bluuebunny/crossref_metadata_2025_split huggingface dataset:
Confining Pt Nanoparticles in Layered Double Hydroxide Derived Hollow Mesoporous MgAl‐Oxide Nanospheres for Boosting Selective Transfer Hydrogenation
Authors: Pan Zhengyi , Zhang Qian , Wang Wenquan , Li Yuanzheng , Wang Guang‐Hui 
Published: August 2024

AbstractCatalytic transfer hydrogenation (CTH) is a safe and effective strategy for producing unsaturated alcohols (UOLs) from biomass‐derived α,β‐unsaturated aldehydes/ketones. Accordingly, the design of CTH catalysts that possess both extreme activity and superior selectivity is highly desirable. Herein, we develop a highly efficient Pt@hMgAl catalyst with Pt nanoparticles (NPs) confined in the layered double hydroxide derived hollow MgAl‐oxide nanospheres (hMgAl), which shows an enhanced catalytic performance in CTH of furfural (FFR) to furfuryl alcohol (FOL) compared to the hMgAl catalyst without Pt NPs inside. It is found that the reaction rate over the Pt@hMgAl (12.8 mmol gcat−1 h−1) is ~26 times higher than that over the hMgAl (0.5 mmol gcat−1 h−1). The excellent catalytic performance of Pt@hMgAl originates from the synergy between Pt‐(Mg−O−Al) interfacial sites, where the acid‐base site of Mg−O−Al activates the C=O bond of FFR, while the nearby Pt site facilitates the dehydrogenation of 2‐propanol. Moreover, the reaction rate over the Pt@hMgAl can further increase to 21.8 mmol gcat−1 h−1 after introducing H2 into the reaction system, where the FOL selectivity is still higher than 99 % due to the synergy of Pt‐(Mg−O−Al) interfacial sites. This work provides a straightforward approach to construct a hollow‐structured catalyst with abundant metal/oxide interfaces, which could significantly enhance the CTH efficiency for α,β‐unsaturated alcohols production.
Performance of Non‐Precious Metal Electrocatalysts in Proton‐Exchange Membrane Fuel Cells: A Review
Authors: Rukmani Krishnan Srivarshini , Verstraete Dries , Aguey‐Zinsou Francois 
Published: August 2024

AbstractPolymer electrolyte membrane fuel cells (PEMFCs) are an important enabler of the nascent hydrogen economy. However, due to the reliance on precious metal catalysts like platinum, reducing the cost and broad penetration of PEMFCs beyond vehicle application remains a challenge. In this respect, alternative non‐precious metal catalysts and other carbon‐based catalysts remain the holy grail toward advanced low‐cost PEMFC. This review summarizes recent progress along the development of non‐precious catalysts and their performance under PEMFC operation. Critical factors such as the activity, stability, and durability of non‐precious metal catalysts and their associated mechanisms including the paths leading to degradation are discussed. Ultimately, the review concludes by highlighting the impressive activity and potential of NPM catalysts and the areas of focus to enable the translation of non‐precious catalysts to commercially viable PEMFC systems.
THz‐EPR‐based Magneto‐Structural Correlations for Cobalt(II) Single‐Ion Magnets With Bis‐Chelate Coordination
Authors: Pohle Maximilian H. , Lohmiller Thomas , Böhme Michael , Rams Michał , Ziegenbalg Sven , Görls Helmar , Schnegg Alexander , Plass Winfried 
Published: August 2024

AbstractNew cobalt(II)‐based complexes with [N2O2] coordination formed by two bis‐chelate ligands were synthesized and characterized by a multi‐technique approach. The complexes possess an easy‐axis anisotropy (D<0) and magnetic measurements show a field‐induced slow relaxation of magnetization. The spin‐reversal barriers, i. e., the splitting of the two lowest Kramers doublets (UZFS), have been measured by THz‐EPR spectroscopy, which allows to distinguish the two crystallographically independent species present in one of the complexes. Based on these experimental UZFS energies together with those for related complexes reported in literature, it was possible to establish magneto‐structural correlations. UZFS linearly depends on the elongation parameter ϵT of the (pseudo‐)tetrahedral coordination, which is given by the ratio between the average obtuse and acute angles at the cobalt(II) ion, while UZFS was found to be virtually independent of the twist angle of the chelate planes. With increasing deviation from the orthogonality of the latter, the rhombicity (|E/D|) increases.
The Key to MOF Membrane Fabrication and Application: the Trade‐off between Crystallization and Film Formation
Authors: Bi Wendie , Han Linxuan , Liu Yutao , Li Libo 
Published: August 2024

AbstractMetal‐organic frameworks (MOFs), owing the merits of ordered and tailored channel structures in the burgeoning crystalline porous materials, have demonstrated significant promise in construction of high‐performance separation membranes. However, precisely because this crystal structure with strong molecular interaction in their lattice provides robust structural integrity and resistance to chemical and thermal degradation, crystalline MOFs typically exhibit insolubility, infusibility, stiffness and brittleness, and therefore their membrane‐processing properties are far inferior to the flexible amorphous polymers and hinder their subsequent storage, transportation, and utilization. Hence, focusing on film‐formation and crystallization is the foundation for exploring the fabrication and application of MOF membranes. In this review, the film‐forming properties of crystalline MOFs are fundamentally analyzed from their inherent characteristics and compared with those of amorphous polymers, influencing factors of polycrystalline MOF membrane formation are summarized, the trade‐off relationship between crystallization and membrane formation is discussed, and the strategy solving the film formation of crystalline MOFs in recent years are systematically reviewed, in anticipation of realizing the goal of preparing crystalline membranes with optimized processability and excellent performance.
Conjugated Coordination Nanosheets with Molecular Rotors for Pseudocapacitors: Nanoarchitectonics and Enhanced Performance
Authors: Ravikumar Ramlal Vishwakarma , Patel Kinjal B. , Raj Savan K. , Srivastava Divesh N. , Kumar Mandal Amal 
Published: August 2024

AbstractHigh‐level pseudocapacitive materials require incorporations of significant redox regions into conductive and penetrable skeletons to enable the creation of devices capable of delivering high power for extended periods. Coordination nanosheets (CNs) are appealing materials for their high natural electrical conductivities, huge explicit surface regions, and semi‐one‐layered adjusted pore clusters. Thus, rational design of ligands and topological networks with desired electronic structure is required for the advancement in this field. Herein, we report three novel conjugated CNs (RV‐10‐M, M=Zn, Ni, and Co), by utilizing the full conjugation of the terpyridine‐attached flexible tetraphenylethylene (TPE) units as the molecular rotors at the center. We prepare binder‐free transparent nanosheets supported on Ni‐foam with outstanding pseudocapacitive properties via a hydrothermal route followed by facile exfoliation. Among three CNs, the high surface area of RV‐10‐Co facilitates fast transport of ions and electrons and could achieve a high specific capacity of 670.8 C/g (1677 F/g) at 1 A/g current density. Besides, the corresponding flexible RV‐10‐Co possesses a maximum energy density of 37.26 Wh kg−1 at a power density of 171 W kg−1 and 70 % capacitance retention even after 1000 cycles.
Emerging Roles of Gossypol in Therapy: Innovations in Prodrug Design and Nanoformulation Frontiers
Authors: Banerjee Arka , Biswas Megha , Shukla Prakash , Pathak Rakesh Kumar 
Published: August 2024

AbstractStimuli activatable systems have the potential to deliver drugs to targeted areas by releasing therapeutic agents in response to diseased specific microenvironments such as the acidic environment commonly found in diseased tissues. This review article focuses on gossypol, a bioactive compound with inherent toxicity attributed to various factors, including the presence of its formyl groups. It highlights the potential of imine‐linked gossypol‐based prodrugs and nanoparticle formulations for targeted delivery and controlled release. The unique presence of polyphenolic cores on gossypol can be utilized to prepare nanoparticles. This review offers valuable insights into designing safer and more effective drug delivery systems by elucidating the masking effect and stimuli‐responsive release mechanisms. Numerous examples demonstrate the conversion of formyl groups to imines, creating prodrugs that mask reactive functionalities and offer pH‐responsive release. This insight can guide the design of combination therapeutics, where a second drug with an amine terminal group can form imine‐linked prodrugs. Additionally, the second part discusses the use of polyphenolic moieties to create stable nanoparticles from infinite polymeric networks. Through a comprehensive examination of gossypol‘s properties and applications, this review emphasizes the broader implications of such a masking strategy for optimizing the therapeutic benefits of many similar bioactive compounds while minimizing adverse effects.
Anti‐Amyloid Aggregation and Anti‐Hyperglycemic Activities of Novel Ruthenium Uracil Schiff Base Compounds
Authors: Makanyane Daniel M. , Mabuza Lindokuhle P. , Ngubane Phikelelani , Khathi Andile , Mambanda Allen , Booysen Irvin N. 
Published: August 2024

AbstractThe formation and characterization of new diamagnetic ruthenium uracil mono‐imine compounds: [(η6‐p‐cymene)RuII(L)Cl][BF4] (L=H2urpda=5‐((pyridin‐2‐yl)methyleneamino)‐6‐aminouracil) for 1, urdpy=6‐amino‐1,3‐dimethyl‐5‐((pyridin‐2‐ylmethylene)amino)uracil) for 2 or urqda=5‐((quinolin‐2‐yl)methyleneamino)‐6‐aminouracil) for 3); cis‐[Ru(bipy)2(urpy)](BF4)2 (4) (urpy=5‐((pyridin‐2‐yl)methyleneamino)uracil) and cis‐[Ru(bipy)2(dapd)] (5) (H2dadp=5,6‐diaminouracil) are described. A ruthenium(IV) uracil Schiff base compound, trans‐[Ru(urpda)(PPh3)Cl2] (6) was also formed. Various physicochemical techniques were utilized to characterize the novel ruthenium compounds. Similarly, the stabilities of 1–3 and 6 monitored in chloro‐containing and the non‐coordinating solvent, dichloromethane show that they are kinetically inert, whereas, in a high nucleophilic environment, the chloride co‐ligands of these ruthenium complexes were rapidly substituted by DMSO. In contrast, the substitution of the labile co‐ligands for these ruthenium complexes by DMSO molecules in a high chloride content was suppressed. Solution chemical reactivities of the different ruthenium complexes were rationalized by density functional theory computations. Furthermore, the binding affinities and strengths between BSA and the respective ruthenium complexes were monitored using fluorescence spectroscopy. In addition, the in vitro anti‐diabetic activities of the novel metal complexes were assessed in selected skeletal muscle and liver cell lines.
Delineation of features, responses, outcomes, and prognostic factors in pediatric PDGFRB‐positive acute lymphoblastic leukemia patients: A retrospective multicenter study
Authors: Zhang Xiaoyan , Wang Yaqin , Tian Xin , Sun Lirong , Jiang Hua , Chu Jinhua , Zhou Fen , Shen Shuhong , Hu Shaoyan , Fang Yongjun , Lai Changcheng , Ju Xiuli , Xu Xiaoxiao , Zhai Xiaowen , Jiang Hui , Yang Minghua , Leung Alex W. K. , Xue Ning , Zhang Yingchi , Yang Jun , Pui Ching‐Hon , Yu Jie , Gao Ju , Hu Qun , Zhu Xiaofan 
Published: August 2024

AbstractBackgroundPDGFRB fusions in acute lymphoblastic leukemia (ALL) is rare. The authors identified 28 pediatric PDGFRB‐positive ALL. They analyzed the features, outcomes, and prognostic factors of this disease.MethodsThis multicenter, retrospective study included 6457 pediatric patients with newly diagnosed PDGFRB fusion ALL according to the CCCG‐ALL‐2015 and CCCG‐ALL‐2020 protocols from April 2015 to April 2022 in 20 hospitals in China. Of these patients, 3451 were screened for PDGFRB fusions.ResultsPediatric PDGFRB‐positive ALL accounted for only 0.8% of the 3451 cases tested for PDGFRB. These patients included 21 males and seven females and 24 B‐ALL and 4 T‐ALL; the median age was 10 years; and the median leukocyte count was 29.8 × 109/L at baseline. Only one patient had eosinophilia. Three patients had an IKZF1 deletion, three had chromosome 5q31‐33 abnormalities, and one suffered from a complex karyotype. The 3‐year event‐free survival (EFS), overall survival (OS), and cumulative incidence of relapse (CIR) were 33.1%, 65.5%, and 32.1%, respectively, with a median follow‐up of 25.5 months. Twenty patients were treated with chemotherapy plus tyrosine‐kinase inhibitors (TKIs) and eight were treated without TKI. Complete remission (CR) rates of them were 90.0% and 63.6%, respectively, but no differences in EFS, OS, or CIR. Univariate analyses showed patients with IKZF1 deletion or measurable residual disease (MRD) ≥0.01% after induction had inferior outcomes (p < .05).ConclusionsPediatric PDGFRB‐positive ALL has a poor outcome associated with high‐risk features. Chemotherapy plus TKIs can improve the CR rate, providing an opportunity for lower MRD levels and transplantation. MRD ≥0.01% was a powerful adverse prognostic factor, and stratified treatment based on MRD may improve survival for these patients.Plain Language Summary

Pediatric acute lymphoblastic leukemia patients with PDGFRB fusions are associated with high‐risk clinical features such as older age, high white blood cell count at diagnosis, high measurable residual disease after induction therapy, and increased risk of leukemia relapse.
Chemotherapy plus tyrosine‐kinase inhibitors can improve the complete remission rate and provide an opportunity for lower measurable residual disease (MRD) levels and transplantation for pediatric PDGFRB‐positive acute lymphoblastic leukemia (ALL) patients.
The MRD level was also a powerful prognostic factor for pediatric PDGFRB‐positive ALL patients.
A smart surveillance system utilizing modified federated machine learning: Gossip‐verifiable and quantum‐safe approach
Authors: Dharani Dharmaraj , Anitha Kumari Kumarasamy 
Published: August 2024

SummaryEdge computing has the capability to process data closer to its point of origin, leading to the development of critical autonomous infrastructures with frequently communicating peers. The proposed work aims to evaluate the effectiveness of security and privacy mechanisms tailored for distributed systems, particularly focusing on scenarios where the nodes are closed‐circuit television (CCTV) systems. Ensuring public safety, object tracking in surveillance systems is a vital responsibility. The workflow has been specifically crafted and simulated for the purpose of weapon detection within public CCTV systems, utilizing sample edge devices. The system's primary objective is to detect any unauthorized use of weapons in public spaces while concurrently ensuring the integrity of video footage for use in criminal investigations. The outcomes of prior research on distributed machine learning (DML) techniques are compared with modified federated machine learning (FML) techniques, specifically designed for being Gossip verifiable and Quantum Safe. The conventional federated averaging algorithm is modified by incorporating the secret sharing principle, coupled with code‐based McEliece cryptosystem. This adaptation is designed to fortify the system against quantum threats. The Gossip data dissemination protocol, executed via custom blockchain atop the distributed network, serves to authenticate and validate the learning model propagated among the peers in the network. It provides additional layer of integrity to the system. Potential threats to the proposed model are analyzed and the efficiency of the work is assessed using formal proofs. The outcomes of the proposed work demonstrate that the trustworthiness and consistency are meticulously preserved for both the model and data within the DML framework on the Edge computing platform.
Adam‐Ladybug Beetle Optimization enabled multi‐objective service placement strategy in fog computing
Authors: Sharma Oshin , Sharma Deepak 
Published: August 2024

SummaryThe Internet of Things (IoT) has transformed every aspect of our lives and has become universal in multiple fields from personnel to government and military applications. However, IoT suffers from the inherent limitation of latency and high computational costs, which can be effectively overcome by using a fog computing framework. However, the key challenge in fog computing is to address the problem of service placement among the nodes, thereby providing optimal utilization of resources and minimizing service time. This research work presents a novel service placement technique, by considering the service placement issue as a multi‐objective optimization problem. Here, a two‐level fog computing network comprising a fog master node and fog cells is considered. The master node is responsible for the service placement of the fog nodes, and the service placement is carried out using the Adam‐Ladybug Beetle Optimization (ALBO) algorithm. Further, multiple objectives, like resource utilization, makespan, response time, service time, cost, and energy consumption are considered to enhance service placement. Moreover, the efficiency of the ALBO for service placement (ALBO_SP) is examined considering service cost, energy consumption, and service time and is found to attain values of 19.009, 73.581 J, and 4.854 s, respectively.
Reaction Kinetics of the Benzylation of Adenine in DMSO: Regio‐Selectivity Guided by Entropy
Authors: Buyens Dominique M. S. , Pilcher Lynne A. , Roduner Emil 
Published: August 2024

AbstractThe factors governing the regio‐selectivity of the alkylation of adenine have been of interest for many years due to the biological importance of adenine derivatives, however, no reaction kinetic studies have been conducted. Herein, we report the rate constants and activation parameters of the benzylation of adenine under basic conditions in DMSO in the absence and presence of 15‐crown‐5 ether using real‐time 1H NMR spectroscopy. The reaction is second‐order for the formation of the N9‐ and N3‐benzyladenine products, with a regio‐selectivity factor 2.3 in favour of the N9‐adduct. The Gibbs free energy of activation amounts to 87±2 kJ mol−1 for both reactions. The formation of the N9‐adduct is more activated by 7 kJ mol−1, but its effect is offset by a less negative activation entropy, demonstrating that the long‐contested reason for the regioselectivity in the benzylation of adenine is dominated by compensation of entropy and enthalpy in the transition state. The kinetic parameters obtained in the presence of the 15‐crown‐5 ether indicate that the crown ether forms a complex with an adenine‐sodium ion‐pair, increasing the activation barrier. However, the Gibbs free energy in the absence and presence of the crown ether remains constant.
HSP47 in human diseases: Navigating pathophysiology, diagnosis and therapy
Authors: Khan Essak. S. , Däinghaus Tobias 
Published: August 2024

AbstractHeat shock protein 47 (HSP47) is a chaperone protein responsible for regulating collagen maturation and transport, directly impacting collagen synthesis levels. Aberrant HSP47 expression or malfunction has been associated with collagen‐related disorders, most notably fibrosis. Recent reports have uncovered new functions of HSP47 in various cellular processes. Hsp47 dysregulation in these alternative roles has been linked to various diseases, such as cancer, autoimmune and neurodegenerative disorders, thereby highlighting its potential as both a diagnostic biomarker and a therapeutic target. In this review, we discuss the pathophysiological roles of HSP47 in human diseases, its potential as a diagnostic tool, clinical screening techniques and its role as a target for therapeutic interventions.
Diversity in Irish and British avifauna assemblages: What can variation in diversity profiles reveal about the forces that drive assemblage composition and structure?
Authors: Groh Camille , Siriwardena Gavin M. , McMahon Barry J. 
Published: August 2024

AbstractIreland and Britain are two islands located at Europe's westernmost edge, both of which act as the final breeding outposts for many bird species within their European ranges. Despite their similar geographic locations and geological histories, Ireland and Britain host different breeding avifauna assemblages. Diversity profiles, which can serve as more robust alternatives to classic diversity indices, were employed in this study to explore disparities in the two islands' breeding avifauna assemblages. Variations in assemblages were explored, along with their potential drivers, through analyses at three levels: island‐scale breeding bird assemblage compositions, island‐scale diversity profiles considering 49 common breeding species, and habitat‐specific diversity profiles considering assemblages in east/central Irish farmland and East Anglian farmland. Analysis of the two islands' breeding avifauna assemblages revealed that the Irish assemblage is a complete subset of the British assemblage. Analyses of Irish and British assemblages at both an island scale and a habitat scale revealed patterns linking land use to trends within the two islands' avifauna assemblages. Irish assemblages contained greater proportions of insectivorous farmland species by abundance, while British assemblages contained greater proportions of seed‐eating farmland species; both trends appeared to be related to structural differences in agricultural land use on the two islands. The British and East Anglian assemblages exhibited higher diversity across all analyses, which appeared to be driven by the assemblages' higher relative abundances of species that were most genetically distinct. This study highlights the ability of diversity profiles to impart more information than classic diversity indices by incorporating species similarity data.
Different phytoplankton stoichiometry and nutrient status in the reservoirs of Fujian Province, China
Authors: Ayub Gohar , Zhou Yuanyuan , Su Yuping , Zheng Luwei , Weng Yuxin , ur Rahman Sami , Zahir Muhammad 
Published: August 2024

AbstractReservoirs have experienced varied degrees of eutrophication in recent years as the effects of climate change and human activities on reservoir ecosystems have intensified. This study looked at the patterns of integrated nutrient status and total phosphorus (TP) concentration in 30 reservoirs in major reservoirs across Fujian Province. Significant connections were identified between TP concentration, trophic status, and total phytoplankton density. 88.9% of the reservoirs were at the middle trophic level by the nutritional status (EI). The average EI of the 25 reservoirs with water supply functions is 39.2, eight reservoirs in coastal areas having EI values more than 45.0. The EI of the Baisha Reservoir in Jiulong River Basin reached 50.3, indicating modest eutrophication. TP concentration levels in the 30 reservoirs of Fujian Province range from 0.01 to 0.08 mg·L−1, representing different functional categories. Algal bloom is more likely to occur in a reservoir with a high nutrient status value. The N/P mass ratios of the 30 reservoirs were all significantly greater than 7.0, with the minimum is 11.0 and the maximum is 136.0, which indicating that these reservoirs were typically phosphorus‐limited.