bluuebunny/crossref_metadata_2025_split huggingface dataset:
Gemeinsame Biosynthese nichtkanonischer C16‐Terpene durch einen Fragmentierungs‐Rekombinations‐Mechanismus
Authors: Xu Houchao , Goldfuss Bernd , Dickschat Jeroen S. 
Published: June 2024

AbstractDie Biosynthese von sechs kürzlich beschriebenen nicht‐kanonischen C16‐Sesquiterpenoiden, die nach antiken griechischen Philosophen benannt sind, darunter Archimeden, Aristotelen, Eratosthen, Pythagoren, α‐Democriten und Anaximandren, wurde durch Dichtefunktionaltheorie‐Rechnungen (DFT) und Isotopenmarkierungsexperimente untersucht. Die Ergebnisse zeigten für alle Verbindungen außer Archimeden einen einzigartigen Fragmentierungs‐Rekombinationsmechanismus, wie er bereits für die Sodorifen‐Biosynthese gezeigt wurde, zusätzlich zu einem bemerkenswerten „Tanz“‐Mechanismus für die Anaximandren‐Biosynthese.
The Modular Synthesis of Sulfondiimidoyl Fluorides and their Application to Sulfondiimidamide and Sulfondiimine Synthesis
Authors: Ding Mingyan , Bell Charles , Willis Michael C. 
Published: June 2024

AbstractA modular synthesis of sulfondiimidoyl fluorides—the double aza‐analogues of sulfonyl fluorides—allowing variation of the carbon and both nitrogen‐substituents is reported. The chemistry uses readily available organometallic reagents, commercial sulfinylamines, simple electrophiles, and N‐fluorobenzenesulfonimide (NFSI), as the starting materials. The reactions are broad in scope, efficient, and scalable. We show that the sulfondiimidoyl fluoride products can be combined with amines to provide sulfondiimidamides, and with organolithium reagents to provide sulfondiimines, and that reactivity in these transformations can be modulated by variation of the N‐substituents.
Nanoscale Metal‐Organic Layer Reprograms Cellular Metabolism to Enhance Photodynamic Therapy and Antitumor Immunity
Authors: Lin Gan , Tillman Langston , Luo Taokun , Jiang Xiaomin , Fan Yingjie , Liu Gang , Lin Wenbin 
Published: June 2024

AbstractAbnormal cancer metabolism causes hypoxic and immunosuppressive tumor microenvironment (TME), which limits the antitumor efficacy of photodynamic therapy (PDT). Herein, we report a photosensitizing nanoscale metal–organic layer (MOL) with anchored 3‐bromopyruvate (BrP), BrP@MOL, as a metabolic reprogramming agent to enhance PDT and antitumor immunity. BrP@MOL inhibited mitochondrial respiration and glycolysis to oxygenate tumors and reduce lactate production. This metabolic reprogramming enhanced reactive oxygen species generation during PDT and reshaped the immunosuppressive TME to enhance antitumor immunity. BrP@MOL‐mediated PDT inhibited tumor growth by >90 % with 40 % of mice being tumor‐free, rejected tumor re‐challenge, and prevented lung metastasis. Further combination with immune checkpoint blockade potently regressed the tumors with >98 % tumor inhibition and 80 % of mice being tumor‐free.
Chirality Interplay between the Interior and Exterior of Metal–Organic Cages
Authors: Ma Chunmiao , Cao Qingcheng , Yu Lu , Ma Zhao , Gan Quan 
Published: June 2024

AbstractA series of metal–organic cages featuring two stereogenic elements, in terms of the twisting of amide moieties within the ligand backbones and the rotation of diazaanthracene segments along the ligand ridges, were exploited. These two chiral components are correlative and serve as relays for transmitting chirality information between the internal and external cages. The chirality information induced by a chiral guest inside the cage cavity can pass through the cage framework and influence the orientation of the diazaanthracene segments on the periphery of the cage. In turn, the chirality of a stereogenic center within the diazaanthracene segments can transfer back into the cavity, enabling discrimination of enantiomeric guests.
Regio‐ and Diastereoselective Synthesis of Polysubstituted Piperidines Enabled by Boronyl Radical‐Catalyzed (4+2) Cycloaddition
Authors: Ding Zhengwei , Wang Zhijun , Wang Yingying , Wang Xicheng , Xue Yuanji , Xu Ming , Zhang Hailong , Xu Liang , Li Pengfei 
Published: June 2024

AbstractPiperidines are widely present in small molecule drugs and natural products. Despite many methods have been developed for their synthesis, new approaches to polysubstituted piperidines are highly desirable. This work presents a radical (4+2) cycloaddition reaction for synthesis of piperidines featuring dense substituents at 3,4,5‐positions that are not readily accessible by known methods. Using commercially available diboron(4) compounds and 4‐phenylpyridine as the catalyst precursors, the boronyl radical‐catalyzed cycloaddition between 3‐aroyl azetidines and various alkenes, including previously unreactive 1,2‐di‐, tri‐, and tetrasubstituted alkenes, has delivered the polysubstituted piperidines in generally high yield and diastereoselectivity. The reaction also features high modularity, atom economy, broad substrate scope, metal‐free conditions, simple catalysts and operation. The utilization of the products has been demonstrated by selective transformations. A plausible mechanism, with the ring‐opening of azetidine as the rate‐limiting step, has been proposed based on the experimental and computational results.
Cavity‐Partitioned Self‐Assembled Cage for Sequential Separation in Aqueous Solutions
Authors: Wang Li‐Juan , Zhang Zi‐En , Zhang Yan‐Zhen , Han Ying‐Feng 
Published: June 2024

AbstractThe concept of pore space partition has emerged as an effective strategy for developing improved coordination‐based supramolecular porous materials with exceptional performance. Herein, we report that a water‐soluble self‐assembled tetrahedral cage 1 with a partitioned cavity shown excellent performance as a multifunctional extractant. The results show that this unique partitioned cavity can efficiently separate halogenated adamantanes, adamantane isomers, and polycyclic aromatic hydrocarbons. Furthermore, the influence of cavity‐partitioned cage 1 on the electrochemical properties of redox‐active molecules and electrochemically driven reversible host–guest process has also been demonstrated. The findings offer valuable insights into the design and development of new type of materials with controlled phase separation and tailored electrochemical properties.
A Stable Site‐Isolated Mono(phosphine)‐Rhodium Catalyst on a Metal‐Organic Layer for Highly Efficient Hydrogenation Reactions
Authors: Guo Qing‐Yun , Wang Zitong , Fan Yingjie , Zheng Haifeng , Lin Wenbin 
Published: June 2024

AbstractPhosphine‐ligated transition metal complexes play a pivotal role in modern catalysis, but our understanding of the impact of ligand counts on the catalysis performance of the metal center is limited. Here we report the synthesis of a low‐coordinate mono(phosphine)‐Rh catalyst on a metal‐organic layer (MOL), P‐MOL • Rh, and its applications in the hydrogenation of mono‐, di‐, and tri‐substituted alkenes as well as aryl nitriles with turnover numbers (TONs) of up to 390000. Mechanistic investigations and density functional theory calculations revealed the lowering of reaction energy barriers by the low steric hindrance of site‐isolated mono(phosphine)‐Rh sites on the MOL to provide superior catalytic activity over homogeneous Rh catalysts. The MOL also prevents catalyst deactivation to enable recycle and reuse of P‐MOL • Rh in catalytic hydrogenation reactions.
Challenges and recent advances in quantitative mass spectrometry‐based metabolomics
Authors: Ghafari Nathan , Sleno Lekha 
Published: June 2024

AbstractThe field of metabolomics has gained tremendous interest in recent years. Whether the goal is to discover biomarkers related to certain pathologies or to better understand the impact of a drug or contaminant, numerous studies have demonstrated how crucial it is to understand variations in metabolism. Detailed knowledge of metabolic variabilities can lead to more effective treatments, as well as faster or less invasive diagnostics. Exploratory approaches are often employed in metabolomics, using relative quantitation to look at perturbations between groups of samples. Most metabolomics studies have been based on metabolite profiling using relative quantitation, with very few studies using an approach for absolute quantitation. Using accurate quantitation facilitates the comparison between different studies, as well as enabling longitudinal studies. In this review, we discuss the most widely used techniques for quantitative metabolomics using mass spectrometry (MS). Various aspects will be addressed, such as the use of external and/or internal standards, derivatization techniques, in vivo isotopic labelling, or quantitative MS imaging. The principles, as well as the associated limitations and challenges, will be described for each approach.
Effect of palm oil methyl ester on coconut oil as a viable bio‐lubricant alternative to traditional mineral‐based oils
Authors: Joseph Mathai , Christopher Kiran , Vaidappilly Gautham S. , Abraham Twinkle , Jofy Adith 
Published: June 2024

AbstractVegetable oils are promoted as a base oil for automobile lubricants due to increased concerns about the environmental damage caused by synthetic and mineral oils‐derived lubricants. Coconut oil exhibits excellent tribological properties but poor cold flow properties. This work investigates the effect of the addition of palm oil methyl ester (POME), obtained from the transesterification of palm oil, on coconut oil by blending it in three proportions with varying volumes and evaluating for lubricant properties namely tribological properties, rheological properties, thermal properties, chemical properties and corrosion and oxidative stabilities. Fatty acid composition are evaluated for the base oil and the blends. The findings show that the addition of POME improves the base oil's pour point and reduces friction and wear. The corrosion test shows only slight tarnishing of copper strips, while the HOOT and chemical tests indicate appreciable resistance to oxidation. Therefore, this blended mixture has the potential to be a viable bio‐lubricant alternative to traditional mineral‐based oils.
Tuning multifunctional behavior of PLA/POE‐g‐GMA/MWCNT nanocomposites: Mechanical, rheological, thermal, thermomechanical, and electromagnetic properties
Authors: Luna Carlos Bruno Barreto , da Silva Fabiano Santana , dos Santos Filho Edson Antônio , Dantas Lorena Vanessa Medeiros , Schmitz Debora Pereira , Soares Bluma Guenther , Wellen Renate Maria Ramos , Araújo Edcleide Maria 
Published: June 2024

AbstractNanocomposites of polylactic acid (PLA) and poly(ethylene‐octene) grafted with glycidyl methacrylate (POE‐g‐GMA) were prepared using multi‐walled carbon nanotubes (MWCNT) as conductive nanofillers. The PLA/POE‐g‐GMA/MWCNT nanocomposites were processed through extrusion and injection molding for rheological, mechanical, electromagnetic, thermal, thermomechanical, and morphological characterization. The carbon nanotubes were dispersed in the PLA/POE‐g‐GMA chain, as seen by Raman spectroscopy. With higher MWCNT content, the complex viscosity (η*) and storage modulus (G') significantly increased in the nanocomposites, suggesting percolation formation. The nanocomposites melt flow index (MFI) results indicated lower fluidity, confirming the trend in η*. Electrical conductivity was optimal for PLA/POE‐g‐GMA/MWCNT (5 phr), reaching a value of 2.21 × 10−6 S/cm and providing electromagnetic shielding of 8 dB across the entire Ku band (12.2–18 GHz). The impact strength of the nanocomposites was higher than that of pure PLA and the PLA/POE‐g‐GMA blend, while the heat deflection temperature (HDT) remained stable at around 56°C. Increased MWCNT content in the nanocomposites promoted recovery of the elastic modulus, tensile strength, and Shore D hardness compared to PLA/POE‐g‐GMA blend. Overall, the results indicate that the PLA/POE‐g‐GMA/MWCNT (5 phr) nanocomposite has potential antistatic applications.
Plasmodium falciparum cysteine protease Falcipain 3: A potential enzyme for proteolytic processing of histone acetyltransferase PfGCN5
Authors: Nagar Poonam , Bhowmick Krishanu , Chawla Aishwarya , Malik Md. Zubbair , Subbarao Naidu , Kaur Inderjeet , Dhar Suman Kumar 
Published: June 2024

AbstractIn spite of 150 years of studying malaria, the unique features of the malarial parasite, Plasmodium, still perplex researchers. One of the methods by which the parasite manages its gene expression is epigenetic regulation, the champion of which is PfGCN5, an essential enzyme responsible for acetylating histone proteins. PfGCN5 is a ∼170 kDa chromatin‐remodeling enzyme that harbors the conserved bromodomain and acetyltransferase domain situated in its C‐terminus domain. Although the PfGCN5 proteolytic processing is essential for its activity, the specific protease involved in this process still remains elusive. Identification of PfGCN5 interacting proteins through immunoprecipitation (IP) followed by LC‐tandem mass spectrometry analysis revealed the presence of food vacuolar proteins, such as the cysteine protease Falcipain 3 (FP3), in addition to the typical members of the PfGCN5 complex. The direct interaction between FP3 and PfGCN5 was further validated by in vitro pull‐down assay as well as IP assay. Subsequently, use of cysteine protease inhibitor E64d led to the inhibition of protease‐specific processing of PfGCN5 with concomitant enrichment and co‐localization of PfGCN5 and FP3 around the food vacuole as evidenced by confocal microscopy as well as electron microscopy. Remarkably, the proteolytic cleavage of the nuclear protein PfGCN5 by food vacuolar protease FP3 is exceptional and atypical in eukaryotic organisms. Targeting the proteolytic processing of GCN5 and the associated protease FP3 could provide a novel approach for drug development aimed at addressing the growing resistance of parasites to current antimalarial drugs.
Treatment of sewage sludge with γ‐ray irradiation for volatile fatty acids and lipid production
Authors: Abbasabadarabi Javad , Asadollahi Mohammad Ali , Amiri Hamid 
Published: June 2024

AbstractThe production of value‐added products from sewage sludge is considered to be one of the solutions for the sustainable management of sludge in wastewater treatment plants (WWTPs). The presence of carbon, nitrogen, and phosphorus sources has made the sewage sludge of WWTPs a valuable and low‐cost substrate for the production of fermentative products. In the current study, a process was developed for microbial lipid production from two types of sewage sludge from a WWTP in northern Isfahan: anaerobic digester inlet sludge (DIS) and anaerobic digester outlet sludge (DOS). This process was based on the release of volatile fatty acids (VFAs) from the sludge by combinations of γ‐ray irradiation, anaerobic digestion, and acidogenic fermentation followed by utilization of VFAs in a microbial process by the oleaginous yeast Cryptococcus aureus UIMC65. After γ‐ray irradiation, the acidogenic fermentation of the treated sludge released 72% of the organic matter content of the sludge with acidification efficiency of 12% leading to 0.516 g L−1 VFAs. The oleaginous fermentation of the released VFAs for 7 days was accompanied by production of 1.58 g L−1 dry cell biomass with 40% lipid content. The results of this study indicate that the sewage sludge from urban WWTP has the potential to be used for the production of microbial lipids.
FOUR FRANKFURT – Neue Hochhäuser in Frankfurt am Main
Authors: Berger Alexander , Ruppert Simon , Torakai Daniel 
Published: June 2024

AbstractIn der Frankfurter City entsteht auf dem ehemaligen Deutsche‐Bank‐Gelände ein beeindruckendes neues Gebäudeensemble aus vier Hochhäusern und einem gemeinsamen sechsgeschossigen Sockelbau (Podium) mit Tiefgarage. Die Hochhäuser sind 233 m (T1), 178 m (T2), 125 m (T3) und 105 m (T4) hoch. Der Rohbau ist inzwischen weitgehend abgeschlossen, Richtfest war im September 2023. Für die Türme T1 und T4 ist Büronutzung vorgesehen, für T2 und T3 Wohnen und Hotel. Die Büroflächen der obersten Etagen des T1 werden die höchsten Deutschlands sein. Die innerstädtische Lage stellt das Projekt vor besondere Herausforderungen. Beispielsweise wurde die Baugrube in Deckelbauweise hergestellt. Die unterschiedlichen Anforderungen an die Nutzung der Türme führte zu unterschiedlichen Bauweisen der Regelgeschosse: Während der Rohbau der Wohntürme in Ortbeton hergestellt wurde, stellte sich für die Bürotürme die Fertigteilbauweise als wirtschaftlichste Bauweise heraus. Der Bericht ist in drei Teile unterteilt. Der erste Teil enthält die Vorstellung des Projekts und Übersichten zu den Bauteilen. Der zweite Teil behandelt die Aussteifung der Türme einschließlich der Maßnahmen zur Erhöhung der Steifigkeiten. Abschließend werden im dritten Teil besondere Bauweisen beschrieben.
Tailoring silk fibroin fibrous architecture by a high‐yield electrospinning method for fast wound healing possibilities
Authors: Zhu Jia‐Chen , Wang Hui , Wu Chen‐Xing , Zhang Ke‐Qin , Ye Hua 
Published: June 2024

AbstractIn this study, a novel array electrospinning collector was devised to generate two distinct regenerated silk fibroin (SF) fibrous membranes: ordered and disordered. Leveraging electrostatic forces during the electrospinning process allowed precise control over the orientation of SF fiber, resulting in the creation of membranes comprising both aligned and randomly arranged fiber layers. This innovative approach resulted in the development of large‐area membranes featuring exceptional stability due to their alternating patterned structure, achievable through expansion using the collector, and improving the aligned fiber membrane mechanical properties. The study delved into exploring the potential of these membranes in augmenting wound healing efficiency. Conducting in vitro toxicity assays with adipose tissue‐derived mesenchymal stem cells (AD‐MSCs) and normal human dermal fibroblasts (NHDFs) confirmed the biocompatibility of the SF membranes. We use dual perspectives on exploring the effects of different conditioned mediums produced by cells and structural cues of materials on NHDFs migration. The nanofibers providing the microenvironment can directly guide NHDFs migration and also affect the AD‐MSCs and NHDFs paracrine effects, which can improve the chemotaxis of NHDFs migration. The ordered membrane, in particular, exhibited pronounced effectiveness in guiding directional cell migration. This research underscores the revelation that customizable microenvironments facilitated by SF membranes optimize the paracrine products of mesenchymal stem cells and offer valuable physical cues, presenting novel prospects for enhancing wound healing efficiency.
Analytical method development and validation for simultaneous estimation of Bempedoic acid and Ezetimibe in pure and its pharmaceutical dosage form by RP‐HPLC
Authors: Suresh Aakash , Balakrishnan Anbarasi , Ramaswamy Vijayamirtharaj , Natesan Senthilkumar 
Published: June 2024

AbstractA simple, accurate and precise method was developed for the simultaneous estimation of the bempedoic acid and ezetimibe in pure and tablet dosage form. The developed method was validated as per International Conference on Harmonization guidelines. The chromatographic separation was achieved isocratically on a Waters‐ C18, 250 × 4.6 mm, 5 μm column. Mobile phase containing K2HPO4–methanol in the ratio 60:40 in buffer at pH 4.3 was pumped through column at a flow rate of 1.0 ml/min. The temperature was maintained at 25°C. The optimized wavelength selected was 242 nm. The separation of bempedoic acid and ezetimibe showed retention times of 3.090 and 4.268 min respectively. The RSD values of the bempedoic acid and ezetimibe were 0.34 and 0.08 respectively. The accuracy of method was determined at three levels (50,100 and 150%). The percentage recovery was obtained as 100.0 and 100.0% for bempedoic acid and ezetimibe, respectively. The limits of determination and quantitation obtained from regression equations of bempedoic acid and ezetimibe were 1.065, 3.550 and 0.203, 0.677, respectively. The regression equation of bempedoic acid is y = 20,795x + 24,168, and it is y = 6,885.7x + 11,000 for ezetimibe. The retention times were decreased and the run time was decreased, so that the method developed is simple and economical that can be adopted for regular quality control tests in industry.
Why we need neurodiversity in brain and behavioral sciences
Authors: Xia Yinghui , Wang Peng , Vincent Jonathan 
Published: June 2024

AbstractIn this article, we present the case for the adoption of a neurodiversity paradigm as an essential framework within the brain and behavioral sciences. We challenge the deficit‐focused medical model by advocating for the recognition of neurocognitive variances—including autism, ADHD, dyslexia, schizophrenia, and bipolar disorder—as natural representations of human diversity. We call for a shift in research and practice towards valuing neurodivergent individuals' unique strengths and contributions and promoting inclusivity and empathy. In critiquing the tendency to pathologize cognitive differences, we argue for a re‐evaluation of therapeutic goals to reflect a more nuanced understanding of neurodiversity. Highlighting the socio‐ethical implications of therapy‐focused research, we urge an appreciation of the potential for innovation and problem‐solving that neurodivergent individuals bring to society. The conclusion is a call to action for an integrated approach in research, policy, and societal attitudes that affirms neurodiversity, fostering an environment in which all forms of cognitive functioning are celebrated as part of human advancement.
Exploring circular consumption: Circular attitudes and their influence on consumer behavior across the product lifecycle
Authors: Testa Francesco , Marullo Cristina , Gusmerotti Natalia Marzia , di Iorio Vinicio 
Published: June 2024

AbstractThis study explores the dynamic and multidimensional domain of circular consumption, emphasizing the relevance of a lifecycle perspective in understanding consumer behaviors within the circular economy. Moving beyond prior research that predominantly focused on specific actions such as recycling or purchasing second‐hand products, we advocate for a more comprehensive understanding of consumer choices throughout a product's lifecycle. Drawing on attitudes theory, we employ item response theory (IRT) models to unveil latent attitudes reflecting diverse circular consumer behaviors. These attitudes, inferred from manifested actions across different product lifecycle stages, include environmental‐centric, resource‐centric, and societal‐centric circular attitudes. The study involves a representative sample of 5,124 respondents across five European countries. Our findings underscore the complexity of consumer motivations in the circular economy, revealing distinct links between circular attitudes and behaviors. This research contributes to a nuanced understanding of circular consumption, emphasizing the importance of a lifecycle approach, and driving the development of robust measurement scales for circular consumer actions.