bluuebunny/crossref_metadata_2025_split huggingface dataset:
Azolopyrimidine‐Based Thioethers: Synthesis via Cross‐Dehydrogenative C−S Coupling and In Silico Evaluation of Anti‐SARS‐CoV‐2 Activity
Authors: Akulov Alexey A. , Silaeva Anastasia I. , Varaksin Mikhail V. , Butorin Ilya I. , Lyapustin Daniil N. , Drokin Roman A. , Kotovskaya Svetlana K. , Zaykovskaya Anna V. , Pyankov Oleg V. , Rusinov Vladimir L. , Charushin Valery N. , Chupakhin Oleg N. 
Published: November 2024

AbstractAzoloazine derivatives are known as promising small molecules that are potentially able to counteract a broad spectrum of RNA viruses including SARS‐CoV‐2. However, a pool of synthetic pathways to provide convenient structural modification of such compounds without de novo construction of the heterocyclic scaffold is rather limited so far. This work proposes an approach to the direct C(sp2)−H functionalization of azolopyrimidine substrates with aromatic thiol residues, mediated by the iodine/persulfate reagent system. The reported herein sulfenylation protocol has afforded a series of previously undescribed azolopyrimidine‐based thioethers obtained in yields of up to 87 %. Applicability of the approach to the selenium‐centered synthons has been demonstrated as well. Besides, the in silico study with regard to the achieved cross‐coupling products has suggested the possible affinity to the SARS‐CoV‐2 main protease (Mpro), as follows from the conducted pharmacophore search and the molecular docking experiments. As a result, the developed synthetic transformation is expected to be of utility in the design of novel antiviral agents based on small azaheterocyclic molecules.
Activation of tert‐Butyl Hydroperoxide by Zr(IV) Stabilized by Polyoxotungstate Scaffolds
Authors: Ivanchikova Irina D. , Maksimchuk Nataliya V. , Marikovskaya Sofia M. , Evtushok Vasilii Yu. , Antonov Artem A. , Yanshole Vadim V. , Kholdeeva Oxana A. 
Published: November 2024

AbstractZr‐monosubstituted polyoxometalates (Zr‐POMs) of the Keggin (Bu4N)8[{PW11O39Zr(μ‐OH)}2] (Zr‐K), Lindqvist (Bu4N)6[{W5O18Zr(μ‐OH)}2] (Zr‐L), and Wells‐Dawson (Bu4N)11H3[{P2W17O61Zr(μ‐OH)}2] (Zr‐WD) structures are capable of heterolytic activation of the environmentally benign oxidant tert‐butyl hydroperoxide (TBHP) and catalyze epoxidation of alkenes and oxidation of alcohols to carbonyl compounds. Catalytic activity of corresponding Ti‐POMs is much lower. Among Zr‐POMs, Zr‐K revealed higher epoxide yields. All Zr‐POMs do not catalyze unproductive TBHP degradation, and epoxide yields with both aqueous and anhydrous TBHP are generally higher than with aqueous H2O2. Regioselectivity of the Zr‐K‐catalyzed limonene epoxidation with TBHP is different from that with H2O2: the more substituted and nucleophilic double bond is preferably epoxidized, pointing to an electrophilic oxygen transfer mechanism. The oxidation rates are first order in catalyst (Zr‐K) and substrate (cyclooctene or cyclohexanol) and show a saturation behavior with increasing concentration of TBHP. Studies by HR‐ESI‐MS, ATR‐FT‐IR, and 31P NMR spectroscopic techniques implicated the formation of zirconium alkylperoxo species upon interaction of Zr‐POMs with TBHP. HR‐ESI‐MS revealed the existence of monomeric and dimeric alkylperoxo complexes, [{PW11O39Zr}((CH3)3COO)]4− and [{PW11O39Zr((CH3)3COO)}2]8−, with predomination of the former, which is most likely the active species responsible for the selective oxidations.
Effects of Cannabidiol Isolated or in Association With Risperidone in an Animal Model of Autism
Authors: Costa Maiara de Aguiar da , Fernandes Gustavo Zanette , Maiochi Eduarda , Ebs Maria Fernanda Pedro , Darós Flávia da Silva , Bolan Sofia Januário , Costa Rosiane Ronchi Nascimento , de Rezende Victória Linden , da Silva Gláucia Crispim , Bitencourt Rafael Mariano , Gonçalves Cinara Ludvig 
Published: November 2024

ABSTRACTAutism spectrum disorder (ASD) is characterized by deficits in communication, social interaction, and repetitive and stereotyped behaviors, with no specific drug therapy available. Studies have found that cannabidiol (CBD) can improve hyperactive and cognitive symptoms in children with ASD. However, little is known about the effect of CBD in combination with other medications, such as risperidone (RISP). This study aimed to evaluate the behavioral and biochemical effects of CBD in animals using a valproic acid (VPA)‐induced ASD animal model. VPA was administered in pregnant Wistar rats on Day 12.5 of gestation to induce the ASD model. From the 10th to the 16th postnatal day (PND), the neurodevelopment of the animals was assessed through eye‐opening, olfactory discrimination, and negative geotaxis behavioral tests. From PNDs 9 to 54, the animals were weighed. They were treated for 21 days with CBD alone (100 mg/kg, by gavage, twice a day) or in combination with RISP (0.1 mg/kg, by gavage, once a day). At PND 55, the animals were evaluated in social interaction and locomotor activity experiments. Finally, after behavioral assessment, the animals were euthanized, the brain was isolated, and oxidative stress parameters were evaluated in the hippocampus and cortex posterior. Animals exposed to VPA showed neurodevelopmental delays in opening their eyes, difficulties in turning around their axis, and took longer time to find the original nest when compared to control animals. They also exhibited impaired sociability and reduced exploratory activity, which indicates model impairments. Interestingly, animals exposed to VPA treated with CBD + RISP significantly improved sociability parameters, whereas isolated CBD did not affect this parameter. In the biochemical analysis, a significant decrease in the hippocampal sulfhydryl content was noted in the CT + CBD group and an increase in the VPA + CBD group. In conclusion, these results suggest that CBD, in combination with RISP, may be an interesting pharmacological approach to reducing ASD‐related symptoms.Summary: Besides the increased prevalence of ASD cases in recent years, there are no medications to improve the central symptoms of autism. Numerous studies discuss CBD as an important medication for improving ASD symptoms; however, it is not known how CBD interacts with commonly used drugs in ASD individuals, such as RISP. This study demonstrated that CBD therapy, only when combined with RISP, improved sociability in a VPA‐induced ASD animal model.
Beyond the Surface: Mesophotic Reefs as Potential Refuges for Shallow Fish Assemblages
Authors: Velasco‐Lozano Manuel Francisco , Ramírez‐Ortiz Georgina , Calderon‐Aguilera Luis Eduardo , Martínez‐Garza Benjamín Alonso , Valencia‐Méndez Omar 
Published: November 2024

ABSTRACTThe deep reef refugia hypothesis suggests that the effects of disturbance decrease as depth increases; thus, reefs in the mesophotic zone potentially serve as refuges for communities in shallower zones. This study challenged this hypothesis by evaluating fish diversity in shallow and mesophotic reefs in a marine protected area in the Gulf of California. During 2021–2022, we conducted 189 5‐min video transects using remotely operated vehicles to document species richness and abundance. We evaluated six biological traits for each species (length, mobility, position, gregariousness, diet, and activity period) to estimate four functional indices (number of entities, richness, originality, and divergence), one phylogenetic index (Δ*), and Hill's numbers for taxonomic and functional indices. Benthic organisms were analyzed to explore relationships with ichthyofauna, while monthly water turbidity satellite data products were transformed into a light attenuation coefficient to identify the mesophotic zone (area between 10% and 0.1% of the incident light at the surface). At the study site, the mesophotic zone was identified to extend to 21 m under optimal conditions, which is shallower than what is typically observed in oligotrophic regions. Generalized linear models revealed significant variations in reef fish composition across spatial (site and zone) and temporal (season and year) dimensions. Additionally, generalized linear mixed models of functional richness and taxonomic Hill's numbers exhibited significantly higher values in the shallow zone. However, functional and phylogenetic indices showed similarities in fish assemblages. Despite differences in fish taxonomic diversity among zones that could be related to less environmental variation and resource availability in deep strata, mesophotic reef fish assemblages presented similar functions. Functions were maintained in mesophotic reefs, which suggests that the two zones are connected and that mesophotic reefs have the potential to act as partial refugia in the face of current and near‐future climate change‐related disturbances that could affect shallow zones.
Plastic Behaviour Buffers Climate Variability in the Wandering Albatross
Authors: Gillies Natasha , Thorley Jack , Weimerskirch Henri , Jenouvrier Stéphanie , Barbraud Christophe , Delord Karine , Patrick Samantha C. 
Published: November 2024

ABSTRACTClimate change has marked effects on global weather patterns and oceanic systems, impacting animal behaviour and fitness in potentially profound ways. Despite this, we lack detailed information about species' responses to climatic variation. Using an 11‐year tracking dataset of over 300 individual birds, we explore the consequences of variation in the southern annular mode (SAM) and southern oscillation index (SOI) for individual behaviour and fitness in wandering albatrosses Diomedea exulans breeding in the Southern Indian Ocean. Our results reveal distinct responses between males and females to climatic variation that align with the impacts of each climatic index on the distinct foraging ranges of each sex. In positive SAM phases, linked to poorer foraging conditions in female ranges and better conditions in male ranges, females exhibited behaviour consistent with reduced foraging success: that is, fewer prey capture attempts and more movement between feeding patches. Males, on the other hand, showed no behavioural change. During positive SOI phases, associated with good foraging conditions in both male and female foraging ranges, both sexes showed evidence of more successful foraging, with birds engaging in more search behaviour, and taking shorter trips with fewer prey capture attempts, together indicating increased food intake per unit time. We found limited evidence for a role of individual variation, as measured through differences in personality, suggesting that plastic responses to climate are sufficiently important so as to obscure inter‐individual variation. Supporting this was the finding that individual breeding success was unaffected by climatic variation, suggesting that plastic foraging behaviour allows albatrosses to mitigate climate impacts and maintain reproductive output.
Energy transfer efficiency rather than productivity determines the strength of aquatic trophic cascades
Authors: Zhou Libin , Luo Mingyu , Hong Pubin , Leroux Shawn , Chen Feizhou , Wang Shaopeng 
Published: November 2024

AbstractTrophic cascades are important determinants of food web dynamics and functioning, yet mechanisms accounting for variation in trophic cascade strength remain elusive. Here, we used food chain models and a mesocosm experiment (phytoplankton–zooplankton–shrimp) to disentangle the relative importance of two energetic processes driving trophic cascades: primary productivity and energy transfer efficiency. Food chain models predicted that the strength of trophic cascades was increased as the energy transfer efficiency between herbivore and predator (predator efficiency) increased, while its relationship with primary productivity was relatively weak. These model predictions were confirmed by a mesocosm experiment, which showed that the strength of trophic cascade increased with predator efficiency but remained unaffected by nutrient supply rate or primary productivity. Combined, our results indicate that the efficiency of energy transfer along the food chain, rather than the total amount of energy fixed by primary producers, determines the strength of trophic cascades. Our study provides an integrative perspective to reconcile energetic and population dynamics in food webs, which has implications for both ecological research and ecosystem management.
Herbivory and allelopathy contribute jointly to the diversity–invasibility relationship
Authors: Wang Jiang , Gao Song , Hong Hefang , Xue Wei , Yuan Jiwei , Wang Xiao‐Yan , van Kleunen Mark , Li Junmin 
Published: November 2024

AbstractAlthough herbivory and allelopathy play important roles in plant invasions, their roles in mediating the effect of plant diversity on invasion resistance remain unknown. In a 2‐year field experiment, we constructed native plant communities with four levels of species richness (one, two, four, and eight species) and used a factorial combination of insecticide and activated carbon applications to reduce herbivory and allelopathy, respectively. We then invaded the communities with the introduced plant Solidago canadensis L. One year after the start of the experiment, there was no statistically significant net effect of species richness on biomass of the invader. However, a structural equation model showed that species richness had a positive direct effect on invader biomass that was partially balanced out by a negative indirect effect of species richness via increased light interception. In the second year, the relationship between invader biomass and species richness was negative when we analyzed the treatment combination with herbivory and allelopathy separately. Therefore, we conclude that joint effects of herbivory and allelopathy may play major roles in driving the diversity–invasibility relationship and should be considered in future studies.
Comparative Effects of Crocin and Losartan on RAGE, TGF‐β, TNF‐α Gene Expression and Histopathological Changes of the Liver Tissue in Rats With Diabetes
Authors: Rajabi Shahnaz , Mohammadi Yaser , Kabiri‐rad Hamid , Rajabi‐moghaddam Mahdiyeh , Farimani Azam Rezaei 
Published: November 2024

ABSTRACTBackground and ObjectivesAGEs, via RAGE, increase the development of hyperglycemia‐induced liver damage, and blocking this axis is associated with a reduction in liver disease progression. The goal of this study was to determine how crocin and losartan influenced RAGE, TNF‐α and TGF‐β gene expression in diabetic rats, as well as histological changes in liver tissue.Materials and MethodsDiabetes was induced in 40 male Wistar rats using Streptozotocin (50 mg/kg, IP). There were five groups of rats: diabetic and healthy groups, diabetic rats given crocin (50 mg/kg), losartan (25 mg/kg) and both (crocin + Los). Serum glucose, ALT and AST levels were measured 4 weeks later. qPCR was used to examine the TNF‐α, TGF‐β and RAGE gene expression in liver tissue.ResultsCrocin was found to be effective in lowering FBG in the diabetes group. The serum levels of ALT and AST decreased in all treated groups, but this decrease was significant in the crocin + Los group (p < 0.05). The relative expression of RAGE, TNF‐α and TGF‐β genes was significantly higher in the diabetes group compared to the healthy group. The expression of these genes decreased in groups treated with crocin and Losartan compared to the diabetes group. The highest reduction in RAGE and TGF‐β gene expression was reported in those treated with crocin + Los. Histopathology results showed that the diabetes group had more bile ducts and necrosis than the healthy control group, which had no tissue changes. Hepatocyte degeneration, bile duct proliferation, inflammatory changes and hepatocyte necrosis were mild in the treated groups, but no hepatocyte necrosis was observed in the crocin + Los group.ConclusionCrocin may be a feasible therapeutic agent for treating diabetes and its symptoms when combined with pharmaceutical medications. Human research is still needed to reach clear conclusions.
Superior Energy Storage Performance in Crosslinked Binary Polymers at High Temperatures Via Confinement Effect
Authors: Liu Yongbin , Xu Yating , Gao Jinghui , Xu Jingzhe , Wu Ming , Liu Zhengwei , Wang Yilong , Lou Xiaojie , Zhong Lisheng 
Published: November 2024

High‐temperature performance of energy storage dielectric polymers is desired for many electronics and electrical applications, but the trade‐off between energy density and temperature stability remains fundamentally challenging. Here, we report a general material design strategy to enhance energy storage performance at high temperatures by crosslinking a polar polymer and a high glass‐transition temperature polymer as a crosslinked binary blend. Such crosslinked binary polymers display a temperature‐insensitive and high energy density behavior of about 6.2 ~ 8.5 J cm−3 up to 110 °C, showing a significant enhancement in thermal resistant properties and consequently outperforming most of the other ferroelectric polymers. Further microstructural investigations reveal that the improved thermal stability stems from the confinement effect on conformational motion of the crosslinking network, which is evidenced by the increased rigid amorphous fraction and steady intermolecular distance of amorphous regions from temperature‐dependent X‐ray diffraction results. Our findings provide a general and straightforward strategy to attain temperature‐stable, high‐energy‐density polymer‐based dielectrics for energy storage capacitors.
Synthesis of 1,4‐Naphthoquinones via Palladium(II)‐Catalyzed Tertiary C−H Alkylation of Olefins Followed by C−C Bond Cleavage
Authors: Zhang Xu , Chang Mengfan , Ni Tongtong , Xu Xuefeng , Li Wenguang , Li Ting 
Published: November 2024

AbstractAn efficient method has been developed for the preparation of 1,4‐naphthoquinones via a palladium‐catalyzed reaction of 2‐aryl‐1,3‐indandiones with olefins. This reaction involves the tertiary C−H alkylation of 2‐aryl‐1,3‐indandiones with olefins to produce a tertiary alcohol, followed by C−C bond cleavage.
The association between resistance training volume load and session rating of perceived exertion in junior developmental female rugby league athletes
Authors: Flannery Layne , Compton Heidi R. , Dascombe Ben J. , West Millicent A. , Secomb Josh L. 
Published: November 2024

AbstractField‐based team sports typically perform mixed‐modality training, incorporating both field‐ and resistance‐based sessions. As such, the availability of useful and reliable methods to monitor the internal and external training loads of all modalities is essential for planning effective training. Twenty‐one junior developmental female rugby league athletes (age: 17.5 ± 0.5 years, height: 167.7 ± 4.6 cm, body mass: 71.1 ± 12.9 kg, and training age: 2.3 ± 1.1 year) performed two to three resistance training sessions a week for 20 weeks (9 weeks preseason and 11 weeks in‐season). The volume load method and session rating of perceived exertion (sRPE) were used to quantify the external and internal load of the resistance training sessions, respectively. Volume load was categorised into either dynamic, plyometric, maximal or repeated efforts. Multiple linear mixed models were performed to determine whether significant relationships were present between the changes in volume load components and sRPE throughout the season. Significant relationships were identified between a decrease in sRPE, with associated increases in absolute and relative overall volume load (T1,725.5 = −2.1, p = 0.04; T1,133.5 = −2.2, p = 0.03), and relative dynamic (T1,24.1 = −8.4, p < 0.01) and lower‐body plyometric efforts (T1,16.8 = −17.2, p < 0.01). Conversely, significant relationships were observed between an increase in sRPE, with associated increases in relative lower‐body (T1,20.3 = 12.9, p < 0.01) and upper‐body repeated efforts (T1,28.5 = 9.7, p = 0.03) as well as relative upper‐body plyometric (T1,71.1 = 2.9, p = 0.01) and maximal efforts (T1,75.3 = 3.4, p < 0.01). These findings highlight the practicality of the volume load method for planning and monitoring resistance training in field‐based team sport athletes, providing useful data for the planning of specific exercises within the in‐season training week.
When to Use Rectangular Waveforms in Dielectrophoresis Application to Increase Separation and Sorting Efficiency
Authors: Boldt Niklas P. , Weirauch Laura , Späth Jana M. , Kerst Uwe , Birkholz Mario , Baune Michael , Thewes Roland 
Published: November 2024

AbstractIn this study, the influence of using rectangular waveforms is comprehensively investigated on the separation and sorting efficiency of dielectrophoretic (DEP) processes. Besides positive effects on DEP experiments, cases of a diminished force due to rectangular waveforms are investigated and discussed. This investigation encompasses two primary experimental setups. First, microparticle‐focusing experiments are carried out using a pair of electrodes within a microfluidic channel. Second, separation experiments are performed using a macroscopic insulator‐based dielectrophoretic filter. The study reveals that harmonics of rectangular signals can have a positive impact on separation or sorting efficiency when compared to sinusoidal waveforms, provided that these harmonics contribute to the overall DEP force with the same sign. This positive effect is found to depend on the ratio between the applied fundamental frequency and the cross‐over frequency in the Clausius–Mossotti factor. However, violating related derived boundary conditions leads to negative effects and a decrease in the DEP net force.
Flow Rate Determination of the Nanoflow Sheath Liquid CE–MS‐Coupling Applying the nanoCEasy Interface
Authors: Höchsmann Alisa , Schairer Jasmin , Schott Oliver , Höneise Ralf , Neusüß Christian 
Published: November 2024

ABSTRACTIn recent years, nanoflow sheath liquid (nanoSL) interfaces have been used more commonly for capillary electrophoresis–mass spectrometry (CE–MS) coupling due to their high sensitivity combined with flexibility in CE separation conditions. So far, the exact amount of sheath liquid (SL) and, thus, the dilution effect remain unknown due to the self‐supplying type of the nanoSL interfaces. To quantify the SL flow rates, we present here an approach for the determination of the flow rate based on isotopically labeled standards using the nanoCEasy interface. SL and pumped CE flow are spiked with atrazine and d5‐atrazine, respectively, enabling the determination of the total flow rate for different electrospray (ES) conditions. Generally, flow rates increase with higher ES voltages. Only at high ES voltages, larger emitter sizes lead to higher flow rates; for low voltages, flow rates are independent of emitter size. Additionally, smaller emitter sizes can generally be operated at lower ES voltages. Visualizing the ES, higher flow rates lead to a larger spray angle. Higher flow rates may decrease the signal intensity by diluting the CE‐separated analytes. Indeed, this effect is observed for the flow‐injected atrazine analytes and in the CE–MS analysis of an amino acid standard mix under aqueous acidic separation conditions. Therefore, lower flow rates are preferred for low electroosmotic flow (EOF) applications. However, in high EOF applications, higher voltages are required to prevent the accumulation of aqueous background electrolyte (BGE) at the emitter tip, which otherwise leads to peak broadening and inefficient ionization. Overall, the presented data enable the selection of stable and sensitive settings for nanoSL interfaces.