bluuebunny/crossref_metadata_2025 huggingface dataset:
A Practical Synthetic Route to Cinnolines: Application to the Design and Synthesis of RSV NNI Inhibitor JNJ‐8003 Analogues
Authors: Van Ham Rick , Lehuédé Valentin , La Torre Mathéo , Matcha Kiran
Published: January 2025

The manuscript describes the development of an efficient synthetic route to cinnolines, facilitating faster access to JNJ‐8003 related Respiratory Syncytial Virus (RSV) non‐nucleoside (NNI) inhibitors. Starting from correctly functionalized aryl halides, a Sonogashira reaction followed by SNAr reaction with hydrazine 1,2‐dicabroxylate reagents provided dihydrocinnolines directly via in situ 6‐endo‐dig cyclization. The dihydrocinnolines were conveniently transformed to corresponding cinnolines in one step. Notably, this three‐step route to cinnolines is more practical and safer than traditional methods that involve hazardous diazo intermediates. The methodology demonstrated a broad substrate scope. Strategic selection of a readily available aryl halide enabled the synthesis of diverse cinnolines that served as JNJ‐8003 analogues through late‐stage functionalization. Furthermore, by capitalizing the inherent reactivity of aryl halides toward SNAr reactions, we explored the synthesis of various heteroaromatic cinnolines. Given the extensive biological properties exhibited by cinnolines, our approach is poised to inspire further investigations in this field.
Switching Photoluminescence Wavelength of Arylated Single‐walled Carbon Nanotubes by Utilizing Steric Hindrance in Reductive Arylation
Authors: Maeda Yutaka , Iguchi Yui , Zhao Pei , Suwa Atsushi , Taki Yasunari , Kawada Kentaro , Yamada Michio , Ehara Masahiro , Kako Masahiro
Published: January 2025

(6,5)‐enriched single‐walled carbon nanotubes (SWCNTs) were reductively arylated using sodium naphthalenide and monosubstituted and disubstituted iodobenzene derivatives to control their photoluminescence (PL) properties. In the reactions with substituted iodobenzenes, the degree of functionalization was influenced by the substituents on the aryl groups depending on their position, which allowed us to realize control of the PL intensity and wavelength. The methyl or methoxy group at the 2‐position and methyl groups at the 3,5‐positions of the phenyl group respectively increased the E11** PL and E11* PL selectivity at ~1230 and ~1100 nm. Methyl groups at the 2,6‐positions emerged two new PL peaks. These PL characteristics were prominently observed in the (6,4) SWCNT adducts, which were separated by gel chromatography. Theoretical calculations of model compounds showed that the effect of the substituent at the ortho‐position on the relative stability of the isomers with different binding configurations was greater for the diarylated SWCNTs than for the hydroarylated SWCNTs. Experimental and theoretical calculation results revealed that the choice of substituents on the benzene ring was effectively used to modulate the PL wavelength, and these substituents had a considerable effect on the favorable binding configuration of the SWCNT adduct and relative stability and PL wavelength of the conformational isomers.
Development of Off‐On Near‐Infrared Fluorescent Probes for Sensitive In Vivo Imaging of Amyloid‐β Species with Enhanced Pharmacokinetics
Authors: Liu Qingchen , Men Yiming , Fang Daqing , Miao Yinxing , Ye Deju , Liu Hong
Published: January 2025

The fluorescent imaging of pathologically accumulated β‐amyloid (Aβ) proteins is of significant importance to the diagnosis of Alzheimer's disease (AD). In the paper, we prepare two new NIR probes, NIR‐1 and NIR‐2, through hydrophilic modification of introducing water‐soluble bioactive groups such as polyethylene glycol (PEG) and morpholine to tune in vivo pharmacokinetics for specific detection of soluble and insoluble Aβ species. The in vitro assessments confirm that both NIR‐1 and NIR‐2 display strong near‐infrared (NIR) fluorescence (FL) enhancement upon interaction with Aβ42 monomers, oligomers or aggregates (λem>670 nm) and show highly sensitive, rapid and selective response towards Aβ42 species. After i. v. injection, each probe showed fast blood‐brain barrier (BBB) penetration and immediately produced intense FL signals in the brain of APP/PS1 AD model mice at 10 min. Moreover, compared with NIR‐2, NIR‐1 bearing a hydrophilic PEG chain displayed not only more rapid clearance but also lower background signal to efficiently distinguish APP/PS1 mice and wild‐type mice with higher signal‐to‐background ratio, which was further validated by ex vivo histological staining of brain tissues. Therefore, due to its excellent pharmacokinetics, NIR‐1 shows great promise as an effective NIR probe for specific detection of Aβ species.
Label‐free 3D cell imaging using hydrogels functionalized with switchable iridium complexes
Authors: Fiorini Federica , Longhi Elena , Lázaro Ariadna , Di Prisco Daria , Tamboia Giulia , Alonci Giuseppe , Menduti Luigi , De Cola Luisa
Published: January 2025

The use of fluorescent labels is the most common tool to visualize cells. However, the internalization of dye molecules often modifies the cell behavior. In this paper we demonstrate that it is possible to transiently label cells using a 3D scaffold, a hydrogel, covalently functionalized with luminescent cyclometalated iridium(III) complexes. The unique feature of our design is that the complexes are emissive only when they interact with the cell membrane while their emission is quenched in water. We exploited this feature to perform real‐time and staining‐free cell visualization and imaging. The hydrogels immerged in culture media are non‐luminescent, however, when cells are added to it, they interact with the iridium complexes, covalently linked to the gel, and their lipophilic membrane “switches on” the luminescence enabling a clear and dynamic, real‐time 3D visualization of cell proliferation. A complete photophysical and biological study of the materials is presented which demonstrates the potential of our methodology for 3D‐realtime cell tracking.
Chlorination‐Supported Shrinkage of C60 Fullerene to Non‐classical C58 Cages
Authors: Brotsman Victor A. , Tamm Nadezhda B. , Kosaya Maria P. , Markov Vitaliy Yu. , Goryunkov Alexey A. , Ioffe Ilya N. , Troyanov Sergey I.
Published: January 2025

We provide important novel insights into skeletal transformations of fullerene by reporting new cases of cage shrinkage in the most abundant C60 fullerene via a C2 loss. High‐temperature (400–500 oC) chlorination of IPR C60 with SbCl5 or SbCl5/SbCl3 mixtures predominantly gives non‐IPR C60Cln compounds via Stone‐Wales rearrangements, but the present study further reveals non‐classical C58Cln chlorofullerenes as by‐products. The new C58(NC1)Cl20 and C58(NC1)Cl24 chlorides have been isolated by air‐free HPLC and structurally characterized by X‐ray crystallography. Their non‐classical carbon cages feature one heptagon, two pairs of fused pentagons, one triple‐pentagon junction, and one quartet of sequentially fused pentagons. However, the chlorination patterns and molecular shapes of C58(NC1)Cl20 and C58(NC1)Cl24 are essentially different. We propose the likely multistep transformation pathways toward the new compounds and further report the chlorination‐promoted formation of chlorofullerenes with still smaller fullerene cages.
Characterization of the Titanium(III) Tris(alkyl) Ti{CH(SiMe3)2}3 and its Conversion to a Dimeric Alkyl‐bridged Titanium(IV) Species
Authors: Power Philip P. , McLoughlin Connor P , Witt Anthony J , Maijala Anni , Shiau Angela A , Rao Guodong , Britt R. David , Tuononen Heikki M
Published: January 2025

The reaction of three equivalents of LiCH(SiMe3)2 with TiCl3(NMe3)2 afforded the rare homoleptic Ti(III) alkyl Ti{CH(SiMe3)2}3 (1) which crystallized as blue needles in 32 % yield. Single crystal X‐Ray data for 1 showed a trigonal pyramidal coordination geometry around titanium, which could be ascribed to weak interactions between the C–H bonds and the Ti(III) atom based on computational results. X‐band EPR spectroscopy give spectral parameters consistent with the proposed Ti(III) formulation. Solutions of 1 are unstable at room temperature owing to intramolecular C–H activation that gave a dimeric Ti(IV) complex [{(Me3Si)2HC}Ti{μ‐CH HSiMe3}]2 (2).
Synthesis of trans‐Fused 3,6‐Anhydro Hexofuranose Frameworks via Catalytic Hydrogenolysis Triggered Debenzylative Intramolecular Acetalation
Authors: Li Yu , Wang Zhi‐mei , Tao Wen‐xiang , Yang Jian‐chen , Tanabe Genzoh , Muraoka Osamu , Li Wei , Xie Wei‐Jia
Published: January 2025

Presented herein is the chemical construction of unprecedented 3,4‐trans‐3,6‐anhydro hexofuranose frameworks. The disfavored 3,6‐anhydro hexofuranosides were effectively established by Pd‐catalyzed debenzylative intramolecular acetalation for the first time. The critical roles of benzyl protection and Pd as catalyst were demonstrated. Various 3,4‐trans‐3,6‐anhydro sugars including sauropunol E was first obtained in satisfactory yields. Pharmaceutical investigation of the sauropunol E and its analogues revealed their potential application as anti‐inflammatory agents.
Towards Improved Peptidic α‐Ketoamide Inhibitors of the Plasmodial Subtilisin‐Like SUB1: Exploration of N‐Terminal Extensions and Cyclic Constraints
Authors: Puszko Anna K. , Batista Fernando A. , Ejjoummany Abdelaziz , Bouillon Anthony , Maurel Manon , Adler Pauline , Legru Alice , Martinez Mariano , Ortega Varga Laura , Hadjadj Margot , Alzari Pedro M. , Blondel Arnaud , Haouz Ahmed , Barale Jean‐Christophe , Hernandez Jean‐François
Published: January 2025

After more than 15 years of decline, the Malaria epidemy has increased again since 2017, reinforcing the need to identify drug candidates active on new targets involved in at least two biological stages of the Plasmodium life cycle. The SUB1 protease, which is essential for parasite egress in both hepatic and blood stages, would meet these criteria. We previously reported the structure‐activity relationship analysis of α‐ketoamide‐containing inhibitors encompassing positions P4‐P2’. Despite compounds with high inhibitory potencies were identified, their antiparasitic activity remained limited, probably due to insufficient cell permeability. Here, we present our efforts to improve it through the N‐terminal introduction of basic or hydrophobic moieties and/or cyclization. Compared to our previous reference compounds 1/2 (Ac‐Ile/Cpg‐Thr‐Ala‐AlaCO‐Asp‐Glu (Oall)‐NH2), we identified analogues with improved Pf‐/PvSUB1 inhibition (IC50 values in the 10–20 nM range) and parasite growth inhibition (up to 98 % at 100 μM). The increase in potency was mainly observed when increasing the overall hydrophobicity of the compounds. Conjugation to the cell penetrating peptide octa‐arginine was also favorable. Finally, the crystal structure of PvSUB1 in complex with compound 15 has been determined at 1.6 Å resolution. Compared to compound 1, this structure extended to the P5 residue and revealed two additional hydrogen bonds.
Application of an Improved Differential Evolution Algorithm in Practical Engineering
Authors: Shen Yangyang , Wu Jing , Ma Minfu , Du Xiaofeng , Niu Datian
Published: January 2025

The differential evolution algorithm, as a simple yet effective random search algorithm, often faces challenges in terms of rapid convergence and a sharp decline in population diversity during the evolutionary process. To address this issue, an improved differential evolution algorithm, namely the multi‐population collaboration improved differential evolution (MPC‐DE) algorithm, is introduced in this article. The algorithm proposes a multi‐population collaboration mechanism and a two‐stage mutation operator. Through the multi‐population collaboration mechanism, the diversity of individuals involved in mutation is effectively controlled, enhancing the algorithm's global search capability. The two‐stage mutation operator efficiently balances the requirements of the exploration and exploitation stages. Additionally, a perturbation operator is introduced to enhance the algorithm's ability to escape local optima and improve stability. By conducting comprehensive comparisons with 15 well‐known optimization algorithms on CEC2005 and CEC2017 test functions, MPC‐DE is thoroughly evaluated in terms of solution accuracy, convergence, stability, and scalability. Furthermore, validation on 57 real‐world engineering optimization problems in CEC2020 demonstrates the robustness of the MPC‐DE. Experimental results reveal that, compared to other algorithms, MPC‐DE exhibits superior convergence accuracy and robustness in both constrained and unconstrained optimization problems. These research findings provide strong support for the widespread applicability of multi‐population collaboration in differential evolution algorithms for addressing practical engineering problems.
Unstructured Text Data Security Attribute Mining Method Based on Multi‐Model Collaboration
Authors: Wang Xiaohan , Du Xuehui , Lv Hengyi , Shang Siyuan , Liu Aodi
Published: January 2025

Access control is a critical security measure to ensure that sensitive information and resources are accessed only by authorized users. However, attribute‐based access control in the big data environment faces challenges such as a large number of entity attributes, poor availability, and difficulty in manual labeling. In this paper, we focus on the problem of mining and optimizing security attributes of unstructured data resources and propose a method for mining security attributes of unstructured textual data based on multi‐model collaboration. First, we utilize unsupervised methods to extract candidate attributes from textual resources, and then weight the results of multiple methods using rough set theory to obtain the optimal result. Second, considering various factors including the text itself and the candidate attributes, we construct a feature vector consisting of 45 categories to represent the candidate attributes. Third, we employ a multi‐model voting method to collaboratively train the attribute mining model and obtain the security attributes of textual resources. Finally, based on HowNet, we optimize the security attributes to achieve automated and intelligent mining of access control data resource security attributes, providing an attribute foundation for precise access control. The experiments indicate that the attribute mining precision rate of the method proposed in this paper can reach up to 92.36%, F1‐score can reach up to 82.51%. The attribute scale can be compressed to 69.59% of its original size after optimization. This method has a greater advantage over other methods and can provide attribute support for access control of large data resources.
Probabilistic Risk Analysis for Catenary System of Heavy‐Haul Railway Based on Casual Inference
Authors: Li Xue , Yan Xiang , Ma Lan , Li Hong , Wang Huawei , Cai Lili , Lu Shuai , Tang Chao , Wei Xilian
Published: January 2025

The reliability of the catenary system is crucial for the safety and efficiency of heavy‐haul railways. This study presents a probabilistic risk analysis model for the catenary system, employing causal inference methods to capture the complex relationships among risk factors. Using historical operational data, we identify key risk contributors such as environmental conditions, vehicular loads, and equipment failures. By combining fault tree analysis (FTA) and failure mode and effects analysis (FMEA), we establish risk propagation pathways. The proposed method utilizes Bayesian networks to quantify conditional probabilities and trace the causal chains leading to potential failures. Through reverse inference, we identify critical risk nodes and their impact on system performance. This approach enhances the accuracy of risk assessment and provides an effective tool for proactive risk management in heavy‐haul railways, aiding in the optimization of maintenance strategies and strengthening the resilience of the catenary system under varying operational conditions.
Perturbing Pentalene: Aromaticity and Antiaromaticity in a Non‐alternant Polycyclic Aromatic Hydrocarbon and BN‐heteroanalogues
Authors: Anstöter Cate , Fowler Patrick W
Published: January 2025

Pentalene (C8H6) and NN‐ and BB‐bridged heterocyclic analogues (BN)4H6, derived by replacement of CC pairs with BN, are taken as  paradigms for tuning of ring‐current (anti)aromaticity by variation of π charge, electronegativity and substitution pattern. 
Ab initio calculation of maps for the π current density induced in these model systems by a perpendicular external magnetic field exhibits the full range of tropicity, from diatropic aromatic to nonaromatic to paratropic antiaromatic, with a
ready rationalisation in terms of an orbital model. 
Further calculations on systems of varying charge in which these motifs are embedded in extended PAH systems with naphthalene and phenanthrene 'clamps' show promise for switching between current patterns and related 
opto‐electronic properties. Particular sensitivity to charge is found for the experimentally accessible NN‐bridged heteropentalene hybrids.
Sustainability of Enzymatic Monomer Synthesis: Evaluation via Comparison of Petrochemical and Enzymatic Alkene Epoxidation by Life Cycle Assessment
Authors: Tannert Robin , Barth Sarah , Hildebrandt Jakob , Taubert Andreas , Weber Jens
Published: January 2025

Life cycle assessment (LCA) was used, next to green chemistry concepts, to compare the full environmental impacts of the epoxidation of a bio‐based monomer, which can be used for the synthesis of vitrimers. On a laboratory scale, the synthesis of the monomer can either be done via a petrochemical route or via an enzymatic reaction pathway. Both reaction pathways were initially optimized to minimize the impact of suboptimal routes on the sustainability evaluation. The subsequent assessment of the enzymatic routes shows lower impact factors for most criteria compared to the petrochemical routes. A significant drawback of the enzymatic reaction, however, is its electricity consumption. The yields of the respective reactions also proved to be crucial; realistic changes in yields revealed the petrochemical reaction to be more sustainable in some cases. LCA is therefore a valuable tool for the preliminary evaluation of the developed synthesis pathways and to identify the critical adjustments needed to increase the sustainability of each reaction.
Sustainable Synthesis of 1,2,3‐Triazoles using Cyrene as a Biodegradable Solvent in Click Chemistry
Authors: Citarella Andrea , Fiori Alessandro , Silvani Alessandra , Passarella Daniele , Fasano Valerio
Published: January 2025

The first successful synthesis of 1,2,3‐triazoles using CyreneTM as a biodegradable and non‐toxic solvent in click chemistry has been developed. In contrast to previous methods, this sustainable approach allows product isolation by simple precipitation in water, eliminating the need for organic solvent extractions and column chromatography purifications, thus minimizing waste consumption while reducing operational costs. The protocol, performed also at gram scale, has broad applicability and versatility, as shown with complex substrates like biologically active coumarins or triazole‐linked bifunctional molecules. Finally, this protocol is also amenable to a three‐component reaction involving organic halides, terminal acetylenes and sodium azide, thus avoiding the isolation of organic azides, difficult‐to‐handle species known for their environmental sensitivity.
Construction of an Indium‐Based Coordination Polymer with Redox Non‐Innocent Ligand for High‐Efficient Electrochemical CO2 Reduction
Authors: Liu Chang , Wang Linqin , Yang Hao , Ding Yunxuan , Zhao Ziqi , Zhang Peili , Li Fei , Sun Licheng , Li Fusheng
Published: January 2025

Developing high‐activity and long‐term stable electrocatalysts for electrochemical CO2 reduction reaction (eCO2RR) to valuable products is still a challenge. An in‐depth understanding of reaction mechanisms and the structure‐function relationship is required for the development of an advanced catalytic eCO2RR system. Herein, a coordination polymer of indium(III) and benzenehexathiol (BHT) was developed as an electrocatalyst (In‐BHT) for eCO2RR to HCOO−, which displayed an outstanding catalytic performance over the entire pH range. However, experimental results revealed significantly different catalytic pathways in the acid and neutral/alkaline solutions, which are attributed to the influence of redox non‐innocent ligands on the rate‐determining step (RDS). In the acid solution, the RDS is the formation of *OCOH intermediate through the proton transfer that originates from H2O in the solution, leading to relatively sluggish kinetics. But in the neutral or alkaline solution, the thiolate groups could be protonated during the catalytic process, and such proton can attack on carbon of absorbed CO2 via an intramolecular proton transfer, promoting the formation of *OCHO intermediate, resulting in faster kinetics. Our findings revealed the pivotal roles of the redox non‐innocent ligands of metal active sites for eCO2RR, providing a new idea for designing highly efficient electrocatalysts.
Energy‐Efficient Communication Using Auto‐Associative Polynomial Convolutional Neural Network in WSN
Authors: Praveen Kanjoor Vamanan , Mary Joe Prathap Pathrose , Ramshankar Nagarajan , Murugesan Sundaram
Published: January 2025

Several changes have been implemented over the years to provide better resource management and service delivery for artificial wireless sensor networks (WSNs) that rely on the Internet of Things (IoT). Here, 5G networks offer high data rates with ultra‐low latency and robust reliability, which is essential for managing the substantial data volumes generated by IoT devices in 5G WSNs. IoT needs an optimal communication network to transmit data among different devices. The whole network is categorized as heterogeneous clusters in clustering. The cluster head (CH) selection achieves proficient data communication to the sink node through the chosen CH. In this manuscript, an energy‐efficient communication using auto‐associative polynomial convolutional neural network in 5G WSN (EEC‐HAPCNN) is proposed for improved data transmission through the selected route. Initially, clustering is done by parallel adaptive canopy k‐means clustering (PaC‐k‐M) algorithm. Then, Tasmanian devil optimization algorithm (TDOA) selects the CH required for facilitating the high capacity and low latency features of 5G. The data are given to sink node through the selected CH utilizing hierarchical auto‐associative polynomial convolutional neural network (HAPCNN) for efficient routing in 5G wireless communication network. The proposed EEC‐HAPCNN method is implemented in NS‐3 (network simulator 3). The proposed approach is examined using performance metrics like throughput, energy consumption, network lifetime, and number of nodes alive. The proposed EEC‐HAPCNN method provides 17.45%, 17.63%, and 18.43% lesser energy consumption and 17.64%, 17.64%, 18.54%, and 19.33% greater network life time compared with existing DBN‐MRFO‐5G‐WSN, IDCNN‐t‐DSBO, DACP‐WSN‐ANN, EEO‐IWSN‐ML, and EECA‐ML‐WSN techniques.
The Burden of Diabetes in the Southeastern Coastal Region of China From 1990 to 2019 and Projections for 2030: A Systematic Analysis of the 2019 Global Burden of Disease Study
Authors: Ding Yating , Cai Xiuli , Ou Yangjiang , Liang Dong , Guan Qing , Zhong Wenling , Lin Xiuquan
Published: January 2025

Aim

This study examined the diabetes burden in Fujian Province, China, from 1990 to 2019, comparing it with China and global levels to inform policymakers.

Materials and Methods

We used data from GBD 2019 to analyse diabetes prevalence, death, and disability‐adjusted life‐years (DALYs). We assessed the average annual percentage change (AAPC) and estimated the impact of 17 risk factors. An age‐period‐cohort model evaluated age, period, and cohort effects on diabetes metrics. Bayesian models forecasted prevalence and DALYs for 2020–2030, with frontier analysis linking DALYs to per capita GDP.

Results

In 2019, Fujian Province had approximately 2,359,179 diabetes cases with a prevalence rate of 4423.82 (95% UI 4004.12–4864.55) per 100,000 and an age‐standardised DALYs of 475.00 (375.63–589.49) per 100,000, both lower than China and global averages. From 1990 to 2019, Fujian Province's age‐standardised mortality rate remained higher than the China average, but the gap narrowed compared with 1990. Elderly males showed a pronounced increase in mortality. The period effect indicated a turning point during 2005–2009. DALYs increased among men and decreased among women over cohorts. By 2030, the DALYs rate is projected to decrease by 6.59%. Frontier analysis showed that compared with the same economic level, the effective difference in diabetes disease burden in Fujian Province was small, but there was room for improvement.

Conclusion

From 1990 to 2019, Fujian Province's age‐standardised diabetes prevalence slightly increased, while mortality and DALYs declined. Significant gender and age disparities existed, highlighting the need for targeted strategies for elderly males. Fujian Province's success in diabetes management can provide a model for other regions.
Enhancing Farm Dams Increases Tadpole Abundance
Authors: Littlefair Michelle , Scheele Ben C. , Lindenmayer David , Evans Maldwyn J.
Published: January 2025

Understanding how agricultural and land management practices affect amphibian biodiversity is essential for conservation efforts in farmland. We investigated the impact of farm dam enhancement on tadpole abundance and growth in a highly modified farming landscape in south‐eastern Australia. We completed detailed surveys on 52 farm dams (artificial ponds or agricultural reservoirs). These dams were categorized into two groups: enhanced (n = 28), which had undergone management activities such as fencing to prevent livestock access and facilitate revegetation, and control (n = 24), which had not received any intervention and were subject to standard management practices similar to adjacent paddocks. Our findings revealed a notable increase in tadpole abundance across all species in enhanced dams, with 92% of all observed tadpoles recorded in these dams. Factors such as higher dissolved oxygen and greater riparian vegetation cover were positively associated with tadpole abundance, while high pH levels showed a negative association. We found no evidence that tadpole growth was influenced by dam enhancement. Concerningly, when the invasive fish Gambusia holbrooki was present, tadpoles were smaller and at earlier developmental stages. Our findings highlight the potential benefits of strategic farm dam management for improving tadpole presence in agricultural landscapes.
Synthesis of Chloro‐Substituted β‐Ketiminate Palladium Complexes, Spectral and Thermal Investigation of their Structures
Authors: Taher Deeb , AlNaimat Sara , Assaf Khaleel I. , Helal Wissam , Korb Marcus
Published: January 2025

The synthesis and characterization of nine palladium(II) complexes featuring β‐ketoiminato ligands of type [Pd(ArNacac)2] (4) with Ar=2‐chlorolphenyl (a); 3‐chlorophenyl (b); 4‐chlorophenyl (c); 2,3‐dichlorophenyl (d); 2,4‐dichlorophenyl (e); 2,6‐dichlorophenyl (f); 3,5‐dichlorophenyl (g); 2,4,5‐trichlorophenyl (h); 2,4,6‐trichlorophenyl (i) is reported. The molecular structure of 4 a–f, 4 h and 4 i in the solid state was confirmed by single‐crystal X‐ray diffraction studies. All eight crystal structures are centrosymmetric, with the metal positioned in a slightly distorted square plane. Intermolecular non‐covalent interactions such as C−H⋅⋅⋅Pd, Cl⋅⋅⋅Cl, Cl⋅⋅ π, C−H⋅⋅⋅Cl, Cl⋅⋅⋅O, C−H⋅⋅ π, and π⋅⋅⋅π play crucial roles in the formation of the supramolecular structures. The crystal structures of 4 b, 4 c, and 4 e revealed unique intermolecular C−H⋅⋅⋅Pd anagostic interactions between the hydrogen atom on the substituted ligand and the palladium centers, which enable the formation of 1‐D polymeric chains. The intermolecular non‐covalent interactions were analyzed using Hirshfeld surface. The proportional contributions of each individual atom to the formation of these non‐covalent interactions are shown in the 2D fingerprint plots. Furthermore, density functional theory (DFT) has been used to compute the energetic estimation of non‐covalent interactions in 4 b, 4 c and 4 e. Furthermore, computational methods such the non‐covalent interaction (NCI) plot index and quantum theory of atoms in molecules (QTAIM) analysis have been used to study the non‐covalent interactions in 4 b, 4 c, and 4 e.
Empirical Evidence of Dynamic Hydrogeomorphic Feature Inundation in a Lowland Floodplain
Authors: Cain Molly R. , Hixson Jase L. , Jones C. Nathan , Rhoads Bruce L. , Ward Adam S.
Published: January 2025

Floodplains along low‐gradient, meandering river systems contain diverse hydrogeomorphic features, ranging from isolated depressions to hydrologically‐connected channels. These ephemerally‐flooded features inundate prior to river water overtopping all banks, enhancing river‐floodplain connectivity during moderately high flow stages. Predicting when and where ecological functions occur in floodplains requires understanding the dynamic hydrologic processes of hydrogeomorphic features, including inundation and exchange. In this study, we examined storm event‐scale inundation and exchange dynamics along a lowland, meandering river system in central Illinois (USA). We monitored surface water presence/absence, surface water level, and groundwater level across floodplain hydrogeomorphic feature types (i.e., isolated depression, backwater channel, and flow‐through channel). Using these data, we evaluated inundation onset and recession characteristics, drivers of groundwater‐surface water interactions, and direction of hydrologic exchange with the river channel. Surface water presence/absence patterns suggested inundation onset timescales were primarily controlled by microtopography and recession timescales were correlated with floodplain elevation. Employing a novel hysteresis approach for characterising groundwater‐surface water interactions, we observed distinct patterns indicating differences in water sources across hydrogeomorphic units and event characteristics. Finally, differences in hydraulic head along floodplain channels revealed that channels with multiple inlets/outlets (i.e., flow‐through channels) conveyed down‐valley flow and channels with single inlets primarily functioned as sinks of river‐derived water to the floodplain with short source periods. These results highlight the heterogeneity of hydrologic processes that occur along lowland, meandering river‐floodplains, and more specifically, point to the important role hydrogeomorphic features play in controlling dynamic connectivity within the river corridor.
Stemflow Measurement on Large Leaning Quercus serrata Trees: Examination of Stem Lean Effect on Stemflow
Authors: Sato Takanori , Ohosawa Khotaro , Ebata Kazunari , Matsumoto Yoshitaka
Published: January 2025

Stemflow measurements were performed on seven Quercus serrata and canopy structure metrics were obtained to identify factors that affect stemflow. Among the seven stems, two exhibited a large stem lean (> 20°). Although a linear relationship between rainfall and stemflow was shown in all trees, stemflow volume on the highly leaning stems (Nos. 6 and 7) was clearly smaller than those on the others. To extract canopy structure metrics effective on stemflow, GLM analysis was conducted. The objective variable was the slope of the regression line a between rainfall and stemflow. Canopy structure metrics as explanatory variables were the diameter at breast height DBH, tree height H, canopy projection area CPA, stem lean parameters L and Ld, and stem length (SL). L is stem lean from the base to the top and Ld is stem lean at breast height. GLMs were constructed using all combinations of explanatory variables. GLMs that included at least one explanatory variable for which a statistically significant had been shown were selected. First, GLMs constructed using DBH, L, and Ld were selected. The relationship between DBH and a was positive, but the R2 value using all data (R2 = 0.39) was smaller than upon excluding stem Nos. 6 and 7 (R2 = 0.85). This indicated the need to consider DBH and stem lean simultaneously. Second, a GLM constructed only using H was selected. R2 values of DBH with H and SL were 0.57 and 0.72, respectively. According to the definition of H, the more the stem leans, the lower H is measured, at the same value of SL. Thus, H was a parameter that includes the effect of stem lean. Our results indicated that it is necessary to consider stem lean when evaluating the process of canopy interception in deciduous broadleaf forests.
Assessing Water Requirements of Groundwater Dependent Ecosystems Using a Water Balance Approach and Streamflow Separation
Authors: Gurieff Lisa B. , Reading Lucy P. , Dawes Les
Published: January 2025

Groundwater supports approximately one ‐third of global water consumption. With increasing pressures on this resource from both anthropogenic users and climatic influences, sustainable management of groundwater has become crucial. This article identifies groundwater requirements by Groundwater Dependent Ecosystems (GDEs) as groundwater evapotranspiration and groundwater discharge to surface water features (baseflow). These requirements are investigated using a soil moisture model combined with a water balance approach, baseflow separation techniques and groundwater level monitoring. The results are compared to groundwater evapotranspiration estimates based on diurnal water level fluctuations. For the period 2000 to 2019, the combined GDE requirements, including groundwater evapotranspiration and environmental baseflow requirements, ranged from 130 to 420 mm/year for the highest ecological indicator level within the study area of approximately 20 km2. These estimates provide valuable information on the short‐term (daily to monthly) to long‐term (yearly to multi yearly) responses to climate variations and can be integrated into water stress assessments. These findings can be used to enhance our understanding of the role of GDEs water requirements and contribute to managing GDEs as part of sustainable management of groundwater resources.
Modelling the Soil Evaporation Loss in Secondary Forests of the Subtropical Monsoon Region, Central South China
Authors: Zhang Yong , Zhang Xinping , Xiao Xiong , Dai Junjie , Jiang Wanjing , Du Zhen , Zhan Xuhong , Liu Lu
Published: January 2025

Under more frequent, extreme global drought events, the use of stable isotopes to quantify soil evaporation losses (SEL) is of great significance for understanding the water supply capacity from soil to plants. During March 2017–September 2019, we continuously monitored meteorological factors, soil temperature (ST) and humidity, and collected precipitation and soil water stable isotope data. The Craig‐Gordon (C‐G) and line‐conditioned excess (lc‐excess) coupled with the Rayleigh fractionation (RL) models were used to quantify SEL in subtropical secondary forests. The results showed: (1) the theoretical evaporation line (EL) slope negatively correlated with air temperature (AT). Water source isotopic values are more positive in autumn and more negative in spring. The aridity index (AI) and soil evaporation loss ratio (f) from both models indicated drier conditions during March–September 2018 compared to 2017 and 2019; (2) comparative analysis showed the C‐G model agreed more closely with measured evapotranspiration (ET0) and water surface evaporation (E) than the RL model, indicating better suitability of the C‐G model in the study region; (3) because the “inverse temperature effect” of the precipitation isotopes, the linear fitting method was not suitable for determining the water source in spring, summer, autumn, and on the annual scale, while the linear fitting method was consistent with the basic principle of soil evaporation in winter. Thus, the theoretical method was more suitable for determining the EL slope in such regions; (4) because of the different fundamentals, the C‐G model positively correlated with AT and negatively correlated with relative humidity (h), while the RL model showed the opposite trends, indicating different applicability. The SEL is influenced by soil thickness, atmospheric evaporation and soil water supply capacity. These findings support stable isotope application techniques for quantifying SEL and are crucial for analysis of soil water resources in subtropical secondary forests.
Intuitionistic Fuzzy Position Embedding Transformer for Motion Artefact Correction in Chemical Exchange Saturation Transfer MRI Series
Authors: Chen Bowei , Khalid Umara , Chai Enhui , Chen Li
Published: January 2025

Chemical Exchange Saturation Transfer (CEST) Magnetic Resonance Imaging (MRI) is a cutting‐edge molecular imaging technique that enables non‐invasive in vivo visualization of biomolecules, such as proteins and glycans, with exchangeable protons. However, CEST MRI is prone to motion artefacts, which can significantly reduce its accuracy and reliability. To address this issue, this study proposes an image registration method specifically designed to correct motion artefacts in CEST MRI data, with the objective of improving the precision of CEST analysis. Traditional registration techniques often suffer from premature convergence to local optima, especially in the presence of rigid motion within the ventricular region. The proposed approach leverages an Intuitionistic Fuzzy Set (IFS) position encoding integrated with a multi‐head attention mechanism to achieve accurate global registration. A custom loss function is designed based on the properties of IFS position encoding to further enhance the model's motion correction capabilities. Experimental results demonstrate that this method provides a more robust and accurate solution for motion artefact correction in CEST MRI, offering new potential for improving the precision of CEST imaging in clinical and research settings.
TWIST1 Regulates FOXM1/β‐Catenin to Promote the Growth, Migration, and Invasion of Ovarian Cancer Cells by Activating MFAP2
Authors: Zhao Lingqin , Song Qian , Zheng Chao , Sun Wei , Chen Yaqing
Published: January 2025

TWIST1 is aberrantly expressed in ovarian cancer (OC). MFAP2 is a downstream target of TWIST1, and we previously found MFAP2 facilitated OC development by activating FOXM1/β‐catenin. We planned to investigate the mechanisms of TWIST1 in OC. GEPIA (a database for gene expression analysis) and UALCAN (a database containing comprehensive cancer transcriptome and clinical patient data) investigated TWIST1's connection to MFAP2 and patient survival in ovarian serous cystadenocarcinoma (OV). Human OC cells (A2780 and CAOV3) were transfected with si‐TWIST1, oe‐TWIST1, oe‐MFAP2, or si‐TWIST1 + oe‐MFAP2. Cellular apoptosis, viability, migration, and invasion were detected. TWIST1, MFAP2, FOXM1, and β‐catenin protein expressions were tested. Dual‐luciferase and ChIP‐qPCR validated the correlation between MFAP2 and TWIST1. Moreover, OC mice were established by injecting OC cells subcutaneously. The pathology, apoptosis, as well as Ki67, TWIST1, MFAP2, FOXM1, and β‐catenin protein levels of tumors were assessed. TWIST1 expression positively correlated with MFAP2 expression, but negatively related to patients' survival in OV. TWIST1 overexpression promoted malignant behaviors, and increased MFAP2, FOXM1, and β‐catenin protein levels for OC cells. TWIST1 knockdown exhibited the opposite trend. In vivo, TWIST1 knockdown disrupted tissue structure, induced apoptosis, decreased Ki67, TWIST1, MFAP2, FOXM1, and β‐catenin protein levels in tumor. Interestingly, MFAP2 overexpression reversed the effects of TWIST1 knockdown in vitro and in vivo. Additionally, dual‐luciferase and ChIP‐qPCR confirmed MFAP2 was a downstream target for TWIST1 in OC. TWIST1 regulated FOXM1/β‐catenin to promote the growth, migration, and invasion of OC cells by activating MFAP2, indicating that targeting TWIST1 may be effective for treating OC.
The Discovery of New Antibody in Autoimmune Disease Using a Novel Approach of Coombs Test Based on Flow Cytometry Method
Authors: Ullah Anwar , Ding Xuewei , Qi* Xia , Liu* Hui
Published: January 2025

Background and Objective

The objective of this study was to investigate the antibody to RBC in autoimmune disease patients with ANA using sensitive Coombs test based on flow cytometry method.

Materials and Methods

Antinuclear antibodies (ANA) of autoimmune disease patients were added to red blood cells (RBCs) of blood group O. At the same time, healthy individuals' serums were also checked. The sample tubes were incubated for 30 min at 37°C. After incubation, each sample was analyzed on flow cytometry.

Results

The agglutination of antinuclear antibodies in autoimmune patients was observed, while in healthy people, there was no agglutination between RBCs and serum. A significant difference was found between the disease group and healthy group (p < 0.0001) showing that a statistical analysis was conducted to compare the presence of ANA agglutination between the two groups. The reported p‐value of less than 0.0001 shows that the observed difference is highly significant. The serum stability test conducted over ten consecutive days demonstrated a CV of 6.90% in the test results, indicating favorable stability.

Conclusion

In conclusion, this study emphasizes the effectiveness of flow cytometry as a valuable tool for detecting RBC‐bound antibodies and new antibodies in autoimmune disease patients. Its high sensitivity and accuracy have the potential to greatly improve diagnostic capabilities in clinical laboratories.
Efficacy of 2‐Mercaptoethane Sulfonate Sodium (MESNA) in the Prevention of Pancreatitis After Endoscopic Retrograde Cholangiopancreatography: A Randomized Open Label Trial
Authors: Sadeghi Amir , Samar Hesamoddin , Abbasinazari Mohammad , Mohammadi Parvaneh , Abazarikia Ali , Ziaie Shadi
Published: January 2025

Background and Aim

Oxidative stress has been considered a factor in the development of post‐endoscopic retrograde cholangiopancreatography pancreatitis (PEP). The present clinical trial evaluated whether adding intravenous mesna to rectal indomethacin could prevent or alleviate PEP.

Methods

An open‐labeled clinical trial was done on 698 participants undergoing endoscopic retrograde cholangiopancreatography (ERCP). Eligible patients received 100 mg indomethacin suppository 30 min before undergoing ERCP. Randomly, the participants received 400 mg intravenous mesna or nothing 30 min before doing the procedure. The PEP incidence and degree were measured in the patients as the main outcome.

Results

The total rate of PEP was equal to 13.7%. No significant difference was seen in the rate and severity of PEP between the mesna plus indomethacin and indomethacin alone arms (14% vs. 13.4%, respectively, p = 0.671). In high‐risk patients, PEP rate and severity were lower in the mesna plus indomethacin group compared with indomethacin alone group and the statistical analysis showed that the difference was significant (41.7% vs. 51.8%, respectively, p = 0.033).

Conclusion

In high‐risk patients undergoing ERCP, a combination of intravenous mesna plus rectal indomethacin may decrease the PEP rate and severity.
Comparative Study of Remimazolam and Midazolam During Sedated Upper Gastrointestinal Endoscopy: A Propensity Score Matching Analysis
Authors: Ichijima Ryoji , Ikehara Hisatomo , Sugita Tomomi , Yamaguchi Daisuke , Nagata Yasuhiko , Ogura Kanako , Esaki Mitsuru , Minoda Yosuke , Ono Hiroyuki , Maeda Yuki , Kiriyama Shinsuke , Sumiyoshi Tetsuya , Kanmura Yuichi
Published: January 2025

Aim

This study aimed to compare the use of remimazolam and midazolam in upper gastrointestinal endoscopy in Japan as a sub‐analysis of data from an investigator‐initiated clinical trial of remimazolam.

Methods and Results

Patients in two groups were matched using propensity score matching. We evaluated the time from the end of the gastrointestinal endoscopy until discharge, the time from the end of the procedure until awakening, and adverse events. Overall, 36 participants from the clinical trial population who underwent upper gastrointestinal endoscopy using remimazolam and 199 patients who underwent the procedure with midazolam during the same period were included in this study. Following propensity score matching, 34 patients in both groups were matched. The median time from the end of the procedure until awakening was 27.0 min (23.0–40.5 min) in the midazolam group (Group M) and 0 min (0–5.0 min) in the remimazolam group (Group R); the median time from the end of the upper gastrointestinal endoscopy until discharge was 39.0 min (35.0–52.5 min) in Group M and 5.0 min (0–5.0 min) in Group R (p < 0.01). Reported adverse events were hypotension and hypoxemia in one patient in Group R.

Conclusion

Compared with midazolam, remimazolam significantly shortened the time to patient awakening and duration until the patient could leave the endoscopy room.

Trial Registration: The main study (REM‐IICT JP1) is registered with the Japan Registry of Clinical Trails: jRCT2031200360
Patient‐derived xenograft model in cancer: establishment and applications
Authors: Gu Ao , Li Jiatong , Li Meng‐Yao , Liu Yingbin
Published: January 2025

The patient‐derived xenograft (PDX) model is a crucial in vivo model extensively employed in cancer research that has been shown to maintain the genomic characteristics and pathological structure of patients across various subtypes, metastatic, and diverse treatment histories. Various treatment strategies utilized in PDX models can offer valuable insights into the mechanisms of tumor progression, drug resistance, and the development of novel therapies. This review provides a comprehensive overview of the establishment and applications of PDX models. We present an overview of the history and current status of PDX models, elucidate the diverse construction methodologies employed for different tumors, and conduct a comparative analysis to highlight the distinct advantages and limitations of this model in relation to other in vivo models. The applications are elucidated in the domain of comprehending the mechanisms underlying tumor development and cancer therapy, which highlights broad applications in the fields of chemotherapy, targeted therapy, delivery systems, combination therapy, antibody–drug conjugates and radiotherapy. Furthermore, the combination of the PDX model with multiomics and single‐cell analyses for cancer research has also been emphasized. The application of the PDX model in clinical treatment and personalized medicine is additionally emphasized.
A novel allosteric driver mutation of β‐glucuronidase promotes head and neck squamous cell carcinoma progression through STT3B‐mediated PD‐L1 N‐glycosylation
Authors: Liu Zhonglong , Meng Xiaoyan , Tang Xiao , Zhang Jian , Zhang Zhiyuan , He Yue
Published: January 2025

Head and neck squamous cell carcinoma (HNSCC) develops and advances because of the accumulation of somatic mutations located in orthosteric and allosteric areas. However, the biological effects of allosteric driver mutations during tumorigenesis are mostly unknown. Here, we mapped somatic mutations generated from 10 tumor‐normal matched HNSCC samples into allosteric sites to prioritize the mutated allosteric proteins via whole‐exome sequencing and AlloDriver, identifying the specific mutation H351Q in β‐glucuronidase (GUSB), a lysosomal enzyme, as a novel allosteric driver mutation, which considerably encouraged HNSCC progression both in vitro and in vivo. Mechanistically, the allosteric mutation of H351Q remarkably attenuated protein trafficking from the endoplasmic reticulum (ER) to lysosomes, leading to ER retention, in which GUSB‐H351Q facilitated the aberrant N‐glycosylation of PD‐L1 through increasing protein stability and mRNA transcripts of the STT3 oligosaccharyltransferase complex catalytic subunit B, an oligosaccharyltransferase complex. Moreover, GUSB‐H351Q reshaped a more immunosuppressive microenvironment featuring increased infiltration of exhausted CD8+ T cells and remodeled tumor metabolism, characterized by increased activity of the purine metabolism pathways and pyruvic acid accumulation. This study provides a mechanism‐driven approach to overcoming HNSCC progression and immune evasion and identifies novel druggable targets based on the presence of GUSB allosteric driver mutation.