bluuebunny/crossref_metadata_2025_split huggingface dataset:
Quasi‐Blackbody, Bidirectional Super Reflection, and New Total Reflection Produced by Periodic Optical Waveguide Networks Based on Three‐Order PT‐Symmetric Substructures
Authors: Wang Qing , Yang Xiangbo , Deng Dongmei , Liu Hongzhan , Wei Zhongchao 
Published: September 2022

AbstractIn this paper, six kinds of periodic optical waveguide networks are designed to study the influence of three‐order parity–time‐symmetric (PT‐symmetric) substructures on the singular optical characteristics. It is found that different characteristics correspond to different PT‐symmetric substructures, and new singular optical characteristics are produced by adjusting the PT‐symmetric substructures. This work demonstrates that these six kinds of systems can create novel quasi‐blackbody, super reflection, and new total reflection, which are significantly different from the corresponding traditional properties and have not been reported yet. These findings may deepen the understanding of PT‐symmetric optical systems and optical waveguide networks, and these new characteristics may possess potential applications in the design of multifunctional optical structures with efficient information processing.
Bestimmung der spezifischen Aktivität von M−N−Cs und die intrinsische Aktivität von tetrapyrrolischen FeN4‐Zentren in der Sauerstoffreduktionsreaktion
Authors: Menga Davide , Guilherme Buzanich Ana , Wagner Friedrich , Fellinger Tim‐Patrick 
Published: September 2022

AbstractM−N−C Elektrokatalysatoren gelten als wahrscheinlichster Ersatz für teure edelmetallbasierte Materialien in elektrokatalytischen Umwandlungen. Ihre Entwicklung wird jedoch mangels Methoden zur Bestimmung der intrinsischen Aktivität unterschiedlicher Aktivzentren, wie z. B. pyrrolischer FeN4‐Zentren in Fe−N−Cs, behindert. Mit neuen Syntheseverfahren, die auf der Prägung von Koordinationszentren mittels Templatreaktion und einer anschließenden Ionenaustauschreaktion Zn‐zu‐Fe basieren, werden seit kurzem isotrope M−N−Cs mit nur einem Aktivzentrum und hervorragender Aktivität hergestellt. Basierend auf diesem Austauschprinzips haben wir hier schonend und in unterschiedlichem Maß Eisen aus den N4‐Bindungsstellen in Fe−N−Cs extrahiert. Katalysatoren mit derselben Morphologie und denselben FeN4‐Zentren, die sich lediglich im Fe‐Gehalt unterscheiden, ermöglichen nun die einfache Bestimmung der Abnahme der Dichte der aktiven Zentren und ihrer spezifischen Wechselzahl. Auf diese Weise erhält man einen Einblick in die spezifische Aktivität von M−N−Cs und bei Single‐Site‐Katalysatoren wird die intrinsische Aktivität des aktiven Zentrums zugänglich. Der neue Ansatz umgeht die Beschränkungen von Methoden, die sich auf Sondenmoleküle stützen, und bietet zusammen mit diesen Techniken ein neues Instrument zur Entfaltung der Komplexität von Fe−N−C‐Katalysatoren und M−N−Cs im Allgemeinen.
Luciferase‐free Luciferin Electrochemiluminescence
Authors: Belotti Mattia , El‐Tahawy Mohsen M. T. , Yu Li‐Juan , Russell Isabella C. , Darwish Nadim , Coote Michelle L. , Garavelli Marco , Ciampi Simone 
Published: September 2022

AbstractLuciferin is one of Nature's most widespread luminophores, and enzymes that catalyze luciferin luminescence are the basis of successful commercial “glow” assays for gene expression and metabolic ATP formation. Herein we report an electrochemical method to promote firefly's luciferin luminescence in the absence of its natural biocatalyst—luciferase. We have gained experimental and computational insights on the mechanism of the enzyme‐free luciferin electrochemiluminescence, demonstrated its spectral tuning from green to red by means of electrolyte engineering, proven that the colour change does not require, as still debated, a keto/enol isomerization of the light emitter, and gained evidence of the electrostatic‐assisted stabilization of the charge‐transfer excited state by double layer electric fields. Luciferin's electrochemiluminescence, as well as the in situ generation of fluorescent oxyluciferin, are applied towards an optical measurement of diffusion coefficients.
Structural Engineering toward Gold Nanocluster Catalysis
Authors: Guan Zong‐Jie , Li Jiao‐Jiao , Hu Feng , Wang Quan‐Ming 
Published: September 2022

AbstractAtomically precise gold nanoclusters provide great opportunities to explore the relationship between the structure and properties of nanogold catalysts. A nanocluster consists of a metal core and a surface ligand shell, and both the core and shell have significant effects on the catalytic properties. Thanks to their precise structures, the active metal site of the clusters can be readily identified and the effects of ligands on catalysis can be disclosed. In this Minireview, we summarize recent advances in catalytic research of gold nanoclusters, emphasizing four strategies for constructing open metal sites, including by post‐treatment, the bulky ligands strategy, the surface geometric mismatch method, and heteroatom doping procedures. We also discuss the effects of ligands on the catalytic activity, selectivity, and stability of gold cluster catalysts. Finally, we present future challenges relating to gold cluster catalysis.
The Role of Heme Peroxo Oxidants in the Rational Mechanistic Modeling of Nitric Oxide Synthase: Characterization of Key Intermediates and Elucidation of the Mechanism
Authors: Mondal Pritam , Ishigami Izumi , Yeh Syun‐Ru , Wijeratne Gayan B. 
Published: September 2022

AbstractMammalian nitric oxide synthase (NOS) mediates the two‐step O2‐dependent oxidative degradation of arginine, and has been linked to a medley of disease situations in humans. Nonetheless, its exact mechanism of action still remains unclear. This work presents the first NOS model system where biologically proposed heme superoxo and peroxo intermediates are assessed as active oxidants against oxime substrates. Markedly, heme peroxo intermediates engaged in a bioinspired oxime oxidation reaction pathway, converting oximes to ketones and nitroxyl anions (NO−). Detailed thermodynamic, kinetic, and mechanistic interrogations all evince a rate‐limiting step primarily driven by the nucleophilicity of the heme peroxo moiety. Coherent with other findings, 18O and 15N isotope substitution experiments herein suffice compelling evidence toward a detailed mechanism, which draw close parallels to one of the enzymatic proposals. Intriguingly, recent enzymatic studies also lend credence to these findings, and several relevant reaction intermediates have been observed during NOS turnover.
Evaluation of the Specific Activity of M−N−Cs and the Intrinsic Activity of Tetrapyrrolic FeN4 Sites for the Oxygen Reduction Reaction
Authors: Menga Davide , Guilherme Buzanich Ana , Wagner Friedrich , Fellinger Tim‐Patrick 
Published: September 2022

AbstractM−N−C electrocatalysts are considered pivotal to replace expensive precious group metal‐based materials in electrocatalytic conversions. However, their development is hampered by the limited availability of methods for the evaluation of the intrinsic activity of different active sites, like pyrrolic FeN4 sites within Fe−N−Cs. Currently, new synthetic procedures based on active‐site imprinting followed by an ion exchange reaction, e.g. Zn‐to‐Fe, are producing single‐site M−N−Cs with outstanding activity. Based on the same replacement principle, we employed a conservative iron extraction to partially remove the Fe ions from the N4 cavities in Fe−N−Cs. Having catalysts with the same morphological properties and Fe ligation that differ solely in Fe content allows for the facile determination of the decrease in density of active sites and their turn‐over frequency. In this way, insight into the specific activity of M−N−Cs is obtained and for single‐site catalysts the intrinsic activity of the site is accessible. This new approach surpasses limitations of methods that rely on probe molecules and, together with those techniques, offers a novel tool to unfold the complexity of Fe−N−C catalyst and M−N−Cs in general.
Catalyst‐ and Base‐free One‐pot, Multicomponent, De Novo Assembly of Structurally Diverse Morpholine Glycoconjugates
Authors: Khanam Ariza , Lal Mohan , Mandal Pintu Kumar 
Published: September 2022

AbstractA catalyst‐, metal‐ and base‐free unprecedented one‐pot multicomponent synthetic strategy has been established for the construction of various substituted morpholine glycoconjugates through four‐component reactions of glycosyl amino alcohol, chloroacetone, acid, and isocyanides. Unexpectedly, this one‐pot approach generates only the cyclized morpholine scaffolds rather than normal Ugi adduct without any external base. This reaction proceeds via in situ formations of Schiff‐base followed by an intramolecular halogen displacement process, finally the Joullie‐Ugi reaction takes place leading to the corresponding products with a mixture of diastereomers.
Aqueous Solutions of a Porous Host–Poly‐L‐lysine Complex with Information on Solids as Different Fluorescence by Guests
Authors: Takahashi Katsuya , Umezane Sota , Ono Toshikazu , Fukutomi Satoshi , Ihara Megumi , Hisaeda Yoshio , Kawasaki Riku , Ikeda Atsushi 
Published: September 2022

AbstractN,N’‐Dipyrid‐3‐yl‐1,4,5,8‐naphthalenediimide linked to two tris(pentafluorophenyl)borane (1) exhibits strong fluorescence emission in the solid state by the formation of a charge‐transfer complex containing small aromatic guest molecules. Hydrophobic 1 was dissolved in water by mixing with poly‐L‐lysine (PLL) as a solubilizing agent. The 1‐PLL complex could include small aromatic guest molecules in water, significantly increasing the fluorescence. The fluorescence maxima of 1 in aqueous solution and solid state were different depending on the guest molecule. Therefore, compound 1 was prepared as aqueous solution with information of fluorescence on solids by complexation with PLL.
Spiro‐OMeTAD as Redox Mediator and Singlet Oxygen Scavenger in Lithium‐Oxygen Batteries
Authors: Possetto David I. , Torres Walter R. , Rueda Héctor , Fungo Fernando , Tesio Alvaro Y. 
Published: September 2022

AbstractLithium‐oxygen batteries (LOBs) are considered one of the new alternatives to lithium‐ion batteries mainly due to its high energy density. Several strategies are pursued in order to avoid parasitic reactions that fade the battery capacity. In this work, it was carried out a photochemical and electrochemical characterization of Spiro‐OMeTAD working as a redox mediator (RM) in the LOBs. By using the Time Resolved Phosphorescence Detection (TRPD) technique together with Rose Bengal, we demonstrate that RM can deactivate the singlet oxygen produced in the cell, decreasing its performance. A concentration of 5 mM Spiro‐OMeTAD in the electrolyte avoids solubility problems, maximizes its catalytic effects during the charge, and is still enough to act as a singlet oxygen scavenger. Finally, lithium nitrate was added to the electrolyte to passivate the metallic lithium anode with the aim to prevent the RM decomposition and the increase of LOBs performance.
A well‐characterized polycistronic‐like gene expression system in yeast
Authors: Mukherjee Minakshi , Wang Zhen Q. 
Published: September 2022

AbstractEfficient expression of multiple genes is critical to yeast metabolic engineering for the bioproduction of bulk and fine chemicals. A yeast polycistronic expression system is of particular interest because one promoter can drive the expression of multiple genes. 2A viral peptides enable the cotranslation of multiple proteins from a single mRNA by ribosomal skipping. However, the wide adaptation of 2A viral peptides for polycistronic‐like gene expression in yeast awaits in‐depth characterizations. Additionally, a one‐step assembly of such a polycistronic‐like system is highly desirable. To this end, we have developed a modular cloning (MoClo) compatible 2A peptide‐based polycistronic‐like system capable of expressing multiple genes from a single promoter in yeast. Characterizing the bi‐, tri‐, and quad‐cistronic expression of fluorescent proteins showed high cleavage efficiencies of three 2A peptides: E2A from equine rhinitis B virus, P2A from porcine teschovirus‐1, and O2A from Operophtera brumata cypovirus‐18. Applying the polycistronic‐like system to produce geraniol, a valuable industrial compound, resulted in comparable or higher titers than using conventional monocistronic constructs. In summary, this highly‐characterized polycistronic‐like gene expression system is another tool to facilitate multigene expression for metabolic engineering in yeast.
Exploring the association of interleukin polymorphisms with aggression and internalizing behaviors in children and adolescents
Authors: Pouget Jennie G. , Bryushkova Lyubov , Koyama Emiko , Zai Clement C. , Fonseka Trehani M. , Mueller Daniel , Kennedy James L. , Beitchman Joseph H. 
Published: September 2022

AbstractBackgroundThere is growing evidence that inflammation influences mental health. Blood interleukin levels, which regulate inflammation, have been linked to aggression and internalizing behaviors. We performed a hypothesis‐driven genetic study to (1) evaluate the association of IL1B, IL2, and IL6 gene variants with aggression and internalizing behaviors and (2) explore gene–environment interactions with childhood adversity in a deeply phenotyped childhood‐onset aggression sample including 255 cases and 226 controls of European ancestry.MethodsWe evaluated the association of putative functional and tag SNPs within IL1B, IL2, and IL6 with aggression case status, parent‐reported internalizing problems, self‐reported anxiety symptoms, and self‐reported depressive symptoms in our sample. We also performed exploratory GxE analyses within cases, testing for statistical interaction between interleukin SNP genotype and childhood adversity for depressive symptoms.ResultsNo significant association was observed between any of the interleukin SNPs and childhood‐onset aggression. We observed association of IL6 variant rs2069827 with depressive symptoms (p = 7.15×10–4), and trends for an interaction between severe childhood adversity and SNPs in IL1B and IL2 for depressive symptoms.ConclusionsOur findings provide preliminary evidence that common variation in IL6 may be associated with depressive symptoms in children and adolescents, and that common variation in interleukin genes may sensitize individuals to the depressogenic effects of traumatic life experiences. Replication in independent samples is needed.
Learning technical courses in architectural education through gamification
Authors: Shareef Sardar S. , Rauf Hozan L. 
Published: September 2022

AbstractThis study aims to identify a method to motivate students to participate in technical courses and apply the knowledge they attain in their design projects. This study proposed gamification using Kahoot for a construction course (one of the technical courses). A quantitative method is applied in the research, and a second‐year, first‐semester class is the case study. Kahoot, a free online platform, was used as a supportive tool to make the course more game‐like and fun. After each class, questions and quizzes were delivered to the students through Kahoot, and they played by answering them. The results show that students enjoyed and engaged in the course and were sufficiently motivated to apply the knowledge they acquired in their design projects. They also suggested gamification for their other courses. This study used a quantitative method for evaluating the experiences of 21 students in one course in one semester. Given the small sample size, the results of this study may not be generalizable to a broader population. For further research, studies may need both a longer timeframe and the application of more techniques and tools of gamification.
The phospholipid flippase ATP8B1 is required for lysosomal fusion in macrophages
Authors: Gómez‐Mellado Valentina E. , Ho‐Mok Kam S. , van der Mark Vincent A. , van der Wel Nicole N. , Grootemaat Anita E. , Verhoeven Arthur J. , Elferink Ronald P. J. Oude , Paulusma Coen C. 
Published: September 2022

AbstractATP8B1 is a phospholipid flippase and member of the type 4 subfamily of P‐type ATPases (P4‐ATPase) subfamily. P4‐ATPases catalyze the translocation of phospholipids across biological membranes, ensuring proper membrane asymmetry, which is crucial for membrane protein targeting and activity, vesicle biogenesis, and barrier function. Here we have investigated the role of ATP8B1 in the endolysosomal pathway in macrophages. Depletion of ATP8B1 led to delayed degradation of content in the phagocytic pathway and in overacidification of the endolysosomal system. Furthermore, ATP8B1 knockdown cells exhibited large multivesicular bodies filled with intraluminal vesicles. Similar phenotypes were observed in CRISPR‐generated ATP8B1 knockout cells. Importantly, induction of autophagy led to accumulation of autophagosomes in ATP8B1 knockdown cells. Collectively, our results support a novel role for ATP8B1 in lysosomal fusion in macrophages, a process crucial in the terminal phase of endolysosomal degradation.
Extraplaque versus intraplaque tracking in chronic total occlusion percutaneous coronary intervention
Authors: Megaly Michael , Buda Kevin , Karacsonyi Judit , Kostantinis Spyridon , Simsek Bahadir , Basir Mir B. , Mashayekhi Kambis , Rinfret Stephane , McEntegart Margaret , Yamane Masahisa , Azzalini Lorenzo , Alaswad Khaldoon , Brilakis Emmanouil S. 
Published: September 2022

AbstractObjectiveTo compare the clinical outcomes after extraplaque (EP) versus intraplaque (IP) tracking in chronic total occlusion (CTO) percutaneous coronary intervention (PCI).BackgroundThe impact of modern dissection and reentry (DR) techniques on the long‐term outcomes of CTO PCI remains controversial.MethodsWe performed a systematic review and meta‐analysis of studies that compared EP versus IP tracking in CTO PCI. Odds ratios (ORs) with 95% confidence intervals (CIs) are calculated using the Der‐Simonian and Laird random‐effects method.ResultsOur meta‐analysis included seven observational studies with 2982 patients. Patients who underwent EP tracking had significantly more complex CTOs with higher J‐CTO score, longer lesion length, and more severe calcification and had significantly longer stented segments. During a median follow‐up of 12 months (range 9–12 months), EP tracking was associated with a higher risk of major adverse cardiovascular events (MACE) (OR 1.50, 95% CI (1.10–2.06), p = 0.01) and target vessel revascularization (TVR) (OR 1.69, 95% CI (1.15–2.48), p = 0.01) compared with IP tracking. There was no difference in the incidence of all‐cause death (OR 1.37, 95% CI (0.67–2.78), p = 0.39), myocardial infarction (MI) (OR 1.48, 95% CI (0.82–2.69), p = 0.20), stent thrombosis (OR 2.09, 95% CI (0.69–6.33), p = 0.19), or cardiac death (OR 1.10, 95% CI (0.39–3.15), p = 0.85) between IP and EP tracking.ConclusionEP tracking is utilized in more complex CTOs and requires more stents. EP tracking is associated with a higher risk of MACE, driven by a higher risk of TVR at 1 year, but without an increased risk of death or MI compared with IP tracking. EP tracking is critically important for contemporary CTO PCI.
Trends in invasive treatment of patients hospitalized with aortic stenosis complicated by cardiogenic shock
Authors: Elkaryoni Ahmed , Cohen David J. , Lopez John J. , Huded Chetan P. , Kennedy Kevin F. , Arnold Suzanne V. 
Published: September 2022

AbstractBackgroundBefore the development of transcatheter aortic valve replacement (TAVR), balloon aortic valvuloplasty (BAV) was the only potential nonsurgical intervention for patients with aortic stenosis complicated by cardiogenic shock. Emergent TAVR is now an option and has shown acceptable outcomes compared with elective TAVR. We explored how treatment patterns for aortic stenosis and cardiogenic shock among patients received invasive intervention have shifted since TAVR was introduced.MethodsWe used the Nationwide In patients Sample to identify nonelective hospitalizations for patient with aortic stenosis complicated by cardiogenic shock who received invasive treatment (TAVR, BAV, or surgical aortic valve replacement [SAVR]). We explored the proportion treated with each treatment modality over time, the patient characteristics and in‐hospital mortality associated with each treatment, and used multivariable logistic regression to examine whether changes in in‐hospital mortality over time differed by treatment.ResultsBetween 2010 and 2019, we identified 9899 hospitalizations for decompensated aortic stenosis with cardiogenic shock during which patients received invasive treatment (TAVR 17.7%, BAV 20.2%, SAVR 62.1%). Use of both TAVR and BAV has increased over time compared with SAVR (TAVR 6.6% ≥ 33.8%, BAV 8.4% ≥ 23.2%, SAVR 91.6% ≥ 43.0%; p < 0.001 for trend). The overall in‐hospital mortality rate was 21.0%, which decreased over time for all treatments (TAVR 20.0% ≥ 18.8%, BAV 66.0% ≥ 25.5%, SAVR 17.7% ≥ 11.8%; linear trend p < 0.001 for each), with lower mortality for TAVR versus BAV at all time points. Patients treated with TAVR (vs. BAV) were less likely to require mechanical ventilation (36.8% vs. 46.3%, p < 0.001) or mechanical circulatory support (22.5% vs. 29.9%, p < 0.001). In the multivariable analysis, the interaction between treatment and time was not significant (p = 0.245), indicating the reduction in in‐hospital mortality over time did not differ among the treatments.ConclusionsSince the introduction of TAVR, there has been a shift toward increased use of nonsurgical invasive treatments (both BAV and TAVR) for aortic stenosis and cardiogenic shock. Although in‐hospital mortality has declined, it remains high in all groups, but particularly among patients treated with BAV, where the severity of cardiogenic shock appears to be higher than in those treated with other modalities.
Sustainable Aviation Fuel from Syngas through Higher Alcohols
Authors: Mäki‐Arvela Päivi , Aho Atte , Simakova Irina , Yu. Murzin Dmitry 
Published: September 2022

AbstractThe current review critically summarizes recent developments in transformations of syngas to higher alcohols. Although higher alcohols have found applications as fuel additives, detergents and plastics for a long while, transformation of alcohols to jet fuel has attained recent interest due to an urgent need to develop jet fuels from sustainable sources. Fermentation of lignocellulosic‐based sugars to ethanol as a technology does not compete with the food chain supply being thus a potentially acceptable route if economically viable. An alternative method is to gasify biomass to produce syngas, which can further be transformed to higher alcohols through several pathways. Jet fuel range alkanes are obtained from alcohols via oligomerisation, dehydration and hydrogenation. The highest space time yields of higher alcohols of 0.61 g/(gcath) is obtained over a bimetallic copper‐iron catalyst supported on a hierarchical zeolite at 300 °C and 5 MPa. Furthermore, copper‐cobalt and cobalt‐manganese compositions are promising for the direct synthesis of higher alcohols from syngas, where one of the challenges is to suppress formation of alkanes and CO2 and increase selectivity to higher alcohols. From the mechanistic point of view, it has been proposed to use dual‐site catalysts, where one site promotes hydrogenation, while the other site is required for the chain growth. In addition to selection of the optimum reaction conditions and catalyst properties, kinetic modelling, thermodynamics and scale up issues are discussed.