bluuebunny/crossref_metadata_2025_split huggingface dataset:
Activating Lattice Oxygen Oxidation Mechanism in Asymmetric [IrO6] Octahedra of Ir‐Based Oxides Toward Superior Acidic Electrochemical Water Oxidation
Authors: Liu Yuying , Liu Ziyi , Li Na , Wang Chao , Wang Huijuan , Ji Qianqian , Hu Fengchun , Tan Hao , Liu Chaocheng , Liu Chenglong , Li Zhi , Feng Sihua , Tang Bing , Liu Ruiqi , Lv Liyang , Cheng Weiren , Yan Wensheng 
Published: September 2024

AbstractThe activation of lattice oxygen oxidation mechanism (LOM) will endow iridium‐based electrocatalysts with desired acid‐available water oxidation activity, compared to the conventional adsorbate evolution mechanism (AEM). However, the inherent symmetric [IrO6] octahedra of commercial Ir‐based catalysts generally thermodynamically favor the AEM pathway contributing to the moderate water oxidation performance. Here, based on typical layered Ca2IrO4 (CIO) modeled materials, the d‐orbitals electron repulsion strategy is demonstrated, via constructing asymmetrically polarized Ir‒O‒Ru configuration in Ru‐CIO, to effectively activate the lattice oxygen participating in water oxidation process for decent oxygen‐related electrocatalytic activity. Specifically, a great increase of ≈700‐fold and ≈170‐fold in mass activity and turnover frequency, respectively, has been realized for the optimal Ru‐CIO electrocatalyst in an acid medium relative to the commercial IrO2 electrocatalysts, where a small overpotential of only 175 mV is required for achieving 10 mA cmgeo‒2. In situ X‐ray fine structure spectroscopies combined with in situ 18O‐ isotope‐labeled differential electrochemical mass spectrometry analyses reveal that desirable LOM has been boosted by the activated lattice oxygen and the flexible Ir(3+δ)+ active sites of asymmetric [IrO6] octahedra, which results in superior OER kinetics for Ir‐based oxide catalysts.
Further Delineation of the Proximal 16p11.2 Microdeletion Syndrome: Novel Findings Among 22 New Individuals
Authors: McRae Anne M. , Duncan Jaime , Drackley Andy , Ing Alexander , Allegretti Valerie , Raski Carolyn R. , Mercier Angelique , Prada Carlos E. , Jurgensmeyer Sarah 
Published: September 2024

ABSTRACTThe recurrent chromosome 16p11.2 BP4‐BP5 microdeletion (MIM #611913) predisposes to a neurodevelopmental disorder with variable associated congenital anomalies and susceptibility to early‐onset obesity. We identified 22 new individuals with proximal 16p11.2 deletions through retrospective data analysis at our institution and performed phenotyping through in‐depth chart review. Our cohort exhibited a spectrum of neurodevelopmental abnormalities largely consistent with other publications, however they also were found to have a higher rate than expected of congenital anomalies, some of which have not yet been reported in association with 16p11.2 microdeletions to our knowledge. This series contributes to the body of data on this population, which we anticipate will continue to evolve along with increased uptake of genetic testing.
Associations of Polygenic Risk for Depression, Traditional Chinese Medicine Constitution, and Depression: A Population‐Based Study in Taiwan
Authors: Hsu Yu‐Cheng , Su Mei‐Hsin , Chen Chia‐Yen , Lin Yen‐Feng , Wang Shi‐Heng 
Published: September 2024

ABSTRACTTo comprehensively investigate the risk factors associated with depression, traditional Chinese medicine constitution (TCMC) has been found to be related to depression. However, the underlying mechanism remains unclear. This study examined the association between the concept of unbalanced TCMCs and major depressive disorder (MDD), investigated the overlapping polygenic risks between unbalanced TCMC and MDD, and performed a mediation test to establish potential pathways. In total, 11,030 individuals were recruited from the Taiwan Biobank, and the polygenic risk score (PRS) for MDD for each participant was calculated using the data from the Psychiatric Genomics Consortium. Unbalanced TCMC were classified as yang‐deficiency, yin‐deficiency, and stasis. The MDD PRS was associated with yang‐deficiency odds ratio [OR] per standard deviation increase in standardized (PRS = 1.07, p = 0.0080), yin‐deficiency (OR = 1.07, p = 0.0030), and stasis constitution (OR = 1.06, p = 0.0331). Yang‐deficiency (OR = 2.07, p < 0.0001) and stasis constitutions (OR = 1.65, p = 0.0015) were associated with an increased risk of MDD. A higher number of unbalanced constitutions was associated with MDD (p < 0.0001). The effect of MDD PRS on MDD was partly mediated by yang‐deficiency (10.21%) and stasis (8.41%) constitutions. This study provides evidence for the shared polygenic risk mechanism underlying depression and TCMC and the potential mediating role of TCMC in the polygenic liability for MDD.
Synthesis of Naphthalenones Via Photo‐Induced Radical Cascade Fluoroalkylation/Cyclization of Alkenes
Authors: Yang Xiaohu , Yang Chunmei , Wan Xiaoqing , Yang Wenchao , Fang Hegui 
Published: September 2024

AbstractHerein, we report a photoredox‐catalyzed fluoroalkylation of activated alkenes via fluorinated alkyl‐centered radical induced radical addition/annulation/SET/deprotonation in a domino fashion using 4CzIPN as photocatalyst. The protocol features room temperature, transition metal free, high yields and simple operation, affording a facile and efficient strategy to access fluorine‐containing naphthalenone.
Enhancing Efficiency and Stability of Inverted Perovskite Solar Cells through Solution‐Processed and Structurally Ordered Fullerene
Authors: Sun Xianglang , Zhang Chunlei , Gao Danpeng , Yu Xinyu , Li Bo , Wu Xin , Zhang Shoufeng , He Yaxin , Yu Zexin , Qian Liangchen , Gong Jianqiu , Li Shuai , Li Nan , Zhu Zonglong , Li Zhong'an 
Published: September 2024

AbstractThe electron transporting layer (ETL) used in high performance inverted perovskite solar cells (PSCs) is typically composed of C60, which requires time‐consuming and costly thermal evaporation deposition, posing a significant challenge for large‐scale production. To address this challenge, herein, we present a novel design of solution‐processible electron transporting material (ETM) by grafting a non‐fullerene acceptor fragment onto C60. The synthesized BTPC60 exhibits an exceptional solution processability and well‐organized molecular stacking pattern, enabling the formation of uniform and structurally ordered film with high electron mobility. When applied as ETL in inverted PSCs, BTPC60 not only exhibits excellent interfacial contact with the perovskite layer, resulting in enhanced electron extraction and transfer efficiency, but also effectively passivates the interfacial defects to suppress non‐radiative recombination. Resultant BTPC60‐based inverted PSCs deliver an impressive power conversion efficiency (PCE) of 25.3 % and retain almost 90 % of the initial values after aging at 85 °C for 1500 hours in N2. More encouragingly, the solution‐processed BTPC60 ETL demonstrates remarkable film thickness tolerance, and enables a high PCE up to 24.8 % with the ETL thickness of 200 nm. Our results highlight BTPC60 as a promising solution‐processed fullerene‐based ETM, opening an avenue for improving the scalability of efficient and stable inverted PSCs.
Catalytic Enantioselective Synthesis of Planar Chiral Pillar[5]arenes via Asymmetric Sonogashira Coupling
Authors: Zhou Xiao‐Hua , Zhang Xin , Song Yi‐Ru , Li Xue , Bao Lin‐Tao , Xu Wei‐Tao , Wang Xu‐Qing , Yang Hai‐Bo , Wang Wei 
Published: September 2024

AbstractAs a novel type of macrocycles with attractive planar chirality, pillar[5]arenes have gained increasing research interest over the past decades, enabling their widespread applications in diverse fields such as porous materials, molecular machines, and chiral luminescence materials. However, the catalytic methodology towards the enantioselective synthesis of planar chiral pillar[5]arenes remains elusive. Here we report a novel method for the enantioselective synthesis of planar chiral pillar[5]arenes via asymmetric Sonogashira coupling, giving access to a wide range of highly functionalized planar chiral pillar[5]arenes, including both homo‐ and hetero‐rimmed ones, with excellent enantioselectivities. Attractively, the resultant planar chiral pillar[5]arenes show great potential for widespread use in many areas such as chiral luminescent materials. This work not only enables the successful synthesis of planar chiral pillar[5]arenes with abundant structural and functional diversity as key building blocks for practical applications but also enriches the asymmetric cross‐coupling methodologies in organic synthetic chemistry.
Clar's Aromatic π‐Sextet Rule for the Construction of Red Multiple Resonance Emitter
Authors: Chen Haowen , Du Mingxu , Qu Cheng , Jin Qian , Tao Zequan , Ji Renjie , Zhao Guimin , Zhou Tao , Lou Yuheng , Sun Yueming , Jiang Wei , Duan Lian , Zhang Yuewei 
Published: September 2024

AbstractDespite the proliferation of multiple resonance (MR) materials in the blue to green spectral ranges, red MR emitters remain scarce in the literature, an area that certainly warrants attention for future applications. Here, through a clever application of classic Clar's aromatic π‐sextet rule, we triumphantly constructed the first red MR emitter by substituting the conventional benzene ring core with anthracene (fewer π‐sextets). Theoretical studies indicate that the quantity of π‐sextets ultimately determines the optical band gap of a molecule, rather than the number of fused benzene rings. Benefiting from the high photoluminescence quantum yield of ~94 % and horizontal dipole ratio of ~90 %, the corresponding narrowband red (luminescence wavelength: 608 nm) organic light‐emitting diode shows a high external quantum efficiency of 27.3 %, with only a slight decrease of 3.7 % at an elevated luminance level of 100,000 cd/m2.
Expanding the Landscape of Phosphorous‐Based Open Shell Species: Stable Mono‐, Di‐, and Trianionic Radicals Based on a Contorted Triphosphaalkene
Authors: Ansari Mohd Asif , Deka Rajesh , Thapper Anders , Orthaber Andreas 
Published: September 2024

AbstractThe stepwise reduction of the highly contorted truxene‐based triphosphaalkene 1 using KC8 led to the isolation of mono‐, di‐, and tri‐anionic species. The solid‐state molecular structures of mono‐ and diradical anionic species were elucidated by single crystal X‐ray diffractions, revealing elongated P−C bonds and a pronounced “indene” aromatization compared to the parent system. All three radical species displayed distinct Electron Paramagnetic Resonance (EPR) spectra, providing compelling evidence for the open‐shell electronic configuration of both the diradical and triradical species—an observation unprecedented in any previously reported phosphorous‐based anionic polyradicals. Mulliken spin density calculations revealed a dominant localization of radical spin on a single phosphorous atom in the monoanion. In the dianion, spin localization is observed on two phosphorous atoms (~34 % each), with a minor contribution from the third phosphorous (0.13 %), while the trianion demonstrates a uniform distribution of spin density (~30 %) across each phosphorous atom.
Constructing Noncytotoxic Organometallic Nanostructures of Ag–BSA–CaCO3
Authors: Rodríguez‐Calderón Ana Gabriela , Núñez‐Anita Rosa Elvira , Holguín‐Momaca José T. , Contreras‐García Maria Eugenia 
Published: September 2024

ABSTRACTA multifunctional nanostructured hybrid composed of metal–protein–ceramic was designed and then synthesized using three different methods: chemical reduction, physical adsorption, and coprecipitation. The processes yielded colloidal spherical silver nanoparticles (AgNPs) enveloped in a bovine serum albumin (BSA) corona, leading to the core–shell structure AgNPs–BSA. To enhance biocompatibility and mitigate potential toxicity associated with metallic nanoparticles, this core–shell structure was coated with a layer of calcium carbonate (CaCO3). In order to analyze the internal structure of the resulting hybrid nanostructure (AgNPs–BSA–CaCO3), a number of samples were produced by focused ion beam (FIB) and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and zeta potential (ζ) measurements. The cytotoxic effect of the samples were evaluated through in vitro tests on mouse macrophage cell line RAW 264.7 ATCC TIB‐71, this was accomplished by calculating the appropriate concentrations from the dose–response curve of AgNPs. Research showed that the AgNPs–BSA–CaCO3 mixture triggered the formation of vaterite; these findings were corroborated by FTIR and Raman techniques. The spherical nanostructures have an average diameter size of 4.3 ± 2 μm and an average roughness (Ra) of 3.11 ± 0.62 μm. Zeta potential (ζ) and isoelectric point studies reveal that this hybrid nanostructure exhibits amphoteric behavior that differs from either AgNPs or AgNPs–BSA alone. Cell viability response exceeded 75%, indicating the noncytotoxic nature of the proposed hybrid nanostructures.
Monometallic/Bimetallic Co‐ZIFs Synthesis, Characterization, and Application for Adsorption of SO2 and CO2 in Continuous Flow System
Authors: Sumbal Sara , Aslam Zaheer , Irshad Umar , Anwar Sobia , Abbas Aamir , Ahmad Waqar , Hamza Ali 
Published: September 2024

ABSTRACTSulfur dioxide is serious ultimatum to human health as well as environment, while carbon dioxide is viewed as one of the primary drivers of the worldwide temperature alteration. Therefore, capturing of these gases is a dynamic research subject attracting much consideration from scientists. Herein, we report synthesis of a series of Co‐ZIF and bimetallic M‐Co‐ZIF adsorbents and application for room temperature adsorption of SO2 and CO2. In this work, the breakthrough curves for the adsorption of sulfur dioxide and carbon dioxide on Co‐ZIF and M‐Co‐ZIF were obtained experimentally and theoretically using a laboratory‐scale fixed bed column at room temperature. In this work, the adsorption capacities and breakthrough points for modified bimetallic M‐Co‐ZIF were found to be relatively higher than parent Co‐ZIF. Notably, a high SO2 uptake capacity of 7.1 mmol/g for Zr‐Co‐ZIF and high CO2 uptake capacity of 69.9 mmol/g for Ni‐Co‐ZIF were achieved. The parent cobalt and bimetallic ZIF materials were characterized by XRD, FTIR, SEM, and nitrogen physisorption. The XRD results confirm the formation of pure phase highly crystalline ZIF materials while BET analysis suggests high surface area of prepared adsorbents. Finally, the results of dynamic adsorption combined with characterization show great potential for preparation of bimetallic ZIF adsorbents for effective SO2 and CO2 adsorption.
Hepatic gluconeogenesis and regulatory mechanisms in lactating ruminants: A literature review
Authors: Wang Guoyan , Zhu Yuanyuan , Feng Dingping , Yao Junhu , Cao Yangchun , Deng Lu 
Published: September 2024

AbstractThe conversion of various non‐sugar substances, such as propionate and lactate, produced by rumen microbial fermentation into glucose by hepatic gluconeogenesis is the main way to ensure an adequate supply of glucose to the mammary gland of ruminants. Unlike monogastric animals, in ruminants, hepatic gluconeogenesis is a continuous and efficient physiological process. Some signaling pathways, transcription factors, and nutrients affect the expression of genes encoding for gluconeogenic rate‐limiting enzymes, which in turn are involved in the regulation of hepatic gluconeogenesis. Although hepatic gluconeogenesis in ruminants has been researched for decades, it still needs to be clarified in depth. Therefore, this review summarizes the process, substrates, and regulatory mechanisms of hepatic gluconeogenesis in ruminants and establishes a theoretical basis for the development of precise nutritional regulation strategies to facilitate high‐quality high‐efficiency lactation. According to the research so far, phosphoenolpyruvate carboxy kinase, fructose‐1,6‐bisphosphatase, and glucose‐6‐phosphatase have been highlighted as the main rate‐limiting enzymes that determine the efficiency of gluconeogenesis. With regard to the underlying mechanisms, protein kinase A, protein kinase B, adenosine 5′‐monophosphate kinase, and mammalian target of rapamycin pathways have been found to regulate the expression of key gluconeogenic genes through transcription factors. Further, supplementation with propionate, certain amino acids, and micronutrients has shown beneficial effects in terms of improving efficiency of gluconeogenesis. Given the complexity of the metabolic pathways involved in hepatic gluconeogenesis in periparturient ruminants, further research is warranted on the regulatory mechanisms involved and the effects of supplementation with various nutrients on milk yield and animal health.
Influence of Alkanolamine Plasmas on Poly(Ethylene Terephthalate) Fibro‐Porous Biomaterial Constructs
Authors: Tucker Bernabe S. , Hernandez‐Moreno Gerardo , Hwang Patrick T. J. , Jun Ho‐Wook , Thomas Vinoy 
Published: September 2024

AbstractThe development of fibrous polymer scaffolds is highly valuable for applications in tissue engineering. Furthermore, there is an extensive body of literature for chemical methods to produce scaffolds that release nitric oxide. However, these methods often use harsh chemistries and leave behind bulk waste. Alkanolamine low‐temperature plasma (LTP) is unexplored and single‐step processing to form nitric oxide (NO) releasing constructs is highly desirable. The major question addressed is whether it is possible to achieve single‐step processing of spun polyester with alkanolamine plasma to achieve nitric oxide releasing capabilities. Herein we report the experiments, processes, and data that support the claim that it is indeed possible to produce such a bio‐functional material for potential biomedical applications, especially in cardiovascular implants. Among the tested alkanolamines, monoethylamine (MEA) plasma treated biomaterial outperformed in comparison with diethanolamine (DEA) and triethanolamine (TEA) in terms of NO release and cellular response.
Vitamin B6 Appended Polypyridyl Co(III) Complexes for Photo‐Triggered Antibacterial Activity
Authors: Mandal Apurba , Rai Rohit , Mandal Arif Ali , Dhar Prodyut , Banerjee Samya 
Published: September 2024

AbstractThree novel polypyridyl‐Co(III)‐vitamin B6 complexes viz., [Co(CF3‐phtpy)(SBVB6)]Cl (Co1), [Co(anthracene‐tpy)(SBVB6)]Cl (Co2), [Co(NMe2‐phtpy)(SBVB6)]Cl (Co3), where 4’‐(4‐(trifluoromethyl)phenyl)‐2,2’:6’,2’’‐terpyridine=CF3‐phtpy, 4’‐(anthracen‐9‐yl)‐2,2’:6’,2’’‐terpyridine=anthracene‐tpy;, 4‐([2,2’:6’,2’’‐terpyridin]‐4’‐yl)‐N,N‐dimethylaniline=NMe2‐phtpy, (E)‐5‐(hydroxymethyl)‐4‐(((2‐hydroxyphenyl)imino)methyl)‐2‐methylpyridin‐3‐ol=H2SBVB6 were successfully developed for aPDT (antibacterial photodynamic therapy) applications. Co1–Co3 exhibited an intense absorption band at ca. 435–485 nm, which is attributed to ligand‐to‐metal charge transfer and was beneficial for antibacterial photodynamic therapy. The distorted octahedral geometry of the complexes with CoIIIN4O2 core was evident from the DFT study. The visible light absorption ability and good photo‐stability of Co1–Co3 made them good photosensitizers for aPDT. Co1–Co3 displayed significant antibacterial responses against gram‐positive (S. aureus) and gram‐negative (E. coli) bacteria upon light exposure (10 J cm−2, 400–700 nm) and showed MIC values between 0.01–0.005 μg mL−1. The aPDT activities of these complexes were due to their ability to damage bacterial cell membranes via ROS generation. Overall, this study shows the photo‐triggered ROS‐mediated bacteria‐killing potential of Co(III) complexes.
Role of B7‐H3 in predicting response to neoadjuvant chemotherapy in muscle‐invasive bladder cancer
Authors: Deol Ekamjit S. , Nabavizadeh Reza , Lavoie Roxane R. , Dumbrava Mihai G. , Horjeti Edlira , Thapa Prabin , Cheville John C. , Frank Igor , Lucien Fabrice 
Published: September 2024

AbstractBackgroundNeoadjuvant platinum‐based chemotherapy offers a modest survival advantage in muscle‐invasive bladder cancer (MIBC) for patients with pathologic response. B7‐H3 (CD276), an immune checkpoint overexpressed in various cancers, including urothelial‐cell carcinoma (UCC), has been associated with chemoresistance and poor oncologic outcomes. We aimed to explore if B7H3 expression on bladder biopsy samples was a predictive biomarker for pathologic response to neoadjuvant platinum‐based chemotherapy.MethodsThis was a retrospective cohort study among MIBC patients receiving neoadjuvant platinum‐based chemotherapy followed by radical cystectomy. All patients underwent routine preoperative biopsy of their tumour. Immunohistochemistry was used to evaluate B7‐H3 expression from pre‐operative specimens. The primary outcome of interest was pathologic complete response (pCR). Statistical analysis included Mann–Whitney U test, Fisher's exact test, Kaplan–Meier method, and Cox regression for survival analysis.ResultsAmong 87 patients analysed, high B7‐H3 expression was found in 44.8% (n = 39) of patients. The median follow‐up periods were similar between the high and low B7‐H3 groups (high expression; 4.29 years [SD 3.04], low expression 3.94 years [SD 3.04], p = 0.60). Only 20.5% of patients with high B7‐H3 expression achieved pCR, compared to 41.7% in the low expression group (p = 0.04). Cox regression showed no significant differences in recurrence‐free or cancer‐specific survival between the high and low B7‐H3 expression groups (p > 0.05).ConclusionHigh B7‐H3 expression is associated with a reduced likelihood of achieving pCR in MIBC patients undergoing neoadjuvant chemotherapy. This suggests B7‐H3's potential as a predictive biomarker for chemotherapy response. Further research is needed to explore the role of B7‐H3 on platinum‐based chemotherapy response in urothelial cancer.
From challenge to innovation: A grassroots study of teachers’ classroom assessment innovations
Authors: DeLuca Christopher , Holden Michael , Rickey Nathan 
Published: September 2024

AbstractWe are at a critical moment for assessment in schools. Teachers are called to navigate advances in classroom assessment research, top‐down assessment policies, and lingering effects of the COVID‐19 pandemic on teaching and learning. Embedded in this context are also systemic challenges to teachers’ assessment practice. This paper analyses these challenges to characterise the current context for teachers’ assessment work and considers teachers’ innovative responses to these challenges. Data are drawn from 168 qualitative responses to a baseline assessment innovation survey across 10 Canadian provinces and territories as well as 10 other international jurisdictions. Eight themes were identified related to teachers’ assessment challenges and innovations, including: negating innovation, the emotions of assessment, grade obsession and the gradeless spectrum, conflicting orientations towards assessment, the use of ‘assessment talk’, data overload, equitable assessment and actions that make learning and assessment visible. These findings directly support the widespread goal of implementing assessments that effectively and consistently serve student learning. The paper concludes with a discussion on how teachers move from facing assessment challenges to engaging in assessment innovations.