bluuebunny/crossref_metadata_2025_split huggingface dataset:
Chemoselective Three‐Component Geminal Cross Couplings of Dihaloalkanes with Cr Catalysis: Rapid Access to Tertiary and Quaternary Alkanes via a Metal–Carbene Intermediate
Authors: Wang Sha , Long Linhong , Zhang Xiaoyu , Ling Liang , Chen Hui , Zeng Xiaoming 
Published: September 2023

AbstractGeminal cross couplings using multiple components enable the formation of several different bonds at one site in the building of tertiary and quaternary alkanes. Nevertheless, there are remaining issues of concern—cleavage of two geminal bonds and control of selectivity present challenges. We report here the geminal cross couplings of three components by reactions of dihaloalkanes with organomagnesium and chlorosilanes or alkyl tosylates by Cr catalysis, affording the formation of geminal C−C/C−Si or C−C/C−C bonds in the creation of tertiary and quaternary alkanes. The geminal couplings are catalyzed by low‐cost CrCl2, enabling the sluggishness of competitive Kumada‐type side couplings and homocouplings of Grignard reagents, in achieving high chemoselectivity. Experimental and theoretical studies indicate that two geminal C‐halide bonds are continuously cleaved by Cr to afford a metal carbene intermediate, which couples with a Grignard reagent, followed by silylation, in the formation of geminal C−C and C−Si bonds via a novel inner‐sphere radical coupling mechanism. These three‐component geminal cross couplings are value‐addition to the synthesis of commercial drugs and bioactive molecules in medicinal chemistry.
Shape Control of Carbon Nanoparticles via a Simple Anion‐Directed Strategy for Precise Endoplasmic Reticulum‐Targeted Imaging
Authors: E Shuang , Xing Yan Zhi , Du Sang , Liu An Min , Gao Zhao , Zhou Quan , Xuan Yang , Zhao Yi Nan , Chen Xu Wei , Zhang Shu Biao 
Published: September 2023

AbstractHerein, small‐sized fluorescent carbon nanoparticles (CNs) with tunable shapes ranging from spheres to various rods with aspect ratios (ARs) of 1.00, 1.51, 1.89, and 2.85 are prepared using a simple anion‐directed strategy for the first time. Based on comprehensive morphological and structural characteristics of CNs, along with theoretical calculations of density functional theory and molecular dynamics simulations, their shape‐control mechanism is attributed to interionic interactions‐induced self‐assembly, followed by carbonization. The endoplasmic reticulum‐targeting accuracy of CNs is gradually enhanced as their shape changes from spherical to higher‐AR rods, accompanied by a Pearson's correlation coefficient up to 0.90. This work presents a facile approach to control the shape of CNs and reveals the relationship between the shape and organelle‐targeting abilities of CNs, thereby providing a novel idea to synthesize CNs that serve as precise organelle‐targeted fluorescent probes.
Anatomical variations in the cerebral arterial circle of the Saimaa (Pusa hispida saimensis) and Baltic ringed seals (Pusa hispida botnica)
Authors: Laakkonen Juha , Nihtilä Heini , Jernvall Jukka 
Published: September 2023

AbstractThe intracranial arterial vascularization of the Saimaa ringed seals (Pusa hispida saimensis; Nordquist, 1899) and Baltic ringed seals (Pusa hispida botnica; Gmelin, 1788) disclosed patterns of anatomical architecture comparable to that of other pinniped species. Arterial silicone casts on skull scaffolds, and magnetic resonance imaging (MRI) showed that the besides joining the caudal communicating arteries upon entering the cerebral arterial circle, the bilateral internal carotid arteries bifurcated as laterally oriented rostral choroidal arteries and rostral cerebral arteries. The latter arteries almost immediately gave off the laterally oriented middle cerebral arteries. Numerous individual variations were evident in differences in the exact branching sites of bilateral vessels or the size or number of arterial branches. Two Saimaa ringed seals had only a tiny foramen for the left internal carotid artery to enter the intracranial space, and the intracranial part of this vessel was short. It did not reach the cerebral arterial circle. The intracranial part of the right internal carotid artery is bifurcated and also supplied the left side of the cerebral arterial circle. Both specimens had aplasia of the left rostral cerebral artery. The intracranial arterial arrangement of Saimaa and Baltic ringed seals reflects the arterial architecture of this body region in terrestrial mammals with little evidence for aquatic adaptations or changes related to thermoregulation.
Remote training of educators in Taiwan to disseminate discrete trial training for students with developmental disabilities
Authors: Chen Ning , Lerman Dorothea C. 
Published: September 2023

AbstractEducators in many areas of the world lack the necessary resources and training to serve students with developmental disabilities effectively. Telehealth technologies and a train‐the‐trainer approach may help disseminate evidence‐based instructional strategies to teachers in underserved areas. In this study, experimenters combined synchronous and asynchronous remote training to prepare six teachers in Taiwan to implement discrete trial training (DTT) with students. First, the experimenter taught three teachers from a private school to implement DTT with their students. Then, they trained these participants to teach another educator at their school. Finally, the three teachers trained those additional educators. Results indicated that the training was effective for all participants and that the DTT skills of the three trainers maintained over time and transferred to their in‐classroom instruction. These findings replicate and extend the current literature suggesting that the use of telehealth and a train‐the‐trainer model is a promising and socially valid method for disseminating ABA to countries with limited resources.
Dietary lithium stimulates female fecundity in Drosophila melanogaster
Authors: Jans Katharina , Lüersen Kai , von Frieling Jakob , Roeder Thomas , Rimbach Gerald 
Published: September 2023

AbstractThe trace element lithium exerts a versatile bioactivity in humans, to some extend overlapping with in vivo findings in the model organism Drosophila melanogaster. A potentially essential function of lithium in reproduction has been suggested since the 1980s and multiple studies have since been published postulating a regulatory role of lithium in female gametogenesis. However, the impact of lithium on fruit fly egg production has not been at the center of attention to date. In the present study, we report that dietary lithium (0.1–5.0 mM LiCl) substantially improved life time egg production in D. melanogaster w1118 females, with a maximum increase of plus 45% when supplementing 1.0 mM LiCl. This phenomenon was not observed in the insulin receptor mutant InRE19, indicating a potential involvement of insulin‐like signaling in the lithium‐mediated fecundity boost. Analysis of the whole‐body and ovarian transcriptome revealed that dietary lithium affects the mRNA levels of genes encoding proteins related to processes of follicular maturation. To the best of our knowledge, this is the first report on dietary lithium acting as an in vivo fecundity stimulant in D. melanogaster, further supporting the suggested benefit of the trace element in female reproduction.
Enhancing the thermostability and catalytic activity of Bacillus subtilis chitosanase by saturation mutagenesis of Lys242
Authors: Guo Jing , Gao Wenjun , Zhang Xuan , Pan Wenxin , Zhang Xin , Man Zaiwei , Cai Zhiqiang 
Published: September 2023

AbstractCatalysis activity and thermostability are some of the fundamental characteristic of enzymes, which are of great significance to their industrial applications. Bacillus subtilis chitosanase BsCsn46A is a kind of enzyme with good catalytic activity and stability, which can hydrolyze chitosan to produce chitobiose and chitotriose. In order to further improve the catalytic activity and stability of BsCsn46A, saturation mutagenesis of the C‐terminal K242 of BsCsn46A was performed. The results showed that the six mutants (K242A, K242D, K242E, K242F, K242P, and K242T) showed increased catalytic activity on chitosan. The catalytic activity of K242P increased from 12971 ± 597 U mg−1 of wild type to 17820 ± 344 U mg−1, and the thermostability of K242P increased by 2.27%. In order to elucidate the reason for the change of enzymatic properties, hydrogen network, molecular docking, and molecular dynamics simulation were carried out. The hydrogen network results showed that all the mutants lose their interaction with Asp6 at 242 site, thereby increasing the flexibility of Glu19 at the junction sites of α1 and loop1. Molecular dynamics results showed that the RMSD of K242P was lower at both 313 and 323 K than that of other mutants, which supported that K242P had better thermostability. The catalytic activity of mutant K242P reached 17820.27 U mg−1, the highest level reported so far, which could be a robust candidate for the industrial application of chitooligosaccharide (COS) production.
Perioperative opioids and survival outcomes in resectable head and neck cancer: A systematic review
Authors: Mastrolonardo Eric V. , Mann Derek S. , Sethi Harleen K. , Yun Bo H. , Sina Elliott M. , Armache Maria , Worster Brooke , Fundakowski Christopher E. , Mady Leila J. 
Published: September 2023

AbstractBackgroundOpioids are a mainstay in pain control for oncologic surgery. The objective of this systematic review is to evaluate the associations of perioperative opioid use with overall survival (OS) and disease‐free survival (DFS) in patients with resectable head and neck cancer (HNC).MethodsA systematic review of PubMed, SCOPUS, and CINAHL between 2000 and 2022 was conducted following the Preferred Reporting Items for Systematic Reviews and Meta‐Analyses guidelines. Studies investigating perioperative opioid use for patients with HNC undergoing surgical resection and its association with OS and DFS were included.ResultsThree thousand three hundred seventy‐eight studies met initial inclusion criteria, and three studies representing 562 patients (intraoperative opioids, n = 463; postoperative opioids, n = 99) met final exclusion criteria. One study identified that high intraoperative opioid requirement in oral cancer surgery was associated with decreased OS (HR = 1.77, 95% CI 0.995–3.149) but was not an independent predictor of decreased DFS. Another study found that increased intraoperative opioid requirements in treating laryngeal cancer was demonstrated to have a weak but statistically significant inverse relationship with DFS (HR = 1.001, p = 0.02) and OS (HR = 1.001, p = 0.02). The last study identified that patients with chronic opioid after resection of oral cavity cancer had decreased DFS (HR = 2.7, 95% CI 1.1–6.6) compared to those who were not chronically using opioids postoperatively.ConclusionAn association may exist between perioperative opioid use and OS and DFS in patients with resectable HNC. Additional investigation is required to further delineate this relationship and promote appropriate stewardship of opioid use with adjunctive nonopioid analgesic regimens.
Differences in mutational signature of diffuse large B‐cell lymphomas according to the primary organ
Authors: Koh Hyun‐Hee , Yoon Sang Eun , Kim Seok Jin , Kim Won Seog , Cho Junhun 
Published: September 2023

AbstractBackgroundComprehensive molecular subtyping of diffuse large B‐cell lymphoma (DLBCL) through genetic profiling has broadened our understanding of DLBCL biology. In this study, we investigated whether DLBCL, not otherwise specified (NOS) shows differences in mutational patterns depending on the primary organ.Patients and MethodsPanel‐based next‐generation sequencing was performed on 345 DLBCL from various primary organs, and patterns of mutations according to primary organs were analyzed.ResultsDLBCL showed a characteristic mutational signature in several primary organs. Among them, the mutational pattern of DLBCL in the breast and ileocecal area was particularly different from that of other DLBCL NOS. In breast DLBCL, MYD88L265P (57.1%), CD79B mutation (42.9%), and CDKN2A/B loss (71.4%) were found at high frequencies, which were similar to the mutation patterns of DLBCL of immune‐privileged sites compared with DLBCL NOS. DLBCL in the ileocecal area showed a characteristic mutation pattern with the most frequent TP53 mutation (52.6%) and 18q21 gain (42.1%). This was also different from the mutational pattern observed in the stomach or other intestines. In discriminant analysis, DLBCL of the breast and ileocecal area tended to form separate genetic constellations from other DLBCL NOS.ConclusionDLBCL NOS has a characteristic mutational profile that depends on the primary organ. In particular, the mutational signature of DLBCL in the breast and ileocecal area was heterogeneous compared with that of other DLBCL NOS. Further research is needed to determine whether primary DLBCL in the breast and ileocecal area can be classified as an independent subtype.
Biomass Separators as a “Lifesaver” for Safe and Long‐Life Lithium Metal Batteries
Authors: Bao Jinxi , Song Xiaohui , Tian Feng , Shi Haiting , Liang Shuaitong , Wang Shuo , Zeng Ming , Xue Yanling , Hong Chunxia , Xu Zhiwei 
Published: September 2023

AbstractThe growth of lithium dendrites and the shuttle of polysulfides in lithium metal batteries (LMBs) have hindered their development. In LMBs, the cathode and anode are separated by a separator, although this does not solve the battery‘s issues. The use of biomass materials is widespread for modifying the separator due to their porous structure and abundant functional groups. LMBs perform more electrochemically when lithium ions are deposited uniformly and polysulfide shuttling is reduced using biomass separators. In this review, we analyze the growth of lithium dendrite and the shuttle of polysulfide in LMBs, summarize the types of biomass separator materials and the mechanisms of action (providing mechanical barriers, promoting uniform deposition of metal ions, capturing polysulfides, shielding polysulfide). The prospect of developing new separator materials from the perspective of regulating ion transport and physical sieving efficiency as well as the application of advanced technologies such as synchrotron radiation to characterize the mechanism of action of biomass separators is also proposed.
Porphyrin‐based Bi‐MOFs with Enriched Surface Bi Active Sites for Boosting Photocatalytic CO2 Reduction
Authors: Cheng Mingjie , Yan Pengfei , Zheng Xiaoli , Gao Bo , Yan Xinying , Zhang Gaoxiang , Cui Xiaomin , Xu Qun 
Published: September 2023

AbstractThe inherent challenges in using metal‐organic frameworks (MOFs) for photocatalytic CO2 reduction are the combination of wide‐range light harvesting, efficient charge separation and transfer as well as highly exposed catalytic active sites for CO2 activation and reduction. We present here a promising solution to satisfy these requirements together by modulating the crystal facet and surface atomic structure of a porphyrin‐based bismuth‐MOF (Bi‐PMOF). The series of structural and photo‐electronic characterizations together with photocatalytic CO2 reduction experiment collectively establish that the enriched Bi active sites on the (010) surface prefer to promote efficient charge separation and transfer as well as the activation and reduction of CO2. Specifically, the Bi‐PMOFs‐120‐F with enriched surface Bi active sites exhibits optimal photocatalytic CO2 reduction performance to CO (28.61 μmol h−1g−1) and CH4 (8.81 μmol h−1g−1). This work provides new insights to synthesize highly efficient main group p‐block metal Bi‐MOF photocatalysts for CO2 reduction through a facet‐regulation strategy and sheds light on the surface structure‐activity relationships of the MOFs.
Nassmechanische Aufbereitung von Bauschutt‐Brechsand mit der Setztechnik – ein Schritt auf dem Weg zum Ersatzbaustoff
Authors: Pienkoß Fabian , Kalbe Ute , Simon Franz-Georg 
Published: September 2023

AbstractDas Recycling von gemischten Baustoffen führt neben der Herstellung von Gesteinskörnungen parallel zu einem stärker schadstoffbelasteten Stoffstrom, der circa ein Drittel der ursprünglichen Masse ausmacht. Dieser sogenannte Brechsand endet derzeit in der Deponierung und wird somit der Kreislaufwirtschaft entzogen. Der vorliegende Beitrag untersucht nun die Aufbereitung dieses Materials unter Verwendung einer Setzmaschine im Pilotmaßstab. Hierbei wird die Eignung dieser Technik evaluiert und das Aufbereitungsprodukt als möglicher Ersatzbaustoff untersucht.
5‐Substituted Uridines with Activity against Gram‐Positive Bacteria
Authors: Makarov Dmitry A. , Negrya Sergey D. , Jasko Maxim V. , Karpenko Inna L. , Solyev Pavel N. , Chekhov Vladimir O. , Kaluzhny Dmitry N. , Efremenkova Olga V. , Vasilyeva Byazilya F. , Chizhov Alexander O. , Avdanina Darya A. , Zhgun Alexander A. , Kochetkov Sergey N. , Alexandrova Liudmila A. 
Published: September 2023

AbstractThe emergence of drug‐resistant strains of pathogenic microorganisms necessitates the creation of new drugs. A series of uridine derivatives containing an extended substituent at the C‐5 position as well as C‐5 alkyloxymethyl, alkylthiomethyl, alkyltriazolylmethyl, alkylsulfinylmethyl and alkylsulfonylmethyl uridines were obtained in order to explore their antimicrobial properties and solubility. It has been shown that new ribonucleoside derivatives have an order of magnitude better solubility in water compared to their 2′‐deoxy analogues and effectively inhibit the growth of a number of Gram‐positive bacteria, including resistant strains of Mycobacterium smegmatis (MIC=15–200 μg/mL) and Staphylococcus aureus (MIC=25–100 μg/mL). Their activity is comparable to that of some antibiotics used in medicine.
Landscape complexity beyond invariance and the elastic manifold
Authors: Ben Arous Gérard , Bourgade Paul , McKenna Benjamin 
Published: September 2023

AbstractThis paper characterizes the annealed, topological complexity (both of total critical points and of local minima) of the elastic manifold. This classical model of a disordered elastic system captures point configurations with self‐interactions in a random medium. We establish the simple versus glassy phase diagram in the model parameters, with these phases separated by a physical boundary known as the Larkin mass, confirming formulas of Fyodorov and Le Doussal. One essential, dynamical, step of the proof also applies to a general signal‐to‐noise model of soft spins in an anisotropic well, for which we prove a negative‐second‐moment threshold distinguishing positive from zero complexity. A universal near‐critical behavior appears within this phase portrait, namely quadratic near‐critical vanishing of the complexity of total critical points, and cubic near‐critical vanishing of the complexity of local minima. These two models serve as a paradigm of complexity calculations for Gaussian landscapes exhibiting few distributional symmetries, that is, beyond the invariant setting. The two main inputs for the proof are determinant asymptotics for non‐invariant random matrices from our companion paper (Ben Arous, Bourgade, McKenna 2022), and the atypical convexity and integrability of the limiting variational problems.
α‐Synuclein Drives Tau's Cytotoxic Aggregates Formation through Hydrophobic Interactions
Authors: Ojeda Ana , Cofré Valentina , Melo Francisco , Caballero Leonardo , Fuentealba Denis , Cornejo Alberto 
Published: September 2023

AbstractTau and α‐synuclein are proteins involved in pathologies known as tauopathies and synucleinopathies, respectively. Moreover, evidence shows that there is a crosstalk between them as is seen in the brains of individuals with sporadic neurodegenerative disorders. Based on that, we present data showing that the hydrophobic α‐peptide 71VTGVTAVAQKTV82 induces the aggregation of the full‐length tau fragment in the absence of heparin assessed by ThT. Moreover, AFM images reveal the presence of straight filaments and amorphous aggregates of full‐length tau in the presence of the α‐peptide. Additionally, ITC experiments showed the interaction of the α‐peptide with tau full‐length (441 amino acids),4R (amino acids from 244 to 369), and both hexapeptides 275VQIINK280 and 306VQIVYK311 through hydrophobic interactions. The Raman spectroscopy spectra showed conformational changes in the Amide region in the aggregates formed with full‐length tau and α‐syn peptide. Furthermore, the incubation of extracellular aggregates with N2a cells showed morphological differences in the cellular body and the nucleus suggesting cell death. Moreover,, the incubation of different types of aggregates in cell culture provokes the release of Lactate dehydrogenase (LDH). Altogether, we found that α‐synuclein peptide can drive the aggregation of full‐length tau‐provoking morphological and structural changes evoking cytotoxic effects.
Integration of Isothermal Enzyme‐Free Nucleic Acid Circuits for High‐Performance Biosensing Applications
Authors: Wang Siyuan , Shang Jinhua , Zhao Bingyue , Wang Huimin , Yang Changying , Liu Xiaoqing , Wang Fuan 
Published: September 2023

AbstractThe isothermal enzyme‐free nucleic acid amplification method plays an indispensable role in biosensing by virtue of its simple, robust, and highly efficient properties without the assistance of temperature cycling or/and enzymatic biocatalysis. Up to now, enzyme‐free nucleic acid amplification has been extensively utilized for biological assays and has achieved the highly sensitive detection of various biological targets, including DNAs, RNAs, small molecules, proteins, and even cells. In this Review, the mechanisms of entropy‐driven reaction, hybridization chain reaction, catalytic hairpin assembly and DNAzyme are concisely described and their recent application as biosensors is comprehensively summarized. Furthermore, the current problems and the developments of these DNA circuits are also discussed.
Facing lethal temperatures: Heat‐shock response in desert and temperate ants
Authors: Araujo Natalia de Souza , Perez Rémy , Willot Quentin , Defrance Matthieu , Aron Serge 
Published: September 2023

AbstractGlobal climate changes may cause profound effects on species adaptation, particularly in ectotherms for whom even moderate warmer temperatures can lead to disproportionate heat failure. Still, several organisms evolved to endure high desert temperatures. Here, we describe the thermal tolerance survival and the transcriptomic heat stress response of three genera of desert (Cataglyphis, Melophorus, and Ocymyrmex) and two of temperate ants (Formica and Myrmica) and explore convergent and specific adaptations. We found heat stress led to either a reactive or a constitutive response in desert ants: Cataglyphis holgerseni and Melophorus bagoti differentially regulated very few transcripts in response to heat (0.12% and 0.14%, respectively), while Cataglyphis bombycina and Ocymyrmex robustior responded with greater expression alterations (respectively affecting 0.6% and 1.53% of their transcriptomes). These two responsive mechanisms—reactive and constitutive—were related to individual thermal tolerance survival and convergently evolved in distinct desert ant genera. Moreover, in comparison with desert species, the two temperate ants differentially expressed thousands of transcripts more in response to heat stress (affecting 8% and 12.71% of F. fusca and Myr. sabuleti transcriptomes). In summary, we show that heat adaptation in thermophilic ants involved changes in the expression response. Overall, desert ants show reduced transcriptional alterations even when under high thermal stress, and their expression response may be either constitutive or reactive to temperature increase.