bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Review on the Analysis of Chiral Molecules as Disease Biomarkers by LC/MS
Authors: Aydoğan Cemil , Çakan Büşra Beltekin , Ali Ashraf 
Published: November 2024

ABSTRACTThe chiral compounds may be biomarker candidates in human metabolism, which indicates the health status of humans. There are many applications in LC/MS that show that chiral small molecules are promising biomarkers for human diseases. Both clinical and commercial analyses of chiral metabolites are necessary due to the enantiomeric ratios of chiral molecules in biological samples may show both human health status and diseases. This review provides current and advanced LC/MS techniques for the separation and analysis of chiral molecules as disease biomarkers. In particular, sample preparation and chromatographic analysis of potential chiral biomarkers in biological samples are presented. The preparation and applications of several chiral columns used in enantiomeric separation of chiral metabolites/biomarkers by advanced LC/MS techniques are discussed. The improvement of these analyses will enable both the discovery of new chiral biomarkers and the prognosis of human diseases.
Green Climate Finance Development and Environmental Air Quality Improvement: Unveiling the Role of Green Technological Progress and Industrial Symbiotic Agglomeration
Authors: Gao Jiazhan , Hua Guihong , Huo Baofeng 
Published: November 2024

ABSTRACTGreen finance represents a transformative approach within the financial sector, markedly influencing both economic growth and environmental stewardship. This study analyzes data spanning 2006 to 2020 from 278 Chinese cities to explore green climate finance (GCF) development's effects on environmental air quality and its operative mechanisms. Results demonstrate a significant positive correlation between GCF development and environmental air quality enhancements. The mediation effect analysis underscores the critical roles of industrial symbiotic networks and green technological progress in facilitating air quality improvements through GCF development. Further investigations delineate a more substantial influence of GCF development on air quality in resource‐dependent and larger urban areas. Non‐linear dynamics between GCF development and air quality enhancements are elucidated through threshold model investigations, indicating varying levels of GCF development effectiveness. This study provides valuable empirical insights for financial policy formulation concerning air quality management and carries profound implications for both theoretical understanding and practical application in the economic and environmental realms.
Hydrodistillation Optimization for Borago officinalis L. Essential Oil and Its Chemical Composition Analysis
Authors: Slama Meriem , Slougui Nabila , Ounnas Dounia , Benaissa Akila , Bataiche Insaf 
Published: November 2024

ABSTRACTThe essential oil extracted from Borago officinalis L. aerial parts using hydrodistillation contains several compounds, although it yields low amounts. For the first time, this study investigated the effects of hydrodistillation parameters and optimized conditions to maximize the yield of B. officinalis essential oil while characterizing its chemical composition using gas chromatography–mass spectrometry. A single‐factor evaluation of three extraction parameters—extraction time, liquid‐to‐solid ratio, and soaking time—revealed optimal conditions of 4 h, 10:1 mL/g, and 2 h, respectively. Subsequently, the Box–Behnken response surface method produced a significant polynomial model, determining optimal conditions of an extraction time of 5 h, a liquid‐to‐solid ratio of 11.06:1 mL/g, and a soaking time of 2 h, 17 min, and 34 s, resulting in an essential oil yield of 0.42%. A total of 21 compounds were identified in B. officinalis essential oil, predominantly nonacosane (29.15%) and phytol (27.92%).
Covalent Organic Framework as Selective Fluorescence Sensors for Cancer Inducing Volatile Organic Compounds
Authors: Mekkeparambath Vaishnavi , Sreejaya M. M. , M Sreelekshmi , K Harikrishnan K. , Anil Kumar Lina , M Kalyani P. , Venkatesh Yarra , Gangopadhyay Moumita 
Published: November 2024

AbstractCertain volatile organic compounds (VOCs), such as formaldehyde, acetone, and ethanol, are overexpressed in some terminal diseases like cancer, diabetes, Alzheimer's, etc. Therefore, high‐precision detection and quantification of VOCs is imperative for early diagnosis of such detrimental diseases. Non‐invasive and accurate fluorescence‐based detection of such analytes has garnered widespread attention. The inherent luminescent properties of covalent organic frameworks (COFs), resulting from their extensive π‐conjugation, have made them suitable for sensing applications. Structural tunability and strong covalent linkers facilitate sensing by COFs. Appropriate choices of linker and skeletal units of the COF can help detect various biologically important analytes selectively. The most common linkers used in this regard is the imine linker, which can undergo excellent hydrogen bonding with different protic VOCs e. g., ethanol, methanol, etc. Besides imine detection, hydrogen bonding also proved useful for detection of aldehydes. Suitable combinations of donors and acceptors enable the COFs to have specific charge transfer interactions with many electron‐rich and electron‐poor VOCs. In this review, we have highlighted the syntheses of selective COFs incorporating linkers designed for sensing cancer‐inducing VOCs. A detailed discussion of the interaction mechanisms between COFs and these VOCs is provided, along with examples from recent literature in this field.
Engineering an Unspecific Peroxygenase From Thielavia terrestris for Specific Terminal Oxidation of Xylene Derivatives
Authors: Wei Jian , Lai Ming‐Yuan , Li Hang‐Cheng , Lu Xin‐Yi , Xu Jian‐He , Yu Hui‐Lei 
Published: November 2024

AbstractXylene and its derivatives are bulk raw materials in the chemical industry, and their oxidation products, including p‐toluic acid and terephthalic acid, are also crucial in the production of fine chemicals. Unspecific peroxygenases (UPOs) are heme‐thiolate enzymes that are capable of oxidizing diverse organic compounds. In this study, a UPO from Thielavia terrestris (TteUPO) showed the ability to oxidize p‐xylene to p‐toluic acid with >99% chemoselectivity. To address the sensitivity of TteUPO to H2O2 during the reaction, a fusion protein of TteUPO and formate oxidase from Aspergillus oryzae (AoFOx) was constructed for in situ H2O2 regeneration. Additionally, site‐directed saturation mutagenesis of TteUPO was performed, giving the mutant F63S/A155 V, which exhibited a 2.4‐fold increase in the specific activity toward p‐xylene compared with wild‐type TteUPO. The engineered fusion protein TteUPOF63S/A155V‐AoFOx achieved 3.8 mM p‐toluic acid under 8 mM p‐xylene loading, which is approximately 60‐fold higher than previously reported p‐toluic acid concentrations through bio‐oxidation. It also showed the capability to convert other monocyclic and polycyclic aromatic hydrocarbons, indicating its potential for the high‐value conversion of xylene and its derivatives.
Scalable Production of Metal Oxide Nanoparticles for Optoelectronics Applications
Authors: Rebecchi Luca , Martin Irene , Albo Ivet Maqueira , Ranjan Priyadarshi , Gatti Teresa , Scotognella Francesco , Rubino Andrea , Kriegel Ilka 
Published: November 2024

AbstractThis work describes the scalability process of a continuous‐injection protocol employed to produce tin‐doped indium oxide nanocrystal dispersions. Different levels of manipulation starting from the synthesis and processing also related to the tuning of the optical response (considering the peculiar combination of UV and NIR absorption with visible transparency) make these materials incredibly versatile. But one of the most attractive features concern the modulation of their charge carrier density through chemical or post‐synthetic doping, as for the case of core‐shell materials, expanding the properties of the core composition. In addition, the colloidal nature of such materials allows for easy solution processing which enables an extensive use in different applications within current thin films base technologies. It is therefore important to push forward the lab‐scale synthesis to properly address the commercial fabrication requirements without any loss in quality. Uniformity is crucial for industrial applications, ensuring predictable performance and facilitating the integration of these nanoparticles into optoelectronic devices. The method here developed allowed a transition from mg‐scale to gram‐scale product mass outputs, while retaining stability in terms of particle size distribution, morphology, crystallinity, and optical properties. This research establishes a robust framework for the scalable production of metal oxide nanoparticles with consistent properties, enhancing their viability for widespread use in optoelectronic applications.
Stimuli‐Responsive Polymers for Tubal Actuators
Authors: Chen Qing , Wu Si 
Published: November 2024

AbstractStimuli‐responsive polymers for tubal actuators have garnered significant attention due to their potential applications in soft robotics, artificial blood vessels, controlled liquid transportation, and microchemical reactors. This perspective emphasizes the advantages, response mechanisms, and fundamental design principles of stimuli‐responsive polymers for tubal actuators. It also addresses the biological and engineering applications, current challenges, and future prospects of stimuli‐responsive polymers for tubal actuators. The discussion categorizes stimuli‐responsive polymers for tubal actuators based on various properties, including liquid crystal elastomer actuators, hydrogel actuators, and shape memory polymer actuators. The subsequent sections focuses on the structural features, design principles, and biological applications of stimuli‐responsive polymers for tubal actuator, elucidating their potential interrelationships. The molecular architectures and design principles are intricately linked to the stimuli‐responsive mechanisms. Finally, this perspective outlines the challenges faced by stimuli‐responsive polymers for tubal actuators. This article aims to facilitate broader applications of stimuli‐responsive polymers for tubal actuators, thereby promoting progress across multiple fields.
Dispersion Forces‐Driven Hierarchical Assembly of Protein‐Like Lanthanide Octamers and Emergent CPL
Authors: Yao Zhiwei , Song Ziye , Yin Sen , Huang Wenru , Gao Ting , Yan Pengfei , Zhou Yanyan , Li Hongfeng 
Published: November 2024

AbstractHierarchical self‐assembly driven by non‐covalent interactions is a prevalent strategy employed by nature to construct sophisticated biomacromolecules, such as proteins. However, the construction of protein‐like superstructures that rely on weaker dispersion forces‐driven hierarchical assembly remains largely unexplored. Here, we report the first example of dispersion forces driving the high‐order assembly of the lanthanide trinuclear circular helicate [HNEt₃]₃[Eu₃(LL)₆] (ΔΔΔ‐1) into a protein‐like lanthanide octamer ((ΔΔΔ‐1)₈‐2). Within the octamer, the forty‐eight (48) menthol groups on the ligands and eighty‐four (84) 1,4‐dioxane solvent molecules contribute to enhanced dispersion forces through conformational adaptation and size‐matching effects. These enhanced dispersion forces not only drive the formation of the hierarchical superstructure but also result in a four‐level chirality transfer from the menthol to the octamer. Benefiting from the homochirality of Eu3+, the octamer is endowed the strong circularly polarized emission (|glum|=0.34, Φoverall=41 %). This understanding of how dispersion forces drive hierarchical self‐assembly provides a foundation for the directed fabrication of more fascinating superstructures.
A Fast Parallel Approach for Neighborhood‐Based Link Prediction by Disregarding Large Hubs
Authors: Sahu Subhajit , Kothapalli Kishore 
Published: November 2024

ABSTRACTLink prediction can help rectify inaccuracies in various graph algorithms, stemming from unaccounted‐for or overlooked links within networks. However, many existing works use a baseline approach, which incurs unnecessary computational costs due to its high time complexity. Further, many studies focus on smaller graphs, which can lead to misleading conclusions. Here, we study the prediction of links using neighborhood‐based similarity measures on large graphs. In particular, we improve upon the baseline approach (IBase), and propose a heuristic approach that additionally disregards large hubs (DLH), based on the idea that high‐degree nodes contribute little similarity among their neighbors. On a server equipped with dual 16‐core Intel Xeon Gold 6226R processors, DLH is on average faster than IBase, especially on web graphs and social networks, while maintaining similar prediction accuracy. Notably, DLH achieves a link prediction rate of 38.1M edges/s and improves performance by for every doubling of threads.
The Manipulation of Ring‐Open Polymerization Process to Boost the Electrochemical Performance for Solid‐State Lithium Metal Batteries
Authors: Cao Jialong , Zhang Mochun , Xu Jing , Wang Mengran , Hong Bo , Lai Yanqing 
Published: November 2024

AbstractSolid‐state polyether electrolytes formed by in‐situ ring‐opening polymerization (ROP) of 1,3‐dioxolane (DOL) have attracted great attention due to their high lithium‐ion conductivity, and good interface compatibility. However, DOL ring‐opening polymerization is difficult to control, resulting in the formation of poly(1,3‐dioxolane) (PDOL) with high molecular weight and high crystallinity, which hinder Li+ diffusion and deteriorate the interfacial contact. Herein, trimethylsilyl isocyanate (IPTS) was introduced into DOL ring‐opening system as a moisture eliminating agent to weaken the Li salt‐based initiating system and regulate the polymerization process. Based on this, the resultant PDOL electrolytes with 3 wt.% IPTS exhibit ionic conductivity of 2.8×10−4 S cm−1, a high Li+ transference number (0.68) and excellent stability with Li anode. The Li|PDOL‐3 %IPTS|Li battery exhibits a stable cycling performance for more than 1100 h under 0.5 mA cm−2 and 0.5 mAh cm−2. Furthermore, the LiFePO4|PDOL‐3 %IPTS|Li cell shows a capacity retention rate of 89.2 % after 200 cycles (25 °C, 1 °C) and 94.5 % (60 °C, 1 °C) after 500 cycles, which is much higher than that of PDOL (6.6 %) after 70 cycles (25 °C, 1 °C). This work provides guidance for the manipulation of ROP process further to enhance the performance of solid‐state lithium metal batteries.
Electrosynthesis of γ‐Butyrolactones by Dehydrogenative (3+2) Annulation
Authors: Yang Dongfeng , Li Xiangwei , Zhu Shuxiang , Zeng Li , Lei Aiwen , Yi Hong 
Published: November 2024

AbstractThe synthetic research for building γ‐butyrolactones is being developed due to the high value of lactone skeletons, commonly found in natural products, functional molecules, bioactive agents and pharmaceuticals. However, reported synthetic methods, including harsh conditions, reliance on volatile activating reagents, and using noble metals, remain challenging. In this work, we present an electro‐oxidative (3+2) annulation of alkenes with 1,3‐diesters, offering an efficient route to γ‐butyrolactones. This approach eliminates the need for external oxidants or bases and substrate pre‐activation. Mechanistic studies suggest that ferrocene acts as a mediator to activate 1,3‐diesters.
Associations between depression and anxiety in midlife and dementia more than 30 years later: The HUNT Study
Authors: Aunsmo Ragnhild Holmberg , Strand Bjørn Heine , Anstey Kaarin J. , Bergh Sverre , Kivimäki Mika , Köhler Sebastian , Krokstad Steinar , Livingston Gill , Matthews Fiona E. , Selbæk Geir 
Published: November 2024

AbstractINTRODUCTIONIt is unclear how midlife depression and anxiety affect dementia risk. We examined this in a Norwegian cohort followed for 30 years.METHODSDementia status at age 70+ in the fourth wave of the Trøndelag Health Study (HUNT4, 2017–2019, N = 9745) was linked with anxiety and depression from HUNT1 (1984–1985), HUNT2 (1995–1997), HUNT3 (2006–2008), and HUNT4. Longitudinal anxiety and depression score, and prevalence trajectories during 1984–2019 by dementia status at HUNT4 were fitted using mixed effects regression adjusting for age, sex, education, and lifestyle and health factors.RESULTSDementia at HUNT4 was associated with higher case prevalence at all waves, from 1.9 percentage points (pp) (95% CI: 0.1–3.7) higher at HUNT1 to 7.6 pp (95% CI: 5.7–9.6) higher at HUNT4.DISCUSSIONOur findings show that depression and anxiety was more common more than 30 years before dementia onset in those who later developed dementia.Highlights
Older individuals with dementia had a higher prevalence of mixed anxiety‐ and depressive symptoms (A + D), both concurrently with and more than three decades prior to their dementia diagnosis.
Older individuals with dementia had higher levels of anxiety, both concurrently and up to two decades prior to their dementia diagnosis.
Depressive symptoms increased by time among those who developed dementia, but not among others.
Results were similar for all cause dementia, Alzheimer's disease, and other types of dementia; however, for vascular dementia, the difference was not significant until dementia was present.
Distinct Requirements for CD4+ T Cell Help for Immune Responses Induced by mRNA and Adenovirus‐Vector SARS‐CoV‐2 Vaccines
Authors: Yong Lyn , Hutchings Claire , Barnes Eleanor , Klenerman Paul , Provine Nicholas M. 
Published: November 2024

ABSTRACTCD4+ T cells have been established as central orchestrators of cellular and humoral immune responses to infection or vaccination. However, the need for CD4+ T cell help to generate primary CD8+ T cell responses is variable depending on the infectious agent or vaccine and yet consistently required for the recall of CD8+ T cell memory responses or antibody responses. Given the deployment of new vaccine platforms such as nucleoside‐modified mRNA vaccines, we sought to elucidate the requirement for CD4+ T cell help in the induction of cellular and antibody responses to mRNA and adenovirus (Ad)‐vectored vaccines against SARS‐CoV‐2. Using antibody‐mediated depletion of CD4+ T cells in a mouse immunization model, we observed that CD4+ T cell help was dispensable for both primary and secondary CD8+ T cell responses to the BNT162b2 and mRNA‐1273 mRNA vaccines but required for the AZD1222 Ad‐vectored vaccine. Nonetheless, CD4+ T cell help was needed by both mRNA and Ad‐vectored vaccine platforms for the generation of antibodies, demonstrating the centrality of CD4+ T cells in vaccine‐induced protective immunity against SARS‐CoV‐2. Ultimately, this highlights the shared and distinct regulation of humoral and cellular responses induced by these vaccine platforms.
Far‐Infrared Spectroscopic Investigation of CoFe Prussian Blue Analogues at Thermally Activated Electron Transfer
Authors: Dronova Maria , Altenschmidt Laura , Bordage Amélie , Rivière Eric , Brubach Jean‐Blaise , Verseils Marine , Balthazar Gregory , Roy Pascale , Bleuzen Anne 
Published: November 2024

AbstractA series of Prussian Blue Analogues (PBAs) having the chemical formula KxCsyCo4[Fe(CN)6](8+x+y)/3⋅nH2O was investigated by variable temperature far‐infrared spectroscopy. The compounds with the lowest amounts of interstitial alkali cations exhibit the thermally activated CoII(High Spin)FeIII ⋅ CoIII(Low Spin)FeII electron transfer, whereas above a threshold of two alkali cations per unit cell the compounds are in the CoIII(Low Spin)FeII electronic state at room temperature and remain in this electronic state over the 300–15 K temperature range. Our variable temperature study shows that FIR spectroscopy turns out to be particularly well‐suited to probe local interactions between the alkali cations in interstitial sites of PBAs and the surrounding cyanide‐bridged bimetallic network as well as to disentangle electronic and structural phenomena involved in the switching properties.
Construction of Heterometallic One‐Dimensional Chain with δ* in the HOMO Using Quadruple Hydrogen Bonds
Authors: Uemura Kazuhiro , Yamada Tomofumi 
Published: November 2024

AbstractMixing [Rh2(acam)4] (acam=acetamidate) with pivalic acid yielded Head and Tail‐[Rh2(acam)2(OPiv)2] (1, where PivOH denotes pivalic acid). The highest occupied and lowest unoccupied molecular orbitals were determined through cyclic voltammetry, electron paramagnetic resonance of the one‐electron oxidized form, and density functional theory calculations. Compound 1 and [Pt2(piam)2(NH3)4](PF6)2 (piam=pivalamidate) formed Rh−Pt bonds, yielding a heterometallic one‐dimensional chain [{Rh2(acam)2(OPiv)2}{Pt2(piam)2(NH3)4}]n(PF6)2n (2), where both complexes are aligned in a repeating pattern. As the Rh atom is equatorially coordinated with one hydrogen‐bond donor nitrogen and three hydrogen‐bond acceptor oxygens, and the Pt atom is coordinated with three nitrogens and one oxygen, quadruple complementary hydrogen bonds effectively support Rh−Pt bonds. The diffuse reflection spectrum of 2 shows three absorption peaks at E1 (3.13 eV), E2 (1.71 eV), and E3 (1.41 eV), which are characteristic of the Rh−Pt bond, indicating the formation of band structure along the one‐dimensional direction.
The effect of retrieval‐induced forgetting for pain‐related memories on child pain‐related outcomes: A randomized experimental study
Authors: Wauters Aline , Daenen Frederick , Van Ryckeghem Dimitri M. L. , Noel Melanie , Vervoort Tine 
Published: November 2024

AbstractBackgroundChildren's inability to forget the negative aspects of a painful event is associated with more anticipatory anxiety at an upcoming pain task and lower pain thresholds; however, the impact of forgetting on children's pain outcomes has not been examined. Retrieval‐Induced Forgetting (RIF) was experimentally induced to investigate whether children would (1) forget more negative details of a previous painful autobiographic event and; (2) report better pain‐related outcomes for an unrelated pain task (i.e., cold pressor task; CPT). Additionally, it was investigated whether the success of RIF was dependent on child characteristics known to influence children's memories for pain (i.e., attention bias to pain, attention switching ability and pain catastrophizing).MethodsHealthy school children (N = 128; 9–16 years old) recalled and rehearsed memory details of two painful autobiographical events, while only children in the randomized RIF group rehearsed positive details. All children underwent two CPTs (before and after RIF) and reported pain‐related outcomes. Two weeks later, children recalled CPT pain and reported on future pain expectancies.ResultsChildren in the RIF group remembered less negative details of their past autobiographical pain events, but also reported a greater reduction in pain‐related fear from the CPT 2 compared to their ratings for CPT 1, than children in the control group. They furthermore expected less pain‐related fear 2 weeks later for a future pain task.DiscussionFindings suggest that RIF is a promising avenue in pediatric pain management that could be harnessed to foster more positive memories and better future pain experiences.Significance StatementRetrieval‐induced forgetting (RIF) makes children forget negative details of a past autobiographical pain experience, decreases experienced pain‐related fear for experimental pain and lowers future pain‐related fear expectancies. Results show a promising role for RIF‐ based memory interventions in the context of paediatric pain care.