bluuebunny/crossref_metadata_2025_split huggingface dataset:
Patients with parosmia respond faster to unpleasant odors than patients with hyposmia: Insights from olfactory event‐related potentials
Authors: Li Zetian , Richter Luisa , Krueger Tanja , Eichwald Herbert , Hähner Antje , Hummel Thomas 
Published: April 2024

AbstractBackgroundDiagnosing parosmia is a challenge. The present study aimed to explore the distinctions between hyposmic patients with and without parosmia utilizing electroencephalography‐derived olfactory event‐related potentials (ERP).MethodsForty‐four patients with hyposmia were enrolled and divided into a group with parosmia (n = 23, mean age ± standard deviation = 48 ± 14 years, seven men) and a group without parosmia (n = 21, age = 52 ± 12 years, seven men) based on the clinical interview. Additionally, 21 healthy controls (mean age = 45 ± 14 years, six men) were included. Various measurements were obtained, including the Sniffin’ Stick test, threshold tests for the odorants furfural mercaptan and 2,6‐nonadienal, a modified Sniffin’ Stick parosmia test, and well‐being ratings. Chemosensory ERPs were recorded separately for each nostril using high‐precision, computer‐controlled air‐dilution olfactometry.ResultsPatients with parosmia had a decreased olfactory function similar to that observed in patients with hyposmia, although the odor sensitivity of patients with severe parosmia remained relatively unaffected. Patients with parosmia reported a decrease in well‐being compared to controls. The severity of parosmia was positively correlated with odor sensitivity. Furthermore, patients with severe parosmia exhibited faster responses to unpleasant odors than patients without parosmia.ConclusionOverall, the present findings support the idea that parosmia predominantly occurs during olfactory recovery, significantly disturbing patients and warranting the development of effective treatments. Notably, the relatively faster responses of hyposmic patients with severe parosmia suggest that the generation of distorted olfactory responses may involve early stages of the processing of olfactory information.
Bottlebrush Networks: A Primer for Advanced Architectures
Authors: Clarke Brandon R. , Witt Connor L. , Ilton Mark , Crosby Alfred J. , Watkins James J. , Tew Gregory N. 
Published: April 2024

AbstractBottlebrush networks (BBNs) are an exciting new class of materials with interesting physical properties derived from their unique architecture. While great strides have been made in our fundamental understanding of bottlebrush polymers and networks, an interdisciplinary approach is necessary for the field to accelerate advancements. This review aims to act as a primer to BBN chemistry and physics for both new and current members of the community. In addition to providing an overview of contemporary BBN synthetic methods, we developed a workflow and desktop application (LengthScale), enabling bottlebrush physics to be more approachable. We conclude by addressing several topical issues and asking a series of pointed questions to stimulate conversation within the community.
Atomically Precise Nanometer‐Sized Pt Catalysts with an Additional Photothermy Functionality
Authors: Wang Runguo , Chen Dong , Fang Liang , Fan Wentao , You Qing , Bian Guoqing , Zhou Yue , Gu Wanmiao , Wang Chengming , Bai Licheng , Li Jin , Deng Haiteng , Liao Lingwen , Yang Jun , Wu Zhikun 
Published: April 2024

AbstractAtomically precise ~1‐nm Pt nanoparticles (nanoclusters, NCs) with ambient stability are important in fundamental research and exhibit diverse practical applications (catalysis, biomedicine, etc.). However, synthesizing such materials is challenging. Herein, by employing the mixture ligand protecting strategy, we successfully synthesized the largest organic‐ligand‐protected (~1‐nm) Pt23 NCs precisely characterized with mass spectrometry and single‐crystal X‐ray diffraction analyses. Interestingly, natural population analysis and Bader charge calculation indicate an alternate, varying charge ‐layer distribution in the sandwich‐like Pt23 NC kernel. Pt23 NCs can catalyze the oxygen reduction reaction under acidic conditions without requiring calcination and other treatments, and the resulting specific and mass activities without further treatment are sevenfold and eightfold higher than those observed for commercial Pt/C catalysts, respectively. Density functional theory and d‐band center calculations interpret the high activity. Furthermore, Pt23 NCs exhibit a photothermal conversion efficiency of 68.4 % under 532‐nm laser irradiation and can be used at least for six cycles, thus demonstrating great potential for practical applications.
Recycling Valuable Alkylbenzenes from Polystyrene through Methanol‐Assisted Depolymerization
Authors: Zeng Lin , Yan Tao , Du Junjie , Liu Chengyuan , Dong Bin , Qian Bing , Xiao Zhou , Su Guangning , Zhou Tao , Peng Zijun , Wang Zhandong , Li Hongliang , Zeng Jie 
Published: April 2024

AbstractThe vast bulk of polystyrene (PS), a major type of plastic polymers, ends up in landfills, which takes up to thousands of years to decompose in nature. Chemical recycling promises to enable lower‐energy pathways and minimal environmental impacts compared with traditional incineration and mechanical recycling. Herein, we demonstrated that methanol as a hydrogen supplier assisted the depolymerization of PS (denoted as PS‐MAD) into alkylbenzenes over a heterogeneous catalyst composed of Ru nanoparticles on SiO2. PS‐MAD achieved a high yield of liquid products which accounted for 93.2 wt % of virgin PS at 280 °C for 6 h with the production rate of 118.1 mmolcarbon gcatal.−1 h−1. The major components were valuable alkylbenzenes (monocyclic aromatics and diphenyl alkanes), the sum of which occupied 84.3 wt % of liquid products. According to mechanistic studies, methanol decomposition dominates the hydrogen supply during PS‐MAD, thereby restraining PS aromatization which generates by‐products of fused polycyclic arenes and polyphenylenes.
Buffer Chain Model for Understanding Crystallization Competition in Conjugated Polymers
Authors: Yu Zi‐Di , Lu Yang , Yao Ze‐Fan , Wu Hao‐Tian , Wang Zi‐Yuan , Pan Chen‐Kai , Wang Jie‐Yu , Pei Jian 
Published: April 2024

AbstractIt remains challenging to comprehensively understand the packing models of conjugated polymers, in which side chains play extremely critical roles. The side chains are typically flexible and non‐conductive and are widely used to improve the polymer solubility in organic solutions. Herein, a buffer chain model is proposed to describe link between conjugated backbone and side chains for understanding the relationship of crystallization competition of conductive conjugated backbones and non‐conductive side chains. A longer buffer chain is beneficial for alleviating such crystallization competition and further promoting the spontaneous packing of conjugated backbones, resulting in enhanced charge transport properties. Our results provide a novel concept for designing conjugated polymers towards ordered organization and enhanced electronic properties and highlight the importance of balancing the competitive interactions between different parts of conjugated polymers.
Strukturelle Einblicke in die Terpencyclasedomänen Zweier Pilzlicher Sesterterpensyntasen und Enzymengineering zur Diversifizierung von Sesterterpenen
Authors: Xu Meng , Xu Houchao , Lei Zhenyu , Xing Baiying , Dickschat Jeroen S. , Yang Donghui , Ma Ming 
Published: April 2024

AbstractÜber die Strukturen und katalytischen Mechanismen von Sesterterpensynthasen (StTSs) ist wenig bekannt, was das strukturbasierte Engineering von StTSs zur Erweiterung der strukturellen Diversität von Sesterterpenen erheblich erschwert. Wir berichten hier über die Kristallstrukturen der Terpencyclisierungsdomänen (TC) von zwei pilzlichen StTSs: der Sesterfisherol‐Synthase (NfSS) und der Sesterbrasiliatrien‐Synthase (PbSS). Beide TC‐Strukturen enthalten Benzyltriethylammoniumchlorid (BTAC), Pyrophosphat (PPi) und Magnesiumionen (Mg2+), wodurch die katalytisch aktiven Zentren klar definiert sind. Eine Kombination aus Theorie und Experimenten, einschließlich der Modellierung carbokationischer Intermediate, ortsgerichteter Mutagenese und Isotopenmarkierungen, lieferte detaillierte Einblicke in die strukturellen Grundlagen der katalytischen Mechanismen. Strukturbasiertes Engineering von NfSS und PbSS führte zur Bildung von 20 Sesterterpenen, darunter 13 neue Verbindungen und vier Epimerpaare mit unterschiedlichen Konfigurationen an C18. Diese Ergebnisse erweitern die strukturelle Vielfalt von Sesterterpenen und liefern wichtige Erkenntnisse für die zukünftige Forschung im Bereich der synthetischen Biologie.
Anion‐Responsive Colorimetric and Fluorometric Red‐Shift in Triarylborane Derivatives: Dual Role of Phenazaborine as Lewis Acid and Electron Donor
Authors: Aota Nae , Nakagawa Riku , de Sousa Leonardo Evaristo , Tohnai Norimitsu , Minakata Satoshi , de Silva Piotr , Takeda Youhei 
Published: April 2024

AbstractPhotophysical modulation of triarylboranes (TABs) through Lewis acid‐base interactions is a fundamental approach for sensing anions. Yet, design principles for anion‐responsive TABs displaying significant red‐shift in absorption and photoluminescence (PL) have remained elusive. Herein, a new strategy for modulating the photophysical properties of TABs in a red‐shift mode has been presented, by using a nitrogen‐bridged triarylborane (1,4‐phenazaborine: PAzB) with a contradictory dual role as a Lewis acid and an electron donor. Following the strategy, PAzB derivatives connected with an electron‐deficient azaaromatic have been developed, and these compounds display a distinct red‐shift in their absorption and PL in response to an anion. Spectroscopic analyses and quantum chemical calculations have revealed the formation of a tetracoordinate borate upon the addition of fluoride, narrowing the HOMO–LUMO gap and enhancing the charge‐transfer character in the excited state. This approach has also been demonstrated in modulating the photophysical properties of solid‐state films.
One‐step Synthesis of Organic Terminal 2D Ti3C2Tx MXene Nanosheets by Etching of Ti3AlC2 in an Organic Lewis Acid Solvent
Authors: Wang Fei , Tian Feng , Xia Xuewen , Pang Zhongya , Wang Shujuan , Yu Xing , Li Guangshi , Zhao Yufeng , Xu Qian , Hu Shen , Ji Li , Zou Xingli , Lu Xionggang 
Published: April 2024

AbstractThe surface and interface chemistry are critical for controlling the properties of two‐dimensional transition metal carbides and nitrides (MXenes). Numerous efforts have been devoted to the functionalization of MXenes with small inorganic ligands; however, few etching methods have been reported on the direct bonding of organic groups to MXene surfaces. In this work, we demonstrated an efficient and rapid strategy for the direct synthesis of 2D Ti3C2Tx MXene nanosheets with organic terminal groups in an organic Lewis acid (trifluoromethanesulfonic acid) solvent, without introducing additional intercalations. The dissolution of aluminum and the subsequent in situ introduction of trifluoromethanesulfonic acid resulted in the extraction of Ti3C2Tx MXene (T=CF3SO3−) (denoted as CF3SO3H−Ti3C2Tx) flakes with sizes reaching 15 μm and high productivity (over 70 %) of monolayers or few layers. More importantly, the large CF3SO3H−Ti3C2Tx MXene nanosheets had high colloidal stability, making them promising as efficient electrocatalysts for the hydrogen evolution reaction.
High‐performance Pyroelectric Property Accompanied by Spin Crossover in a Single Crystal of Fe(II) Complex
Authors: Liu Chengdong , Li Yun , Tang Zheng , Gao Kai‐Ge , Xie Jing , Tao Jun , Yao Zi‐Shuo 
Published: April 2024

AbstractPyroelectric materials hold significant potential for energy harvesting, sensing, and imaging applications. However, achieving high‐performance pyroelectricity across a wide temperature range near room temperature remains a significant challenge. Herein, we demonstrate a single crystal of Fe(II) spin‐crossover compound shows remarkable pyroelectric properties accompanied by a thermally controlled spin transition. In this material, the uniaxial alignment of polar molecules results in a polarization of the lattice. As the molecular geometry is modulated during a gradual spin transition, the polar axis experiences a colossal thermal expansion with a coefficient of 796×10−6 K−1. Consequently, the material's polarization undergoes significant modulation as a secondary pyroelectric effect. The considerable shift in polarization (pyroelectric coefficient, p=3.7–22 nC K−1cm−2), coupled with a low dielectric constant (ϵ′=4.4–5.4) over a remarkably wide temperature range of 298 to 400 K, suggests this material is a high‐performance pyroelectric. The demonstration of pyroelectricity combined with magnetic switching in this study will inspire further investigations in the field of molecular electronics and magnetism.
Metal–Organic Framework‐Based Hetero‐Phase Nanostructure Photocatalysts with Molecular‐Scale Tunable Energy Levels
Authors: Yuan Kuo , Liu Zongyang , Yan Zhuang , Yun Qinbai , Song Tianqun , Guo Jun , Zhang Xiaotao , Zhong Dichang , Tang Zhiyong , Lu Tongbu , Hu Wenping 
Published: April 2024

AbstractAs an effective method to modulate the physicochemical properties of materials, crystal phase engineering, especially hetero‐phase, plays an important role in developing high‐performance photocatalysts. However, it is still a huge challenge but significant to construct porous hetero‐phase nanostructures with adjustable band structures. As a kind of unique porous crystalline materials, metal–organic frameworks (MOFs) might be the appropriate candidate, but the MOF‐based hetero‐phase is rarely reported. Herein, we developed a secondary building unit (SBU) regulating strategy to prepare two crystal phases of Ti‐MOFs constructed by titanium and 1,4‐dicarboxybenzene, i.e., COK and MIL‐125. Besides, COK/MIL‐125 hetero‐phase was further constructed. In the photocatalytic hydrogen evolution reaction, COK/MIL‐125 possessed the highest H2 yield compared to COK and MIL‐125, ascribing to the Z‐Scheme homojunction at hetero‐phase interface. Furthermore, by decorating with amino groups (i.e., NH2‐COK/NH2‐MIL‐125), the light absorbing capacity was broadened to visible‐light region, and the visible‐light‐driven H2 yield was greatly improved. Briefly, the MOF‐based hetero‐phase possesses periodic channel structures and molecularly adjustable band structures, which is scarce in traditional organic or inorganic materials. As a proof of concept, our work not only highlights the development of MOF‐based hetero‐phase nanostructures, but also paves a novel avenue for designing high‐performance photocatalysts.
The Tandem Nitrate and CO2 Reduction for Urea Electrosynthesis: Role of Surface N‐Intermediates in CO2 Capture and Activation
Authors: Huang Xingmiao , Li Yangfan , Xie Shijie , Zhao Qi , Zhang Boyang , Zhang Zhiyong , Sheng Hua , Zhao Jincai 
Published: April 2024

AbstractElectrochemical reduction of CO2 and nitrate offers a promising avenue to produce valuable chemicals through the using of greenhouse gas and nitrogen‐containing wastewater. However, the generally proposed reaction pathway of concurrent CO2 and nitrate reduction for urea synthesis requires the catalysts to be both efficient in both CO2 and nitrate reduction, thus narrowing the selection range of suitable catalysts. Herein, we demonstrate a distinct mechanism in urea synthesis, a tandem NO3− and CO2 reduction, in which the surface amino species generated by nitrate reduction play the role to capture free CO2 and subsequent initiate its activation. When using the TiO2 electrocatalyst derived from MIL‐125‐NH2, it intrinsically exhibits low activity in aqueous CO2 reduction, however, in the presence of both nitrate and CO2, this catalyst achieves an excellent urea yield rate of 43.37 mmol ⋅ g−1 ⋅ h−1 and a Faradaic efficiency of 48.88 % at −0.9 V vs. RHE in a flow cell. Even at a low CO2 level of 15 %, the Faradaic efficiency of urea synthesis remains robust at 42.33 %. The tandem reduction procedure was further confirmed by in situ spectroscopies and theoretical calculations. This research provides new insights into the selection and design of electrocatalysts for urea synthesis.
Adaptive and Robust Vitrimers Fabricated by Synergy of Traditional and Supramolecular Polymers
Authors: Wang Jiao , You Wei , Chen Liya , Xiao Ding , Xiao Xuedong , Shan Tianyu , Liu Yang , Liu Ming , Li Guangfeng , Yu Wei , Huang Feihe 
Published: April 2024

AbstractVitrimers offer a unique combination of mechanical performance, reprocessability, and recyclability that makes them highly promising for a wide range of applications. However, achieving dynamic behavior in vitrimeric materials at their intended usage temperatures, thus combining reprocessability with adaptivity through associative dynamic covalent bonds, represents an attractive but formidable objective. Herein, we couple boron‐nitrogen (B−N) dative bonds and B−O covalent bonds to generate a new class of vitrimers, boron‐nitrogen vitrimers (BNVs), to endow them with dynamic features at usage temperatures. Compared with boron‐ester vitrimers (BEVs) without B−N dative bonds, the BNVs with B−N dative bonds showcase enhanced mechanical performance. The excellent mechanical properties come from the synergistic effect of the dative B−N supramolecular polymer and covalent boron‐ester networks. Moreover, benefiting from the associative exchange of B−O dynamic covalent bonds above their topological freezing temperature (Tv), the resultant BNVs also possess the processability. This study leveraged the structural characteristics of a boron‐based vitrimer to achieve material reinforcement and toughness enhancement, simultaneously providing novel design concepts for the construction of new vitrimeric materials.
Bending performance changes during prolonged canine eruption in saber‐toothed carnivores: A case study of Smilodon fatalis
Authors: Tseng Z. Jack 
Published: April 2024

AbstractThe canine of saber‐toothed predators represents one of the most specialized dental structures known. Hypotheses about the function of hypertrophied canines range from display and conspecific interaction, soft food processing, to active prey acquisition. Recent research on the ontogenetic timing of skull traits indicates the adult canine can take years to fully erupt, but the consequences of prolonged eruption on inferences of canine functional morphology are missing from current discourse and have not been quantified. Here I evaluate hypotheses about adult canine bending strength and stiffness, respectively, during eruption in the felid Smilodon fatalis. Simulated eruption sequences of three adult canines were generated from specimen models to assess shifting cross‐sectional geometry properties, and bending strength and stiffness under laterally directed loads were estimated using finite element analysis. Consistent with beam theory expectations, S. fatalis canine cross‐sectional geometry is optimized for increased bending strength with increased erupted height. However, canine cross‐sectional geometry changes through eruption exaggerate rather than minimize lateral deflection. Spatial constraint for maximum root length from adjacent sensory structures in the maxilla and the recently identified universal power law are hypothesized to limit the growth capacity of canine anteroposterior length and, consequently, maintenance of bending stiffness through eruption. Instead, the joint presence of the deciduous and adult canines for >50% of the adult canine eruption period effectively increases canine mediolateral width and brings bending strength and stiffness estimates closer to theoretical optima. Similarly prolonged retention of deciduous canines in other sabertooths suggests dual‐canine buttressing is a convergently evolved strategy to maximize bending strength and stiffness.
Modified Citrus Pectin (MCP) Confers a Renoprotective Effect on Early‐Stage Nephropathy in Type‐2 Diabetic Mice
Authors: Mahmoud Hager M. , Abdel‐Razik Abdel‐Razik H. , Elrehany Mahmoud A. , Othman Eman M. , Bekhit Amany A. 
Published: April 2024

AbstractDiabetic nephropathy (DN) is a significant global health concern with a high morbidity rate. Accumulating evidence reveals that Galectin‐3 (Gal‐3), a β‐galactoside‐binding lectin, is a biomarker in kidney diseases. Our study aimed to assess the advantageous impacts of modified citrus pectin (MCP) as an alternative therapeutic strategy for the initial and ongoing progression of DN in mice with type 2 diabetes mellitus (T2DM). The animal model has been split into four groups: control group, T2DM group (mice received intraperitoneal injections of nicotinamide (NA) and streptozotocin (STZ), T2DM+MCP group (mice received 100 mg/kg/day MCP following T2DM induction), and MCP group (mice received 100 mg/kg/day). After 4 weeks, kidney weight, blood glucose level, serum kidney function tests, histopathological structure alterations, oxidative stress, inflammation, apoptosis, and fibrosis parameters were determined in renal tissues. Our findings demonstrated that MCP treatment reduced blood glucose levels, renal histological damage, and restored kidney weight and kidney function tests. Additionally, MCP reduced malondialdehyde level and restored glutathione level, and catalase activity. MCP demonstrated a notable reduction in inflammatory and apoptosis mediators TNF‐α, iNOS, TGF‐βRII and caspase‐3. Overall, MCP could alleviate renal injury in an experimental model of DN by suppressing renal oxidative stress, inflammation, fibrosis, and apoptosis mediators.
Plant‐Derived Coumarins: A Narrative Review of Their Structural and Biomedical Diversity
Authors: Younes Areej Hazem , Mustafa Yasser Fakri 
Published: April 2024

AbstractPlant‐derived coumarin (PDC) is a naturally occurring heterocyclic backbone that belongs to the benzopyrone family. PDC and its based products are characterized by low toxicity and high distribution in a variety of herbal treatments that have numerous therapeutic potentials. These include anticoagulants, antibacterials, anti‐inflammatory agents, anticancer agents, antioxidants, and others. So, it may be appropriate to investigate the qualities and potential bioactivities of PDCs. This article provides an overview of the biomedical potentials, availability, and clinical use possibilities of PDCs, with a focus on their important modes of action, using information on various pharmacological qualities discovered. The data used in this study came from published research between 2015 and 2023. We reviewed a selection of databases, including PubMed, Scopus, Web of Science, and Google Scholar, during that period. In conclusion, because of their abundance in medicinal plants, the clinical biochemistry attributes of PDCs are currently of interest. In a variety of medical specialties, PDCs serve a useful role as therapeutic agents.
Advances and Strategies towards Synthesis of Aspidosperma Indole Alkaloids Goniomitine
Authors: Ji Cong‐Bin 
Published: April 2024

AbstractGoniomitine is of the aspidosperma alkaloid family, with an angularly fused tetracyclic skeleton housing an all‐carbon quaternary carbon chiral center alongside an aminal functional group. This natural product has garnered attention as a synthetic target due to its intriguing molecular architecture and anti‐proliferative activity in recent years. Following the first synthesis of (−)‐goniomitine by Takano in 1991, synthetic chemists have developed various methods. This review provides an overview of the methodologies used in the synthesis of goniomitine in racemic and enantiopure forms via divergent construction indole framework, indole functionalization, and the integrated oxidation/reduction/cyclization (iORC) sequence from 1991 to 2023.