bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dual‐Catalytic Structural Isomerisation as a Route to α‐Arylated Ketones
Authors: Lunic Danijela , Vystavkin Nikita , Qin Jingyang , Teskey Christopher J. 
Published: July 2024

AbstractIsomerisation reactions provide streamlined routes to organic compounds which are otherwise hard to directly synthesise. The most common forms are positional, geometrical or stereochemical isomerisations which involve the relocation of a double bond or a change in relative location of groups in space. In contrast, far fewer examples of structural (or constitutional) isomerisation exist where the connectivity between atoms is altered. The development of platforms capable of such rearrangement poses a unique set of challenges because chemical bonds must be selectively cleaved, and new ones formed without overall addition or removal of atoms. Here, we show that a dual catalytic system can enable the structural isomerisation of readily available allylic alcohols into more challenging‐to‐synthesise α‐arylated ketones via a H‐atom transfer initiated semi‐pinacol rearrangement. Key to our strategy is the combination of a cobalt catalyst and photocatalyst under reductive, protic conditions which allows intermediates to propagate catalytic turnover. By providing an unusual disconnection to structural motifs which are difficult to access through direct arylation, we anticipate inspiring other advanced catalytic isomerisation strategies that will further retrosynthetic logic for complex molecule synthesis.
Near Ultraviolet‐Excitable Cyan‐Emissive Hybrid Copper(I) Halides Nonlinear Optical Crystals with Near‐Unity Photoluminescence Quantum Yield and High‐Efficiency X‐ray Scintillation
Authors: Qi Jing‐Li , Guo Yue , Wu Jiajing , Huang Qiao‐Feng , Xu Jun‐Jie , Yan Shu‐Fang , Liu Wenlong , Guo Sheng‐Ping 
Published: July 2024

AbstractDesigning and synthesizing multifunctional hybrid copper halides with near ultraviolet (NUV) light‐excited high‐energy emission (<500 nm) remains challenging. Here, a pair of broadband‐excited high‐energy emitting isomers, namely, α‐/β‐(MePh3P)2CuI3 (MePh3P=methyltriphenylphosphonium), were synthesized. α‐(MePh3P)2CuI3 with blue emission peaking at 475 nm is firstly discovered wherein its structure contains regular [CuI3]2− triangles and crystallizes in centrosymmetric space group P21/c. While β‐(MePh3P)2CuI3 featuring distorted [CuI3]2− planar triangles shows inversion symmetry breaking and crystallizes in the noncentrosymmetric space group P21, which exhibits cyan emission peaking at 495 nm with prominent near‐unity photoluminescence quantum yield and the excitation band ranging from 200 to 450 nm. Intriguingly, β‐(MePh3P)2CuI3 exhibits phase‐matchable second‐harmonic generation response of 0.54×KDP and a suitable birefringence of 0.06@1064 nm. Furthermore, β‐(MePh3P)2CuI3 also can be excited by X‐ray radioluminescence with a high scintillation light yield of 16193 photon/MeV and an ultra‐low detection limit of 47.97 nGy/s, which is only 0.87 % of the standard medical diagnosis (5.5 μGy/s). This work not only promotes the development of solid‐state lighting, laser frequency conversion and X‐ray imaging, but also provides a reference for constructing multifunctional hybrid metal halides.
Thiosemicarbazones and derived tin complexes: Synthesis, structural analysis and in vitro evaluation against bacterial and cancer cells
Authors: Ibrahim Ahmed B. M. , Mayer Peter , Abbas Safaa M. 
Published: July 2024

Two complexes of Sn (IV), Sn (IV)‐TSC 1 and Sn (IV)‐TSC 2, with the ligands 4‐(2,4‐dimethylphenyl)‐1‐([pyridin‐2‐yl]methylene)thiosemicarbazide (TSC 1) and 4‐(2,5‐dimethoxyphenyl)‐1‐([pyridin‐2‐yl]methylene)thiosemicarbazide (TSC 2) were synthesized. X‐ray crystallographic investigation of Sn (IV)‐TSC 2 afforded valuable information on its octahedral geometry, monoclinic lattice and C 1 2/c 1 space group. The ligands are monoanionic tridentate via a deprotonated thiol sulfur atom and two nitrogen atoms of pyridine and azomethine moieties. These atoms coordinate tin alongside three independent chlorine atoms making the tin atoms in the complexes tetravalent, despite of incorporating tin (II) chloride in the reactions. Solutions of the ligands TSC 1 and TSC 2 (20 mg/ml in dimethyl sulfoxide) induced growth inhibitions only to Staphylococcus aureus (14 and 10 mm) and Escherichia coli (15 and 10 mm) bacteria. But the complexes displayed activities against four bacterial species, that is, S. aureus, E. coli, Bacillus subtilis and Pseudomonas aeruginosa (complex Sn (IV)‐TSC 1, complex Sn (IV)‐TSC 2 and ampicillin showed inhibition diameters with 12–14, 13–14 and 21–26 mm). All TSC ligands and coordination compounds induced cytotoxicity in MCF‐7 cancer and BHK normal cells. The compounds TSC 1, TSC 2, Sn (IV)‐TSC 1, Sn (IV)‐TSC 2 and doxorubicin inhibited the MCF‐7 (BHK) cells with IC50 values of 68.9 (126.6), 145.4 (110.6), 22.6 (16.7), 34.2 (16.1) and 9.66 (36.42) μM, respectively.
High‐Speed and Long‐Distance Spin‐Wave Propagation in Spinel γ‐Fe2O3 Epitaxial Thin Films
Authors: Tang Siyi , Yao Lihao , Sarker Md Shamim , Liao Zhiqiang , Ma Kaijie , Yamahara Hiroyasu , Tabata Hitoshi , Seki Munetoshi 
Published: July 2024

AbstractIn spin wave (SW) devices, the modulation of SWs for computational units is necessary, imposing extremely high demands on material systems. In this study, high‐quality epitaxial‐grown spinel γ‐Fe2O3 thin films on conductive Nb‐doped SrTiO3 substrates, achieving fast‐speed, high‐frequency, and long‐distance SW propagation in this ferrimagnetic material, are developed. A novel two‐step film growth technique using pulsed laser deposition is proposed and optimized, and the damping constant, exchange stiffness, and anisotropies of γ‐Fe2O3 are determined. Compared to reported semiconductor magnetic materials, these epitaxial‐grown γ‐Fe2O3 thin films exhibit a significantly lower damping constant of 10−2, representing a substantial advancement. Using finite‐difference calculations, SW propagation is simulated, and vital information on transmission distance and dispersion curves is obtained. Experimental results show excellent agreement with these simulations. By applying a voltage to both sides of the conducting substrate, current across the film and SW device, resulting in the frequency shift of the SWs, is generated. These results demonstrate that high‐quality γ‐Fe2O3 films developed through the two‐step growth method can efficiently propagate SWs, offering possibilities for various modulation methods in SW‐based computing devices. This study positions spinel γ‐Fe2O3 as a promising ferrimagnetic candidate for future applications in efficient SW modulation within computational systems.
The effect of used cooking oil composition on the specific CO2e emissions embodied in HEFA‐SPK production
Authors: Mannion Liam A. , Redington Conor , Kelly Mark , Bell Aron , Dooley Stephen 
Published: July 2024

AbstractIn this study, the correlation between the composition, hydrogen/carbon (H/C) ratio, and hydrogen/oxygen (H/O) ratio of a used cooking oil (UCO) and the specific emissions embodied in the derived hydroprocessed esters and fatty acids synthetic paraffinic kerosene (HEFA‐SPK) is investigated. It is shown that HEFA‐SPK produced from UCOs with low concentrations of C18:1, high concentrations of C18:2, and low H/C ratios utilize less energy and more hydrogen during Fuel Production. Hence, HEFA‐SPK produced from such UCOs will embody higher gCO2e for fossil hydrogen utilization scenarios, and lower gCO2e for green hydrogen utilization scenarios compared with other UCOs. Conversely, it is shown that HEFA‐SPK produced from UCOs with high concentrations of C18:1, low concentrations of C18:2 and high H/C ratios utilize more energy and less hydrogen during Fuel Production. Hence, HEFA‐SPK derived from such UCOs will embody lower gCO2e for fossil hydrogen utilization scenarios, and higher gCO2e for green hydrogen utilization scenarios compared with other UCOs. Monte Carlo simulation gives the emissions embodied in Fuel Production a 95% confidence interval for all UCO‐derived HEFA‐SPK, showing a similar uncertainty for all compositions. A maximum of +1.1 gCO2e/MJSAF and −1.0 gCO2e/MJSAF is obtained for the upper and lower bounds respectively for the emissions embodied during HEFA‐SPK production from UCO. The application of the correlations founded in this study allows for the prediction of the specific emissions embodied in the feedstock‐to‐fuel conversion of any UCO, providing the C18:1 concentration, C18:2 concentration, H/C ratio and H/O ratio of the UCO is known.
Investigating the detection of the novel doping‐relevant peptide kisspeptin‐10 in urine using liquid chromatography high‐resolution mass spectrometry
Authors: Colpaert Thibo , Risseeuw Martijn , Deventer Koen , Van Eenoo Peter 
Published: July 2024

AbstractKisspeptin‐10 is a peptide hormone capable of increasing circulating follicle‐stimulating hormone, luteinizing hormone and testosterone levels in humans. Clinically, these effects suggest its use as a treatment for infertility. However, its testosterone‐increasing effect indicates potential misuse in sports. As such, it is included in the 2024 World Anti‐Doping Agency Prohibited List. This work describes the successful validation of an initial testing procedure (screening) and a confirmation procedure for kisspeptin‐10 in urine using liquid chromatography–mass spectrometry. Additionally, kisspeptin‐10 was incubated in human serum to mimic endogenous metabolism to improve method sensitivity, as previous research had demonstrated a rapid elimination time of only 30 min after injection (in rats). Four metabolites, corresponding to peptide fragments y9, y8, y7 and y5, were found and added to the ITP in full scan mode. A degradation product discovered during early experimentation was found to probably be caused by oxidation of the tryptophan residue into a kynurenine residue. Further research should elucidate the kinetic parameters of the reaction to improve product stability. Using the validated confirmation procedure, a black‐market vial of kisspeptin‐10 was analysed. The product contained no unexpected impurities, although it appeared to have undergone more degradation than the purchased reference standard.
Design and Characterization of Neutral Linker‐Based Bis‐Intercalator via Computer Simulations: Balancing DNA Binding and Cellular Uptake
Authors: Pant Pradeep 
Published: July 2024

AbstractBis‐intercalators refer to a class of chemical compounds known for their unique ability to simultaneously intercalate, or insert, into DNA at two distinct sites. These molecules typically feature two intercalating moieties connected by a linker, allowing them to engage with DNA base pairs at multiple locations. The bis‐intercalation phenomenon plays a significant role in altering the DNA structure, affecting its stability, and potentially influencing various cellular processes. These compounds have gained considerable attention in medicinal chemistry and biochemistry due to their potential applications in cancer therapy, where they may interfere with DNA replication and transcription, leading to anticancer effects. Traditionally, these molecules often possess a high positive charge to enhance their affinity for the negatively charged DNA. However, due to a high positive charge, their cellular uptake is compromised, along with their enhanced potential off‐target effects. In this study, we utilized bis‐intercalator TOTO and replaced the charged linker segment (propane‐1,3‐diammonium) with a neutral peroxodisulphuric acid linker. Using molecular modeling and computer simulations (500 ns, 3 replicas), we investigated the potential of the designed molecule as a bis‐intercalator and compared the properties with the control bis‐intercalator bound to DNA. We observed that the designed bis‐intercalator exhibited improved DNA binding (as assessed through MM‐PBSA and Delphi methods) and membrane translocation permeability. With an overall reduced charge, significantly less off‐target binding of the designed molecule is also anticipated. Consequently, bis‐intercalators based on peroxodisulphuric linkers can potentially target DNA effectively, and their role in the future design of bis‐intercalators is foreseen.
M6A modification and T cells in adipose tissue inflammation
Authors: Yang Xiaoting , Tang Haojun , Sun Xuan , Gui Qingjun 
Published: July 2024

AbstractAdipose tissue in the obese state can lead to low‐grade chronic inflammation while inducing or exacerbating obesity‐related metabolic diseases and impairing overall health.T cells, which are essential immune cells similar to macrophages, are widely distributed in adipose tissue and perform their immunomodulatory function; they also cross‐talk with other cells in the vascular stromal fraction. Based on a large number of studies, it has been found that N6 methyl adenine (m6A) is one of the most representative of epigenetic modifications, which affects the crosstalk between T cells, as well as other immune cells, in several ways and plays an important role in the development of adipose tissue inflammation and related metabolic diseases. In this review, we first provide an overview of the widespread presence of T cells in adipose tissue and summarize the key role of T cells in adipose tissue inflammation. Next, we explored the effects of m6A modifications on T cells in adipose tissue from the perspective of adipose tissue inflammation. Finally, we discuss the impact of m6a‐regulated crosstalk between T cells and immune cells on the prospects for improving adipose tissue inflammation research, providing additional new ideas for the treatment of obesity.
Cerium oxide nanoparticles display antioxidant and antiapoptotic effects on gamma irradiation‐induced hepatotoxicity
Authors: Saif‐Elnasr Mostafa , Samy Esraa M. , Abdel‐Khalek Assmaa Fathi 
Published: July 2024

AbstractThroughout radiotherapy, radiation of the hepatic tissue leads to damage of the hepatocytes. We designed the current study to examine how cerium oxide nanoparticles (CONPs) modulate gamma irradiation‐induced hepatotoxicity in rats. Animals received CONPs (15 mg/kg body weight [BW], ip) single daily dose for 14 days, and they were exposed on the seventh day to a single dose of gamma radiation (6 Gy). Results showed that irradiation increased serum aspartate aminotransferase, alanine aminotransferase, and alkaline phosphatase activities. Furthermore, it elevated oxidative stress biomarker; malondialdehyde (MDA) and inhibited the activities of antioxidant enzymes (superoxide dismutase and glutathione peroxidase) in hepatic tissues homogenate. Additionally, hepatic apoptotic markers; caspase‐3 (Casp‐3) and Casp‐9 were elevated and the B‐cell lymphoma‐2 (Bcl‐2) gene level was decreased in rats exposed to radiation dose. We observed that CONPs can modulate these changes, where CONPs reduced liver enzyme activities, MDA, and apoptotic markers levels, in addition, it elevated antioxidant enzyme activities and Bcl‐2 gene levels, as well as improved histopathological changes in the irradiated animals. So our results concluded that CONPs had the ability to act as radioprotector defense against hepatotoxicity resulted during radiotherapy.
Primary pancreatic hydatid cyst: A rare case report and diagnostic challenges
Authors: Zahir Shokouh Taghipour , Rafiee Amirhossein , Kargar Saeed 
Published: July 2024

Key Clinical MessageIn cystic lesions of the pancreas, hydatid cyst should be considered in the differential diagnoses and its presence should be ruled out before any invasive interventions. Serological tests along with imaging studies related to hydatid cyst diagnostic indicators should be performed in people who live in Echinococcus granulosus endemic areas and suffer from cystic lesions of the gastrointestinal tract.AbstractPrimary pancreatic hydatid cysts, caused by the tapeworm Echinococcus granulosus, represent a rare occurrence often challenging to diagnose due to their similarity to other pancreatic conditions. This case report outlines a 67‐year‐old male presenting with jaundice and cholestasis but lacking typical symptoms associated with pancreatic hydatid cysts. Laboratory findings revealed elevated bilirubin levels, liver enzyme abnormalities, and tumor markers, prompting imaging studies that indicated a cystic mass near the pancreatic head. Misdiagnosed initially as a mucinous cystic neoplasm, the patient underwent Whipple surgery, unveiling a large cystic lesion upon examination.
Axially Chiral N‐Oxide Catalysts for the Allylation and Crotylation of Aromatic Aldehydes: Exploiting Nonlinear Effects
Authors: Romero‐Arenas Antonio , Ramírez‐López Pedro , Iglesias‐Sigüenza Javier , Fernández Rosario , Ros Abel , Lassaletta José M. 
Published: July 2024

AbstractA new family of IAN‐type amine N‐oxides is presented as catalysts for the allylation and crotylation of aromatic aldehydes with allyltrichlorosilanes. These reaction exhibit a remarkably positive nonlinear effect which enables utilization of the catalysts in subenantiopure form. As enantiopure catalysts are not required under this regime, the synthesis of these N‐oxides is straightforward through catalytic asymmetric synthesis, avoiding lenghty synthesis from the chiral pool or resolution of diastereoisomers. Studies of the corresponding crotylation with Z‐ and E‐crotylsilanes suggest that the reaction proceeds through a chair‐like transition state.
Evaluation of meadow fescue grass cultivars seeded with alfalfa in New York state
Authors: Tacoma‐Fogal Rink , Cherney Jerome H. , Cherney Debbie J. R. 
Published: July 2024

AbstractAlfalfa–grass mixtures sown in the northeastern United States provide high‐quality dairy forage, and meadow fescue (Festuca pratensis Huds.) may improve the quality of these mixtures. Our objectives were to evaluate competitiveness and nutritive value of nine meadow fescue (MF) cultivars in New York State at spring harvest. Three farms, two in central New York State and one in northern New York state, were used. Conventional alfalfa (Medicago sativa L.) was sown (15 lb acre−1) to nine MF cultivars (three tetraploid and six diploid) and one tall fescue Lolium arundinaceum (Schreb.) ‘Darbysh’ cultivar in a randomized complete block design with four field replicates at each field site at three seeding rates (1, 2, and 3 lb acre−1). Grass proportion in mixtures was estimated visually. Grass samples were collected shortly before first harvest and analyzed for neutral detergent fiber, neutral detergent fiber digestibility (NDFD), acid detergent fiber, in vitro digestibility, and crude protein. Most meadow fescue cultivars maintained a grass proportion between 20%–45% across farms and growing seasons when seeded at 1lb acre−1. Seeding rates above 1lb acre−1 resulted in grass proportions above the recommended 20–30% grass proportion rate. Drought in early 2022 resulted in an average drop in grass percentage of 16.9% units for meadow fescue in mixtures, compared to 2021. Nutritive value of cultivars varied among farms and over growing seasons. Meadow fescue cultivars averaged 2.7% units higher NDFD than tall fescue, and cultivars with consistently high NDFD were Hidden Valley, SW Revansch, SW Minto, and Schwetra. Tetraploid cultivars averaged 4.0% units lower NDF compared to diploid cultivars, which is very advantageous for grass in alfalfa–grass mixtures.
Changes in root and nutrient uptake of chickpea affected by organic fertilizers and inoculation with arbuscular mycorrhizal fungi and Rhizobium
Authors: Malekian Babak , Parsa Mehdi , Fallah Mohammad Hassan , Vessal Saeedreza , Khorassani Reza 
Published: July 2024

AbstractAlthough humans have studied biological nitrogen (N) fixation for nearly two centuries, our understanding of how legumes–microbiome interactions impact agroecosystem function is still evolving. To understand the effects of organic fertilizers and dual inoculation with Rhizobium and arbuscular mycorrhizal fungi (AMF) on root activity, N fixation and nutrient uptake of chickpea (Cicer arietinum), a two‐year greenhouse study was conducted in 2020–2021 at the research station of Ferdowsi University of Mashhad, Iran. The experiment design was a randomized complete blocks in the factorial arrangement with three replications. The first factor consisted of two seedbeds including S1 (field soil) and S2 (soil + humic acid + 40 ton ha−1 cattle manure). The second factor included inoculation with Rhizobium alone, mycorrhiza alone, both Rhizobium and mycorrhiza and non‐inoculated treatment. The results showed that the application of organic fertilizers increased the number of nodules, nodule weight, AMF colonization, leaf N content, leaf P content, root volume, root biomass and N uptake of chickpea, significantly. Also, the effect of seed inoculation was significant on all studied parameters where the highest root biomass (2 g), root volume (3.6 cm3) and leaf phosphorus (0.54%) were obtained in co‐inoculated treatments. There was no significant difference between the effect of single inoculation of Rhizobium and dual inoculation of mycorrhiza and Rhizobium on nodule number, nodule weight, leaf N and N uptake of chickpea. Generally, rhizobia and AMF can benefit nutrient uptake and root activity of chickpea, potentially leading to higher crop production.
Copper(I) Induced Phase Transition and 1D Growth in Cesium Lead Bromide Cubic Nanocrystals
Authors: Sunny Fency , Mane Pratap , Chakraborty Brahmananda , Kalarikkal Nandakumar , Kurukkal Balakrishnan Subila 
Published: July 2024

AbstractLead halide perovskites have been explored ardently in the past decade owing to their excellent photophysical properties. High‐temperature cation exchange reactions have been employed to improve the stability and performance in perovskite lattice, but lacks control over size, shape, and stoichiometry. Herein, the solution phase interaction of cesium lead bromide (CsPbBr3) nanocrystals with monovalent and bivalent copper ions, under ambient conditions is systematically investigated. The introduction of Cu1+ explicitly initiates a one‐dimensional growth with a distinct phase transition, that is from cubic to orthorhombic, while Cu2+ induces a partial exchange with Pb2+ with no phase change. DFT calculations suggest that Cu1+ induces structural distortion via Cs1+ substitution, altering the Goldschmidt tolerance factor and perovskite octahedral tilting, leading to the phase transition. Additionally, the oleic acid/amine ligands used to stabilize the nanocrystals, are preferentially etched away to form complexes with Cu1+, initializing an oriented growth of the nanocubes to nanorods. A mechanistic investigation of the evolution of the nanorods gave insights on tuning the tolerance factor via room temperature modifications and cation exchanges in perovskites for anisotropy and morphology tuning. This effortlessly obtained perovskite nanorods with Cu1+ could find effective applications in optoelectronics, and as novel photocatalysts.