bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Electrosynthesis of 1,3,4‐Oxadiazoles from N‐Acyl Hydrazones
Authors: Chen Luke , Thompson James D. F. , Jamieson Craig 
Published: September 2024

AbstractThe 1,3,4‐oxadiazole is a widely encountered motif in the areas of pharmaceuticals, materials, and agrochemicals. This work has established a mediated electrochemical synthesis of 2,5‐disubstituted 1,3,4‐oxadiazoles from N‐acyl hydrazones. Using DABCO as the optimal redox mediator has enabled a mild oxidative cyclisation, without recourse to stoichiometric oxidants. In contrast to previous methods, this indirect electrochemical oxidation has enabled a broad range of substrates to be accessed, with yields of up to 83 %, and on gram scale. The simplicity of the method has been further demonstrated by the development of a one‐pot procedure, directly transforming readily available aldehydes and hydrazides into valuable heterocycles.
Decarboxylative and Decarbonylative Borylation of Carboxylic Acids and Their Derivatives†
Authors: Li Xiaoxian , Wu Lipeng 
Published: September 2024

Comprehensive SummaryBoronate esters are highly valued in synthetic and pharmaceutical industries for their versatility in creating C—C and C—X bonds. They also find applications as catalysts in chemical transformations as well as stimuli‐responsive materials in materials science. Some alkyl boronates themselves also show promising applications in medicinal chemistry. In the past few decades, chemists have been devoted to developing new methods or new starting materials for synthesizing boronate esters. Carboxylic acids and their derivatives are privileged chemical entities due to their readily availability or natural abundance, structural diversity, and chemical stability. Hence, the transformation of carboxylic acid and their derivatives to alkyl/aryl boronate esters has seen its fast development in the past decade. This review summarized the state‐to‐art development of decarboxylative and decarbonylative borylation of carboxylic acids and their derivatives to aryl and alkyl boronate esters.
Key ScientistsThe decarboxylative and decarbonylative borylation of carboxylic acids and their derivatives started only in the past decade. In 2016, the decarbonylative borylation of carboxylic esters and amides was reported by Zhuangzhi Shi and Magnus Reuping's groups. Then, in 2017, studies on the decarboxylative borylation of redox‐active esters such as NHPI esters started to receive increasing attention by Aggarwal, Baran, Fu, Glorius, and Li's groups. From 2018 to 2023, large numbers of studies on the decarboxylative and decarbonylative borylation of carboxylic acids and their derivatives using transition‐metal‐catalyst, organo‐catalyst, or under photochemical or electrochemical conditions emerged. Due to space limitations, only pictures of scientists who have contributed more than two works in this area are shown herein.
Highly Stable Binary Cross‐Linkable Organic Nonlinear Optical Materials Using Different Acceptors Based on Huisgen Cycloaddition Reaction
Authors: Zhang Yu , Zhang Weijun , Bo Shuhui , He Wenlong , Liu Chuying , Wang Jiahai , Liu Fenggang 
Published: September 2024

Comprehensive SummaryHow to obtain organic electro‐optic materials with large electro‐optic coefficients, high glass transition temperature, and good optical transparency remains a challenge in this field. To solve this problem, we introduce groups that can undergo Huisgen cycloaddition reactions into the donor and electron bridge of chromophores with large hyperpolarizability using tetrahydroquinoline as the donor. Binary cross‐linkable chromophores TLD1‐2 with CF3‐TCF as the acceptor and chromophores TLD3‐4 with 5Fph‐TCF as the acceptor were synthesized. After poling and crosslinking, the Tg of TLD1/TLD2 and TLD3/TLD4 were raised to 152 and 174 °C, respectively. The electro‐optical coefficients of chromophores TLD1/TLD2 and TLD3/TLD4 were as high as 312 pm/V and 287 pm/V, respectively. The long‐term alignment stability test showed that after being left at 85 °C for 500 h, the cross‐linked film TLD3/TLD4 can still maintain more than 98% of the original electro‐optical coefficient value, which is higher than that of TLD1/TLD2 (93%). The chromophore TLD3‐4 exhibited much blue‐shifted maximum absorption wavelengths (~40 nm) compared to TLD1‐2 which was beneficial for reducing optical loss in the device. The combination of high electro‐optic coefficient, strong stability, and excellent optical transparency makes the TLD series of binary cross‐linked materials very promising for practical high‐performance electro‐optic devices.
A Predictive Nomogram of In‐Hospital Mortality After 48 h for Atrial Fibrillation Patients in the Coronary Care Unit
Authors: Wang Wenhui , Liu Linlin , Jin Lu , Hu Bo 
Published: September 2024

ABSTRACTBackgroundPatients with atrial fibrillation (AF) suffer a higher risk of death, and it is necessary to develop prediction tools for mortality risk in critically ill patients with AF. This study aimed to develop a novel predictive nomogram of in‐hospital mortality after 48 h in the coronary care unit (CCU) for patients with AF.MethodsWe collected information on CCU patients with AF from the “Medical Information Mart for Intensive Care‐III” database and developed a nomogram model for predicting the all‐cause mortality risk after 48 h in the hospital. Key variables were selected by univariate logistic and least absolute shrinkage and selection operator regression. The independent predictors with p < 0.05 were screened out by multivariate logistic regression. A predictive nomogram was constructed using these independent predictors, and the model calibration and discrimination were evaluated.ResultsThis study finally enrolled 1248 CCU patients with AF, and the in‐hospital mortality was 17% (209/1248). The predictive nomogram was constructed by 13 selected independent predictors, including age, smoking status, acute kidney injury, chronic obstructive pulmonary disease, ventricular arrhythmia, shock, urea, red cell distribution width, leucocytosis, continuous renal replacement therapy, continuous positive airway pressure, anticoagulation, and heart rate. The area under the curve of the nomogram was 0.803 (95% confidence interval 0.771–0.835). The nomogram was verified to have good accuracy and calibration.ConclusionsThis study developed a novel nomogram containing age, acute kidney injury, and heart rate that can be a good predictor of potential in‐hospital mortality after 48 h in CCU patients with AF.
Ultrasound‐Assisted Synthesis of Pyrazoline Derivatives as Potential Antagonists of RAGE‐Mediated Pathologies: Insights from SAR Studies and Biological Evaluations
Authors: Dascălu Anca‐Elena , Furman Christophe , Lancel Steve , Lipka Emmanuelle , Liberelle Maxime , Boulanger Eric , Ghinet Alina 
Published: September 2024

AbstractIn the context of age‐related disorders, the receptor of advanced glycation end products (RAGE), plays a pivotal role in the pathogenesis of these conditions by triggering downstream signaling pathways associated with chronic inflammation and oxidative stress. Targeting this inflammaging phenomenon with RAGE antagonists holds promise for interventions with broad implications in healthy aging and the management of age‐related conditions. This study explores the structure‐activity relationship (SAR) of pyrazoline‐based RAGE antagonists synthesized using an ultrasound‐assisted green one‐pot two‐steps methodology. Our investigation identifies phenylurenyl‐pyrazoline 2 g as a promising candidate, demonstrating superior efficiency compared to the reference antagonist Azeliragon (IC50=13 μM). Compound 2 g exhibits potent inhibition of the AGE2‐BSA/sRAGE interaction (IC50=22 μM) and favorable affinity in Microscale Thermophoresis (MST) assays (Kd=17.1 μM), along with a favorable safety profile, with no apparent cytotoxicity observed in vitro in the MTS assay. These findings underscore the potential of pyrazoline‐derived RAGE antagonists as therapeutic agents for addressing age‐related disorders.
The Role of Frustrated Lewis Pair in Catalytic Transfer Hydrogenation of Furfural using Nickel Single‐Atom Catalysts: A Theoretical Study
Authors: Zhang Jin , Jian Changping , Wang Fang‐Fang , Zhang Wei , Tian Zhi , Chen De‐Li 
Published: September 2024

AbstractThe burgeoning field of frustrated Lewis pair (FLP) heterogeneous catalysts has garnered significant interest in recent years, primarily due to their inherent ability to activate H‐source molecules, thereby facilitating hydrogenation reactions. In this study, non‐precious transition metal atoms were anchored onto several models of pyridinic nitrogen incorporated graphene sheet. Theoretical calculations substantiated energy barriers as low as 0.10 eV for isopropanol activation, thereby positioning these catalysts as highly promising candidates for catalytic transfer hydrogenation of furfural. Electronic structure analyses revealed that the H−O bond breakage in isopropanol molecules was significantly facilitated by the presence of FLP sites within the catalysts. Notably, both Ni‐C2N and Ni‐N6‐C demonstrated exceptional potential as selective catalysts for the hydrogenation of furfural into furfuryl alcohol, exhibiting remarkably low barriers of only 0.65–0.72 eV for the rate‐determining steps. The findings in this study are helpful to design FLP containing single atom catalysts for hydrogenation reactions.
N‐Aromatic Complexation in Tetraphenyl Porphyrin Iron (III)‐Pyridine: Evidence of Spin‐Flip via Gas‐Phase Electronic Spectroscopy
Authors: Uleanya Kelechi O. , Wilson Sarah A. , Dessent Caroline E. H. 
Published: September 2024

AbstractThere is growing interest in the electronic properties of metalloporphyrins especially in relation to their interactions with other molecular species in their local environment. Here, UV‐VIS laser photodissociation spectroscopy in vacuo has been applied to an iron‐centred metalloporphyrin (FeTPP+) and its N‐aromatic adduct with pyridine (py) to determine the electronic effect of complexation. Both the metalloporphyrin (FeTPP+) and pyridine adduct (FeTPP+⋅py) absorb strongly across the spectral region studied (652–302 nm: 1.91–4.10 eV). Notably, a large blue shift was observed for the dominant Soret band (41 nm) upon complexation (0.47±0.02 eV), indicative of strong pyridine binding. Significant differences in the profiles (i. e. number and position of bands) of the electronic spectra are evident comparing FeTPP+ and FeTPP+⋅py. Time‐dependent density functional theory calculations were used to assign the spectra, revealing that the FeIII spin‐state flips from S=3/2 to S=5/2 upon complexation with pyridine. For FeTPP+, all bright spectral transitions are found to be π‐π* in character, with electron density variously distributed across the porphyrin and/or its phenyl substituents. Similar electronic excitations are observed for FeTPP+⋅py, with an additional bright transition which involves charge transfer from the porphyrin to the pyridine moiety.
Theoretical Insight into Fluorination on Low‐Cost A‐π‐D‐π‐A Type Donor Materials for All‐Small‐Molecule Organic Photovoltaic Cells
Authors: Nong Jia‐Qian , Han Jin‐Hong , Pan Jian , Zhao Zhi‐Wen , Wang Yan‐Ling , Pan Qing‐Qing , Liu Su‐Qin , Fan Hong‐Hong 
Published: September 2024

AbstractLow‐cost organic photovoltaic (OPV) devices have shown enormous potential in large‐scale industrial applications. And it has attracted widespread attention in the past few decades. However, the photophysical characteristics of these budget‐friendly materials haven't been explored much. Here, low‐cost small materials, including small molecule 1 (asm1) with ortho‐fluorinated side chain and small molecule 2 (asm2) with meta‐fluorinated side chain were selected to probe the fluorination effect on the absorption spectra, electrochemical energy levels, electrostatic potential (ESP), etc. The results show that the molecules asm1 and asm2 have good planarity of the backbone. And the meta‐fluorinated side chain of asm2 contributes more to the highest occupied molecular orbital and less to the lowest unoccupied molecular orbital than asm1. Moreover, differences in ESP are found between donor and acceptor materials. Furthermore, strong and broad light absorption in the visible region of these low‐cost molecules is observed, resulting in a better short‐circuit current density for the devices constructed by the donors asm1, asm2, and acceptor Y6. In addition, more charge transfer mechanisms are characterized for the asm1/Y6 system. The introduction of ortho‐fluorination in the conjugated side chain of the molecule is a favorable approach, which will provide theoretical guidance for further molecular design experiments.
Silicon Nanowires via Metal‐Assisted Chemical Etching for Energy Storage Applications
Authors: Mateen Abdul , Khan Abdul Jabbar , Zhou Zidong , Mujear Altaf , Farid Ghulam , Yan Wei , Li Haojie , Li Jiawen , Bao Zhihao 
Published: September 2024

AbstractSilicon nanowires (SiNWs) have demonstrated great potential for energy storage due to their exceptional electrical conductivity, large surface area, and wide compositional range. Metal‐assisted chemical etching (MACE) is a widely used top‐down technique for fabricating silicon micro/nanostructures. SiNWs fabricated by MACE exhibit significant surface areas and diverse surface chemistry. Since the material composition and surface chemistry have a significant impact on the electrochemical energy storage performance, integrating SiNWs with diverse materials like porous carbon, metal oxides/sulfides, and polymers, can establish composites with excellent properties. Hence, it is imperative to meticulously fabricate SiNW‐based materials with customizable morphologies and enhanced electrochemical energy‐storage performance. This review provides an in‐depth study of recent advancements in SiNW‐based materials with enhanced performance for energy storage systems, such as supercapacitors (SCs) and lithium‐ion batteries (LIBs). It includes a concise overview of the history, MACE synthesis, and characteristics of SiNWs. Further, it also explores the key elements that influence the MACE process of SiNWs and delves into structural engineering. Additionally, we introduce recent advances in SiNW‐based materials for the design of high‐performance energy‐storage devices, namely SCs and LIBs. Finally, we present the crucial future prospects of SiNW‐based materials for energy‐storage applications.
γδ T cells in immune‐mediated kidney disease
Authors: Waterhölter Alex , Krebs Christian F. , Panzer Ulf 
Published: September 2024

AbstractImmune‐mediated kidney diseases, including glomerulonephritis (GN), represent a diverse spectrum of disorders characterized by inflammation within the glomerulus and other renal compartments. Despite recent advances, the immunopathogenesis of these diseases remains incompletely understood. Current therapeutic approaches based on nonspecific immunosuppression often result in suboptimal outcomes and significant side effects, highlighting the need for tailored interventions. The complexity of the immune system extends beyond classical T‐cell immunity, with the emergence of unconventional T cells — γδ T cells, NKT cells, and MAIT cells — that exhibit a semi‐invariant nature and unique functions that bridge innate and adaptive immunity. γδ T cells exhibit unique homing and activation mechanisms and respond to different ligands, implying a multifaceted role in immune regulation. The understanding of γδ T‐cell involvement in kidney disease lags behind conventional T‐cell research. However, advances in immune cell analysis technologies offer promising avenues for elucidating their precise functions. This review synthesizes the current knowledge on γδ T cells in renal diseases, explores potential therapeutic strategies, and presents a roadmap for future research directions.
Reduction in mucosal‐associated invariant T cells (MAIT) in APECED patients is associated with elevated serum IFN‐γ concentration
Authors: Hetemäki Iivo , Sarkkinen Joona , Wong Huai Hui , Heikkilä Nelli , Laakso Saila , Miettinen Simo , Mäyränpää Mikko I. , Mäkitie Outi , Arstila T Petteri , Kekäläinen Eliisa 
Published: September 2024

AbstractMucosal‐associated invariant T cells (MAIT) are innate‐like lymphocytes enriched in mucosal organs where they contribute to antimicrobial defense. APECED is an inborn error of immunity characterized by immune dysregulation and chronic mucocutaneous candidiasis. Reduction in the frequency of circulating MAITs has been reported in many inborn errors of immunity, but only in a few of them, the functional competence of MAITs has been assessed. Here, we show in a cohort of 24 patients with APECED, that the proportion of circulating MAITs was reduced compared with healthy age and sex‐matched controls (1.1% vs. 2.6% of CD3+ T cells; p < 0.001) and the MAIT cell immunophenotype was more activated. Functionally the IFN‐γ secretion of patient MAITs after stimulation was comparable to healthy controls. We observed in the patients elevated serum IFN‐γ (46.0 vs. 21.1 pg/mL; p = 0.01) and IL‐18 (42.6 vs. 13.7 pg/mL; p < 0.001) concentrations. Lower MAIT proportion did not associate with the levels of neutralizing anti‐IL‐22 or anti‐IL‐12/23 antibodies but had a clear negative correlation with serum concentrations of IFN‐γ, IL‐18, and protein C‐reactive protein. Our data suggest that reduction of circulating MAITs in patients with APECED correlates with chronic type 1 inflammation but the remaining MAITs are functionally competent.
Systematic literature review of the humanistic and economic burden of focal epilepsy and primary generalized tonic–clonic seizures in adults
Authors: Boccaletti Simona , Lucas Eleanor , Nixon Annabel , Boskovic Nikolina , Di Dato Giorgio 
Published: September 2024

AbstractThis systematic literature review (SLR) assessed the humanistic and economic burden of focal epilepsy and primary generalized tonic–clonic seizures (PGTCS) in adults to evaluate these domains in both populations and identify evidence gaps to inform future research. A search was conducted on December 7, 2022, using MEDLINE and Embase to identify studies published from 2012 onwards reporting humanistic burden (patient‐reported or caregiver‐reported outcomes or utilities, qualitative evaluations), economic burden (productivity loss, caregiver and societal costs of epilepsy), and sleep‐related outcomes. Of the 2830 citations identified, 136 were included. Most studies were in the focal epilepsy population; very few studies reported outcomes in the PGTCS population. The presence of epilepsy‐specific instruments varied based on the domain evaluated. Epilepsy exerted considerable humanistic and economic burden. Indicators of poor disease control (e.g., high seizure frequency, resistance to anti‐seizure medications, polypharmacy) increased epilepsy burden. Seizure frequency and type, disease severity, and polypharmacy also affected work productivity. Adults with epilepsy, particularly focal epilepsy, reported higher indirect costs, more sick days accrued, and early entry into retirement. Caregivers similarly reported high productivity loss and absenteeism related to caregiving duties. The results of this SLR highlight the high humanistic and economic burden of focal epilepsy and PGTCS, although limited data were available for the PGTCS population. The results include patient‐reported outcome data specific to focal epilepsy and PGTCS, expanding the limited humanistic burden evidence identified in previous reviews, and show the effect of poor disease control on individuals' lives and as a driver of indirect costs.Plain Language SummaryOur systematic literature review identified studies that evaluated the impact of focal epilepsy and primary generalized tonic–clonic seizures on patients and their caregivers. We found that focal epilepsy negatively impacted patients' mental health and sleep and was associated with higher indirect costs and lower work productivity in people with more severe disease. The impact of primary generalized tonic–clonic seizures on patients was rarely reported, and future research is needed.
Total electricity generation dynamics analysis and renewable energy impacts in South Africa
Authors: Mutombo Ntumba Marc‐Alain , Numbi Bubele Papy , Tafticht Tahar 
Published: September 2024

AbstractThis research explores the dynamics of total electricity generation (TEG) in South Africa through an analysis of data from the International Energy Agency database from 1990 to 2020. A comprehensive examination of various energy sources, including coal, oil, biofuels, nuclear, hydro, solar photovoltaic (PV), solar thermal, and wind, is conducted to ascertain their respective contributions to TEG. Employing the R software environment, the study employs a methodical analytical framework encompassing meticulous data preparation, statistical analysis, and model formulation. The data preparation phase involves intricate processes such as structuring, cleansing, and visualization aimed at eliminating stochastic variables and outliers. Missing data are addressed through the application of the Piecewise Cubic Hermite Interpolating Polynomial method. Subsequent statistical analyses are informed by tests for normality and homogeneity of variance, revealing deviations from normality and disparate variances across energy source groups. Consequently, non‐parametric methodologies such as the Kruskal–Wallis test are adopted. Findings underscore the significant role of nuclear energy in TEG despite facing challenges. Model development entails the construction of multiple linear regression models with varying predictor sizes, with Model m06 emerging as the optimal choice, incorporating key predictors such as coal, nuclear, and solar PV. Rigorous diagnostic assessments confirm the robustness of Model m06 and its suitability for TEG prediction. Comparative analysis against actual data validates its superior performance, characterized by minimal errors and high predictive accuracy. The efficacy of Model m06 in capturing TEG dynamics underscores its utility for informing energy planning initiatives. Recommendations derived from the study advocate for prioritizing renewable energy integration, infrastructure investment, research endeavors, monitoring mechanisms, and public awareness campaigns to advance sustainable energy development goals in South Africa.