bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stereoselective Synthesis of Polysubstituted Conjugated Dienes Enabled by Photo‐Driven Sequential Sigmatropic Rearrangement
Authors: Ji Xin , Shen Chaoren , Ni Yuhao , Si Zhi‐Yao , Wang Yuzhu , Zhi Xinrong , Zhao Yuting , Peng Huiling , Liu Lu 
Published: April 2024

AbstractWe here reported a highly stereoselective method for the synthesis of polysubstituted conjugated dienes from α‐aryl α‐diazo alkynyl ketones and pyrazole‐substituted unsymmetric aminals under mild conditions, which was promoted by photo‐irridation and involved with 1,6‐dipolar intermediate and quadruple sigmatropic rearrangements, was successfully developed. In this transformation, the cleavage of four bonds and the recombination of five bonds were implemented in one operational step. This protocol provided a modular tool for constructing dienes from amines, pyrazoles and α‐alkynyl‐α‐diazoketones in one‐pot manner. The results of mechanistic investigation indicated that the plausible reaction path underwent the 1,6‐sigmatropic rearrangement instead of the 1,5‐sigmatropic rearrangement.
Novel Photocatalyst Based on Through‐Space Charge Transfer Induced Intersystem Crossing Enables Rapid and Efficient Polymerization Under Low‐Power Excitation Light
Authors: Liang Hui , Zhang Xue , Lu Manlin , Chen Xi , Li Weiqiang , Li Shangru , Li Ming‐De , Zhao Jianzhang , Huo Yanping , Ji Shaomin 
Published: April 2024

AbstractCurrently, most photoredox catalysis polymerization systems are limited by high excitation power, long polymerization time, or the requirement of electron donors due to the precise design of efficient photocatalysts still poses a great challenge. Herein, we propose a new approach: the creation of efficient photocatalysts having low ground state oxidation potentials and high excited state energy levels, along with through‐space charge transfer (TSCT) induced intersystem crossing (ISC) properties. A cabazole‐naphthalimide (NI) dyad (NI‐1) characterized by long triplet excited state lifetime (τT=62 μs), satisfactory ISC efficiency (ΦΔ=54.3 %) and powerful reduction capacity [Singlet: E1/2 (PC+1/*PC)=−1.93 eV, Triplet: E1/2 (PC+1/*PC)=−0.84 eV] was obtained. An efficient and rapid polymerization (83 % conversion of 1 mM monomer in 30 s) was observed under the conditions of without electron donor, low excitation power (10 mW cm−2) and low catalyst (NI‐1) loading (<50 μM). In contrast, the conversion rate was lower at 29 % when the reference catalyst (NI‐4) was used for photopolymerization under the same conditions, demonstrating the advantage of the TSCT photocatalyst. Finally, the TSCT material was used as a photocatalyst in practical lithography for the first time, achieving pattern resolutions of up to 10 μm.
Preserving Mesoporosity in Type III Porous Liquids through Dual‐layer Surface Weaving
Authors: Li Siqi , Wang Dongxu , Lee Yongjin , Li Tao 
Published: April 2024

AbstractThe fundamental limitation for pore preservation in a Type III porous liquid (T3PL) is the need for a small aperture from the porous filler to realize size exclusion of a bulky solvent. We present a dual‐layer surface weaving strategy that can disregard this limitation and achieve micro‐ and mesoporous metal–organic framework (MOF)‐based T3PLs even with apertures much larger than the solvent molecules. By first weaving a tight network of poly(tert‐butyl methacrylate) on the MOF surface, the poly(dimethylsiloxane) (PDMS) solvent can be effectively excluded from the pores while smaller guest molecules such as CO2, C2H4, and H2O can freely access the interior, as confirmed by low‐pressure adsorption isotherms. Further application of a PDMS‐containing polymer coating helps lower the viscosity of the PL due to increased particle dispersibility. This strategy has resulted in the successful construction of T3PLs with aperture sizes up to 3.1 nm.
Recent Advances in Environmentally Friendly Dual‐crosslinking Polymer Networks
Authors: Zhang Mingyue , Choi Woosung , Kim Minju , Choi Jinyoung , Zang Xuerui , Ren Yujing , Chen Han , Tsukruk Vladimir , Peng Juan , Liu Yijiang , Kim Dong Ha , Lin Zhiqun 
Published: April 2024

AbstractEnvironmentally friendly crosslinked polymer networks feature degradable covalent or non‐covalent bonds, with many of them manifesting dynamic characteristics. These attributes enable convenient degradation, facile reprocessibility, and self‐healing capabilities. However, the inherent instability of these crosslinking bonds often compromises the mechanical properties of polymer networks, limiting their practical applications. In this context, environmentally friendly dual‐crosslinking polymer networks (denoted EF‐DCPNs) have emerged as promising alternatives to address this challenge. These materials effectively balance the need for high mechanical properties with the ability to degrade, recycle, and/or self‐heal. Despite their promising potential, investigations into EF‐DCPNs remain in their nascent stages, and several gaps and limitations persist. This Review provides a comprehensive overview of the synthesis, properties, and applications of recent progress in EF‐DCPNs. Firstly, synthetic routes to a rich variety of EF‐DCPNs possessing two distinct types of dynamic bonds (i.e., imine, disulfide, ester, hydrogen bond, coordination bond, and other bonds) are introduced. Subsequently, complex structure‐ and dynamic nature‐dependent mechanical, thermal, and electrical properties of EF‐DCPNs are discussed, followed by their exemplary applications in electronics and biotechnology. Finally, future research directions in this rapidly evolving field are outlined.
Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites
Authors: Zhao Yonggui , Wan Wenchao , Erni Rolf , Pan Long , Patzke Greta R. 
Published: April 2024

AbstractMetal‐based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X‐ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure–activity relationships of low‐crystalline cobalt sulfide (L−CoS) catalysts toward overall water splitting. The operando results for L−CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S−Co−Co−S moieties as the true catalytically active species. In comparison, during the acidic HER, L−CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co−S−Co configurations. Further operando characterizations highlight the crucial formation of high‐valent Co4+ species in L−CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co‐LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.
Selective Defluorination of Trifluoromethyl Substituents by Conformationally Induced Remote Substitution
Authors: Jesani Mehul H. , Schwarz Maria , Kim Shiwhu , Evans Finlay L. , White Alexander , Browning Alex , Abrams Roman , Clayden Jonathan 
Published: April 2024

AbstractThe selective reduction of an aromatic trifluoromethyl substituent to a difluoromethyl substituent may be achieved by base‐promoted elimination to form a difluoro‐p‐quinomethide which is trapped by an intramolecular nucleophile. High yields are obtained when the nucleophilic trap entails the conformationally favoured cyclisation of an aminoisobutyric acid (Aib) derivative. The resulting cyclised difluoromethyl‐substituted arylimidazolidinone products are readily converted to versatile difluoromethyl‐substituted aldehydes by reduction and hydrolysis. Defluorination is successful on a range of benzenoid (both para and ortho CF3‐substituted) and heterocyclic substrates. Double defluorination may likewise be achieved sequentially, or in a single step, from an Aib dipeptide derivative.
Structural Insights Into the Terpene Cyclization Domains of Two Fungal Sesterterpene Synthases and Enzymatic Engineering for Sesterterpene Diversification
Authors: Xu Meng , Xu Houchao , Lei Zhenyu , Xing Baiying , Dickschat Jeroen S. , Yang Donghui , Ma Ming 
Published: April 2024

AbstractLittle is known about the structures and catalytic mechanisms of sesterterpene synthases (StTSs), which greatly hinders the structure‐based engineering of StTSs for structural diversity expansion of sesterterpenes. We here report on the crystal structures of the terpene cyclization (TC) domains of two fungal StTSs: sesterfisherol synthase (NfSS) and sesterbrasiliatriene synthase (PbSS). Both TC structures contain benzyltriethylammonium chloride (BTAC), pyrophosphate (PPi), and magnesium ions (Mg2+), clearly defining the catalytic active sites. A combination of theory and experiments including carbocationic intermediates modeling, site‐directed mutagenesis, and isotope labeling provided detailed insights into the structural basis for their catalytic mechanisms. Structure‐based engineering of NfSS and PbSS resulted in the formation of 20 sesterterpenes including 13 new compounds and four pairs of epimers with different configurations at C18. These results expand the structural diversity of sesterterpenes and provide important insights for future synthetic biology research.
Impact of olive leaves powder addition on extra virgin olive oil: Sensory, quality, nutritional and volatile compounds implications
Authors: Álvares Andressa Anelo , Silva Lucas Tolio , Cavalcante Luana Souza , Pires Dafne Marcelle Alves , Machado Isabel Cristina Kasper , Aboy Ana Lúcia , Mello Wendell , Scheid Camila , Merib Josias , Garavaglia Juliano 
Published: April 2024

AbstractOlive leaves currently represent a waste from olive oil industry that can be reused as source of polyphenols and other compounds. The objective of this study was to test whether incorporation of olive leaf powder directly in olive oils can enhance and modify its chemical‐sensory quality. Thus, leaves from cultivar “Koroneiki” were washed, sanitized, dried (37–40°C for 48 h) and milled until obtaining a powder that was added to “Arbequina” and “Koroneiki” extra virgin olive oils, at 1% and 3%. The oils were stored in dark conditions at room temperature and samples were checked after 0, 3, 6 and 12 months. The quality parameters, sensory properties, and nutrition quality (total phenolics, antioxidant, oleuropein and alpha‐tocopherol) were evaluated. The olive leaves affected quality and chemical composition, mainly increasing resistance to oxidation, which was not verified in samples without leaves addition. The incorporation of leaves powder significantly increased the contents of C6‐C5 alcohols/aldehydes, intensity of the green fruity and bitter, also artichoke, herbs, tomato leaf, olive leaves and banana peels sensations.
Determination of hydroxyl value of vegetable oils‐based polyols through ring‐preopening, solvent‐extraction, and acetylation method
Authors: Li Jun , Li Wenlong , Ye Zihan , Sun Yuewen , Gong Weijian , Wang Yiming , Bi Yanlan 
Published: April 2024

AbstractVegetable oils‐based polyols prepared by epoxidation‐hydroxylation often have the phenomenon of the coexistence of epoxy and hydroxyl groups due to different ring‐opening degrees. The acylation method recommended by the American Society of Testing Materials (ASTM) standard (D1957‐86) and the Association of Official Analytical Chemists (AOAC) standard (965.32) is applicable only to fatty alcohols in oils and fats and their derivatives but not to vegetable oils‐based polyols since the residual epoxy groups in vegetable oils‐based polyols lead the tested hydroxyl value (OHV) to be higher than the actual OHV. A method combining ring‐preopening of residual epoxy groups, ether extraction of ring‐preopened vegetable oils‐based polyols, and subsequent acetylation by acetic anhydride‐acetic acid was established for OHV determination of vegetable oils‐based polyols. The accuracy of the method was verified by the known theoretical OHVs of short‐chain alcohols and simulated vegetable oils‐based polyols. The absolute values of relative deviations for OHVs of short‐chain alcohols and simulated vegetable oils‐based polyols were within 1.0% and 3.1%, respectively, which indicates the feasibility of the established method in eliminating the negative effects of residual epoxy groups in vegetable oils‐based polyols on OHV determination as well as accurately determining and evaluating the OHV of vegetable oils‐based polyols. The method can broaden the range of OHV determination up to 1800 mg KOH/g. The ratio of acetic anhydride and acetic acid and reaction time are key factors affecting the complete degree of acetylation, which can be regulated mutually in accurately determining the OHV of vegetable oils‐based polyols according to the practice. It is the first time, to our best knowledge, to establish a method to eliminate the negative effects of residual epoxy groups in vegetable oils‐based polyols on OHV determination. The established method provides a feasible method for polyol industry to accurately evaluate the product quality of vegetable oils‐based polyols.
“Spine to the future”—A narrative review of anatomy engagement
Authors: Taylor Adam M. , Wessels Quenton 
Published: April 2024

AbstractAnatomy has been integral to medical and health education for centuries, it has also had a significant role in wider public life, as an educational resource, a link to their health, and also as a darker deterrent. Historically, public engagement in anatomy is hallmarked by public dissections of convicted criminals across the globe. Artists, specifically non‐medical men, such as Leonardo da Vinci, are reported to have participated in public dissection. Dissection would later rekindle public interest in anatomy as graverobbing led to the reform and regulation of anatomy in many countries. In recent years, there has been growing interest from the public in learning more about their bodies as health and well‐being become of paramount importance, particularly following the COVID‐19 pandemic. Anatomy sits in a prime position to direct and instigate conversations around health, well‐being, and body image. Every human on earth possesses a perfect resource to look at and learn about. Models, art‐based anatomical activities, and crafts provide active learning opportunities for the wider public around anatomy. Most recently, apps, games, and extended reality provide novel and insightful learning opportunities for the public relating to the body. Finally, training and resources must also be made available from institutions and professional bodies to anatomists to enable them to deliver engagement in an already congested and educationally heavy schedule. This resurgence of interest in anatomical public engagement sees anatomy re‐enter the public spotlight, with more appropriate resources and educational settings to offer engagement with the aim of benefiting the public.
Bewertung und Ertüchtigung von genieteten Gitterträgern in Dachkonstruktionen
Authors: Franz Hannah , Rinke Mario 
Published: April 2024

AbstractMetallkonstruktionen des 19. und frühen 20. Jahrhunderts, wie z. B. Industrie‐, Bahnhofs‐ und Markthallen, sind ein kostbares und nutzbares Erbe. Der Erhalt dieser Konstruktionen durch die Beibehaltung oder Anpassung ihrer Nutzung ist von wirtschaftlichem, ökologischem und denkmalpflegerischem Interesse. Dabei ist die genaue Bewertung ihrer Tragfähigkeit durch Nachrechnung eine Herausforderung. In Frankreich sind genietete Gitterträger in Dachkonstruktionen aus den Jahren 1850–1930 sehr verbreitet und weisen rechnerisch Stabilitätsprobleme auf, die zu vorbeugenden Verstärkungsmaßnahmen führen. Dieser Beitrag stützt sich auf die Untersuchung von solchen Tragwerkskomponenten und schlägt eine neue, ganzheitliche Bewertungsmethode vor, welche Bauingenieurwesen, Konstruktionsgeschichte und Denkmalpflege miteinander verbindet und eine solide Grundlage für die Ausarbeitung von vernünftigen, d. h. möglichst minimalen Verstärkungen bilden soll. Diese Herangehensweise könnte auf Eisen‐ und Stahlkonstruktionen des 19. und frühen 20. Jahrhunderts sowie auf die meisten bestehenden Bauwerke ausgeweitet werden.
Luminescence of Sm3+ in double perovskite‐type Ba2SrWO6 for insect trapping
Authors: Li Haoquan , Wu Haoyi , Zhang Lei , Qin Shuyu , Song Jianjun , Jin Yahong , Hu Yihua 
Published: April 2024

AbstractThe predominant method for pest control has been the use of pesticides, which have been shown to have detrimental effects on soil, freshwater, and crop quality. Therefore, the development of novel and sustainable crop protection strategies has become increasingly imperative. In this study, a novel orange–red emitting Ba2SrWO6: Sm3+ phosphor was synthesized using the high‐temperature solid‐state reaction. Under ultraviolet excitation, the phosphors showed obvious emission peaks at 575, 614, and 662 nm. The Ba2SrWO6: Sm3+ was used to fabricate a fluorescence film with polydimethylsiloxane (PDMS), and attracted twice as many insects as the blank control group under 365 nm ultraviolet light. This material holds great potential as a fluorescent agent for insect trapping in the pest control fields of tea, cotton, eggplant, rice, potato, grape, and other agricultural industries. Our findings provide an eco‐friendly approach to pest management for the increment of food production.
Machine learning approaches to predict TAS2R receptors for bitterants
Authors: Ferri Francesco , Cannariato Marco , Deriu Marco Agostino , Pallante Lorenzo 
Published: April 2024

AbstractBitter taste involves the detection of diverse chemical compounds by a family of G protein‐coupled receptors, known as taste receptor type 2 (TAS2R). It is often linked to toxins and harmful compounds and in particular bitter taste receptors participate in the regulation of glucose homeostasis, modulation of immune and inflammatory responses, and may have implications for various diseases. Human TAS2Rs are characterized by their polymorphism and differ in localization and function. Different receptors can activate various signaling pathways depending on the tissue and the ligand. However, in vitro screening of possible TAS2R ligands is costly and time‐consuming. For this reason, in silico methods to predict bitterant‐TAS2R interactions could be powerful tools to help in the selection of ligands and targets for experimental studies and improve our knowledge of bitter receptor roles. Machine learning (ML) is a branch of artificial intelligence that applies algorithms to large datasets to learn from patterns and make predictions. In recent years, there has been a record of numerous taste classifiers in literature, especially on bitter/non‐bitter or bitter/sweet classification. However, only a few of them exploit ML to predict which TAS2R receptors could be targeted by bitter molecules. Indeed, the shortage and incompleteness of data on receptor‐ligand associations in literature make this task non‐trivial. In this work, we provide an overview of the state of the art dealing with this specific investigation, focusing on three ML‐based models, namely BitterX (2016), BitterSweet (2019) and BitterMatch (2022). This review aims to establish the foundation for future research endeavours focused on addressing the limitations and drawbacks of existing models.
A rapid and sensitive LC–MS/MS method for quantifying oxycodone, noroxycodone, oxymorphone and noroxymorphone in human plasma to support pharmacokinetic drug interaction studies of oxycodone
Authors: Hulskotte Lotte M. G. , Wilbrink‐Pijffers Inge , Arbouw Maurits E. L. , Benoist Guillemette E. , Jansman Frank G. A. , van Berlo‐van de Laar Inge R. F. 
Published: April 2024

AbstractA sensitive and reliable LC–MS/MS method was developed and validated for the quantification of oxycodone and metabolites in human plasma. The method has a runtime of 6 min and a sensitivity of 0.1 μg/L for all analytes. Sample preparation consisted of protein precipitation. Separation was performed on a Kinetix biphenyl column (2.1 × 100 mm, 1.7 μm), using ammonium formate 5 mm in 0.1% aqueous formic acid and methanol LC–MS grade 100% in gradient elution at a flow rate of 0.4 ml/min. Detection was performed in multiple reaction monitoring mode using positive electrospray ionization. The method was linear over the calibration range of 0.1–25.0 μg/L for oxycodone, noroxycodone and noroxymorphone and 0.1–5.0 μg/L for oxymorphone. The method demonstrated good performance in terms of intra‐ and interday accuracy (86.5–110.3%) and precision (CV 1.7–9.3%). The criteria for the matrix effect were met (CV < 15%) except for noroxymorphone, for which an additional method was applied to compensate for the matrix effect. Whole blood samples were stable for 4 h at room temperature. Plasma samples were stable for 24 h at room temperature and 3 months at −20°C. Furthermore, the method was successfully applied in a pharmacokinetic drug interaction study of oxycodone and enzalutamide in patients with prostate cancer.
Business reporting of Sustainable Development Goals: Global trends and implications
Authors: Thammaraksa Chonlawan , Gebara Caroline Herlev , Hauschild Michael Zwicky , Pontoppidan Caroline Aggestam , Laurent Alexis 
Published: April 2024

AbstractWith a reported insufficient progress toward achieving the Sustainable Development Goals (SDGs), improving knowledge on the uptake and use of SDGs within the private sector is imperative. To address this need, we examine the SDG reporting characteristics of 8500 companies using a global business and governance database. Our results show no correlation in reporting specific goals, which could impede progress toward other goals. A disconnection between corporate sustainability performances and SDG reporting is also observed, meaning companies may select and report specific SDGs arbitrarily without rooting them with actual sustainability performances. These findings question the motivation and effectiveness of current SDG reporting and call for more guidance on SDG indicator selection and performance assessment. Looking ahead, SDG communication practices are anticipated to change due to the advent of new corporate sustainability reporting regulations. We therefore call for continuous monitoring of SDG adoption, uptake, and communication in businesses.