bluuebunny/crossref_metadata_2025_split huggingface dataset:
Intramolecular Ferromagnetism in Di‐Nuclear 3 d‐Transition‐Metal Single‐Molecule Magnets by Pseudo‐Serial Arrangement
Authors: Wakizaka Masanori , Sato Tetsu , Yoshino Yuko , Takaishi Shinya , Yamashita Masahiro 
Published: December 2022

AbstractDi‐nuclear citrate complexes, [CH6N3]2[M2(citH)2(H2O)4] ⋅ 2H2O (citH4=citric acid; M=FeII (Fe‐2), CoII (Co‐2), and NiII (Ni‐2)), are synthesized. The ligand, citH3−, is deprotonated only at the three carboxy groups, which is different from the previously reported tetra‐nuclear structures with cit4− ligands. Magnetic measurements reveal that these complexes have intramolecular ferromagnetism with J=∼0 cm−1 (Ni‐2), 0.02 cm−1 (Co‐2), and 0.04 cm−1 (Fe‐2). Co‐2 and Fe‐2 show slow magnetic relaxation, and are field‐induced SMMs with activation energy of spin‐reversal Ueff=27 cm−1 (Co‐2) and 4.2 cm−1 (Fe‐2). Density functional theory calculations indicate that the uniaxial anisotropy along the z‐axis of each metal ion center forms the pseudo‐serial arrangement, leading to intramolecular ferromagnetism via the magnetic dipole interaction. This work demonstrates the creation of ferromagnetic SMMs by the magnetic dipole engineering of 3d di‐nuclear metal ion centers.
Molecular Design and Crystal Chemistry of Polyfluorinated Naphthalene‐bis‐phenylhydrazimides with Superior Thermal and Polymorphic Stability and High Solution Processability
Authors: Abbinante Vincenzo Mirco , Zambra Marco , García‐Espejo Gonzalo , Pipitone Candida , Giannici Francesco , Milita Silvia , Guagliardi Antonietta , Masciocchi Norberto 
Published: December 2022

AbstractNaphthalene tetracarboxylic diimides (NDIs) are highly promising air‐stable n‐type molecular semiconductor candidates for flexible and cost‐effective organic solar cells and thermoelectrics. Nonetheless, thermal and polymorphic stabilities of environmentally stable NDIs in the low‐to‐medium temperature regime (<300 °C) remain challenging properties. Structural, thermal, spectroscopic, and computational features of polyfluorinated NDI‐based molecular solids (with up to 14 F atoms per NDI molecule) are discussed upon increasing the fluorination level. Slip‐stacked arrangement of the NDI cores with suitable π–π stacking and systematically short interplanar distances (<3.2 Å) are found. All these materials exhibit superior thermal stability (up to 260 °C or above) and thermal expansion coefficients indicating a response compatible with flexible polymeric substrates. Optical bandgaps increase from 2.78 to 2.93 eV with fluorination, while LUMO energy levels decrease down to −4.37 eV, as shown per DFT calculations. The compounds exhibit excellent solubility of 30 mg mL−1 in 1,4‐dioxane and DMF.
Direct Observation of Charge, Energy, and Hydrogen Transfer between the Backbone and Nucleobases in Isolated DNA Oligonucleotides
Authors: Liu Min , O'Reilly David , Schwob Lucas , Wang Xin , Zamudio‐Bayer Vicente , Lau J. Tobias , Bari Sadia , Schlathölter Thomas , Poully Jean‐Christophe 
Published: December 2022

AbstractUnderstanding how charge and energy, as well as protons and hydrogen atoms, are transferred in molecular systems as a result of an electronic excitation is fundamental for understanding the interaction between ionizing radiation and biological matter on the molecular level. To localize the excitation at the atomic scale, it was chosen to target phosphorus atoms in the backbone of gas‐phase oligonucleotide anions and cations, by means of resonant photoabsorption at the L‐ and K‐edges. The ionic photoproducts of the excitation process were studied by a combination of mass spectrometry and X‐ray spectroscopy. The combination of absorption site selectivity and photoproduct sensitivity allowed the identification of X‐ray spectral signatures of specific processes. Moreover, charge and/or energy as well as H transfer from the backbone to nucleobases has been directly observed. Although the probability of one versus two H transfer following valence ionization depends on the nucleobase, ionization of sugar or phosphate groups at the carbon K‐edge or the phosphorus L‐edge mainly leads to single H transfer to protonated adenine. Moreover, our results indicate a surprising proton‐transfer process to specifically form protonated guanine after excitation or ionization of P 2p electrons.
Alcohols as Efficient Intermolecular Initiators for a Highly Stereoselective Polyene Cyclisation Cascade
Authors: Aynetdinova Daniya , Jacques Reece , Christensen Kirsten E. , Donohoe Timothy J. 
Published: December 2022

AbstractThe use of benzylic and allylic alcohols in HFIP solvent together with Ti(OiPr)4 has been shown to trigger a highly stereoselective polyene cyclisation cascade. Three new carbon‐carbon bonds are made during the process and complete stereocontrol of up to five new stereogenic centers is observed. The reaction is efficient, has high functional group tolerance and is atom‐economic generating water as a stoichiometric by‐product. A new polyene substrate‐class is employed, and subsequent mechanistic studies indicate a stereoconvergent mechanism. The products of this reaction can be used to synthesize steroid‐analogues in a single step.
Non‐linear steady‐state data reconciliation: Theoretical perspective and practical scenarios
Authors: Soni Rahul K. , Dash Swagatika , Chinthapudi Eswaraiah 
Published: December 2022

AbstractData reconciliation (DR) is one of the primary error handling methods to reduce measurement errors in industries that may otherwise cause misleading information about the plant. In this article, the mathematical aspects of measurement errors and their treatment by DR are discussed in detail. The flaws in the existing DR methods have been identified and re‐investigated. More importantly, the feasibility and health check‐up of the DR problem have been discussed. The primary objective of the work is to develop a DR code based on the observations made in the present study, which involves DR solutions by both successive linearization (SL) and sequential quadratic programming (SQP) schemes. Benchmarking of the code with standard cases showed its wider suitability in solving DR problems. The algebraic SL method was found suitable for proper data health check‐ups and reliable solutions, whereas SQP was robust. The developed code was tested successfully for a chemical plant as well.
Flexible nanoscale co‐continuous structures prepared by controlled crazing of ethylene‐octene elastomers and in‐situ polymerization of conductive networks
Authors: Kornberg Anton B. , Thompson Michael R. , Zhu Shiping 
Published: December 2022

AbstractAn approach based on controlled crazing and post‐polymerization was used to incorporate a nanoscaled conductive co‐continuous network into commercial ENGAGE™ Polyolefin Elastomers (POEs). Three POE films of differing crystallinity and phase morphology were stretched in a reactive mixture of acrylic polymerization precursors that possessed an affinity for the olefinic materials and acted as a surface‐active agent for craze promotion. As a result, a rigid acrylic hydrogel phase was grown in the void space associated with crazing, which prevented the formed channels from collapsing after mechanical stresses were removed. The hydrogel phase offered ion conductivity properties to the POE. Simply replacing the acrylic monomer with an aniline emulsion for polymerization did not lead to the same outcome in terms of a continuous network; the materials became insulative after the removal of mechanical stresses due to fragmentation of the polyaniline channels from the unrestrained elastic relaxation of the POE. This problem was overcome by solution‐casting POE with polycaprolactone (PCL) into films and, subsequently, partially dissolving and leaching PCL from the blend while a sample was stretched in an aniline emulsion medium containing formic acid. The residual PCL left in the crazes reinforced the polyaniline to prevent fragmentation, allowing the formation of a highly electron‐conductive secondary phase.
Flotation response of coal washery reject fines: Characteristics, process optimization, and oxidation
Authors: Hazare Gayatri Deepaksingh , Pradhan Soumya Sucharita , Dash Nilima , Dwari Ranjan Kumar 
Published: December 2022

AbstractThe present paper outlines the characterization, electrokinetic behaviour, and flotation response of rejected coking coal fines with 32.5% ash generated in a coal washery in Eastern India. The response methodology and central composite rotatable design (RSM‐CCRD) were used for the process modelling and optimization of the flotation process using diesel, methyl isobutyl carbinol (MIBC), and sodium hexametaphosphate as a collector, frother, and depressant to maximize ash reduction, yield, and combustible recovery. At optimum condition, a 9.7% clean ash coal was achieved with a 63% yield at collector, frother, and depressant dosages of 0.78, 0.31, and 0.80 kg/ton, respectively. The model prediction and experimental data corroborated sufficiently. Subsequently, within 1 year, the fines oxidized and did not float with the collector. Fourier‐transform infrared spectroscopy (FTIR) confirmed surface oxidation on oxidized coal. The oxidized coal responded favourably to acid oil, a vegetable oil refinery waste. With acid oil as a collector, the oxidized coal can upgrade to 12% clean ash coal with a 60% yield; the combustible recovered is 80%. The work indicates successful upgradation of fresh and oxidized coal using the froth flotation process.
Ionic Radius Dependent Kinetic Behavior for the Self‐Assemblyand Chiral Amplification of Lanthanide Tetrahedral Cages
Authors: Hu Shao‐Jun , Guo Xiao‐Qing , Zhou Li‐Peng , Cai Li‐Xuan , Tian Chong‐Bin , Sun Qing‐Fu 
Published: December 2022

Comprehensive SummaryUnderstanding the kinetic process during the self‐assembly and chiral amplification of metal‐organic polyhedra (MOPs) is critical for the rational preparation of chiral MOPs. Herein, we report the ionic radius dependent kinetic processes for the self‐assembly and chiral amplification of Ln4L4‐type (Ln, Lanthanides; L, ligand) lanthanide tetrahedral cages. The chiral Eu4(LR)4 tetrahedral cage is structurally characterized by nuclear magnetic resonance (NMR), electrospray ionization time‐of‐flight mass spectrometry (ESI‐TOF‐MS), and single crystal X‐ray diffraction. Kinetic study on the stereo‐controlled self‐assembly of circularly polarized luminescence (CPL)‐active Ln4(LR)4 (Ln = LaIII, PrIII and EuIII) tetrahedra manifests that the larger ionic radius of Ln leads to faster assembly rates. Mixed‐ligand cage assembly experiments with chiral LR/S, achiral Lac and Ln (1 : 3 : 4 molar ratio) reveal that the self‐assembly and chiral amplification occur synchronously for the LaIII and PrIII cages, while two distinct steps, i.e., first self‐assembly and then chiral amplification, are observed for the EuIII cage. Such distinct kinetic behavior is attributed to different ligands exchange rates among the mixed‐ligand Ln4L4 cages. This work provides fundamental guidance for fabrication and property‐optimization of chiral lanthanide‐based molecular materials.
Anthrazoline Photocatalyst for Promoting Esterification and Etherification Reactions via Photoredox/Nickel Dual Catalysis
Authors: Zhu Xiaolin , Fan Qiujin , Luo Wei , Wang Danfeng , Jia Yihui , Li Heyang , Wang Zhen , Xiao Qi , He Xiaoming 
Published: December 2022

Comprehensive SummaryHere, we demonstrate a readily prepared anthrazoline photocatalyst, which can effectively promote C—O bond formation reactions with the aid of Ni(II) complex. This methodology enables the esterification (36 examples) and etherification (8 examples) with a broad range of scope, allowing aryl and alkyl halides coupled with diverse carboxylic acids/alcohols. Our metal‐free photocatalysts have a potential broad application, may serve as an alternative to some iridium and ruthenium based photocatalysts, and are of potential importance to the pharmaceutical industry.
Clinical Drug‐Drug Interaction Between Vatiquinone, a 15‐Lipoxygenase Inhibitor, and Rosuvastatin, a Breast Cancer Resistance Protein Substrate
Authors: Lee Lucy , Murase Katsuyuki , Ma Jiyuan , Thoolen Martin 
Published: December 2022

AbstractVatiquinone is a small‐molecule inhibitor of 15‐lipoxygenase in phase 3 development for patients with mitochondrial disease and Friedreich ataxia. The objective of this analysis was to determine the effect of vatiquinone on the pharmacokinetic profile of rosuvastatin, a breast cancer resistance protein substrate. In vitro investigations demonstrated potential inhibition of BCRP by vatiquinone (half maximal inhibitory concentration, 3.8 µM). An open‐label, fixed‐sequence drug‐drug interaction study in healthy volunteers was conducted to determine the clinical relevance of this finding. Subjects received a single dose of 20‐mg rosuvastatin followed by a 7‐day washout. On days 8 through 14, subjects received 400 mg of vatiquinone 3 times daily. On day 12, subjects concomitantly received a single dose of 20‐mg rosuvastatin. The geometric mean ratio for maximum plasma concentration was 77.8%; however, the rosuvastatin disposition phase appeared unaffected. The geometric mean ratios for the area under the plasma concentration–time curve from time 0 to time t and from time 0 to infinity were 103.2% and 99.9%, respectively. Mean rosuvastatin apparent elimination half‐life was similar between treatment groups. These results demonstrate that vatiquinone has no clinically relevant effect on the pharmacokinetics of rosuvastatin.
Glycolytic Wave Patterns in a Simple Reaction‐diffusion System with Inhomogeneous Influx: Dynamic Transitions
Authors: Kumar Premashis , Gangopadhyay Gautam 
Published: December 2022

AbstractAn inhomogeneous profile of chemostatted species generates a rich variety of patterns in glycolytic waves depicted in a Selkov reaction‐diffusion framework here. A key role played by diffusion amplitude and symmetry in the chemostatted species profile in dictating the fate of local spatial dynamics involving periodic, quasiperiodic, and chaotic patterns and transitions among them are investigated systematically. More importantly, various dynamic transitions, including wave propagation direction changes, are illustrated in interesting situations. Besides numerical results, our analytical formulation of the amplitude equation connecting complex Ginzburg‐Landau and Lambda‐omega representation shed light on the phase dynamics of the system. This systematic study of the glycolytic reaction‐diffusion wave is in line with previous experimental results in open spatial reactor and will provide a knowledge about the dynamics that shape and control biological information processing and related phenomena.
Does Urea Preferentially Interact with Amide Moieties or Nonpolar Sidechains? A Question Answered Through a Judicious Selection of Model Systems
Authors: Ajayi Simisola , Asakereh Iman , Rezasoltani Hanieh , Davidson David , Khajehpour Mazdak 
Published: December 2022

AbstractThe transfer model suggests that urea unfolds proteins mainly by increasing the solubility of the amide backbone, probably through urea‐induced increase in hydrogen bonding. Other studies suggest that urea addition increases the magnitude of solvent‐solute van der Waals interactions, which increases the solubility of nonpolar sidechains. More recent analyses hypothesize that urea has a similar effect in increasing the solubility of backbone and sidechain groups. In this work, we compare the effects of urea addition on the solvation of amides and alkyl groups. At first, we study the effects of urea addition upon solvent hydrogen bonding acidity and basicity through the perturbation in the fluorescence spectrum of probes 1‐AN and 1‐DMAN. Our results demonstrate that the solvent's hydrogen bonding properties are minimally affected by urea addition. Subsequently, we show that urea addition does not perturb the intra‐molecular hydrogen bonding in salicylic acid significantly. Finally, we investigate how urea preferentially interacts with amide and alkyl groups moieties in water by comparing the effects of urea addition upon the solubility of acetaminophen and 4‐tertbutylphenol. We show that urea affects amide and t‐butyl solubility (lowers the transfer free energy of both amide (backbone) and alkyl (sidechain) groups) in a similar fashion. In other words, preferential interaction of urea with both moieties contributes to protein denaturation.
Managing interspecies competition to improve spring pasture maturity, nutritive value, and biomass
Authors: Mercier Kelly M. , Billman Eric D. , Soder Kathy J. , Jaramillo David M. , Goslee Sarah C. , Adler Paul R. 
Published: December 2022

AbstractIn much of the United States, wet springs often cause poor field conditions leading to harvest and/or grazing delays and subsequent reductions in forage nutritive value. The objective of this study was to compare monocultures and combinations of orchardgrass (Dactylis glomerata L.), chicory (Cichorium intybus L.), and white clover (Trifolium repens L.) to determine the effects of interspecies competition on plant maturity, nutritive value, and forage mass over two consecutive springs. It was hypothesized that shade and competition from chicory would delay orchardgrass maturity resulting in greater nutritive value and an extended harvest or grazing window for high‐nutritive value forage. Mixtures containing chicory delayed orchardgrass maturity by at least 9 days in the first spring as compared to orchardgrass monocultures and orchardgrass‐white clover mixtures. Even with decreased chicory mass in the second year (due to drought and winterkill), both 1:1:1 and 4:1:1 (ratio of seeds per hectare) orchardgrass–white clover–chicory mixtures provided greater forage mass and nutritive value (crude protein and net energy) yield over 2 years compared to an orchardgrass monoculture; however, only the 1:1:1 orchardgrass–white clover–chicory mixture provided greater benefits to forage mass and nutritive value yield when compared to orchardgrass–white clover mixtures that are commonly found on farms. This study showed that chicory inclusion provides benefits to orchardgrass and orchardgrass–white clover pastures when planted in appropriate seed proportions; however, increasing chicory longevity will require further investigation to provide continued benefits in perennial cool‐season grass and legume pasture systems.
Covalent Grafting of a Nickel Thiolate Catalyst onto Covalent Organic Frameworks for Increased Photocatalytic Activity
Authors: Wang Jixian , Li Lei , Jiang Shan , Young David J. , Ren Zhi‐Gang , Li Hong‐Xi 
Published: December 2022

AbstractCovalent organic frameworks (COFs) have recently emerged as prospective photoactive materials with noble Pt as a cocatalyst for photocatalytic hydrogen evolution. In this work, a series of SH‐group‐functionalized covalent organic frameworks, TpPa‐1‐SH‐X, is prepared by reaction of p‐phenylenediamine (Pa) and 1,3,5‐triformylphloroglucinol (Tp) with p‐NH2C6H4SH as a modulating agent. The reaction of TpPa‐1‐SH‐X with NiII acetylacetonate Ni(acac)2 gave nickel thiolate‐immobilized TpPa‐1 (TpPa‐1‐SNi‐X). The highest hydrogen evolution rate was 10.87 mmol h−1 g−1, which was an enhancement of 16.47, 3.83, and 1.84 times than that of the parent TpPa‐1, covalent‐bond‐free [(p‐NH2C6H4S)2Ni]n/TpPa‐1‐SH‐10, and 3 wt % Pt‐deposited TpPa‐1, respectively. This enhanced photocatalytic hydrogen evolution is ascribed to enhanced crystallinity, the use of NiII thiolate as a cocatalyst and covalent bonding between the cocatalyst and TpPa‐1.
Sling‐shot spider optimization algorithm based packet length control in wireless sensor network and Internet of Things‐based networks
Authors: R Adhi Lakshmi , S Pavalarajan 
Published: December 2022

SummaryWireless sensor network (WSN) is a well‐developed domain suitable in the optimal collection and processing of information needed for the present world. For processing and transmitting the correct data by the network, it is affected by many disrupting factors like interference, battery life, distance between the nodes, and redundant data. There have been many methods proposed in the past. Among all the disrupting factors, routing has been the most studied problem in the WSN literature, whereas packet length sizing has been the most untouched topic compared to routing. Sizing the packet lengths to transmit it through the network is important to get error‐free data and run an energy‐efficient network. In this paper, we propose a sling‐shot spider optimization (S2SO) algorithm for packet length optimization in WSN and Internet of Things (IoT)‐based networks. The S2SO algorithm is developed based on the spider's unique behavior of catching prey. The proposed algorithm is implemented in three types of networks: 1‐hop, 2‐hop, and multi‐hop networks. A mathematical model for the communication channel, energy efficiency, and energy consumption is developed for all three types of networks. The proposed packet length optimization model is simulated in MATLAB software and compared with conventional bio‐inspired algorithms. The results show that the proposed algorithm is very fast in finding the optimal results and transmits optimal packet size with low error rate of 0.2 p.u. and a high efficiency of 98%.
Factors influencing the participation of Black and White Americans in Alzheimer's disease biomarker research
Authors: Eliacin Johanne , Hathaway Elizabeth , Wang Sophia , O'Connor Caitlin , Saykin Andrew J. , Cameron Kenzie A. 
Published: December 2022

AbstractIntroductionAlzheimer's disease (AD) is a public health priority. AD biomarkers may vary based on race, but the recruitment of diverse participants has been challenging.MethodsThree groups of Black and White participants with and without prior research advocacy or participation were interviewed individually or in focus groups to better understand perspectives related to AD biomarker research participation. A rapid qualitative data analytic approach was used to analyze the data.ResultsIdentified barriers to AD biomarker research participation included hesitancy due to fear, distrust of research and researchers, lack of relevant knowledge, and lack of research test results disclosure. Drivers for engagement in biomarker research procedures included knowledge about research, AD, and related clinical procedures, perceived benefits of participation, and outreach from trusted sources.DiscussionParticipants’ comments related to the need for diversity in research and desire for results disclosure suggest opportunities to engage Black individuals.Highlights
Black Americans experience more salient barriers to Alzheimer's disease (AD) biomarker research participation.
Concerns about research diversity influence research participation decisions.
Research test disclosure may affect research participation and retention.
Urolithin A suppresses tumor progression and induces autophagy in gastric cancer via the PI3K/Akt/mTOR pathway
Authors: Zhang Yingjing , Jiang Lin , Su Pengfei , Yu Tian , Ma Zhiqiang , Liu Yuqin , Yu Jianchun 
Published: December 2022

AbstractUrolithin A (UA) is a microbial metabolite of natural polyphenols ellagitannins and ellagic acid with well‐established antitumor properties against various malignancies. However, the exact role of UA in gastric cancer (GC) progression remains largely unclear. In the present study, we investigated the effects and potential mechanisms of UA in GC in vitro and in vivo. Our results revealed that UA could suppress GC cell proliferation, inhibit migration and invasion, promote apoptosis, and induce autophagy via the phosphatidylinositol‐3‐kinase/protein kinase B/mammalian target of rapamycin pathway in vitro. The autophagy inhibitors 3‐methyladenine and chloroquine augmented the inhibitory effect of UA on proliferation and promoted apoptosis, implying that UA mediated the cytoprotective role of autophagy. Meanwhile, the in vivo experiments showed that UA effectively suppressed tumor growth, enhanced the therapeutic effects, and alleviated chemotherapy toxicity in xenograft models. Overall, these findings offer novel insights into the role of UA in tumor therapy and suggest that UA may possess potential therapeutic applications for GC.