bluuebunny/crossref_metadata_2025_split huggingface dataset:
First case of progressive solitary sclerosis with relapsing attacks: A 49‐year‐old woman
Authors: Asadollahzadeh Elnaz , Shahmaei Vahid , Ebadi Zahra , Johari Mohammad‐Sadegh , Rezaeimanesh Nasim , Naser Moghadasi Abdorreza 
Published: November 2024

Key Clinical MessageThis case highlights a rare form of solitary sclerosis with a relapsing pattern, contrasting with the typical single attack and nonrelapsing nature of the disease. Despite the lack of new lesions on MRI, This case demonstrates that, despite the rarity of this variant, a relapsing form of solitary sclerosis can occur and should be considered a differential diagnosis.AbstractProgressive solitary sclerosis is characterized by isolated demyelinating damage to the central nervous system in the spinal cord and brainstem, leading to progressive motor impairment. We describe the case of a 49‐year‐old woman who suffered several recurrent attacks of right hemiparesis over time. The patient initially responded well to methylprednisolone pulse therapy without maintenance therapy. However, subsequent episodes resulted in mild residual symptoms and the progression of her condition. Clinical examination revealed normal cranial nerve function, decreased sensation in the right limbs, and abnormal signal findings on MRI of the cervical spine. Laboratory tests, vasculitis screening, cerebrospinal fluid (CSF) analysis, and brain/spinal cord angiography were all within normal limits. Based on these findings and the patient's clinical presentation, a diagnosis of progressive solitary sclerosis with relapsing attacks was made. Rituximab treatment was initiated with administration of a first dose of 1000 mg, followed by a second dose 6 months later.
Approaching Dynamic Behaviors of Life through Systems Chemistry
Authors: Gu Ruirui , Lambertsen Larsen Kim , Wang Ali , Tan Junjun 
Published: November 2024

AbstractThe intricate interplay of metabolic reactions and molecular assembly in living systems enables spatiotemporally organization and gives rise to diverse dynamic behaviors that characterize life. Over the last decades, research efforts have increasingly focused on replicating the remarkable properties and characteristics of living systems, driving the rapid growth of systems chemistry. This young discipline which generally studies interacting molecular networks and emergent system‐level properties, behaviors, and functions, offers new concepts and tools to tackle the complexity of life. In this review paper, we have explored seminal research and recent advancements in recreating dynamic behaviors of life with systems chemistry. We believe that the recreation of the dynamic behaviors of life through systems chemistry would set the initial steps to obtain synthetic life de novo.
One‐Electron NO to N2O Pathways via Heme Models and Lewis Acid: Metal Effects and Differences from the Enzymatic Reaction
Authors: Chu Jia‐Min , Khade Rahul L. , Nguyen Vy , Richter‐Addo George B. , Zhang Yong 
Published: October 2024

AbstractSome pathogens use heme‐containing nitric oxide reductases (NORs) to reduce NO to N2O as their defense mechanism to detoxify NO and reduce nitrosative stress. This reduction is also significant in the global N cycle. Our previous experimental work showed that Fe and Co porphyrin NO complexes can couple with external NO to form N2O when activated by the Lewis acid BF3. A key difference from conventional two‐electron enzymatic reaction is that one electron is sufficient. However, a complete understanding of the entire reaction pathways and the more favorable reactivity for Fe remains unknown. Here, we present a quantum chemical study to provide such information. Our results confirmed Fe's higher experimental reactivity, showing advantages in all steps of the reaction pathway: easier metal oxidation for NO reduction and N−O cleavage as well as a larger size to expedite the N/O coordination mode transition. The Co system, with a similar product energy as the enzyme, shows potential for further development in catalytic NO coupling. This work also offers the first evidence that this new one‐electron NO reduction is both kinetically competitive and thermodynamically more favorable than the native pathway, supporting future initiatives in optimizing NO reduction agents in biology, environment, and industry.
Cross‐Electrophile Couplings (XECs) between Similar Electrophile Reagents
Authors: Lei Jie , Yu Shan , Xu Zhi‐Gang 
Published: November 2024

Comprehensive SummaryCross‐electrophile couplings (XEC), a crucial subset of cross‐coupling reactions, center on the formation of robust C—C bonds through the union of two electrophiles. Usually, such reactions have primarily been catalyzed by transition metals. However, with the steady advancements in photochemical and electrochemical technologies, XEC reactions have significantly progressed and broadened their scope, allowing for the utilization of a wider array of tolerable functional groups, thus revealing vast application prospects. This review aims to systematically summarize the current prevalent types of electrophiles and delve into their specific application examples within XEC reactions involving electrophiles with identical functional groups. Specifically, XECs between the same type of halides have received considerable attention, whereas carboxylic acids and alcohols are still in the early stages of investigation. Furthermore, certain other common electrophiles remain unexplored in this context. Moreover, this review underscores the remarkable contributions of photochemistry and electrochemistry in the field of XEC reactions, aiming to provide valuable insights and inspiration for researchers. Also, this review hopes to spark further interest in XEC reactions, thereby fueling the continuous development and advancement of this exciting area of research.
Key ScientistsSince the 1960s, advancements in the XEC reaction have been substantial, driven primarily by the application of transition metal catalysts. In this area, many distinguished scientists have contributed their wisdom and efforts. Particularly noteworthy is that, during the systematic study of XEC reactions with the identical functional groups, in 2016, MacMillan achieved a photocatalytic XEC reaction between aryl bromides and alkyl bromides; in 2020, Weix successfully realized a nickel‐catalyzed XEC reaction between aryl chlorides and alkyl chlorides. Concurrently, contributions from researchers such as Mei, Wolf, Sevov, Lin, Shen, Browne, Zhang, and Qiu have expanded the scope of XEC reactions to various halides. By 2022, MacMillan and Baran achieved a significant milestone in the XEC between carboxylic acids, further broadening the scope of research in this area. Also, advancements in the XEC of alcohols have been noted, with researchers including Weix, Lian, Tu, and Stahl conducting pioneering work and successfully executing the XEC of protective groups. It is foreseen that the ongoing research endeavors will primarily concentrate on the expansion of diverse electrophiles.
Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters†
Authors: Zhu Yu‐Shen , Li Jia‐Xin , Zhao Hao‐Tian , Su Bo 
Published: November 2024

Comprehensive SummaryVicinal stereogenic centers are ubiquitous structural scaffolds in both natural products and synthetic compounds, yet their enantioselective construction remains a significant challenge in organic synthesis. Organoboron compounds are of paramount importance in synthetic chemistry due to their ability to undergo facile transformations, yielding diverse essential chemical bonds such as carbon‐carbon, carbon‐oxygen, carbon‐nitrogen, and carbon‐halogen bonds. Transition‐metal‐catalyzed asymmetric borylative functionalizations of internal alkenes offer a promising strategy for the enantioselective installation of two adjacent chiral centers across carbon‐carbon bonds. By leveraging the versatile transformations of the newly introduced boryl unit, this approach holds great potential for expanding the structural diversity of vicinal stereogenic scaffolds. In this concise review, we aim to highlight recent advancements in transition‐metal‐catalyzed asymmetric borylative functionalizations of internal alkenes, underscore their utility as a versatile approach for constructing vicinal stereogenic centers, and discuss unsolved challenges and future directions in this field.
Key Scientists
Role of H2O2 as Oxidant and H2O as Co‐Catalyst Over Anatase‐TiO2(101) for Conversion of Methane to Methanol
Authors: Charakhwal Kanishka , Agarwal Vishal 
Published: November 2024

AbstractComputations based on density functional theory are carried out to examine the mechanism of photocatalytic oxidation of methane to methanol with H2O2 as oxidant and water as co‐catalyst over anatase TiO2(101) surface. The reaction proceeds with hydrogen abstraction from methane followed by the formation of surface methoxy species, which is reduced to methanol. We compare the reaction energetics for C−H dissociation in the presence and absence of surface defect, but find no discernible impact of O‐vacancy on methane oxidation. In comparison, hydroxyl produced as a result of H2O2 or H2O photo‐decomposition dramatically reduces the barrier for CH3‐H bond cleavage. The reaction proceeds further by the reduction of surface methoxy group and is the rate‐limiting step for methanol formation. Additionally, we find that methyl can also react with water to form methanol with a considerably lower barrier, suggesting an active involvement of water for methanol formation. We also study the role of water as a co‐catalyst and observe significant reduction in barriers, facilitated by alternate pathway for proton transfer. The reaction pathways presented provide valuable insights into the mechanism of methane oxidation in the presence of H2O2 as oxidant and demonstrate the rate‐enhancing role of water for these steps.
Deciphering the Ce3+ to Ce4+ Evolution: Insight from X‐ray Raman Scattering Spectroscopy at Ce N4,5 Edges
Authors: Das Soumya K. , Longo Alessandro , Bianchi Eugenio , Bordenca Claudio V. , Sahle Christoph J. , Pia Casaletto Maria , Mirone Alessandro , Giannici Francesco 
Published: October 2024

AbstractCerium oxide, or ceria, (CeO2) is one of the most studied materials for its wide range of applications in heterogeneous catalysis and energy conversion technologies. The key feature of ceria is the remarkable oxygen storage capacity linked to the switch between Ce4+ and Ce3+ states, in turn creating oxygen vacancies. Changes in the electronic structure occur with oxygen removal from the lattice. Accordingly, the two valence electrons can be accommodated by the reduction of support cations where the electrons can be localized in empty f states of Ce4+ ions nearby due to small polaron hopping resulting in the formation of Ce3+. Quantifying the different oxidation states in situ is crucial to understand and model the reaction mechanism.Beside the different techniques that have been used to quantify Ce3+ and Ce4+ states, we discuss the use of X‐ray Raman Scattering (XRS) spectroscopy as an alternative method. In particular, we show that XRS can observe the oxidation state changes of cerium directly in the bulk of the materials under realistic environmental conditions. The Hilbert++ code is used to simulate the XRS spectra and quantify accurately the Ce3+ and Ce4+ content. These results are compared to those obtained from in situ X‐ray Diffraction (XRD) collected in parallel and the differences arising from the two different probes are discussed.
Xylose Acetals ‐ a New Class of Sustainable Solvents and Their Application in Enzymatic Polycondensation
Authors: Komarova Anastasia O. , Warne Cicely M. , Pétremand Hugo , König‐Mattern Laura , Stöckelmaier Johannes , Oostenbrink Chris , Guebitz Georg M. , Luterbacher Jeremy , Pellis Alessandro 
Published: October 2024

AbstractThe use of organic solvents in academic research and industry applications is facing increasing regulatory pressure due to environmental and health concerns. Consequently, there is a growing demand for sustainable solvents, particularly in the enzymatic synthesis and processing of polyesters. Biocatalysts offer a sustainable method for producing these materials; however, achieving high molecular weights often necessitates use of solvents. In this work, we introduce a new class of alternative aprotic solvents with medium polarity produced directly from agricultural waste biomass in up to 83 mol % yield (on xylan basis). The new solvents have a largely unmodified xylose core and acetal functionality, yet they show no peroxide formation and provide reduced flammability risk. We also demonstrate their successful application in enzymatic polycondensation reactions with Candida antarctica lipase B (CaLB). In particular, the solvent dibutylxylose (DBX) outperformed the hazardous solvent diphenyl ether and facilitated polycondensation of the lignin‐derived diester pyridine‐2,4‐dicarboxylate, yielding polyesters with a Mn of >15 kDa. Computational modelling studies provided further insight into the molecular structure and dynamics of CaLB in the presence of new solvents. Lastly, up to 98 wt % of the new xylose acetals were successfully recovered and recycled, further contributing to the sustainability of the overall process.
Development of Enriched ROA With Dilated Hybrid Network for Automatic Modulation Classification Framework in CRNs
Authors: N Venkateswara Rao , Krishna B. T. 
Published: October 2024

ABSTRACTAutomatic modulation classification (AMC) is explained as accurately identifying a modulation of a received signal. AMC systems are a significant component of cognitive radio network (CRN) systems. It is difficult to perform modulation classification on an unsettled radio signal without any previous knowledge of the signal's properties. In this work, the deep learning‐aided AMC is suggested to solve the difficulties of the existing models. In the proposed approach, the modulation classification is attained by performing two steps: (a) data collection and (b) classification. Initially, the required data related to the cognitive environment is collected from online resources. Later, the garnered data are passed to the classification phase. The AMC is performed by the adaptive and dilated hybrid network (ADHN), which is the combination of a temporal convolution network (TCN) and a gated recurrent unit (GRU). The ADHN accurately classifies the modulation even in a noisy environment. The classification performance of the ADHN is further boosted by tuning the parameters of this network via the enriched remora optimization algorithm (EROA). This proposed modulation classification model is suitable for various channels. The comparative validation is performed to ensure the usefulness of the designed system via several measures. By experimental analysis, the proposed system acquires the high value of accuracy, precision, and f1‐score by 94.2, 80.2, and 86.7, respectively, when compared with classical approaches. In addition to this, other metrics are considered and obtained with more true value and less false value. Thus, it ensures the effectiveness of classifying the modulation types in CRNs.
A Sensing and Tunable Two‐Element MIMO Unified Five‐Antenna via Circuit Model for WLAN Cognitive Radio
Authors: Vattiprolu Sandeep Kiran , Nella Anveshkumar 
Published: November 2024

ABSTRACTThis paper presents a five‐element antennas system formed by integrating one sensing and four reconfigurable communicating antennas on a single substrate for cognitive radio applications in the 2.4 and 5 GHz WLAN bands. The five antennas are termed as A‐1, A‐2, A‐3, A‐4, and A‐5, where A‐1 is designed to sense in the 2.4 (2.4–2.484 GHz) and 5 GHz (5.15–5.875) bands. Antenna A‐2, exhibiting two‐element MIMO configuration with A‐3, is designed to communicate in the 5 GHz band, whereas Antenna A‐4, also exhibiting two‐element MIMO configuration with A‐5, operates in the 2.4 GHz band. Each communicating antenna is incorporated with a varactor diode to accomplish continuous frequency tuning operations. Simulated maximum peak gains of A‐1, A‐2, and A‐4 are 7.07, 2.65, and 2.15 dBi, respectively. A good mutual coupling, of less than −15 dB, is noted between the sensing and communicating antennas. MIMO diversity parameters are found to be ECC ≤ 0.01, TARC ≤ −10 dB, DG ≤ 10 dB, and CCL ≤ 0.4. Overall dimensions of the proposed structure are 80 mm × 100 mm × 1.2 mm. The antenna lumped element circuit models developed in ADS software also present good matching with EM simulation. A prototype of the proposed antenna system is fabricated to validate the simulation results. Because the proposed antenna can sense the WLAN bands using the dual‐band antenna (A‐1) and can be able to communicate at the identified spectrum holes using the reconfigurable NB antennas (A‐2 to A‐5), this antenna system is an appropriate module for the cognitive radio applications in WLAN bands.
The Micropaleoecology Framework: Evaluating Biotic Responses to Global Change Through Paleoproxy, Microfossil, and Ecological Data Integration
Authors: Woodhouse Adam , Swain Anshuman , Smith Jansen A. , Sibert Elizabeth C. , Lam Adriane R. , Dunne Jennifer A. , Auderset Alexandra 
Published: October 2024

ABSTRACTThe microfossil record contains abundant, diverse, and well‐preserved fossils spanning multiple trophic levels from primary producers to apex predators. In addition, microfossils often constitute and are preserved in high abundances alongside continuous high‐resolution geochemical proxy records. These characteristics mean that microfossils can provide valuable context for understanding the modern climate and biodiversity crises by allowing for the interrogation of spatiotemporal scales well beyond what is available in neo‐ecological research. Here, we formalize a research framework of “micropaleoecology,” which builds on a holistic understanding of global change from the environment to ecosystem level. Location: Global. Time period: Neoproterozoic‐Phanerozoic. Taxa studied: Fossilizing organisms/molecules. Our framework seeks to integrate geochemical proxy records with microfossil records and metrics, and draws on mechanistic models and systems‐level statistical analyses to integrate disparate records. Using multiple proxies and mechanistic mathematical frameworks extends analysis beyond traditional correlation‐based studies of paleoecological associations and builds a greater understanding of past ecosystem dynamics. The goal of micropaleoecology is to investigate how environmental changes impact the component and emergent properties of ecosystems through the integration of multi‐trophic level body fossil records (primarily using microfossils, and incorporating additional macrofossil data where possible) with contemporaneous environmental (biogeochemical, geochemical, and sedimentological) records. Micropaleoecology, with its focus on integrating ecological metrics within the context of paleontological records, facilitates a deeper understanding of the response of ecosystems across time and space to better prepare for a future Earth under threat from anthropogenic climate change.
Visible‐Light‐Driven Efficient Photocatalytic Reduction of Cr(VI) in a Wide pH Range by Two New Isopolymolybdate‐Based Ni(II)‐Complexes
Authors: Zhang Chao‐Nan , Zhang Zhong , Wang Xiu‐Li 
Published: October 2024

AbstractThe development of new catalytic materials for the fast and efficient photocatalytic reduction of toxic Cr(VI) to less toxic Cr(III) across a wide pH range of water environment has become one of the most challenging topics. Herein, two new isopolymolybdate‐based Ni(II)‐complexes [NiII(bcbpy)2(β‐Mo8O26)0.5 (H2O)] ⋅ 4H2O (BHU‐5) and [NiII(bcbpy)2[θ‐Mo8O26)0.5] ⋅ 4H2O (BHU‐6, Hbcbpy=1‐(4‐carboxybenzyl)‐4,4′‐bipyridinium) were synthesized via a hydrothermal reaction with the mixture of Na2MoO4 ⋅ 2H2O, NiCl2 ⋅ 6H2O and HbcbpyCl ligands. Single‐crystal X‐ray diffraction analysis displays that BHU‐5 and BHU‐6 contain binuclear nickel‐bcbpy units, which in association with different isopolymolybdates, and forming distinct 1D chain and 2D layer network structures, respectively. When used as photocatalysts for the reduction of Cr(VI), BHU‐5 and BHU‐6 exhibited distinct photocatalytic activities, achieving Cr(VI) removal efficiencies of 92 % and 98 % under visible light irradiation within 45 min. These efficiencies surpass those of the pristine HbcbpyCl, Na2MoO4 ⋅ 2H2O, NiCl2 ⋅ 6H2O and most reported polymolybdate‐based catalysts. Moreover, BHU‐5 and BHU‐6 demonstrated high efficiencies in removing Cr(VI) and maintained high structural stability across a wide pH range of 3.5–11.5. The influence of different structures on catalytic efficiency was further studied. The photocatalytic mechanism and reaction kinetics were investigated in detail.
Development, implementation, and evaluation of a 3D‐printed high‐fidelity pediatric mannequin with expected hard‐to‐intubate airway
Authors: Puggelli Luca , Mencarelli Marta , Serio Paola , Furferi Rocco , Amoretti Francesca , Volpe Yary 
Published: November 2024

AbstractClinical simulation is fundamental for the healthcare staff to learn and enhance their procedural skills without causing harm to the patients. Despite its importance, in literature appears a deficiency of pediatric pathological mannequins, especially those simulating difficult airway management due to the obstruction of the passage of tubes, fiberscopes, or catheters. Given the importance of simulating complex scenarios in the medical staff's training, the authors decided to realize a modular high‐fidelity pathological mannequin with nasal access using reverse engineering and additive manufacturing techniques within T3Ddy, a joint laboratory between Meyer Children's Hospital of Florence and the Department of Industrial Engineering of the University of Florence. The mannequin is developed from diagnostic images of a significant 30‐month‐old polymalformative patient also affected by Pierre‐Robin syndrome modifying the tracheobronchial tree to reproduce an abnormal status. Rigid parts and silicone cast molds are manufactured using 3D‐printed ABS/ASA while platinum‐cure‐silicones are used for the soft ones. Meyer's anesthesiologists collaborated to the realization providing feedback during design and production. The device is evaluated with a 5‐point Likert scale questionnaire and results in a useful tool for the training of procedural skills related to difficult intubation as its realism, anatomical geometry, and tactic feedback are positively evaluated.
Optimizing Heat Transfer in Heat Pipes Using Hybrid Nanofluids With Multi‐Walled Carbon Nanotubes and Alumina
Authors: Dhairiyasamy Ratchagaraja , Gabiriel Deepika 
Published: October 2024

ABSTRACTThis study investigates the thermal performance of heat pipes using hybrid nanofluids composed of multi‐walled carbon nanotubes (MWCNT) and aluminum oxide (Al2O3) nanoparticles. The aim was to assess the effects of nanoparticle concentration (0.1%–0.5%), filling ratio (60%–90%), heat input (50–80 W), and inclination angle (0°–90°) on thermal resistance and heat transfer coefficient (HTC). Hybrid nanofluids were prepared using ultrasonic homogenization, and their stability was confirmed by zeta potential analysis, showing a reduction from −60 to −48 mV over 30 days. Experimental results revealed that the thermal resistance decreased with increasing filling ratio and inclination angle, reaching a minimum of 0.80 K/W at a 90° angle, 90% filling ratio, and 80 W heat input. Similarly, the overall HTC increased with these parameters, peaking at 2250 W/m2 K under the same conditions. At a 0.5% nanoparticle concentration, the HTC improved by up to 40% compared with conventional fluids. The thermal conductivity of the hybrid nanofluid also rose significantly, from 0.7 W/m K at 30°C to 1.5 W/m K at 90°C, outperforming distilled water. These findings highlight the potential of hybrid nanofluids to enhance heat pipe efficiency, particularly in high‐power applications, by optimizing nanoparticle concentration, filling ratio, and inclination angle.