catalyst, the prototypical [Ru(bpy)3]2+ (bpy=2,2’‐bipyridine) used as a photosensitizer, and sodium ascorbate as an electron donor. Under inert atmosphere, we show that two electrons can be successively accumulated on the catalyst as the fates of the photogenerated UrFeII and UrFeI reduced species are tracked. In the presence of CO2, the catalytic cycle is kick‐started providing further evidence on CO2 activation by the UrFe catalyst in its formal FeI oxidation state.
Utilizing “Latent” Carbon: Repositioning Hydrogen‐Bonded Synthons and Assemblies via Halogen Bonding to π‐Systems
Authors: Vainauskas Jogirdas , Wahrhaftig‐Lewis Alexander , Friščić Tomislav
Published: May 2024

Molecules bearing carboxylic acid, amide, and hydroxyl groups are ubiquitous in crystal engineering, where robust hydrogen‐bonded synthons centred on these functionalities enable reliable crystal structure design. We now show that halogen bonding to the carbon π‐system of such molecules, traditionally ignored in crystal engineering, permits the recognition and directional assembly of the resulting hydrogen‐bonded structural subunits, leaving the archetypal hydrogen‐bonded ring, ladder, and chain homosynthons intact, but repositioned in space. When applied to heteromolecular synthons, this enables rearranging more complex hydrogen‐bonded motifs and the evolution of binary cocrystals into ternary ones through “latent” carbon‐based recognition sites, demonstrating a rational approach to build higher‐order solid‐state supramolecular assemblies.
Facile way of preparing PMMA@TiO2@SiO2 (P@T@S) composite microspheres with high haze and light transmittance for diffusion film
Authors: He Liangyong , Yang Yuqing , Yang Bin , Hu Weiqiang , Zheng Zhengzhi , Lu Tianyu , He Haijia , Qian Jiasheng , Chen Yaoyang , Zhang Weiguo , Ke Yuchao
Published: May 2024

In recent years, optical diffusion film materials with high transmittance and high haze have been widely reported, while there is relatively rare research on their functionalization and practical application especially in real scenario. In this work, optical diffusion films using polymethyl methacrylate (PMMA)@TiO2@SiO2 (P@T@S) composite microspheres were fabricated, which exhibited sufficiently high light transmittance and haze. The binding mode of PMMA microspheres and nanoparticles suggested that PMMA microspheres with a positive surface potential combined with nanoparticles with a negative surface potential through electrostatic attraction to achieve mutual binding. The prepared P@T@S composite microspheres showed better heat and swelling resistance than those of PMMA microspheres. The P@T@S diffusion film, whose excellent light diffusion effect was clearly demonstrated, exhibited the best optical performance among all optical diffusion films prepared. After passing through the P@T@S diffusion film, the laser light was not only uniform but also bright. The findings from this work can provide some insight into further research on optical diffusion films applied in optoelectronic device areas.
Dynamic Adaptive Porous Cu Current Collector for Low N/P Ratio Li Metal Batteries
Authors: Chen Jianyu , Fu Wei , Zhang Shihao , Zhang Fanlai , Zhou Jiayi , Ma Yanwen , Zhao Jin
Published: May 2024

Porous copper (Cu) current collectors effectively suppress the growth of lithium (Li) dendrites and enhance the stability of Li metal anodes. However, the current development of porous Cu hosts generally involves a high proportion of Cu, mostly rigid structures, small pore volumes, and low Li utilization. Here, we propose a dynamic adaptive porous Cu (DAP−Cu) host, which is lightweight with a high pore volume, fabricated using a large aspect ratio of Cu nanowires as the building blocks. This DAP−Cu allows for the precise loading of metallic Li, and the symmetric battery assembled with Li/DAP−Cu electrode operates at the high current density of 5 mA cm−2 for 4000 hours while exhibiting a low polarization voltage of ~60 mV. The Li/DAP−Cu anode achieves high‐performance compatibility with LiFePO4 and sulfur cathodes, with optimal N/P ratios of 1.20 : 1 and 4.0 : 1, respectively. Full and pouch cells with low N/P ratios exhibit exceptionally high specific capacities and long‐term cycling life. The establishment of standards for the matching of anodes and cathodes provides a reference for the quantitative preparation of electrode materials and is of significant guidance for enhancing the efficient utilization of metallic Li.
Validation of mobile phone use recall in the multinational MOBI‐kids study
Authors: van Wel Luuk , Huss Anke , Kromhout Hans , Momoli Franco , Krewski Daniel , Langer Chelsea E. , Castaño‐Vinyals Gemma , Kundi Michael , Maule Milena , Miligi Lucia , Sadetzki Siegal , Albert Alex , Alguacil Juan , Aragones Nuria , Badia Francesc , Bruchim Revital , Goedhart Geertje , de Llobet Patricia , Kiyohara Kosuke , Kojimahara Noriko , Lacour Brigitte , Morales‐Suarez‐Varela Maria , Radon Katja , Remen Thomas , Weinmann Tobias , Vrijheid Martine , Cardis Elisabeth , Vermeulen Roel ,   MOBI‐Kids consortium
Published: May 2024

Potential differential and non‐differential recall error in mobile phone use (MPU) in the multinational MOBI‐Kids case–control study were evaluated. We compared self‐reported MPU with network operator billing record data up to 3 months, 1 year, and 2 years before the interview date from 702 subjects aged between 10 and 24 years in eight countries. Spearman rank correlations, Kappa coefficients and geometric mean ratios (GMRs) were used. No material differences in MPU recall estimates between cases and controls were observed. The Spearman rank correlation coefficients between self‐reported and recorded MPU in the most recent 3 months were 0.57 and 0.59 for call number and for call duration, respectively. The number of calls was on average underestimated by the participants (GMR = 0.69), while the duration of calls was overestimated (GMR = 1.59). Country, years since start of using a mobile phone, age at time of interview, and sex did not appear to influence recall accuracy for either call number or call duration. A trend in recall error was seen with level of self‐reported MPU, with underestimation of use at lower levels and overestimation of use at higher levels for both number and duration of calls. Although both systematic and random errors in self‐reported MPU among participants were observed, there was no evidence of differential recall error between cases and controls. Nonetheless, these sources of exposure measurement error warrant consideration in interpretation of the MOBI‐Kids case–control study results on the association between children's use of mobile phones and potential brain cancer risk.
Investigating environmentally sustainable consumption: A diary study of home‐based consumption behaviors
Authors: Barone Ada Maria , Grappi Silvia , Romani Simona
Published: May 2024

This study analyzes three environmentally sustainable household consumption behaviors (optimizing the use of domestic water, minimizing food waste, and minimizing plastic packaging usage) through the model of goal‐directed behavior. The findings show that attitudes, subjective norms, perceived behavioral control, anticipated emotions, and habits are all significant predictors of the desire to adopt sustainable consumption behaviors, which directly fosters the intention to adopt these behaviors. Intention–behavior links were unique for each behavior; minimizing plastic packaging usage was the most difficult behavior to implement. This study offers useful insights into people's sustainable consumption goals and their intentions to adopt responsible consumption behaviors. A generalizable model of environmentally sustainable household behaviors that considers the three behaviors simultaneously is presented. This study suggests that business and policy strategies that could successfully promote sustainability in the household might proceed by, for example, empowering consumers or changing their habits.
Beyond analytics: Using computer‐aided methods in educational research to extend qualitative data analysis
Authors: Vieira Camilo , Ortega‐Alvarez Juan D. , Magana Alejandra J. , Boutin Mireille
Published: May 2024

This study proposes and demonstrates how computer‐aided methods can be used to extend qualitative data analysis by quantifying qualitative data, and then through exploration, categorization, grouping, and validation. Computer‐aided approaches to inquiry have gained important ground in educational research, mostly through data analytics and large data set processing. We argue that qualitative data analysis methods can also be supported and extended by computer‐aided methods. In particular, we posit that computing capacities rationally applied can expand the innate human ability to recognize patterns and group qualitative information based on similarities. We propose a principled approach to using machine learning in qualitative education research based on the three interrelated elements of the assessment triangle: cognition, observation, and interpretation. Through the lens of the assessment triangle, the study presents three examples of qualitative studies in engineering education that have used computer‐aided methods for visualization and grouping. The first study focuses on characterizing students' written explanations of programming code, using tile plots and hierarchical clustering with binary distances to identify the different approaches that students used to self‐explain. The second study looks into students' modeling and simulation process and elicits the types of knowledge that they used in each step through a think‐aloud protocol. For this purpose, we used a bubble plot and a k‐means clustering algorithm. The third and final study explores engineering faculty's conceptions of teaching, using data from semi‐structured interviews. We grouped these conceptions based on coding similarities, using Jaccard's similarity coefficient, and visualized them using a treemap. We conclude this manuscript by discussing some implications for engineering education qualitative research.
Development of Putative Bivalent Dicovalent Ligands for the Adenosine A1 Receptor
Authors: Payne China M. , Baltos Jo‐Anne , Langiu Monica , Sinh Lu Cam , Tyndall Joel D. A. , Gregory Karen J. , May Lauren T. , Vernall Andrea J.
Published: May 2024

Accumulating evidence suggests that G protein‐coupled receptors (GPCRs) can exist and function in homodimer and heterodimer forms. The adenosine A1 receptor (A1R) has been shown to form both homodimers and heterodimers, but there is a lack of chemical tools to study these dimeric receptor populations. This work describes the synthesis and pharmacological evaluation of a novel class of bivalent GPCR chemical tools, where each ligand moiety of the bivalent compound contains a sulfonyl fluoride covalent warhead designed to be capable of simultaneously reacting with each A1R of an A1R homodimer. The novel compounds were characterised using radioligand binding assays, including washout assays, and functionally in cAMP assays. The bivalent dicovalent compounds were competitive A1R antagonists and showed evidence of covalent binding and simultaneous binding across an A1R homodimer. Greater selectivity for A1R over the adenosine A3 receptor was observed for bivalent dicovalent over the equivalent monovalent compounds, indicating subtype selectivity can be achieved with dual occupation by a bivalent dicovalent ligand.
Generalized lichen planus pigmentosus and a new management approach
Authors: Araghi Farnaz , Beyki Farideh , Rakhshan Azadeh , Farshi Hamideh Moravvej
Published: May 2024

Key Clinical Message

Generalized lichen planus pigmentosus significantly improved with the daily administration of Tofacitinib at a dosage of 15 mg.
Combining computer‐based rehabilitative approach with tDCS for recovering of aphasia: Implications from a single case study
Authors: Contrada Marianna , Scarfone Federica , Iozzi Antonella , Carozzo Simone , Vatrano Martina , Nicoletta Maria Grazia , Nudo Giuseppe , Quintieri Maria , Tonin Paolo , Cerasa Antonio
Published: May 2024

Key Clinical Message

We present a case of a single left hemisphere temporal–parietal stroke with subacute global aphasia and severe verbal apraxia and moderate dysphagia. The patient underwent a combined transcranial direct current stimulation (tDCS) over the left dorsolateral prefrontal cortex (DLPFC) and language stimulation with Virtual Reality Rehabilitation System (VRRS). Patient was treated in a 1‐h session, for 5 days a week, for 4 consecutive weeks. After treatment, evident improvements in the comprehension of oral and written language, swallowing abilities, and caregiver burden were detected. Power spectrum analysis of EEG data revealed significant enhancements of θ, α, and β waves from baseline to follow‐up. These preliminary results seem to confirm the reliability of the tDCS translational application in conjunction with computer‐based cognitive treatment for language disorders in a patient with stroke‐induced aphasia.
Robust, Reproducible, and Scalable Synthesis of Silver Nanocubes
Authors: Zhang Dong , Chen Yidan , Huang Yu‐Shan , Huang Qijia , Kwan Li Kei , Xia Younan
Published: May 2024

It remains a challenge to accomplish colloidal synthesis of noble‐metal nanocrystals marked by high quality, large quantity, and batch‐to‐batch consistency. Here we report a self‐airtight setup for achieving robust, reproducible, and scalable production of Ag nanocubes with uniform and controlled sizes from 18 to 60 nm. Different from the conventional open‐to‐air setup, the self‐airtight system makes it practical to stabilize the reaction condition by minimizing the loss of volatile reagents. The new setup also allows us to easily optimize the amount of O2 (from air) trapped in the system, ensuring burst nucleation of single‐crystal seeds, followed by their slow growth into nanocubes. Most significantly, the new setup allows for the production of Ag nanocubes at gram quantities without sacrificing uniformity, corner/edge sharpness, controlled size, and high purity across different batches. The availability of high‐quality Ag nanocubes in such a large quantity is anticipated to substantially boost their use in applications related to plasmonics, catalysis, and biomedicine.
Systems and Methods for Continuous Evolution of Enzymes
Authors: Chen Anqi , Zhang Xinge Diana , Đelmaš Aleksandra Đurđević , Weitz David A. , Milcic Karla
Published: May 2024

Directed evolution generates novel biomolecules with desired functions by iteratively diversifying the genetic sequence of wildtype biomolecules, relaying the genetic information to the molecule with function, and selecting the variants that progresses towards the properties of interest. While traditional directed evolution consumes significant labor and time for each step, continuous evolution seeks to automate all steps so directed evolution can proceed with minimum human intervention and dramatically shortened time. A major application of continuous evolution is the generation of novel enzymes, which catalyze reactions under conditions that are not favorable to their wildtype counterparts, or on altered substrates. The challenge to continuously evolve enzymes lies in automating sufficient, unbiased gene diversification, providing selection for a wide array of reaction types, and linking the genetic information to the phenotypic function. Over years of development, continuous evolution has accumulated versatile strategies to address these challenges, enabling its use as a general tool for enzyme engineering. As the capability of continuous evolution continues to expand, its impact will increase across various industries. In this review, we summarize the working mechanisms of recently developed continuous evolution strategies, discuss examples of their applications focusing on enzyme evolution, and point out their limitations and future directions.
Migration of Condensed Aromatic Hydrocarbons During Alkyne‐Vinylidene Rearrangements
Authors: Korb Marcus , Ghazvini Seyed M. B. H. , Low Paul J.
Published: May 2024

Diarylacetylenes ArC≡CAr featuring condensed aromatic hydrocarbon fragments (Ar) such as naphthalene, anthracene, phenanthrene and pyrene were converted into vinylidene ligands by 1,2‐migration reactions within the coordination sphere of half‐sandwich complexes [MII(dppe)Cp]+ (MII = RuII, FeII). Comparison of the extent of conversion of the alkyne substrates to the vinylidene complexes [Ru{=C=CAr2}(dppe)Cp]+ with those obtained from acetylenes functionalized by smaller groups (H, CH3, Ph) show that the molecular volume (VM) of the migrating group and relief of steric congestion plays a role during the rearrangement process. Conversely, the H‐atoms from the larger condensed ring aryl groups that are in close proximity to the migrating sites also have a significant influence on the efficacy and extent of the reaction by restricting access of the alkyne to the metal center, resulting in a less effective migration reaction. This combination of competing steric factors (acceleration due to relief of steric congestion and restricted access of the alkyne moiety to the reaction site) is exemplified by the facile migration of 1‐pyryl entities and the low yields of vinylidene products formed from 1,2‐bis(9‐anthryl)acetylene.
Cation‐Stacking Approach Enabling Interconversion between Bis(xanthylium) and its Reduced Species
Authors: Kikuchi Moto , Tadokoro Tomoki , Tachibana Takuya , Suzuki Shuichi , Suzuki Takanori , Ishigaki Yusuke
Published: May 2024

Cyclophane‐type dications with two units of xanthylium were designed, with the expectation that intramolecular interaction between cation units could induce changes in absorption and redox behavior. The desired dications were synthesized via the macrocyclic diketone as a key intermediate, which was efficiently obtained by a stepwise etherification. X‐ray and UV/Vis measurements revealed that the cyclophane‐type dications adopt a stacking structure in both the crystal and solution. Due to the intramolecular interaction caused by π–π stacking of the xanthylium units, a considerable blue shift compared to the corresponding monocations and a two‐stage one‐electron reduction process were observed in the dications. Furthermore, upon electrochemical reduction of dications, the formation of biradicals via radical cation species was demonstrated by UV/Vis spectroscopy with several isosbestic points at both stages. Therefore, the cation‐stacking approach is a promising way to provide novel properties due to perturbation of their molecular orbitals and to stabilize the reduced species even though they have open‐shell characters.
Organoselenium Compounds in Medicinal Chemistry
Authors: Gallo‐Rodriguez Carola , Rodriguez Juan B.
Published: May 2024

The chemical and biological interest in this element and the molecules bearing selenium has been exponentially growing over the years. Selenium, formerly designated as a toxin, becomes a vital trace element for life that appears as selenocysteine and its dimeric form, selenocystine, in the active sites of selenoproteins, which catalyze a wide variety of reactions, including the detoxification of reactive oxygen species and modulation of redox activities. From the point of view of drug developments, organoselenium drugs are isosteres of sulfur‐containing and oxygen‐containing drugs with the advantage that the presence of the selenium atom confers antioxidant properties and high lipophilicity, which would increase cell membrane permeation leading to better oral bioavailability. This statement is the paramount relevance considering the big number of clinically employed compounds bearing sulfur or oxygen atoms in their structures including nucleosides and carbohydrates. Thus, in this article we have focused on the relevant features of the application of selenium in medicinal chemistry. With the increasing interest in selenium chemistry, we have attempted to highlight the most significant published data on this subject, mainly concentrating the analysis on the last years. In consequence, the recent advances of relevant pharmacological organoselenium compounds are discussed.
Aniquinazoline B, a Fungal Natural Product, Activates the μ‐Opioid Receptor
Authors: Damiescu Roxana , Elbadawi Mohamed , Dawood Mona , Klauck Sabine M. , Bringmann Gerhard , Efferth Thomas
Published: May 2024

The development of new μ‐opioid receptor (MOR) agonists without the undesirable side effects, such as addiction or respiratory depression, has been a difficult challenge over the years. In the search for new compounds, we screened our chemical database of over 40.000 substances and further assessed the best 100 through molecular docking. We selected the top 10 compounds and evaluated them for their biological activity and potential to influence cyclic adenosine monophosphate (cAMP) levels. From the tested compounds, compound 7, called aniquinazoline B, belonging to the quinazolinone alkaloids class and isolated from the marine fungus Aspergillus nidulans, showed promising results, by inhibiting cAMP levels and in vitro binding to MOR, verified through microscale thermophoresis. Transcriptomic data investigation profiled the genes affected by compound 7 and discovered activation of different pathways compared to opioids. The western blot analysis revealed compound 7 as a balanced ligand, activating both p‐ERK1/2 and β‐arrestin1/2 pathways, showing this is a favorable candidate to be further tested.
Hybrid catalyst‐assisted synthesis of multifunctional carbon derived from Camellia shell for high‐performance sodium‐ion batteries and sodium‐ion hybrid capacitors
Authors: Mao Hanshu , Yang Sisi , Yang Yingjun , Yang Jinyue , Yuan Guizhi , Zheng Mingtao , Hu Hang , Liang Yeru , Yu Xiaoyuan
Published: May 2024

Biomass‐derived carbon as energy storage materials have gradually attracted widespread attention due to their low cost, sustainability, and inherent structural advantages. Herein, hard carbon (H‐1200) and porous carbon (PC‐800) for sodium‐ion batteries (SIBs), sodium‐ion capacitors (SICs) half cells and sodium‐ion hybrid capacitors (SIHCs) have been synthesized from the same biomass precursor of Camellia shells through different treatments. H‐1200 synthesized by directly high‐temperature carbonization possesses a rational graphitic layer structure and plentiful heteroatoms. When applied as anode for SIBs, it exhibits a reversible capacity of 365.5 mAh g–1 at 25 mA g–1 and capacity retention 89.0% after 400 cycles at 200 mA g–1. Additionally, PC‐800 prepared by catalytic carbonization of K2C2O4/CaC2O4 hybrid catalyst has a sophisticated porous structure and a high surface area of 2186.9 m2 g–1. When employed as a cathode for SICs, it delivers a maximum capacity 104.2 mAh g–1 at 100 mA g–1 and 35.0 mAh g–1 at 5 A g–1. Furthermore, the all carbon assembled SIHC (H‐1200||PC‐800) using H‐1200 as anode and PC‐800 as cathode, features a broad output voltage range (0.01 ~ 4.1 V), high energy density of 161.5 Wh kg–1, power density of 12896.1 W kg–1, and superior capacity retention of 90.32% after 10000 cycles at 10 A g–1. This research result provide a new horizon for constructing low‐cost and large‐scale production of biomass derived carbon for energy storage materials.
Small Changes, Big Impact: Radical Formation of Perylene Monoimides in Photoredox Catalysis
Authors: Hagmeyer Nina , Costabel Daniel , Hofmeister Elisabeth , Nabiyan Afshin , Max Johannes , Schacher Felix H. , Peneva Kalina , Dietzek‐Ivanšić Benjamin
Published: May 2024

The use of organic molecules as photosensitizers in photoredox catalysis is an attractive research field as it has the potential to replace conventionally used photosensitizers, which are based on rare metals. In the context of light‐driven hydrogen evolution catalysis, the radical formation of two perylene monoimide dyes (PMIs) was studied by means of electron paramagnetic resonance (EPR) and UV/Vis spectroscopy. The PMIs were reduced and oxidized both photochemically and electrochemically to study the changes in absorption and EPR signature. A distinct differentiation between the two PMIs as well as a comparison between the oxidative and reductive processes can be made by EPR measurements. UV/Vis measurements showed different features under redox conditions. This study addresses a gap in understanding the radical intermediate formation during photocatalytic processes.
Fluoride Ions Post‐Treatment Regulates Interfacial Charge Separation and Transport to Promote Solar Water Splitting of Bismuth Vanadate
Authors: Liu Xiaogang , Zhang Xin , Chen Mengyu , Zhang Xing , Cao Kangzhe
Published: May 2024

Herein, we propose a simple and effective fluoride (F−) ions post‐treatment method to improve the solar water splitting performance of monoclinic BiVO4 (abbreviated as BVO). The surface modification of BVO with functional F− ions not only facilitates the transfer and separation efficiency of carriers at the electrode/electrolyte interface but also promotes the adsorption and activation of water, resulting in a photocurrent of 3.2 mA/cm2 at a bias voltage of 1.2 VRHE. Furthermore, the transfer and separation of carriers in the bulk and on the surface are further regulated by the oxygen vacancies induced by F− ions, thereby enhancing the PEC water splitting performance of BVO. Notably, the experimental findings demonstrate that the introduce of F− ions into the KBi electrolyte enhances the photo‐charging process of BVO. Specifically, at a bias voltage of 0.6 VRHE, the BVO‐0.12F sample exhibits a stable photocurrent of 1.2 mA/cm2, which is twice as high as that of the initial BVO sample. Remarkably, our study unveils that the addition of F− ions into the KBi electrolyte solution plays a pivotal role in facilitating the separation of charge carriers and promoting interfacial charge transport. Consequently, this further leads to a substantial enhancement in the solar water splitting performance for BVO‐0.12F photoanode.
Photocatalytic Three‐Component α‐Trifluoroalkyl‐β‐Heteroarylation of Unactivated Alkenes with Trifluoroacetates
Authors: He Yang , Wang Wenlin , An Yuanyuan , Zheng Danqing
Published: May 2024

We herein disclose a direct and practical photocatalytic three‐component α‐trifluoroalkyl‐β‐heteroarylation of various unactivated alkenes with trifluoroacetates and quinoxalin‐2(1H)‐ones. The reaction takes place via a photoinduced LMCT process, allowing efficient synthesis of a variety of 3‐fluoroalkylated quinoxalin‐2(1H)‐one derivatives in moderate to excellent yields under mild reaction conditions.
Fire safety research of rubber floor covering in a China ice sports center
Authors: Nan Tianchen , Zhang Huayun , Wu Dongli
Published: May 2024

This article examines the fire safety of rubber flooring used in an ice sports center in China. The fire characteristics and parameters of the rubber floor were determined through material fire tests. Subsequently, a fire safety analysis was conducted using the fire intrinsic safety method. Additionally, numerical simulation was employed to investigate fire and evacuation scenarios, particularly when the safety grade of the floor decoration materials falls below standard requirements. The results indicate that, under specific safety conditions, the ice sports center can utilize B1 grade rubber flooring in the required area while ensuring compliance with fire safety standards.
Bayesian benchmark dose risk assessment with mixed‐factor quantal data
Authors: Glisovic‐Bensa Mirjana , Piegorsch Walter W. , Bedrick Edward J.
Published: May 2024

Benchmark analysis is a general risk estimation strategy for identifying the benchmark dose (BMD) past which the risk of exhibiting an adverse environmental response exceeds a fixed, target value of benchmark response. Estimation of BMD and of its lower confidence limit (BMDL) is well understood for the case of an adverse response to a single stimulus. In many environmental settings, however, one or more additional, secondary, qualitative factor(s) may collude to affect the adverse outcome, such that the risk changes with differential levels of the secondary factor. Bayesian methods for estimation of the BMD and BMDL have grown in popularity, and a large variety of candidate dose–response models is available for applying these methods. This article applies Bayesian strategies to a mixed‐factor setting with a secondary qualitative factor possessing two levels to derive two‐factor Bayesian BMDs and BMDLs. We present reparameterized dose–response models that allow for explicit use of prior information on the target parameter of interest, the BMD. We also enhance our Bayesian estimation technique for BMD analysis by applying Bayesian model averaging to produce the BMDs and BMDLs, overcoming associated questions of model adequacy when multimodel uncertainty is present. An example from environmental carcinogenicity testing illustrates the calculations.
Electrical and optical properties of environmental friendly Li(1‐x)Smx/3NbO3 ceramics for high‐temperature energy storage applications
Authors: Satyarthi Satyendra Kumar , Singh Vishwa Pratap , Verma Harish , Singh Akhilesh Kumar
Published: May 2024

This research article delves into the synthesis and characterization of Li(1‐x)Sm(x/3)NbO3 ceramic, employing a high‐energy ball milling process. The investigation explores the incorporation of Sm3+ at the Li+1 site across a range of compositions (x = 0, 0.01, 0.02, 0.03, 0.04, 0.05). Structural analysis, using x‐ray diffraction (XRD) and Rietveld structural refinement, establishes that within the investigated composition range, no significant changes in the crystal structure are evident. The x‐ray photoelectron spectroscopy revealed the presence of oxygen vacancies as well as the stable oxidation state of different elements like O2−, Nb5+, Sm3+, and Li1+. At sintering temperature 1050°C, the average grain sizes vary approximately from 1.5 to 3.8 μm for different compositions with regular grain morphology. The UV‐Vis analysis reveals a noteworthy reduction in the band gap to 3.09 eV for the x = 0.01 composition. Photoluminescence studies exhibit distinct green, orange, and red bands, with the highest intensity observed for x = 0.01, showcasing promising optical properties. The dielectric permittivity of Sm‐substituted compositions surpasses the response of pure LiNbO3, demonstrating an increasing trend with temperature in the frequency range 100 Hz‐1 MHz intriguingly, no Curie temperature is observed up to 500°C for any composition. The polarization vs electric field hysteresis loop response highlights better polarization characteristics at the room temperature and maximum polarization is 0.66 μC/cm2 for the composition x = 0.05. The energy storage response of the developed compositions is investigated, which reveals a maximum efficiency of 46.64% for x = 0.04 in Li(1‐x)Sm(x/3)NbO3. The tunable optical properties, enhanced dielectric response, and notable energy efficiency of these high TC ceramics suggest their utility across diverse applications. These findings not only contribute to the understanding of functional ceramic materials but also pave the way for their optimized utilization in advanced technological applications, particularly in energy storage devices under nonambient conditions at high temperatures.
Exploring the instability in the food security due to nitrogen fertilizer regulatory policy
Authors: Tirgariseraji Mohammad , Nejadhashemi A. Pouyan , Jafari Yaghoob , Persson Tomas , Sabouni Mahmood Sabouhi , Mirzabaev Alisher , Nikouei Alireza , Froshani Naser Shahnoushi
Published: May 2024

The nitrogen regulatory policy (NRP) solution is introduced as a mitigation measure against environmental nitrogen losses and keeps food production in the Safe Operating Space of the Nitrogen Planetary Boundary. Meanwhile, scientific research shows that steps taken to reduce environmental harm can increase the unpredictability of calorie production from crops. This study sought to investigate the impact of NRP solutions on the level of risk of accessibility to calorie sources from domestic production, the variations in calorie sources by livestock and non‐livestock diet components, and the responses of different dietary preferences, namely, poor, medium, and rich livestock protein diets, against NRP solutions in the Zayandeh‐Rud River basin, Iran. We developed the aggregate household food security index (AHFSI) and combined it with outputs of crop simulation model to examine how changes in dietary energy supplies under three NRP scenarios—low, moderate, and high nitrogen fertilizer application—affect the stability of three regional dietary preferences. The comparison of NRP scenarios movements realized that increases (or decreases) in nitrogen fertilizer rates contradicted the stability in AHFSI. Additionally, a one‐unit change in the average calories from non‐livestock sources, such as wheat and potatoes, results in greater fluctuations in the standard deviations of produced calories compared to changes in meat and dairy production. We proposed that in order to prevent adverse effects of NRP solutions on food security, mitigation strategies addressing the NRP solution should be structured based on (i) regional heterogeneities, (ii) type of crops, that is, food and feed crops, (iii) the range of nitrogen rates movement; (iv) and the socioeconomic background related to dietary preferences or economic deciles of food expenditure.
Ameliorative effect of aqueous avocado seed extract against chromium‐induced oxidative stress and cellular damage in rabbit kidney
Authors: Okail Hanan A. , Anjum Sadia , Emam Nahed M. , Abdel‐Gaber Rewaida , Dkhil Mohamed A. , El‐Ashram Saeed , Ibrahim Mona A.
Published: May 2024

The accumulation of chromium in renal tissues promotes the generation of reactive oxygen species (ROS), leading to oxidative stress, genomic and cellular harm, and ultimately necrotic and apoptotic cell death induced by free radicals. Hence, the utilization of antioxidant phytochemicals becomes crucial for cellular defense against oxidative damage. This study endeavors to explore the potential protective effects of an aqueous avocado seed extract (ASE) on rabbit kidneys exposed to chromium‐induced damage. Fifteen adult rabbits were distributed into three groups: Group 1 was kept as the control. The second and third groups received a daily dose of K2Cr2O7 (5 mg/kg) intraperitoneally for 2 weeks. While the third group was given an oral dose of ASE (400 mg/kg). In rabbits administered with Cr (VI), kidney homogenates showed a marked increase in Malondialdehyde (MDA) (69.3 ± 4.1 nmol/g) along with a decrease in glutathione (59 ± 5.8 nmol/mg) content and the activity superoxide dismutase (SOD) (0.5 ± 0.05 U/mg protein), glutathione peroxidase (GPx) (16.7 ± 1.1 μmol/mg protein), and catalase (CAT) (73.8 ± 3.9 U/g protein) compared to the levels in control group. Also, the gene expression data for the enzymes SOD, GPx, and CAT dropped dramatically in kidney tissue following Cr (VI) injection. Additionally, Bowman's capsule and glomerulus showed degenerative alterations in the kidney's histopathology and immunohistochemistry. ASE treatment when administered along with Cr (VI) enhanced the activity and gene expression of antioxidant enzymes and improved histopathological conditions. The findings of this study unequivocally show that avocado seed extract, which is rich in phenolic derivatives, is a potent nephroprotective agent that inhibits nephrotoxicity induced by Cr (VI) in rabbits.
Sulforaphane and ophthalmic diseases
Authors: Zhang Yichi , Zhao Xiaojing , Liu Yang , Yang Xiuxia
Published: May 2024

Sulforaphane (SFN) is an organosulfur compound categorized as an isothiocyanate (ITC), primarily extracted from cruciferous vegetables like broccoli and cabbage. The molecular formula of sulforaphane (SFN) is C6H11NOS2. SFN is generated by the hydrolysis of glucoraphanin (GRP) through the enzyme myrosinase, showing notable properties including anti‐diabetic, anti‐inflammatory, antimicrobial, anti‐angiogenic, and anticancer attributes. Ongoing clinical trials are investigating its potential in diseases such as cancer, neurodegenerative diseases, diabetes‐related complications, chronic kidney disease, cardiovascular disease, and liver diseases. Several animal carcinogenesis models and cell culture models have shown it to be a very effective chemopreventive agent, and the protective effects of SFN in ophthalmic diseases have been linked to multiple mechanisms. In murine models of diabetic retinopathy and age‐related macular degeneration, SFN delays retinal photoreceptor cell degeneration through the Nrf2 antioxidative pathway, NF‐κB pathway, AMPK pathway, and Txnip/mTOR pathway. In rabbit models of keratoconus and cataract, SFN has been shown to protect corneal and lens epithelial cells from oxidative stress injury by activating the Keap1‐Nrf2‐ARE pathway and the Nrf‐2/HO‐1 antioxidant pathway. Oral delivery or intraperitoneal injection at varying concentrations are the primary strategies for SFN intake in current preclinical studies. Challenges remain in the application of SFN in eye disorders due to its weak solubility in water and limited bioavailability because of the presence of blood–ocular barrier systems. This review comprehensively outlines recent research on SFN, elucidates its mechanisms of action, and discusses potential therapeutic benefits for eye disorders such as age‐related macular degeneration (AMD), diabetic retinopathy (DR), cataracts, and other ophthalmic diseases, while also indicating directions for future clinical research to achieve efficient SFN treatment for ophthalmic diseases.
Effects of jujube (Ziziphus jujuba mill.) fruit extracts on oxidative stress: A systematic review and meta‐analysis of rodent studies
Authors: Zhu Di , Zhu Yu , Tan Hao , Ding Rui , Dai Qiangqiang , Du Xiaoming , Liu Yulin , Yue Rensong
Published: May 2024

This study aimed to evaluate the effects of jujube (Ziziphus jujuba Mill.) fruit extracts on oxidative stress levels in rodent models. Animal studies meeting the inclusion criteria were retrieved from PubMed, Web of Science, Embase, China National Knowledge Infrastructure (CNKI), Wanfang Data Knowledge Service Platform, and VIP Periodical Service Platform. The Systematic Review Center for Laboratory Animal Experimentation (SYRCLE) risk‐of‐bias tool was used to evaluate the risk of bias in the included studies. A meta‐analysis was performed based on the guidelines provided in the Cochrane Handbook for Systematic Reviews of Interventions (CHSRI) by using Stata 17.0 software. Nineteen studies were included in the meta‐analysis. Jujube fruit extracts significantly decreased the level of malonaldehyde (MDA) and increased the levels of superoxide dismutase (SOD) and glutathione peroxidase (GSH‐Px). Meanwhile, there was no significant improvement in the catalase (CAT) levels. In addition, there was considerable heterogeneity in the results of the meta‐analysis. The results of the subgroup analysis indicated that the animal model, type of extracts, and source of target parameters may have contributed to the heterogeneity. Jujube fruit extracts are healthy and effective antioxidant dietary supplements that may be an effective adjunctive therapy for diseases in which oxidative stress is a major pathological factor. However, the overall methodological quality of the included studies was low, and additional research is warranted.
Longitudinal microstructural alterations surrounding subcortical ischemic stroke lesions detected by free‐water imaging
Authors: Nägele Felix L. , Petersen Marvin , Mayer Carola , Bönstrup Marlene , Schulz Robert , Gerloff Christian , Thomalla Götz , Cheng Bastian
Published: May 2024

In this study we explore the spatio‐temporal trajectory and clinical relevance of microstructural white matter changes within and beyond subcortical stroke lesions detected by free‐water imaging. Twenty‐seven patients with subcortical infarct with mean age of 66.73 (SD 11.57) and median initial NIHSS score of 4 (IQR 3–7) received diffusion MRI 3–5 days, 1 month, 3 months, and 12 months after symptom‐onset. Extracellular free‐water and fractional anisotropy of the tissue (FAT) were averaged within stroke lesions and the surrounding tissue. Linear models showed increased free‐water and decreased FAT in the white matter of patients with subcortical stroke (lesion [free‐water/FAT, mean relative difference in %, ipsilesional vs. contralesional hemisphere at 3–5 days, 1 month, 3 months, and 12 months after symptom‐onset]: +41/−34, +111/−37, +208/−26, +251/−18; perilesional tissue [range in %]: +[5–24]/−[0.2–7], +[2–20]/−[3–16], +[5–43]/−[2–16], +[10–110]/−[2–12]). Microstructural changes were most prominent within the lesion and gradually became less pronounced with increasing distance from the lesion. While free‐water elevations continuously increased over time and peaked after 12 months, FAT decreases were most evident 1 month post‐stroke, gradually returning to baseline values thereafter. Higher perilesional free‐water and higher lesional FAT at baseline were correlated with greater reductions in lesion size (rho = −0.51, p = .03) in unadjusted analyses only, while there were no associations with clinical measures. In summary, we find a characteristic spatio‐temporal pattern of extracellular and cellular alterations beyond subcortical stroke lesions, indicating a dynamic parenchymal response to ischemia characterized by vasogenic edema, cellular damage, and white matter atrophy.