bluuebunny/crossref_metadata_2025_split huggingface dataset:
First Example of Single‐Crystal Nanodiamonds Immobilized in Porous SiO2‐Aerogel Matrix: Synthesis and Characterization
Authors: Fomina Irina G. , Gozhikova Inna O. , Sipyagina Nataliya A. , Straumal Elena A. , Kopitsa Gennady P. , Mazilkin Andrey A. , Eliseev Andrei A. , Efimov Nikolay N. , Zavorotny Yury S. , Shvidchenko Alexander V. , Vul' Alexander Y. , Eremenko Igor L. , Lermontov Sergey A. 
Published: August 2024

AbstractA first composite material containing uniformly dispersed disaggregated detonation nanocrystalline diamonds (DNDs) in SiO2 aerogel matrix was prepared. The synthetic protocol included hydrolysis of tetramethyl orthosilicate (Si(OMe)4, TMOS) by hydrosol of surface carboxylated DNDs with a typical size of 4–5 nm with DMSO serving as a cosolvent and a stabilizer of DND single crystals. Composite samples containing DNDs in silica aerogel matrix in concentration 1.0, 0.1 and 0.01 % w/w were prepared at ambient temperature. HRTEM data revealed that DNDs nanocrystals were uniformly distributed in aerogel and did not form aggregates. Textural and optical composites’ properties were determined.
A Synopsis on CO2 Capture by Synthetic Hydrogen Bonding Receptors
Authors: Giri Monalisa , Guchhait Tapas 
Published: August 2024

AbstractCarbon dioxide (CO2) is one of the most abundant greenhouse gases in Earth's atmosphere and responsible for global warming. Therefore, aerial CO2 capture and sequestration has become a major task for human community. Though several adsorbents for CO2 including activated carbon, zeolites, metal‐organic frameworks (MOFs), and other surface‐modified porous materials are well developed, the supramolecular approaches using synthetic hydrogen‐bonding receptors are less explored. This review article highlights the synthetic development of various artificial receptors and their properties toward fixation of aerial CO2 as carbonate (CO32−), bicarbonate (HCO3−), or carbamate (−NHCOO−/>NCOO−) ions, induced by excess fluoride (F−) or hydroxide (OH−) ions as their tetrabutylammonium salts. The utilization of encapsulated carbonate/bicarbonate/carbamate complexes in anion exchange metathesis for separation of oxyanions from aqueous solutions are also discussed. In addition, the release of CO2 and regeneration of receptor molecules are described in a number of occasions. Most importantly, the formation of anion complexes as crystalline materials in solid‐state is described in terms of supramolecular chemistry and correlated with their solution‐state properties. Finally, the types of receptors containing various functional groups are scrutinized in CO2 uptake, storage, and release processes and hints of endeavours for future research are delineated.
Thermal Migration to Recover Spent Pt/C Catalyst
Authors: Du Yu , Wang Ran , Huang Tao , Yang Xupin , Yan Shicheng , Zou Zhigang 
Published: August 2024

AbstractRecovery of spent Pt/C catalyst is a sustainable low‐cost route to promote large‐scale application of hydrogen fuel cells. Here, we report a thermal migration strategy to recover the spent Pt/C. In this route, the ZIF‐8 is used to produce nitrogen doped porous carbon (NC) with abundant pyrimidine nitrogen sites as the new support. Subsequently, the spent Pt/C, NC, and NH4Cl etching reagent are mixed and heated at 900 °C to thermally migrate Pt from Pt/C onto NC with the help of NH4Cl etching reagent. The thermal‐volatilized Pt tends to be captured by the pyrimidine nitrogen sites of NC support, thus producing the Pt clusters or 4–5 nm Pt particles. The recovered Pt/NC catalyst exhibits the highly stable oxygen reduction activities with a mass activity of 0.6 A mgPt−1 after 30000‐cycle accelerated durability test.
A Photoenzymatic Pathway for Gram‐Scale Synthesis of 25‐Hydroxyvitamin D3
Authors: Xu Caihong , Huang Yawen , Li Huanhuan , Shen Qianqian , Wang Feng , Shi Jianjun , Duan Peigao , Zhang Wuyuan 
Published: August 2024

AbstractVitamin D and its analogues play a crucial role in promoting the well‐being of both humans and animals. However, the current synthesis of this vital class of nutrients heavily relies on chemical transformations, which suffer from low step‐ and atom‐efficiency due to lengthy synthetic pathways. To enhance sustainability in the chemical industry, it is necessary to develop alternative synthetic processes. Herein, we present a photoenzymatic approach for synthesizing 25‐hydroxyvitamin D3 from 7‐dehydrocholesterol. In this sequential synthesis, 7‐dehydrocholesterol is initially hydroxylated at the C25 C−H bond, resulting in an 85 % conversion to 25‐hydroxyl‐7‐dehydrocholesterol. Subsequently, by employing photo‐irradiation using a monochromatic LED ultraviolet light source in a batch reactor and thermal isomerization, 25‐hydroxyvitamin D3 is obtained in satisfactory yield. This photoenzymatic process significantly reduces the need for purification steps and allows for gram‐scale synthesis of the target product. Our work offers a selective, efficient, and environmentally friendly method for synthesizing 25‐OH‐vitamin D3, addressing the limitations of current synthetic approaches.
Design, synthesis, molecular modeling, in vitro evaluation of novel piperidine‐containing hydrazone derivatives as cholinesterase inhibitors
Authors: Tok Fatih , Baltaş Nimet , Abas Burçin İrem , Tatar Yılmaz Gizem , Kaya Süleyman , Koçyiğit‐Kaymakçıoğlu Bedia , Çevik Özge 
Published: August 2024

AbstractIn an effort to develop new and effective therapeutic agents for Alzheimer's disease, a series of hydrazone derivatives bearing piperidine rings have been designed and synthesized. The chemical structures of the compounds were characterized by various spectroscopic techniques. In vitro antioxidant and cholinesterase activities of the compounds were evaluated. Among the compounds, N12 exhibited the most antioxidant activity in all methods (CUPRAC, FRAP, DPPH, ABTS). In vitro acetylcholinesterase (AChE) activity results of the compounds showed good IC50 values between 14.124 ± 0.084 and 49.680 ± 0.110 µM were obtained (IC50 = 38.842 ± 0.053 µM for Donepezil). Among the compounds, N7 and N6 are much more effective derivatives than the standard compound donepezil with IC50 values of 14.124 ± 0.084 and 17.968 ± 0.072 µM, respectively. In vitro, butyrylcholinesterase (BChE) inhibition values of the compounds were between 13.505 ± 0.025 and 52.230 ± 0.027 μm. Among the compounds, N6 has the highest BChE inhibition with an IC50 value of 13.505 μm in the series. The cytotoxicity and AChE inhibitory activity of the compounds on SH‐SY5Y cell lines were also evaluated. Kinetic studies were also performed to determine the behavior of the compounds as competitive or noncompetitive inhibitors. The binding modes of N6, which was determined to be highly effective according to in vitro analyses, with AChE and BChE were investigated using molecular docking studies, and the stability of the complexes was determined by molecular dynamics simulations. These findings indicated that AChE and BChE enzymes maintained their overall structural stability and compactness during interactions with compound N6.
Targeted degradation of KRAS protein in non‐small cell lung cancer: Therapeutic strategies using liposomal PROTACs with enhanced cellular uptake and pharmacokinetic profiles
Authors: Wang Xiaowen , Su Linyu , Niu Chong , Li Xiao , Wang Ruijie , Li Bo , Liu Sha , Xu Yuwen 
Published: August 2024

AbstractThe role of KRAS mutation in non‐small cell lung cancer (NSCLC) initiation and progression is well‐established. However, “undruggable” KRAS protein poses the research of small molecule inhibitors a significant challenge. Addressing this, proteolysis‐targeting chimeras (PROTACs) have become a cutting‐edge treatment method, emphasizing protein degradation. A modified ethanol injection method was employed in this study to formulate liposomes encapsulating PROTAC drug LC‐2 (LC‐2 LPs). Precise surface modifications using cell‐penetrating peptide R8 yielded R8‐LC‐2 liposomes (R8‐LC‐2 LPs). Comprehensive cellular uptake and cytotoxicity studies unveiled that R8‐LC‐2 LPs depended on concentration and time, showcasing the superior performance of R8‐LC‐2 LPs compared to normal liposomes. In vivo pharmacokinetic profiles demonstrated the capacity of DSPE‐PEG2000 to prolong the circulation time of LC‐2, leading to higher plasma concentrations compared to free LC‐2. In vivo antitumor efficacy research underscored the remarkable ability of R8‐LC‐2 LPs to effectively suppress tumor growth. This study contributed to the exploration of enhanced therapeutic strategies for NSCLC, specifically focusing on the development of liposomal PROTACs targeting the “undruggable” KRAS protein. The findings provide valuable insights into the potential of this innovative approach, offering prospects for improved drug delivery and heightened antitumor efficacy.
Adult Offspring of Deer Mouse Breeding Pairs Selected for Normal and Compulsive‐Like Large Nesting Expression Invariably Show the Same Behavior Without Prior In‐Breeding
Authors: Stoppel Heike , Harvey Brian H. , Wolmarans De Wet 
Published: August 2024

ABSTRACTObsessive‐compulsive disorder is a neuropsychiatric condition with notable genetic involvement. Against this background, laboratory‐housed deer mice of both sexes varyingly present with excessive and persistent large nesting behavior (LNB), which has been validated for its resemblance of clinical compulsivity. Although LNB differs from normal nesting behavior (NNB) on both a biological and cognitive level, it is unknown to what extent the expression of LNB and NNB is related to familial background. Here, we randomly selected 14 NNB‐ and 14 LNB‐expressing mice (equally distributed between sexes) to constitute 7 breeding pairs of each phenotype. Pairs were allowed to breed two successive generations of offspring, which were raised until adulthood (12 weeks) and assessed for nesting expression. Remarkably, our findings show that offspring from LNB‐expressing pairs build significantly larger nests compared to offspring from NNB‐expressing pairs and the nesting expression of the offspring of each breeding pair, irrespective of parental phenotype or litter, is family specific. Collectively, the results of this investigation indicate that LNB can be explored for its potential to shed light on heritable neurocognitive mechanisms that may underlie the expression of specific persistent behavioral phenotypes.
Adaptive interventions for advancing in situ wildlife disease management
Authors: Wilkinson Vicky , Richards Shane A. , Burgess Leah , Næsborg‐Nielsen Christina , Gutwein Katja , Vermaak Yolandi , Mounsey Kate , Carver Scott 
Published: August 2024

AbstractThere is a critical need for advancements in disease management strategies for wildlife, but free‐living animals pose numerous challenges that can hinder progress. Most disease management attempts involve fixed interventions accompanied by post hoc outcome assessments focused on success or failure. Though these approaches have led to valuable management advances, there are limitations to both the rate of advancement and amount of information that can be gained. As such, strategies that support more rapid progress are required. Sarcoptic mange, caused by epidermal infection with Sarcoptes scabiei mites, is a globally emerging and re‐emerging panzootic that exemplifies this problem. The bare‐nosed wombat (Vombatus ursinus), a marsupial endemic to southeastern Australia, is impacted by sarcoptic mange throughout its geographic range and enhanced disease management capabilities are needed to improve upon existing in situ methods. We sought to advance in situ wildlife disease management for sarcoptic mange in free‐living bare‐nosed wombats, implementing an adaptive approach using fluralaner (Bravecto, MSD Animal Health) and a structured process of learning and method‐optimisation. By using surveillance of treated wombats to inform real‐time management changes, we have demonstrated the efficacy of topically administered fluralaner at 45 and 85 mg/kg against sarcoptic mange. Importantly, we observed variation in the effects of 45 mg/kg doses, but through our adaptive approach found that 85 mg/kg doses consistently reduced mange severity. Through modifying our surveillance program, we also identified individual‐level variation in wombat observability and used this to quantify the level of surveillance needed to assess long‐term management success. Our adaptive intervention represents the first report of sarcoptic mange management with fluralaner in free‐living wildlife and evaluation of its efficacy in situ. This study illustrates how adapting interventions in real time can advance wildlife disease management and may be applicable to accelerating in situ improvements for other host–pathogen systems.
From darkness to twilight: Morphological divergence between cave and surface‐subterranean ecotone Niphargus species
Authors: Biró Anna , Balázs Gergely , Fišer Žiga , Fišer Cene , Horváth Gergely , Herczeg Gábor 
Published: August 2024

AbstractSubterranean and surface habitats are in stark contrast in several environmental factors. Therefore, adaptation to the subterranean environment typically impedes the (re)colonisation of surface habitats. The genus Niphargus includes amphipod crustaceans that primarily occupy subterranean habitats. All its species show typical adaptations to the subterranean environment. However, some Niphargus species occur in surface‐subterranean ecotones. To understand whether (i) habitat‐based phenotypic divergence is present between the cave and the ecotone species and (ii) similar phenotypes emerge independently in each ecotone, we studied morphological divergence between four cave and four ecotone Niphargus species based on 13 functional morphological traits. To account for different selection acting on the sexes, we included both males (N = 244) and females (N = 222). Nine out of 13 traits showed habitat‐divergence. Traits related to feeding and crawling were shorter, while traits related to oxygenation were larger in ecotone species. Eleven out of 13 traits were sexually dimorphic. Traits related to oxygenation and crawling were larger in females, while the trait related to swimming was larger in males. We found that the extent of sexual dimorphism differs between the habitats in eight traits related to sensing, feeding, oxygenation and crawling. Additionally, we found that in certain traits related to sensing and oxygenation, habitat‐related differences are only present in one sex, but not the other. We conclude that the detected differences between the cave and the ecotone species indicate divergent evolution, where similarities among the different species within habitat type indicate convergent evolution. The high degree of sexual dimorphism paired with differences in sexual dimorphism between the habitats in certain traits suggest that sexual and fecundity selections have comparable effects to environmental selection. Thus, studies of habitat‐dependent adaptations investigating one sex only, or not considering sexual dimorphism, can lead to erroneous conclusions.
A matter of scale: Identifying the best spatial and temporal scale of environmental variables to model the distribution of a small cetacean
Authors: Goh Tiffany , Jessopp Mark , Rogan Emer , Pirotta Enrico 
Published: August 2024

AbstractThe importance of scale when investigating ecological patterns and processes is recognised across many species. In marine ecosystems, the processes that drive species distribution have a hierarchical structure over multiple nested spatial and temporal scales. Hence, multi‐scale approaches should be considered when developing accurate distribution models to identify key habitats, particularly for populations of conservation concern. Here, we propose a modelling procedure to identify the best spatial and temporal scale for each modelled and remotely sensed oceanographic variable to model harbour porpoise (Phocoena phocoena) distribution within the Irish Exclusive Economic Zone. Harbour porpoise sightings were recorded during dedicated line‐transect aerial surveys conducted in the summers of 2016, 2021 and 2022. Binary generalised additive models were used to assess the relationships between porpoise presence and oceanographic variables at different spatial (5–40 km) and temporal (daily, monthly and across survey period) scales. Selected variables included sea surface temperature, thermal fronts, chlorophyll‐a, sea surface height, mixed layer depth and salinity. A total of 30,514 km was covered on‐effort with 216 harbour porpoise sightings recorded. Overall, the best spatial scale corresponded to the coarsest resolution considered in this study (40 km), while porpoise presence showed stronger association with oceanographic variables summarised at a longer temporal scale. Habitat models including covariates at coarse spatial and temporal scales may better reflect the processes driving availability and abundance of resources at these large scales. These findings support the hypothesis that a multi‐scale approach should be applied when investigating species distribution. Identifying suitable spatial and temporal scale would improve the functional interpretation of the underlying relationships, particularly when studying how a small marine predator interacts with its environment and responds to climate and ecosystem changes.
Small towns limit dispersal and reduce genetic diversity in populations of Texas horned lizards
Authors: Wall Ashley E. , Biffi Daniella , Ackel Alexis , Moody Raymond W. , Stevens Tom K. , Williams Dean A. 
Published: August 2024

AbstractThere is a general expectation that urban populations will be fragmented and the movement of individuals will be restricted leading to low effective population sizes, low genetic diversity, higher inbreeding, and higher differentiation than populations living in more continuous habitat. In this study, we compare the genetic diversity and differentiation of Texas horned lizards that are found in four small towns (Kenedy, Karnes City, Rockdale, and Smithville) in Texas and at Tinker Air Force Base, Oklahoma to populations that occur in 16 natural areas and to an introduced population in South Carolina. We also present more detailed spatial genetic data and home range data for several of the towns. Texas horned lizards (Phrynosoma cornutum) living in small towns have lower genetic diversity, higher differentiation, and smaller effective population sizes than populations located in more natural areas. There was evidence for human‐mediated movement of lizards into town; however, it has not been enough to counteract the effects of drift. Home range size is smaller in town than in more natural areas. Genetic patterns suggest dispersal occurs over short distances and is inhibited across areas with a high percent of impervious surface and major roads. These data suggest that effective planning to maintain suitable habitat and corridors to facilitate movement is critical to maintaining small terrestrial species like the Texas horned lizard and must be integrated into the early stages of urban development.
Fine‐scale phenotypic variation of a large herbivore in a pulsed environment
Authors: Foley Aaron M. , Gann Kory , Hewitt David G. , DeYoung Randy W. , Fulbright Timothy E. , Ortega‐S. J. Alfonso , Campbell Tyler A. 
Published: August 2024

AbstractThe resource rule hypothesis predicts that geographic differences in body size among populations of organisms are due to the amount, availability, and quality of food resources. For instance, the body size of large herbivores is often correlated with soil characteristics because better soils produce better forage. In semiarid environments, rainfall variation is an important driver of forage availability, especially highly nutritious annual forbs. Thus, in such pulsed‐resource environments, it is unclear whether the body size of large herbivores is influenced by fixed resources correlated with soil characteristics, irregular resource pulses correlated with rainfall, or both. Furthermore, it is not clear whether phenotypic expression is a function of forage quality or quantity. During the early autumns of 2011–2018, we captured 4554 white‐tailed deer (Odocoileus virginianus) on seven rangeland sites in the semiarid climate of South Texas, USA. The sites range from coastal to 140 km inland and represent gradients in both soil texture and annual rainfall. We recorded age‐ and sex‐specific indices of skeletal size, antler size, and body mass. Site‐specific soil characteristics explained most of the variation in skeletal size; percent sand was inversely related to skeletal size. For environmentally sensitive phenotypes (antler size and body mass), both soil characteristics and rainfall were influencers; increases in rainfall reduced the negative effect of sand. Percent sand and rainfall were positively correlated with annual biomass of preferred forbs, yet all phenotypic traits declined with increases in forb quantity. Increases in percent shrub cover increased all phenotype sizes. Our data suggest that the phenotypic expression of large herbivores in semiarid environments is driven by forage quality via edaphic characteristics rather than forage quantity via rainfall. Specifically, less sand in the soil allows for the development of shrub communities, which in turn provide a consistent source of forage in a variable, pulsed‐rainfall environment. Although forbs are of higher quality, they are highly ephemeral. The availability of a consistent source of forage may enable white‐tailed deer to extend time invested in body growth, which results in greater phenotype size. Our findings align with the resource rule hypothesis that identifies resource availability as a fundamental element explaining geographical variation in phenotypic expression.
[4+2]‐Cycloaddition Reactions to Corannulene Accelerated by η6‐Coordination of Ruthenium Complexes
Authors: Lebcir Amir , Boukhari Abbes , Solà Miquel , García‐Rodeja Yago 
Published: August 2024

AbstractThe influence of different (LRu)nII (L=Cp– (n=1, 2); C6H6) moieties η6‐coordinated to corannulene ((CpRu)+, (Benzene)Ru2+ and (CpRu)22+) has been explored by using the Activation Strain Model (ASM) of reactivity together with the Energy Decomposition Analysis (EDA) scheme. The results obtained have been compared with those obtained for the non‐coordinated corannulene counterpart. It has been observed that the presence of the ruthenium moiety favors both kinetically and thermodynamically the [4+2]‐cycloaddition reaction with cyclopentadiene. The factors governing these differences depend on the nature of the [Ru] complex. Whereas the interaction energy is solely responsible for the lower activation energy for the monocationic system (CpRu)+, not only the higher interaction but also the lower strain energy explain the much higher reactivity observed for the dicationic systems ((C6H6)Ru2+ and (CpRu)22+). In this latter case, the Pauli repulsion energy term is the factor controlling the differences in the interaction energies, following the so‐called Pauli repulsion‐lowering concept. Finally, when η6‐coordinating mono‐ or dicationic ruthenium complexes, although the [4+2]‐cycloaddition reaction in the external rim bonds remains the thermodynamically and kinetically more favourable, the cycloaddition becomes also thermodynamically feasible in some internal bonds.
Visible Light‐Induced Radical Tandem Cyclization of o‐Isocyanodiaryl Amines with Arylthiodifluoroalkyl 2‐Pyridyl Sulfones or Difluormethyl‐ Bromides
Authors: Liang Yong‐Xin , Ai Qing‐Wen , Yang Zi‐Xuan , Zhao Yu‐Long 
Published: August 2024

AbstractA visible‐light‐induced photoredox‐catalyzed radical tandem cyclization of o‐isocyanodiaryl amines with arylthiodifluoroalkyl 2‐pyridyl sulfones or difluormethyl bromides has been realized for the first time. The reaction works with a broad range of substrates and provides a simple and efficient method for the synthesis of 11‐difluoromethyl‐substituted dibenzodiazepines from easily available starting materials in very mild conditions.