bluuebunny/crossref_metadata_2025_split huggingface dataset:
Controlling Electron Delocalization in Vanadium‐Based Hybrid Bronzes through Molecular Templation
Authors: Wan Suchen , Musielak Nicole , Oliver Allen G. , Jaffe Adam 
Published: November 2023

AbstractWe show that the conductivity of hybrid vanadium bronzes—mixed‐valence organic–inorganic vanadium oxides—can be tuned over six orders of magnitude through judicious choice of molecular component. By systematically varying the steric profile, charge density, and propensity to hydrogen bond across a series of eight diammonium‐based molecules, we engender multiple distinct motifs of V−O connectivity within the two‐dimensional vanadium oxide layers of a family of bulk crystalline hybrid materials. A combination of single‐crystal and powder X‐ray diffraction analysis, variable‐temperature electrical transport measurements, and a range of spectroscopic methods, including UV/Visible diffuse reflectance, X‐ray photoelectron, and electron paramagnetic resonance are employed to probe how vanadium oxide layer topology correlates with electron localization. Specifically, alkylammonium molecules yield hybrids featuring more corrugated layers that contain V−O tetrahedra as well as a higher ratio of corner‐sharing to edge‐sharing polyhedra and that exhibit highly localized electronic behavior, while alkyl bipyridinium molecules yield more regular layers with polyhedral edge‐sharing that show substantially delocalized electronic behavior. This work allows for the development of design principles based on structure–property relationships and brings the charge transport capabilities of hybrid vanadium bronzes to more technologically relevant levels.
Control of Intermediates and Products by Combining Droplet Reactions and Ion Soft‐Landing
Authors: Yang Fangshun , Urban Raphael D. , Lorenz Jonas , Griebel Jan , Koohbor Nima , Rohdenburg Markus , Knorke Harald , Fuhrmann Daniel , Charvat Ales , Abel Bernd , Azov Vladimir A. , Warneke Jonas 
Published: November 2023

AbstractDespite being recognized primarily as an analytical technique, mass spectrometry also has a large potential as a synthetic tool, enabling access to advanced synthetic routes by reactions in charged microdroplets or ionic thin layers. Such reactions are special and proceed primarily at surfaces of droplets and thin layers. Partial solvation of the reactants is usually considered to play an important role for reducing the activation barrier, but many mechanistic details still need to be clarified. In our study, we showcase the synergy between two sequentially applied “preparative mass spectrometry” methods: initiating accelerated reactions within microdroplets during electrospray ionization to generate gaseous ionic intermediates in high abundance, which are subsequently mass‐selected and soft‐landed to react with a provided reagent on a substrate. This allows the generation of products at a nanomolar scale, amenable to further characterization. In this proof‐of‐concept study, the contrasting reaction pathways between intrinsically neutral and pre‐charged reagents, respectively, both in microdroplets and in layers generated by ion soft‐landing are investigated. This provides new insights into the role of partially solvated reagents at microdroplet surfaces for increased reaction rates. Additionally, further insights into reactions of ions of the same polarity under various conditions is obtained.
21‐Carba‐23‐selenaporphyrinoid Dyads—An Azepine Unit as a Merging Motif
Authors: Berlicka Anna , Foryś‐Martowłos Paulina , Białek Michał J. , Stasiak Katarzyna , Walczak Aleksandra , Wójcik Agnieszka , Białońska Agata , Latos‐Grażyński Lechosław 
Published: November 2023

AbstractThe oxidation of 10,15‐diaryl‐21‐carba‐23‐selenaporphyrinoids resulted in the creation of dyads. The dimerization process follows a [5+2] cycloaddition path with the formation of an azepine unit. The arrays display two direct bonds between the peripheral carbocyclic carbon atoms of one carbaselenaporphyrinic subunit and the central carbon and nitrogen atoms of the second subunit. This results in a unique canted arrangement of two carbaporphyrinoid planes resembling an open seashell‐like motif.
A Chiral Emissive Conjugated Corral for High‐Affinity and Highly Enantioselective Recognition in Water
Authors: Fu Rong , Zhao Qing‐Yu , Han Han , Li Wen‐Li , Chen Fang‐Yuan , Tang Chun , Zhang Wei , Guo Si‐Dan , Li Dai‐Yuan , Geng Wen‐Chao , Guo Dong‐Sheng , Cai Kang 
Published: November 2023

AbstractAccurately distinguishing between enantiomeric molecules is a fundamental challenge in the field of chemistry. However, there is still significant room for improvement in both the enantiomeric selectivity (KR(S)/KS(R)) and binding strength of most reported macrocyclic chiral receptors to meet the demands of practical application scenarios. Herein, we synthesized a water‐soluble conjugated tubular host—namely, corral[4]BINOL—using a chiral 1,1′‐bi‐2‐naphthol (BINOL) derivative as the repeating unit. The conjugated chiral backbone endows corral[4]BINOL with good fluorescent emission (QY=34 % ) and circularly polarized luminescence (|glum| up to 1.4×10−3) in water. Notably, corral[4]BINOL exhibits high recognition affinity up to 8.6×1010 M−1 towards achiral guests in water, and manifested excellent enantioselectivity up to 18.7 towards chiral substrates, both of which represent the highest values observed among chiral macrocycles in aqueous solution. The ultrastrong binding strength, outstanding enantioselectivity, and facile accessibility, together with the superior fluorescent and chiroptical properties, endow corral[4]BINOL with great potential for a wide range of applications.
Exploration of entropy analysis and viscous dissipation on radially convective flow of (Cu‐Al2O3:H2O) hybrid nanofluid over a stretching disk
Authors: Venkateswarlu Bhumarapu , Narayana Panyam Venkata Satya , Joo Sang Woo 
Published: November 2023

AbstractThe current research work deals with the impact of suction/injection on the thermally radiating convective flow generated by a nonlinear stretched disk. The energy equation is addressed by the presence of thermal radiation and the energy dissipative function. This work was carried out with the help of the Das and Tiwari (single‐phase nanofluid) models and the Maxwell Garnett and Brinkman nanofluid models for the analysis of entropy generation. In the present model, nanoparticles of copper (Cu) and alumina (Al2O3) are being used with water (H2O) as the base fluid. The governing nonlinear partial differential equations are transformed into ordinary differential equations with the assistance of appropriate similarity variables. These transformed equations are then solved using the bvp4c function, a built‐in function in MATLAB software. The investigation examines the influence of various factors on the velocity and temperature fields, entropy generation, skin friction, and heat transfer rate. The findings show that suction decreases velocity and temperature by 6.59%, while injection has the opposite effect. Viscous dissipation increases velocity by 5.13% and temperature by 17.94% in hybrid nanofluids. Higher Prandtl numbers reduce velocity and temperature by 6% in nanofluids but boost them by 5.45% and 18.81% in hybrid nanofluids with radiation growth. As volume fraction rises, Al2O3/H2O nanofluid speed falls by 5.37%, but Cu‐Al2O3/H2O hybrid nanofluid temperature increases by 13.09% and surface drag force increases by 12%. The entropy of the hybrid nanofluid increases by 5.84%, 8.19%, and 14.04% with Eckert number, suction, and Prandtl number but decreases by 10.08% with temperature difference. The Nusselt number of nanofluid decreases by 10.58% and 12.40% with Eckert number and radiation, but hybrid particles increase it by 10.31% with intensified Prandtl number. These findings offer valuable insights for potential applications of hybrid nanofluids in heat transfer and cooling systems.
Investigation on the influence of sulfonic substitution in polyacrylamides for minimizing drag in turbulent flow of slickwater fluids
Authors: Korlepara Navneeth Kumar , Patel Nikhil , Dilley Christopher , Deysarkar Asoke Kumar , Kulkarni Sandeep D. 
Published: November 2023

AbstractThe use of slickwater fluids for fracking is key for accessing unconventional shale/tight‐sand reservoirs. To mitigate the frictional losses observed during the injection, drag reducers like sulfonated polyacrylamides (SPAMs) are added to the slickwater fluids. The current study presents a unique controlled investigation that examines the impact of sulfonic group substitution, ranging from 5 to 25 wt%, in SPAMs. The molecular weight of the polymers is kept constant at ~7.5–7.8 million Daltons. The investigation is two‐pronged: first part is comprised of drag reduction (%DR) performance of the polymers in fluids of varying salinities on a laboratory flow‐loop. The results obtained indicated the inter‐dependence of fluid salinity and sulfonic substitution on the polymer performance; for example, %DR deterioration of SPAM with 5 wt% substitution was 24.7%; to the contrary, the deterioration was only 15.6% for SPAM with 25 wt% substitution with rise in fluid salinity from 150 ppm to 110 k ppm. The second part of study included in development of a physics‐based model where the polymer relaxation response (Weissenberg number) was improvised to accommodate the impact of governing parameters and then, successfully correlated with the %DR performance using phenomenological equations for the studied range of parameters.
Tailored biodegradable films via extrusion blow molding using PBS, PBAT, and TPS
Authors: de Beluci Natália de Camargo Lima , dos Santos Juliana , de Carvalho Fabíola Azanha , Yamashita Fabio 
Published: November 2023

AbstractResearch to replace synthetic polymers with biodegradable polymers is on the rise because common plastics have generated serious ecosystem problems. Films with thermoplastic starch (TPS), poly(butylene succinate) (PBS), poly(butylene adipate‐co‐butylene terephthalate (PBAT), and citric acid (CA) were produced by blown extrusion. They were characterized by blow‐up ratio (BUR), water vapor permeability (WVP), soluble ratio (SR), water sorption isotherm, and thermogravimetric (TG) techniques. Films were uniform and showed BUR > 205%. The different proportions of PBS and PBAT significantly influenced the WVP of the films. All samples had WVP with an order of magnitude similar to other blends with high starch content (10−6 g m−1 day−1 Pa−1). CA efficiently decreased the WVP of the PBS/PBAT/TPS formulations (15/15/70% and 20/10/70% by mass) by 25.2% and 24.7% compared to the acid‐free formulations. There was no significant difference in SR (19.0%–20.1%). These materials were sensitive to moisture since the equilibrium moisture content increased pronouncedly from water activity of 0.5. Films showed good thermal stability, with a maximum decomposition temperature close to pure polyesters. CA did not increase the thermal stability of blends, probably because of the low content used (0.1%). Given the outcomes of this study, these films could be deemed appropriate for applications in food packaging.
A crosslinked waterborne poly(urethane‐urea) oligomer enables mechanically strong waterborne polyacrylate–poly(urethane‐urea) hybrid films with superior film‐forming ability
Authors: Fan Xiangqian , Zhai Xianming , Liu Lei , Zhang Jing , Li Lin , Wang Jiarong 
Published: November 2023

AbstractIn this article, a crosslinked waterborne poly(urethane‐urea) (WPUU) is synthesized based on the terminal aromatic amine polyether (DP‐1000) and aliphatic isophorone diisocyanate. Then WPUU is compound with acrylate monomer by emulsion polymerization to produce waterborne polyacrylate–poly(urethane‐urea) (WPUUA) hybrid emulsions. Compared with waterborne polyacrylate (WPA) film, the film‐forming ability of WPUUA film is improved and the surface roughness Ra and Rq of WPUUA film decreases from 47.5 and 36.4 nm to 35.2 and 18.8 nm, respectively. Meanwhile, the mechanical properties of WPUUA films are significantly improved compared to WPA film. In addition, the performances of WPUUA hybrid films can be modified according to requirements by adjusting the molar ratio between DP‐1000 and polyisocyanate. As a result, these WPUUA hybrid emulsions have great application potential in waterborne coatings and other fields.
CCD imagers for the Transiting Exoplanet Survey Satellite from benchtop to space environment
Authors: Suntharalingam Vyshnavi , Prigozhin Ilya , Warner Keith , Young Douglas , Woods Deborah , Berthiaume Gregory 
Published: November 2023

AbstractThe Transiting Exoplanet Survey Satellite (TESS) is a Massachusetts Institute of Technology‐led NASA Explorer‐class mission planned to spend 2 years discovering transiting exoplanets by an all‐sky survey. The observatory contains four wide field‐of‐view camera systems for a total of 16.8 Megapixel, low‐noise, low‐power CCD detectors. Now over 5 years beyond its launch date and 10 years after the CCD design tape out, we report on our approach for managing camera system development, with particular emphasis on the design, fabrication, and testing of the silicon detectors, developed on 200‐mm high‐resistivity wafer substrates. Finally, we present implications of the CCD manufacture observed in the on‐orbit performance.
Toleranzfreie Montage modularer Betontragwerke
Authors: Stindt Jan , Frey Alex Maximilian , Forman Patrick , Lanza Gisela , Mark Peter 
Published: November 2023

AbstractModulare Tragwerke erfordern maßhaltige Bauteile, da große prozess‐ oder materialbedingte Maßabweichungen bei einzelnen Modulen die Montage zur Gesamtstruktur verhindern. Im Beitrag wird dazu eine Methode zur optimalen Platzierung auf Basis von Metaheuristiken vorgestellt. Sie hilft kostenintensive Nacharbeitungen zu vermeiden. Das Konzept wird auf Wabenstrukturen angewendet, in denen die einzelnen Module durch Permutation getauscht werden. Mit dem sog. Tabu Search und dem Simulated Annealing werden methodisch zwei Lösungsverfahren verwendet. Dazu werden die maximalen Knotenabweichungen der assemblierten Module mit einer direkten Kinematik ermittelt und mit dem zulässigen Nennlochspiel von Schraubenverbindungen verglichen, um die Montierbarkeit der Module zu beurteilen. Berücksichtigt werden zum einen Toleranzen aus dem Schwinden des Betons und zum anderen solche aus den Produktionsschritten der Fertigung. Im Vergleich zu einer zufälligen Anordnung der Module gelingt die Reduzierung maximaler Knotenabweichungen von 9 mm auf das normierte Nennlochspiel von 3 mm mithilfe der Metaheuristiken. Wabenstrukturen mit einer Breite von ca. 7 m und einer Höhe bis 45 m, die besonders sensitiv hinsichtlich der Montierbarkeit sind, benötigen damit keine Nacharbeit mehr. Dabei erweist sich der Tabu Search mit sechsmal weniger Rechenzeit und bis zu 24 % geringeren zu kompensierenden Abweichungen als der deutlich effizientere Lösungsalgorithmus. Ein Beispiel zeigt die praktische Anwendung.
Further evaluation of a hands‐on‐shoulder plus praise procedure to reduce toe walking
Authors: Wilder David A. , Sheppard Christina , Izquierdo Franchesca , Flynn Kira 
Published: November 2023

AbstractIdiopathic toe walking (ITW) refers to ambulation with a toe‐to‐toe gait in the absence of a known cause. Although it is exhibited by typically developing children, it is more common among children with autism spectrum disorder (ASD). Persistent ITW can cause several long‐term medical problems, including ankle deformities and balance and posture abnormalities. In the current study, we first conducted a series of no interaction or alone conditions to verify that ITW exhibited by four children with ASD persisted in the absence of social consequences. We then evaluated a hands‐on‐shoulder plus praise procedure in which gentle pressure is applied to participants' shoulders to prompt their heels to contact the ground, along with praise for appropriate steps in order to reduce ITW. Results suggest that the procedure was effective with all participants, and measures of social validity indicate that caregivers approved of the procedure. We discuss the results in terms of the putative mechanisms responsible for the effects of the procedure as well as the conditions under which the procedure might be used.
SARC‐F as a screening tool to detect computed tomography‐based sarcopenia and myosteatosis among older adults with cancer
Authors: Hess Daniel L. , Harmon Christian , Bhatia Smita , Williams Grant R. , Giri Smith 
Published: November 2023

AbstractBackgroundThe European Working Group on Sarcopenia in Older People (EWGSOP) recommends SARC‐F as a tool for identifying sarcopenia among older adults. However, the role of SARC‐F among older adults with cancer remains unexplored. We aimed to evaluate the diagnostic utility of SARC‐F to identify those with sarcopenia, or low muscle mass (using skeletal muscle index [SMI]), and myosteatosis (using skeletal muscle density [SMD]) from computed tomography (CT) imaging and the association of SARC‐F with all‐cause mortality.MethodsOlder adults (≥60 years) presenting for initial consultation at UAB medical oncology clinic who underwent geriatric assessment were enrolled in a prospective cohort study. We identified study participants who completed SARC‐F screening and had available CT imaging within 60 days of study enrollment. Using single‐slice CT images at the L3 vertebral level, we computed SMI and SMD using published methods. Sarcopenia and myosteatosis were defined using published cutpoints. We calculated the sensitivity and specificity of SARC‐F for detecting low muscle mass and low muscle density using published thresholds. Finally, we computed the impact of SARC‐F and CT measures on overall survival using Kaplan–Meier curves and Cox regression models, after adjusting for age, sex, cancer type, and cancer stage.ResultsWe identified 212 older adults with a median age of 68.8 years; with 60.8% males, 76.6% whites, and pancreatic cancer (21.2%) being the most common malignancy. In the overall cohort, 30.7% had abnormal SARC‐F using published cutpoints. SARC‐F ≥ 4 had a sensitivity of 35% and a specificity of 76% to identify low muscle mass. SARC‐F ≥ 4 had a sensitivity of 38% and a specificity of 74% to identify low muscle density. Those with SARC‐F ≥ 4 and low SMI/SMD had worse survival compared to those with low SMI/SMD alone. Incorporating SARC‐F improved survival prognostication beyond SMI and SMD (HR = 3.1; p < 0.001; Harrel's C from 0.73 to 0.76).ConclusionsSARC‐F as a screening tool has limited diagnostic utility for identifying older adults with low muscle mass and/or density. However, SARC‐F retains prognostic value independent of CT‐based muscle measures in predicting mortality among older adults with cancer.
5‐Aza‐2′‐deoxycytidine‐mediated DNA hypomethylation with and without concurrent insulin resistance suppresses myotube mitochondrial capacity
Authors: Rivera Caroline N. , Kamer Madison M. , Cook Norah E. , McGovern Macey R. , Watne Rachel M. , Wommack Andrew J. , Vaughan Roger A. 
Published: November 2023

AbstractType 2 diabetes is characterized by elevated blood glucose and reduced insulin sensitivity in target tissues. Moreover, reduced mitochondrial metabolism and expressional profile of genes governing mitochondrial metabolism (such as peroxisome proliferator‐activated receptor gamma coactivator 1‐alpha [PGC‐1α]) are also reduced during insulin resistance. Epigenetic regulation via DNA methylation of genes including PGC‐1α may contribute to diminished mitochondrial capacity, while hypomethylation of PGC‐1α (such as that invoked by exercise) has been associated with increased PGC‐1α expression and favorable metabolic outcomes. The purpose of the present report is to characterize the effects of DNA hypomethylation on myotube metabolism and expression of several related metabolic targets. C2C12 myotubes were treated with 5‐Aza‐2′‐deoxycytidine (5‐Aza) for either 24 or 72 h both with and without hyperinsulinemic‐induced insulin resistance. Mitochondrial and glycolytic metabolism were measured via oxygen consumption and extracellular acidification rate, respectively. Metabolic gene and protein expression were assessed via quantitative real time polymerase chain reaction and western blot analysis, respectively. Though expression of PGC‐1α and other related targets remained unaltered, insulin resistance and 5‐Aza treatment significantly reduced mitochondrial metabolism. Similarly, peak glycolytic metabolism was diminished by 5‐Aza‐treated cells, while basal glycolytic metabolism was unaltered. 5‐Aza also reduced the expression of branched‐chain amino acid (BCAA) catabolic components, however BCAA utilization was enhanced during insulin resistance with 5‐Aza treatment. Together the present work provides proof‐of‐concept evidence of the potential role of DNA methylation in the regulation of mitochondrial metabolism and the potential interactions with insulin resistance in a model of skeletal muscle.
Bacterial Isothiocyanate Biosynthesis by Rhodanese‐Catalyzed Sulfur Transfer onto Isonitriles
Authors: Mlotek Mandy D. , Dose Benjamin , Hertweck Christian 
Published: November 2023

AbstractNatural products bearing isothiocyanate (ITC) groups are an important group of specialized metabolites that play various roles in health, nutrition, and ecology. Whereas ITC biosynthesis via glucosinolates in plants has been studied in detail, there is a gap in understanding the bacterial route to specialized metabolites with such reactive heterocumulene groups, as in the antifungal sinapigladioside from Burkholderia gladioli. Here we propose an alternative ITC pathway by enzymatic sulfur transfer onto isonitriles catalyzed by rhodanese‐like enzymes (thiosulfate:cyanide sulfurtransferases). Mining the B. gladioli genome revealed six candidate genes (rhdA–F), which were individually expressed in E. coli. By means of a synthetic probe, the gene products were evaluated for their ability to produce the key ITC intermediate in the sinapigladioside pathway. In vitro biotransformation assays identified RhdE, a prototype single‐domain rhodanese, as the most potent ITC synthase. Interestingly, while RhdE also efficiently transforms cyanide into thiocyanate, it shows high specificity for the natural pathway intermediate, indicating that the sinapigladioside pathway has recruited a ubiquitous detoxification enzyme for the formation of a bioactive specialized metabolite. These findings not only elucidate an elusive step in bacterial ITC biosynthesis but also reveal a new function of rhodanese‐like enzymes in specialized metabolism.