bluuebunny/crossref_metadata_2025 huggingface dataset:
Design and Structure of Electrolytes for All‐Weather Aqueous Zinc Batteries
Authors: Xiong Tianbai , Guo Yalan , Wang Xin
Published: December 2024

Rechargeable aqueous zinc batteries (AZBs) utilizing water‐borne electrolytes are intrinsically safe electrochemical devices that are promising in next‐generation energy storage. Such application requires adaptivity to global climate, especially at grid‐scale, thus their stability of electrochemical performance at varying temperatures is critical. Many essential properties of AZBs, i.e., ion transfer, redox kinetics, etc., are largely governed by the aqueous electrolytes in the batteries because of the relatively limited stable phase temperature of water. This limitation is extremely vital in cold regions since charging and discharging become more difficult at the sub‐zero range due to water freezing. Despite the development of various electrolyte strategies in recent years, comprehensive reviews focusing on this topic remain limited. This research reviews the diverse reasons underneath the failure of AZBs at extreme temperatures and provides a thorough analysis of possible resolutions from an electrolyte perspective. It starts with the challenges faced by AZBs at both high and low temperatures concerning the electrolytes. Different strategies addressing these challenges are discussed, providing insights into aqueous batteries under extreme temperature conditions. Finally, the review concludes with a summary and outlook on the design and structure of electrolytes for all‐weather AZBs, integrating innovative strategies from both aqueous and non‐aqueous battery systems.
Self‐Assembled Nanoparticles with Well‐Defined Oligosaccharide Promote Osteogenesis by Regulating Golgi Stress Response
Authors: Niu Pingping , Zhao Liman , Yang Jing , Ding Yanan , Xu Xiaoqiao , Li Sijin , Song Lige , Chen Guosong , Sun Yao
Published: December 2024

Osteoporosis, a prevalent disease characterized by low bone density and increased fracture risk, poses significant health challenges for the elderly. Current treatments offer short‐term benefits but are limited by long‐term efficacy and adverse effects, highlighting the need for new strategies. Chondroitin sulfate polysaccharides (CS), a major component of the bone matrix, are crucial for bone and cartilage health. However, their role in osteoporosis is understudied due to the heterogeneity of natural CS. we found reduced CS levels in osteoporosis patients and developed CS4‐NP, a self‐assembled tetrasaccharide nanoparticle that mimics CS's structure. CS4‐NP, which efficiently delivers the active CS4, significantly improves bone mass in ovariectomized osteoporosis models. It activates the Activating Transcription Factor 4‐Cystathionine gamma‐Lyase signaling axis in pre‐osteoblasts, enhancing osteogenesis. our findings suggest that CS4‐NP, an oligosaccharide‐based nanomaterial, could address the limitations of current treatments and provide a viable strategy for osteoporosis.
Gas Empowered Dual‐Cascade Strategy for Augmented Single‐Atom Nanotherapies
Authors: Liu Yong , Li Xiao‐Qiong , Yu Qiao , Kang Bin , Zhao Xueli , Xu Jing‐Juan
Published: December 2024

Single‐atom nanotherapies have received numerous attention in malignant oncotherapy. However, the insufficient enzyme substrate and the upregulation of heat shock proteins during therapeutic interventions are seldom concurrently noticed. Herein, a novel gas empowered dual‐cascade synergistic treatment strategy is demonstrated with domino effect, which can sequentially reinforce single‐atom nanozyme (SAzyme)‐based enzymatic therapeutics and mild photothermal therapy (PTT) (< 45 °C). In the proof‐of‐concept study, Fe single atom nanozyme (Fe/SAzyme) loaded with hydrogen sulfide (H2S) donor NaHS is developed for HSPs‐silencing mediated mild PTT. The generated H2S suppresses the catalase activity to achieve “intracellular H2O2 conservation”, thereby furnishing the enzyme substrate to Fe/SAzyme to produce abundant cytotoxic hydroxyl radicals (·OH) for augmented enzymatic therapeutics. Then, excess ·OH induced mitochondrial dysfunction blocks adenosine triphosphate (ATP) energy supply to realize cellular energy remodeling, which hinders overexpression of HSPs and enhances mild PTT of Fe/SAzyme both in vitro and vivo. Consequently, the gas‐triggered dual‐cascade strategy achieves domino H2S/·OH/mitochondrial dysfunction synergistic effect, endowing SAzymes with maximum antitumor efficacy via enzymatic therapeutics combined with mild PTT. This dual‐cascaded gas/enzymatic/mild PTT synergistic oncotherapy not only exhibits a new pathway for gas‐facilitated mild PTT, but also offers a valuable paradigm for the application of “1 + 1 + 1 > 3” multimodal synergistic tumor therapy.
Electrical Dissipation Factor Measurements of Droplet Impact‐Derived Microgels with Different Topological Structures
Authors: Wang Lei , Ding Xuerong , Hu Yiheng , Li Qiurui , Bian Yibing , Duan Yefan , Lu Shujie , Han Hongbin , Gu Ning , Sun Jianfei
Published: December 2024

Topology, the study of properties that are invariant under continuous transformations, in which the number of pores (genus) is a profound concept that determines a number of properties that have been verified in many microscopic systems, but have not been studied in macroscopic materials. Microgels are widely used materials, and based on microfluidics, regular, stable, and reproducible microgels can be prepared, but studies from the perspective of topological principles have not been reported. In this paper, a system based on a boric acid ester rapid cross‐linking strategy that can rapidly capture topological changes during the transient process of droplet‐to‐ring transition is proposed. The electrical dissipation properties associated with different transient topologies during the process are also investigated, demonstrating that the change of topological structures in macroscopic materials also affected their electrical properties, laying the foundation for the design of modulated macroscopic micro structured materials based on topology theory.
Polymorphing Hydrogels Regulated by Photo‐reactive DNA Cross‐links
Authors: Roh Junho , Park Seongjun , Kim Hoeseong , Kim Woojin , Kim Jinho , Park Cheolheon , Choi Hansol , Song Seowoo , Choi Eunjin , Choi Yeongjae
Published: December 2024

Polymorphing hydrogels can morph into another structure on demand with reprogrammable features. This concept extends the degree of morphing beyond that of traditional shape‐morphing hydrogels, which predetermine their morphing capabilities at the fabrication stage. However, current polymorphing hydrogels face limitations due to the need for complex, non‐sustained responsiveness or additional chemical steps for reconfigurable morphing. Here, photo‐reactive DNA‐cross‐linked polymorphing hydrogels are presented that enable polymorphing under patterned light. The photo‐reactive DNA cross‐links act as a regulator in changing the shapes of the hydrogels by adjusting the lengths of the cross‐links depending on the wavelength of light, which allows precise and dynamic morphing in a programmable way through a one‐pot reaction. The high programmability involving spatiotemporal controllability and reprogrammable features offers advanced solutions for multifunctional soft machines and applications requiring complex processes.
Rare‐Metal‐Free Ultrabroadband Near‐Infrared Phosphors
Authors: Zheng Guojun , Lou Chenjie , Yuan Zeyue , Xiao Wenge , Shang Longbing , Zhong Jiyou , Tang Mingxue , Qiu Jianrong
Published: December 2024

Trivalent chromium (Cr3+) is an attractive near‐infrared (NIR) emitter, but its ultrabroadband NIR emission is limited to host crystals containing large amounts of rare‐metal elements and usually suffers from low internal quantum efficiency (IQE) and poor thermal stability. Here, a class of high‐performance, rare‐metal‐free ultrabroadband NIR phosphors, are reported by revealing that weak‐field Cr3+ centers featuring broadband NIR emission with near‐unity IQEs are intrinsic, though in trace quantities, to Cr3+ doped MgAl2O4 spinel (MAS) and its derivatives well‐known for their narrowband far‐red emission. It is shown that such weak‐field Cr3+ centers stem from cation inversion ubiquitous in spinel compounds, and their quantity can be increased simply by superstoichiometric Al2O3/Ga2O3. Then SiO2 is introduced into Al2O3‐excess MAS to break the inversion symmetry of Cr3+ centers for greatly improving the probabilities of their otherwise parity‐forbidden 3d–3d transitions. The as‐fabricated phosphor‐converted light‐emitting diodes are capable of emitting ultrabroadband NIR light with high photoelectric efficiency (16.0%) and optical power (180.8 mW), and excellent spectral stability, which apparently outperforms existing state‐of‐the‐art devices.
Cobalt‐Based Materials in Supercapacitors and Batteries: A Review
Authors: Goudar Jyothi A. , S. N. Thrinethra , Chapi Sharanappa , M. V. Murugendrappa , Saeb Mohammad Reza , Salami‐Kalajahi Mehdi
Published: December 2024

Energy demand has become a persistent concern and high‐performance energy storage systems have increasingly undergone development. Supercapacitors and batteries pose great impact on energy storage and garner a great deal of attention from technologies and researchers alike. The performance of energy saving devices is primarily determined by the electrode material in terms of high specific capacitance, excellent conductivity, remarkable natural abundance, and unique electrochemical qualities, also large surface area. Cobalt (Co)‐based materials are unique electrode materials widely used in energy storage devices. Nevertheless, a combination of Co and ferrite materials such as nickel, zinc, and copper, or Co/nonferrite materials like metal–organic frameworks and layered double hydroxides has improved their ultimate efficiency. This review deals with energy storage applications of Co‐based materials, categorizing ferrites, their electrochemical characterization, performance, also design and manufacturing intended to supercapacitors and batteries applications. Summarizing the main outcomes of the literature on batteries and supercapacitors, energy storage systems comprising Co‐based materials combined with carbon nanotubes, graphene, silica, copper, zinc, nickel, cadmium, ferrous, and lanthanum are reviewed and discussed. Lithium‐ion batteries are investigated specifically, and perspectives on Co‐based ferrite development for future generations of supercapacitors and batteries are outlined.
From Desbuquois Dysplasia to Multiple Epiphyseal Dysplasia: The Clinical Impact of a CANT1 Variant Across Five Unrelated Families
Authors: Daşar Tuğba , Ürel Demir Gizem , İmren Gözde , Utine Gülen Eda , Yilmaz Güney , Şimşek Kiper Pelin Özlem
Published: December 2024

Multiple epiphyseal dysplasia (MED) is a heterogeneous group of chondrodysplasia characterized by arthralgia, early onset osteoarthropathy, and the radiographic findings of small, flat, and irregular‐shaped epiphyses. Some patients with MED have mild short stature as well. MED is genetically heterogeneous caused by pathogenic variants in COMP, MATN3, COL9A1, COL9A2, COL9A3, and SLC26A2. In 2017, pathogenic variants in CANT1, which are responsible for Desbuquois dysplasia, have also been reported in the genetic etiology of MED. To date, only three patients have been reported with CANT1‐related MED. Herein, we present clinical and radiographic findings of six additional patients from five unrelated families, all sharing the same c.375G > C; p.(Trp125Cys) variant in CANT1 gene. These patients exhibited the features of multiple epiphyseal dysplasia, along with some similarities to Desbuquois dysplasia, thereby broadening the clinical spectrum of CANT1‐related disorders.
“Angular” Spirocyclic Azetidines: Synthesis, Characterization, and Evaluation in Drug Discovery
Authors: Kirichok Alexander A. , Tkachuk Hennadii , Levchenko Kostiantyn , Granat Dmitry , Yegorova Tetyana , Lesyk Dmytro , Anisiforova Anna , Holota Yuliia , Zomchak Viktoriia , Bodenchuk Iryna , Kosach Viktoriia , Borysko Petro , Korzh Rodion A. , Al‐Maali Galeb , Kubyshkin Vladimir , Rzepa Henry S. , Mykhailiuk Pavel K.
Published: December 2024

The previously neglected “angular” spirocyclic azetidines have been synthesized, characterized, and validated in drug discovery. We have shown that these compounds could act as bioisosteres for common saturated six‐membered heterocycles. Their incorporation into the structure of the anticancer drug Sonidegib (instead of morpholine), and Danofloxacine (instead of piperazine) provided novel patent‐free analogs with similar physicochemical properties and high activity.
Weakly Solvating Cyclic Ether‐Based Deep Eutectic Electrolytes for Stable High‐Temperature Lithium Metal Batteries
Authors: Yang Yanru , Li Qin , Li Huan , Ruan Jiafeng , Wang Fengmei , Li Ziyue , Yang Jinyu , Zhang Jiayun , Çağlayan Uğur , Sun Dalin , Fang Fang , Kunduraci Muharrem , Wang Fei
Published: December 2024

Deep eutectic electrolytes (DEE) have emerged as an innovative approach to address the instability and safety issues of lithium metal batteries at elevated temperatures. However, in practice, there is often an undesirable incompatibility between the eutectic mixture and electrodes, and also an insufficient reduction stability of DEE due to the increased Li+ concentration. Herein, we designed a new DEE by utilizing weakly solvating tetrahydropyran (THP) solvent. Due to the high reduction resistance of THP and concentrated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), this DEE demonstrates enhanced compatibility with Li metal anode and high temperature tolerance with LiMn2O4 cathode. The Li||LiMn2O4 cell (1.6 mAh cm−2) shows a high capacity retention of 96.02 % after 600 cycles at room temperature. More importantly, this Li||LiMn2O4 cell achieves a remarkable high‐temperature performance with a high capacity retention of 91.72 % after 120 cycles and low self‐discharge after storage for 240 hours at a high temperature of 55 °C, which is critical for LiMn2O4 cathode. Overall, this electrolyte design provides an alternative pathway for the development of DEEs for high‐temperature and high‐voltage lithium metal batteries, which can also be expanded to other batteries.
Skeletal Rearrangement of Azo Compounds Enables Low‐Potential, High‐capacity Organic Anodes for Rechargeable Alkaline Batteries
Authors: Zhao Jiapeng , Zhang Wenjin , Du Dawei , Liu Zhihao , Ji Weixiao , Huang He , Pang Siping
Published: December 2024

The widespread adoption of rechargeable alkaline batteries is plagued by the performance‐limiting metal anodes, which are prone to (electro)chemical corrosion and raise environmental or economic concerns. Organic redox‐active materials offer a potential solution, but they typically struggle with dissolution‐induced degradation and insufficiently negative reduction potentials. Herein, we introduce benzo[c]cinnoline and its derivatives (collectively referred to as BCCs), a class of aromatic azo compounds with fused‐ring structure, as promising organic anode materials. BCCs exhibit pronounced aromaticity and Brønsted basicity, conferring low reduction potentials and intrinsic insolubility in alkaline solutions. Paired with the industrially established nickel hydroxide cathode, these batteries deliver excellent capacity (297 mAh g−1anode), high output voltage of 1.3 V, and extended cycle life (≈16000 cycles). Notably, they also operate efficiently at extremely low temperatures down to −85 °C with an 8 M KOH electrolyte. We further explore the feasibility for all‐organic alkaline batteries by paring BCCs with the dihydro form of 4,4’‐azopyridine, utilizing azo compounds for both anode and cathodes. This chemistry harnesses the unique properties of small organic molecules to enable all‐organic batteries with high capacity of 236 mAh g–1, fast charging at 1200 C, and easy recyclability.
Heterogeneous Catalysis of Molecular‐Like Au8M(PPh3)8n+ Clusters Cultivated in Mesoporous SBA‐15
Authors: Sun Tianqi , Ge Bingqing , Huang Shuangshuang , Wang Xiuwen , Tian Yiqi , Cai Xiao , Ding Weiping , Zhu Yan
Published: December 2024

It is a dream of researchers to be able to tailor the catalytic performances by adjusting heterogeneous catalysts at the atomic level. Atomically precise metal clusters provide us with the possibility to achieve this challenge. Here, we design a push‐and‐pull synthesis strategy coupled with TiOx coating to prepare the heterogeneous catalysts denoted as TiOx/Au8M@SBA via cultivating atomically precise Au8M(PPh3)8n+ (M=Pd, Pt or Au; n=2 for Pd/Pt and 3 for Au) clusters in mesoporous molecular sieve. The catalysts are made up of the three functional units, which include Au8M(PPh3)8n+ clusters that can act as the active sites, the pore environment of the SBA‐15 that can announce a catalysis show for the clusters with precise number of atoms maintained during the chemical reactions, and the TiOx coating that can further inhibit the migration of the clusters under reaction conditions. The selective hydrogenation of acetylene performed in the fixed‐bed reactor taken, for example, we learn how the atom‐by‐atom tailoring of a heterogeneous catalyst can switch on elusive heterogeneous mechanisms with cluster catalysis. This work sheds light on the fundamental insight into catalysis origin of heterogeneous catalysts and achieves a distinguished level of detail for cluster catalysis.
A Nanofiltration Membrane Preparation Process Based on Polyethyleneimine Diffusion Modulation and Surface Modification
Authors: Gu Kaifeng , Wang Jianyu , Fang Chuanjie , Zhu Liping
Published: December 2024

Nanofiltration (NF) membranes play a huge role in industrial manufacturing with their unique selective permeability. Membrane material and structure are the main factors affecting the effectiveness of NF separation. Typically, NF membranes are produced by interfacial polymerization (IP). Therefore, control of the IP process is particularly important. This work provides a NF membrane preparation process by combining internal modulation of the separation layer and surface modification. The diffusion of polyethyleneimine (PEI) molecules is accelerated by the introduction of ethanol and cetyltrimethylammonium bromide into the PEI aqueous phase solution, resulting in the formation of a loose interior. In addition, the high selectivity is maintained by high molecular weight PEI modifying. After optimizing the process, the NF membrane permeate flux and selectivity can be increased compared to the blank group (MgCl2 desalination from 90% to 97%, permeate flux from 17 to 35 L m−2 h−1). The resulting PEI/TMC NF membranes also show excellent separation properties in mixed salt applications for magnesium‐lithium separation.
Simultaneously Improving the Fire Safety and Antistatic Property of Polycarbonate via Incorporation of P‐Si Containing Flame Retardant and Carboxylated Carbon Nanotubes
Authors: Song Xiaoqing , Shan Xueying , Huang Huiling , Luo Zhonglin , Wang Biaobing
Published: December 2024

To address the trade‐off among the fire resistance, antistatic property and mechanical properties, a P‐Si containing flame retardant (PPSO) and carboxylated multiwalled‐carbon nanotubes (MWCNT‐COOH) were incorporated into PC by melt blending method. The results showed that the PC composite containing both 1.3 wt% PPSO and 0.5 wt% MWCNT‐COOH achieved UL‐94 V‐0 rating and good antistatic property. The peak heat release rate and total smoke production were reduced by 46% and 39%, respectively. Meanwhile, the mechanical performances were also slightly improved. The better flame retardant efficiency was ascribed to the quenching effect of phosphorus‐containing free radicals and the synergistic effect of PPSO and MWCNT‐COOH on promoting the formation of continuous and compact char residues.
Biobased Reactive Flame Retardant With the Phenylethylamine Structure for Enhancing Flame Retardancy and Mechanical Properties of Epoxy Resins
Authors: Ren Jiexiang , Chen Song , Hou Yudong , Deng Xiaocong , Tian Lu , Ma Chao , Huang Sheng‐chao , Lu Cuifen
Published: December 2024

A bio‐based reactive flame retardant (PVD) was synthesized using vanillin, phenethylamine, and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO). This study aimed to enhance epoxy resin's fire resistance and evaluate the strength of EP/PVD composites for eco‐friendly specialized applications. The chemical structure of PVD was confirmed using Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. The effect of PVD on the curing kinetics of EP was studied using non‐isothermal differential scanning calorimetry (DSC). During combustion, PVD releases ∙PO2 and ∙PO radicals, which capture the active ∙H and ∙OH radicals generated during the combustion of EP. This results in a significant quenching effect, thereby achieving flame retardancy. EP with 7.5 wt% PVD and 0.49 wt% phosphorus (EP/PVD‐7.5) exhibited a V‐0 rating in UL‐94 vertical burning tests and a limiting oxygen index (LOI) of 32.4%. Additionally, compared to pure EP, EP/PVD‐7.5 showed a 41.7% reduction in the peak heat‐release rate during cone calorimetry tests. The dual‐phase flame‐retardant effect of PVD was confirmed by the analysis of the residual char and its pyrolysis behavior. Furthermore, EP/PVD exhibits superior mechanical properties and transparency compared to pure EP, indicating that PVD holds promise as a flame retardant for EP.
Removal of Amoxicillin Using a New Adsorbent: Silver Nanoparticle Modified With Poly(ε‐Caprolactone)‐Block‐Poly(L‐Lactide) Copolymer
Authors: Şahin Muradiye , Mısır Murat , Arslan Yasin
Published: December 2024

The aim of this study is to develop innovative hybrid materials with high adsorption capacity for removing amoxicillin from aqueous media. The study synthesized an AB‐type poly(ε‐caprolactone)‐block‐poly(L‐lactide) copolymer (PCL‐b‐PLLA) containing silver nanoparticles (Ag NP). A novel initiator, 2,4‐difluorobenzyl alcohol (1), was used to initiate the sequential ring‐opening polymerization (ROP) of ε‐CL and L‐LA, with tin octanoate Sn(Oct)2 as the catalyst. PCL (2) was synthesized by ROP of ε‐CL at 115°C, using (1) as an initiator and Sn(Oct)2 as the catalyst. Subsequently, PCL‐b‐PLLA (3) was obtained via ROP of L‐LA at 120°C in toluene, with (2) as a macroinitiator. The structures of the homo‐ and block copolymers were characterized using FT‐IR and 1H NMR. Ag NP was synthesized via a green method using Helichrysum arenarium extract. Polymer‐based composites containing Ag NPs possess functional surface properties that enhance selectivity and permeability, making them effective biocompatible adsorbents for removing contaminants from water. The nanoparticle content in the PCL‐b‐PLLA/Ag NP hybrid was analyzed by UV–Vis and TEM. For amoxicillin removal, both PCL‐b‐PLLA and PCL‐b‐PLLA/Ag NP were tested, achieving a maximum of 82% removal at pH 4.5 and 25°C. Adsorption studies were conducted in pure water and three wastewater samples to assess amoxicillin selectivity.
Cranial morphology and phylogenetic reassessment of Barreirosuchus franciscoi (Crocodylomorpha, Notosuchia), a Peirosauria from the Late Cretaceous of Brazil
Authors: Fachini Thiago S. , Godoy Pedro L. , Montefeltro Felipe C. , Langer Max C.
Published: December 2024

With nearly 30 living species of relatively similar ecological traits, Crocodylomorpha is represented today by only a small fraction of its past diversity. The well‐documented crocodylomorph fossil record has revealed more than 500 taxa, with much higher ecological and morphological diversity than their extant counterparts. An example of such astonishing diversity is the Late Cretaceous rocks of the Bauru Group (southeast Brazil), from which numerous taxa are known, belonging to the clade Notosuchia. These were predominantly terrestrial taxa, some of which exhibited traits associated with omnivorous or even herbivorous feeding behaviors, such as Sphagesauridae, whereas others were adapted to a carnivore diet, such as Baurusuchidae and Peirosauridae. Among these is Barreirosuchus franciscoi, originally described as a neosuchian (Trematochampsidae) but later interpreted as a peirosaurid notosuchian. Even though included in recent morphological and phylogenetic analyses, B. franciscoi still lacked a more detailed description. Here, we provide an in‐depth description of the cranial elements of B. franciscoi, using data from computed tomography and a broad sample of comparative material, including living and fossil crocodylomorphs. Also, the neuro‐cavities, including the endocast, nasopharyngeal duct, and the olfactory region, were digitally reconstructed. Finally, a new phylogenetic analysis recovered B. franciscoi nested within Peirosauria, forming the Itasuchidae clade with other potentially semiaquatic species: Rukwasuchus yajabalajekundu, Pepesuchus deiseae, and Itasuchus jesuinoi. The morphological and phylogenetic reassessment of B. franciscoi indicates a semiaquatic form, highlighting the ecological diversity of notosuchians from the Bauru Group as well as the capacity of notosuchians to explore a myriad of environments.
UPLC Estimate of Sofosbuvir and Ledipasvir Utilizing Greenness Tool in Conjunction With an Analytical Quality by Design
Authors: Bairam Ravinder , Mahesh Kemmasaram , Tatapudi Hemant Kumar , Thoom Shruthi
Published: December 2024

Ledipasvir in combination with sofosbuvir approved by regulatory bodies used to treat chronic hepatitis C. The present work investigates the design and development of a new, quick, green, and selective UPLC (ultra‐performance liquid chromatography) approach to concurrently quantify sofosbuvir and ledipasvir. Optimization with Box–Behnken design paired the green analytical method and quality by design‐based risk assessment. A mobile phase of 65%:35% ethanol by volume and phosphate buffer (15 mM; pH 3.0) was used, with a flow rate of 0.28 mL per minute, to achieve the best chromatographic separation. With linearities ranging from 20 to 100, 4.5–22.5 μg/mL, and R2 values of 0.9999 and 0.9997, respectively, the established UPLC‐PDA technique proved sensitive and specific for sofosbuvir and ledipasvir. The stability‐indicating test findings demonstrate the degradation under the relevant stress conditions. The most environmentally friendly results were found when the level of environmental sustainability was evaluated using four advanced metrics: GAPI, AES, AMGS, and AGREE. Based on the findings, we came to the conclusion that the UPLC technique that was developed would be effective for the concurrent analysis of sofosbuvir and ledipasvir in tablet medication.
Unpacking Proximity for Sustainability in Short Food Supply Chains
Authors: León‐Bravo Verónica , Borrello Belinda , Ciccullo Federica , Caniato Federico
Published: December 2024

Short food supply chains (SFSCs) have been frequently named as sustainable alternatives to global chains, associated with the concept of local chain, and emphasizing the role of geographical proximity for achieving sustainability. However, it is also recognized that geographical proximity is not enough to build SFSCs and create a sustainable impact. A multi‐dimensional approach identifies three types of proximity: geographical, relational, and informational proximity to define SFSCs. Hence, the aim of this study is to extend that body of literature by investigating the role of relational and informational proximities in SFSCs. We analyze a set of 23 companies in four food industry sectors in Italy to characterize the practices implemented to build proximity, upstream and downstream, in their supply chains. Our findings reveal a combination of different practices along the three proximity dimensions that define SFSCs. These results allow also to underline how specific practices for relational and information proximity are paramount for attaining sustainability objectives in SFSCs.
Identification of Metabolites From Halamphora Sp. and Its Correlation With Quorum Sensing Inhibitory Activity via UHPLC‐ESI‐MS/MS‐Based Metabolomics and Molecular Networking
Authors: Abd Ghafar Siti Zulaikha , Muthukrishnan Sarmila , Zolkeflee Nur Khaleeda Zulaikha , Natrah Ikhsan , Abas Faridah
Published: December 2024

The UHPLC‐MS/MS metabolomics approach was employed to profile and characterize multi‐components in Halamphora sp. extracted with different solvents that contribute to quorum sensing inhibitory (QSI) activity. A total of 37 and 34 metabolites were tentatively identified from negative and positive ion modes, respectively. The metabolites have been assigned to various groups, including fatty acids, glycolipids, sterols, diazines, flavonoids, peptides, carotenoids, and pigments. Multivariate data analysis showed that the QSI activity in the acetone extract was due to tumonoic acid A, terpeptin derivatives, pheophorbide A, hydroxyhexadeca‐1,5‐dien‐3‐ynoxy]propane‐1,2‐diol, l‐methionyl‐l‐tyrosine, stearidonic, hexadecadienoic, tricosenoic, palmitic, and linolenic acids. These metabolites were more concentrated and differed significantly in acetone extract compared to other extracts. Acetone extract displayed a cluster of nodulisporic acid and fucoxanthin through MS/MS‐based molecular networking (MN) platform. The present study shows that the liquid chromatography mass spectrometry (LCMS)‐based metabolomics and MN effectively identify QSI‐active metabolites in Halamphora sp. extracts, which can be promoted as a natural antifoulant.
PCET‐Driven Reactivity of Neptunyl(VI) Yields Oxo‐Bridged Np(V) and Np(IV) Species
Authors: Mikeska Emily R. , Wilson Richard E. , Blakemore James D.
Published: December 2024

Two unconventional polynuclear complexes of neptunium (Np) featuring mono‐
‐oxo motifs have been accessed by proton‐coupled electron transfer (PCET) reactivity involving the dissolution of neptunyl(VI) diacetate dihydrate (
HOAc) in methanol followed by addition of a pentadentate Schiff‐base ligand. One complex is a mixed‐valent [Np
,Np
,Np
] trimer with two bridging
‐oxos and the other is a [Np
,Np
] dimer featuring a single
‐oxo. In both complexes the outer Np centers are capped with terminal oxo ligands. Spectroscopic and spectrokinetic studies aimed at elucidating mechanistic details of complex formation in this system show that intermediate multinuclear [Np
(OAc)]
species form prior to metal chelation by the ligand; electrolysis experiments demonstrate that production of Np(V) gives rise to asynchronous proton transfer that does not occur otherwise (in the Np(VI) state) as well as condensation with loss of
and formation of the polynuclear complexes. We attribute the oxo‐deficient nature of these products, with respect to conventional actinyl ([AnO
]
) species, to the reduction/condensation reaction sequence of PCET.
Expanding the Toolset of Biomolecular NMR with Efficient and Cost‐Effective 17O‐Labeling via Bacterial Expression
Authors: Tian Ziya , Truong Erica , Hu Wenhao , Fan Jiaxing , Fu Riqiang , Cross Timothy A. , Lin Xinsong , Zhang Rongfu , Hu Yan‐Yan
Published: December 2024

Oxygen plays a central role in biomolecular structures and functions, with 17O NMR emerging as a powerful tool for elucidating biomolecular properties. However, the low natural abundance of the NMR‐active isotope, 17O (0.0373 %), presents a significant hurdle to its widespread application. Here, we introduce a rapid and cost‐effective approach for amino acid‐specific 17O‐labeling of recombinant proteins. Using a common bacterial expression system and with a 30‐minute rapid synthesis protocol of 17O‐labeled amino acids via mechanochemical saponification, we have generated Leu‐ and Phe‐specific 17O‐labeled recombinant proteins derived from diverse organisms, including CrgA and FtsQ from Mycobacterium tuberculosis and E protein from SARS‐CoV‐2 virus, demonstrating the applicability of our technique for amino acids known to be isotopically labeled without scrambling. We have acquired magic‐angle‐spinning 17O NMR of these proteins to confirm the successful 17O labeling and illustrate the sensitivity of 17O NMR to the protein's local structural environments. Our work significantly broadens the accessibility of 17O‐NMR, empowering researchers to delve deeper into protein biophysics and biochemistry. This approach opens new avenues for understanding cellular processes at the molecular level by providing an effective tool for investigating oxygen‐related interactions and chemistry within biomolecules.
Noncovalent Bonding in d and f‐Type Coordination Compounds and Lattices. A Case Study
Authors: Toader Ana Maria , Buta Maria Cristina , Cimpoesu Fanica , Ferbinteanu Marilena
Published: December 2024

Using as example the [Fe(bpca)(μ‐bpca)Gd(NO3)4]×4CH3NO2×CH3OH system, where Hbpca=bis(2‐pyridilcarbonyl)amine), we perform the analysis of bonding components inside the d and f coordination units and between molecular entities from crystal. Aside the nominal long‐range interactions between molecular components of the crystal, we considered that the bonding inside the coordination units is also not a covalent regime. We performed Density Functional Theory (DFT) calculations, with plane‐waves (PW), in band‐structure mode, and with atom‐centred bases, by molecular procedures. Observing that the PW‐DFT frame is free of basis set superposition errors, which is an important methodological hint underlined here, we estimated various non‐covalent terms. E.g. the interaction between inversion‐related FeGd units amounts −394.47 kcal/mol, only about −37 kcal/mol being due to Coulomb effects, the remainder being assignable to dispersion forces. One FeGd binuclear interacts with the closest methanol molecule by −9.30 kcal/mol and by −36.57 kcal/mol with the set of four nitromethane molecules. The energy decomposition analysis of molecular calculations showed, aside the expected ionic character (about 82 % of the total cohesion energy of lanthanide ion in molecule), the important role of empty 5d orbitals. The d virtuals are contributing with 68.4 kcal/mol, out of 97.15 kcal/mol quantity estimated as ligand‐to‐metal donor‐acceptor effects.
Breaking Scaling Relations for Enhanced Electrochemical CO2 Reduction to CO by Introducing Soft Metal Dopants to Thiolates‐Protected Coinage Metal Nanoclusters
Authors: Efremov Vladimir , Choi Minji , Choi Myeongjin , Yoo Jong Suk
Published: December 2024

Density functional theory calculations are employed to investigate the effects of various metal dopants on thiolates‐protected transition metal nanoclusters (NCs) for CO2 reduction, focusing on deviations from the linear scaling relation between COOH* and CO* for high CO selectivity. We first explore the most favorable positions for different dopants in several M25 (M=parent metal) NCs and assess the potential for ligand removal under reducing conditions. Furthermore, we construct an activity volcano for CO production in D1M24 (D=dopant) NCs, revealing that NCs composed of coinage parent metals with group 12 metal dopants exhibit the most significant deviation from the scaling relation. This behavior is attributed to the tendency of these NCs to bind COOH* in a bidentate form, which stabilizes the O atom of COOH* through interactions with the oxyphilic dopants. As a result, several group 12 metal doped coinage metal NCs are identified as new promising candidates for syngas production due to their high activity towards both CO and H2 production.
Control of Instabilities in Resonant Converters Using Half‐Period Time Delay Output Feedback
Authors: Mandal Kuntal , Al‐Numay Mohamed , Li Zhen , El Aroudi Abdelali
Published: December 2024

Bifurcation phenomena in power electronic converters lead to undesired instabilities. In this paper, different types of bifurcations are identified, which can occur in a series load resonant converter with the variation of the parameters for example, input voltage, load resistance, and so forth. These instabilities are associated mainly to three different bifurcations: (a) Neimark–Sacker, (b) saddle–node, and (c) symmetry breaking bifurcations. Due to the symmetry property of load resonant converters, a half‐period time delay output feedback control is used to avoid all of these instabilities. The ideal time delay is realized by a first‐order all‐pass‐filter. The stability analysis is performed and the values of the feedback gains are determined to identify the stable domain in the parameter space. By identifying the unstable orbits, the analytical stability analysis helps to understand as well as to control the mechanisms of these instabilities, which extends the stability domain of the system. This study can also be extended to other load resonant converters where the symmetry property naturally exists.
Inter‐atrial block as a predictor of adverse outcomes in patients with HFpEF
Authors: Weerts Jerremy , Mourmans Sanne G.J. , Lopez‐Martinez Helena , Domingo Mar , Aizpurua Arantxa Barandiarán , Henkens Michiel T.H.M. , Achten Anouk , Lupón Josep , Rocca Hans‐Peter Brunner‐La , Knackstedt Christian , Bayés‐Genís Antoni , van Empel Vanessa P.M.
Published: December 2024

Aims

Inter‐atrial block (IAB), a marker of electrical atrial dysfunction, is associated with an increased risk of atrial fibrillation (AF) and adverse events in various populations. The prognostic impact of IAB in heart failure (HF) with preserved ejection fraction (HFpEF) remains unknown. The aim of this study is to determine the prevalence of IAB and the association of IAB and AF with adverse events in HFpEF across different healthcare settings.

Methods and results

To identify electrical atrial dysfunction, baseline ECG's and medical history were analysed in HFpEF patients in an ambulatory setting and after recent HF hospitalisation. Patients were categorised into (i) HFpEFNo IAB, (ii) HFpEFIAB, or (iii) HFpEFAF. Adverse events included HF hospitalisation, cardiac/sudden death and a composite of both. The ambulatory cohort included 372 patients [mean age 75 ± 7 years, 252 (68%) females]. The recently hospitalised cohort included 132 patients [mean age 81 ± 10 years, 80 (61%) females]. Ambulatory patients included 17 (4%) HFpEFnoIAB, 114 (31%) HFpEFIAB and 241 (65%) HFpEFAF, while recently hospitalised patients included 31 (23%), 73 (55%) and 28 (21%), respectively. After 33 months of follow‐up of ambulatory patients, composite endpoints occurred in 0 (0%) HFpEFnoIAB, 12 (11%) HFpEFIAB [HR 4.1 (95% CI 0.5–522.6)] and 59 (24%) HFpEFAF patients [HR 10.1 (95% CI 1.5–1270.4), P < 0.001]. Recently hospitalised patients showed a similar trend, with composite endpoints in 10 (32%) HFpEFnoIAB, 31 (42%) HFpEFIAB (HR 1.5 [95% CI 0.7–3.1]) and 22 (79%) HFpEFAF (HR 3.8 [95% CI 1.8–8.1], P < 0.001).

Conclusions

Progressive stages of electrical atrial dysfunction appeared to be prognostic markers of adverse outcomes in ambulatory and recently hospitalised patients with HFpEF. Ambulatory patients with HFpEF and no early stages of electrical atrial dysfunction showed to be at very low risk for adverse outcomes. Whether such patients benefit less strict management remains to be investigated.
The prognostic value of the Dandel's index in patients undergoing tricuspid transcatheter edge‐to‐edge repair
Authors: Kassar Mohammad , Brugger Nicolas , Stolz Lukas , Gerçek Muhammed , Fortmeier Vera , Kresoja Karl‐Patrik , von Stein Jennifer , Koell Benedikt , Rottbauer Wolfgang , Goebel Bjoern , Denti Paolo , Achouh Paul , Rassaf Tienush , Barreiro‐Perez Manuel , Boekstegers Peter , Rück Andreas , Zdanyte Monika , Adamo Marianna , Vincent Flavien , Schlegel Philipp , von Bardeleben Ralph‐Stephan , Wild Mirjam G. , Toggweiler Stefan , Konstandin Mathias H. , Van Belle Eric , Metra Marco , Geisler Tobias , Estévez‐Loureiro Rodrigo , Luedike Peter , Karam Nicole , Maisano Francesco , Lauten Philipp , Kessler Mirjam , Kalbacher Daniel , Iliadis Christos , Lurz Philipp , Windecker Stephan , Hausleiter Jörg , Rudolph Volker , Praz Fabien
Published: December 2024

Aims

Conventional parameters of right ventricular (RV) function are load‐dependent and therefore do not accurately reflect contractility in patients with relevant tricuspid regurgitation (TR). RV adaptability to load has been characterized using the Dandel's index in patients with heart failure, but its prognostic value in patients undergoing tricuspid transcatheter edge‐to‐edge repair (T‐TEER) has not been investigated so far.

Methods and results

From the EuroTR registry (2019 to 2022), patients with complete datasets and a minimum of 2‐years of follow‐up were included. RV functional parameters (i.e. tricuspid annular plane systolic excursion [TAPSE], fractional area change [FAC], TAPSE/systolic pulmonary arterial pressure [sPAP]), as well as a echocardiographic RV load adaptation index (Dandel's index) were assessed and their predictive value in terms of all‐cause mortality evaluated using logistic multivariate logistic regression. The majority of the 364 patients had secondary TR (96%) and were severely symptomatic (New York Heart Association class ≥III; 92%). At 2‐year follow‐up, 36% of patients had died. Functional RV parameters (TAPSE: hazard ratio [HR] 0.72, 95% confidence interval [CI] 0.62–0.84; FAC: HR 0.73, 95% CI 0.59–0.91), coupling index (TAPSE/sPAP: HR 0.8, 95% CI 0.65–0.99) and Dandel's index (HR 0.67, 95% CI 0.53–0.85) were all associated with mortality at 2 years in univariable analyses. In a multivariate logistic regression model, the Dandel's index maintained its predictive value (p < 0.001), along with TAPSE and absence of signs of right heart failure, with an optimal threshold of 20.5 determined by the receiver‐operating characteristic analysis. This threshold also successfully predicted cardiac hospital readmission. A multivariate analysis was conducted to identify parameters linked to RV function and predicting clinical outcomes.

Conclusion

Assessment of the RV capacity to adjust for changes in loading conditions predicted mortality in patients with severe symptomatic TR undergoing T‐TEER. The use of a multiparametric approach including the Dandel's index to assess RV function had an incremental value for the stratification of patients into subgroups with different prognosis.
Synergistic Beneficial Effects of Flaxseed (Linum usitatissimum L.) Oil and Olive (Olea europaea L.) Oil Against Metabolic Dysfunction Associated Fatty Liver and Its Complications
Authors: Noreen Sana , Hashmi Bushra , Tufail Tabussam , Ikram Ali , Arshad Muhammad Tayyab , Gnedeka Kodjo Théodore
Published: December 2024

Flaxseed and olive oil effectively treat numerous diseases and health conditions, particularly metabolic disorders. Traditional medicine has used both oils for managing cardiovascular disease, diabetes, gastrointestinal dysfunctions, metabolic‐dysfunction‐associated fatty liver disease (MAFLD), obesity, and more. This review explores the bioactive and polyphenolic compounds in flaxseed and olive oils that provide anti‐inflammatory, antioxidant, anti‐microbial, hepatoprotective, cardioprotective, antidiabetic, and gastroprotective benefits. Flaxseed oil contains beneficial compounds like alpha‐linolenic acid (ALA), lignans, ferulic acid, p‐coumaric acid, and phytosterols. It contributes to its therapeutic effects on fatty liver disease and other conditions. Olive oil contains phenolic compounds, including oleic acid, hydroxytyrosol, and tocopherols, which are similarly linked to metabolic health benefits, especially in managing MAFLD. The purpose of this review is to elucidate the mechanisms of action of these bioactive compounds, highlighting their potential in managing various metabolic diseases.
Neuropsychiatric Symptoms Associated With Frontotemporal Atrophy in Older Adults Without Dementia
Authors: Liampas Ioannis , Siokas Vasileios , Stamati Polyxeni , Kyriakoulopoulou Panayiota , Tsouris Zisis , Zoupa Elli , Folia Vasiliki , Lyketsos Constantine G. , Dardiotis Efthimios
Published: December 2024

Objectives

We investigated the association between neuropsychiatric symptoms (NPS) and frontotemporal atrophy (FTA) in older adults without dementia. We hypothesized that the odds of having NPS would be increased in the presence of FTA.

Methods

NACC participants ≥ 50 years old with available data on FTA were considered for eligibility. Those with a diagnosis of mild cognitive impairment (MCI) and those who were cognitively unimpaired (CU) were separately analyzed. NPS were quantified on the Neuropsychiatric Inventory Questionnaire. Binary logistic regression models estimated the association (odds ratios and 95% confidence intervals are provided) between FTA and having each of 11 NPS (psychotic symptoms were grouped together) in CU and MCI individuals.

Results

FTA data were available for 3165 participants with MCI and 4051 CU: 207 and 55 had FTA on structural MRI studies, respectively. In the MCI group, the presence of FTA was associated with higher odds of having elation [2.42(1.33–4.40), p = 0.004], aberrant motor behavior [2.43(1.61–3.69), p < 0.001], appetite disorders [2.15(1.52–3.04), p < 0.001], apathy [2.05(1.48–2.85), p < 0.001] and disinhibition [2.02(1.38–2.96), p < 0.001]. The odds of having specific NPS were not significantly elevated in CU individuals with FTA. Of note, the size and direction of the associations were indicative of a potential relationship between FTA and specific NPS (most notably elation, aberrant motor behavior, appetite disorders and anxiety); in light of the small number of CU individuals with FTA we believe this analysis was underpowered and obscured several true associations.

Conclusions

FTA was associated with higher odds of some NPS in older adults with MCI but not with normal cognition.
DCFU‐Net: Rethinking an Effective Attention and Convolutional Architecture for Retinal Vessel Segmentation
Authors: Xian Yongli , Zhao Guangxin , Chen Xuejian , Wang Congzheng
Published: December 2024

Morphological changes in retinal vessels are early indicators of cardiovascular and various fundus diseases. However, accurately segmenting thin blood vessels remains a challenge due to the complexity of the vascular structure and the irregularity of pathological features. This paper proposes a dual chain fusion U‐Net (DCFU‐Net) for the precise segmentation of retinal vessels. The network consists of a multi‐level segmentation network and a fusion network. The multi‐level segmentation network is designed with a dual chain architecture to generate segmentation results for both thick and thin vessels simultaneously. The fusion network combines the segmented thin and thick vessels with the original image, facilitating the generation of accurate segmentation outcomes. Notably, traditional convolution structures in the DCFU‐Net are replaced by dynamic snake convolutions (DS‐Conv). DS‐Conv is designed to adaptively focus on slender and tortuous local features, accurately capturing vascular structures. The shared weight residual block, integrating DS‐Conv and residual structures, which is called DS‐Res block. It serves as the backbone of the DCFU‐Net, enhancing feature extraction capabilities, while significantly reducing computational resource consumption. Additionally, this paper rethinks effective components of the Transformer architecture, identifying the inverted residual mobile block (IRMB) as a key element. By extending the DS‐Conv‐based IRMB into effective attention‐based (EAB) blocks, the network mitigates the loss of semantic information, thereby addressing inherent limitations. The DCFU‐Net is evaluated on three publicly available datasets: DRIVE, STARE, and CHASE_DB1. Qualitative and quantitative analyses demonstrate that the segmentation results of DCFU‐Net outperform state‐of‐the‐art methods.