bluuebunny/crossref_metadata_2025_split huggingface dataset:
Probing Interfacial Electronic Effects on Single‐Molecule Adsorption Geometry and Electron Transport at Atomically Flat Surfaces
Authors: Yu Zhou , Xu Yu‐Xing , Su Jun‐Qing , Radjenovic Petar M. , Wang Ya‐Hao , Zheng Ju‐Fang , Teng Botao , Shao Yong , Zhou Xiao‐Shun , Li Jian‐Feng 
Published: April 2021

AbstractClarifying interfacial electronic effects on molecular adsorption is significant in many chemical and biochemical processes. Here, we used STM breaking junction and shell‐isolated nanoparticle‐enhanced Raman spectroscopy to probe electron transport and adsorption geometries of 4,4′‐bipyridine (4,4′‐BPY) at Au(111). Modifying the surface with 1‐butyl‐3‐methylimidazolium cation‐containing ionic liquids (ILs) decreases surface electron density and stabilizes a vertical orientation of pyridine through nitrogen atom σ‐bond interactions, resulting in uniform adsorption configurations for forming molecular junctions. Modulation from vertical, tilted, to flat, is achieved on adding water to ILs, leading to a new peak ascribed to CC stretching of adsorbed pyridyl ring and 316 % modulation of single‐molecule conductance. The dihedral angle between adsorbed pyridyl ring and surface decreases with increasing surface electronic density, enhancing electron donation from surface to pyridyl ring.
Sustainable Lithium‐Metal Battery Achieved by a Safe Electrolyte Based on Recyclable and Low‐Cost Molecular Sieve
Authors: Chang Zhi , Qiao Yu , Yang Huijun , Cao Xin , Zhu Xingyu , He Ping , Zhou Haoshen 
Published: April 2021

AbstractAs one typical clean‐energy technologies, lithium‐metal batteries, especially high‐energy‐density batteries which use concentrated electrolytes hold promising prospect for the development of a sustainable world. However, concentrated electrolytes with aggregative configurations were achieved at the expense of using extra dose of costly and environmental‐unfriendly salts/additives, which casts a shadow over the development of a sustainable world. Herein, without using any expensive salts/additives, we employed commercially‐available low‐cost and environmental‐friendly molecular sieves (zeolite) to sieve the solvation sheath of lithium ions of classic commercialized electrolyte (LiPF6‐EC/DMC), and resulting in a unique zeolite sieved electrolyte which was more aggregative than conventional concentrated electrolytes. Inspiringly, the new‐designed electrolyte exhibited largely enhanced anti‐oxidation stability under high‐voltage (4.6 volts) and elevated temperature (55 °C). NCM‐811//Li cells assembled with this electrolyte delivered ultra‐stable rechargeabilities (over 1000 cycles for half‐cell; 300 cycles for pouch‐cell). More importantly, sustainable NCM‐811//Li pouch‐cell with negligible capacity decay can also be obtained through using recyclable zeolite sieved electrolyte. This conceptually‐new way in preparing safe and highly‐efficient electrolyte by using low‐price molecular sieve would accelerate the development of high‐energy‐density lithium‐ion/lithium‐metal batteries.
Synthesis and characterization of PVC‐TFC hollow fibers for forward osmosis application
Authors: Al‐Musawy Wafaa Kh. , Al‐Furaiji Mustafa H. , Alsalhy Qusay F. 
Published: April 2021

AbstractForward osmosis (FO) is considered among the most encouraging water desalination processes as a result of its high performance and low energy demand. Thin‐film composite (TFC) hollow fibers (HF) were synthesized and examined in the FO process. Three different concentrations of polyvinyl chloride (PVC) support polymer were fabricated via the phase inversion technique. The polyamide layer was synthesized on the outer surface of the PVC‐HF substrate via interfacial polymerization (IP) reaction. To the best of our knowledge, PVC HF was used in this research for the first time as a support for TFC‐FO membranes. PVC HFs have high‐quality specifications that are expected to have outstanding performance in TFC‐FO applications, especially for water desalination. The obtained membranes were characterized using contact angle measurement, scanning electron microscopy, atomic force microscope and Fourier‐transform Infrared. The performance of the PVC‐TFC HF was examined in the FO under standard conditions. Results showed that the membrane fabricated with a lower concentration of PVC substrate exhibited higher water flux in comparison to the higher concentration PVC membrane. Changing the concentration of PVC from 15% to 18% reduced water flux from 25 to 13 L m−2 h−1; however, salt flux also decreased from 8 to 3 g m−2 h−1.
4D printed stereolithography printed plant‐based sustainable polymers: Preliminary investigation and optimization
Authors: Danish Mohd. , Vijay Anirudh P. , Karunakaran C. , Rajamohan Vasudevan , Mathew Arun Tom , Koziol Krzysztof , Thakur Vijay Kumar , Kannan C. , Balan A. S. S. 
Published: April 2021

AbstractThe increasing demand for applying shape memory polymer to tissue culture and biomedical engineering has opened up research opportunities in the field of 4D Printing. The biocompatibility of the scaffolds as a culture medium resulted in the use of plant‐based polymers to provide an ambient environment for the growth of cells. This research investigates the 4D printing of acrylated epoxidized soybean oil (AESO), a plant‐based shape polymer. The objective of the present work is to establish the relationship between the 4D printing parameters (laser power frequency and print speed) and different properties of the printed material viz. tensile stress, surface roughness, wettability, recovery time, strain fixity and glass transition temperature. The maximum fixity was about 85%, while the recovery time as low as 1.6 s. The print parameters are optimized using regression modeling and multi‐objective optimization techniques. The shape memory effect of the polymer is demonstrated by printing samples at the optimized conditions. Dynamic mechanical analysis is performed to evaluate the variation in the glass transition temperature of AESO at specific print parameters. The adoption of an optimal set of laser frequency and print speed is found to improve the properties of AESO, while built by micro stereolithography (micro‐SLA).
A Tetradentate Phosphonate Ligand‐based Ni‐MOF as a Support for Designing High‐performance Proton‐conducting Materials
Authors: Chakraborty Debabrata , Ghorai Arijit , Chowdhury Avik , Banerjee Susanta , Bhaumik Asim 
Published: April 2021

AbstractDeveloping a robust metal‐organic framework (MOF) which facilitates proton hopping along the pore channels is very demanding in the context of fabricating an efficient proton‐conducting membrane for fuel cells. Herein, we report the synthesis of a novel tetradentate aromatic phosphonate ligand H8L (L=tetraphenylethylene tetraphosphonic acid) based Ni‐MOF, whose crystal structure has been solved from single‐crystal X‐ray diffraction. Ni‐MOF [Ni2(H4L)(H2O)9(C2H7SO)(C2H7NCO)] displays a monoclinic crystal structure with a space group of P 21/c, a=11.887 Å, b=34.148 Å, c=11.131 Å, α=γ=90°, β=103.374°, where a nickel‐hexahydrate moiety located inside the void space of the framework through several H‐bonding interactions. Upon treatment of the Ni‐MOF in different pH media as well as solvents, the framework remained unaltered, suggesting the presence of strong H‐bonding interactions in the framework. High framework stability of Ni‐MOF bearing H‐bonding interactions motivated us to explore this metal‐organic framework material as proton‐conducting medium after external proton doping. Due to the presence of a large number of H‐bonding interactions and the presence of water molecules in the framework we have carried out the doping of organic p‐toluenesulfonic acid (PTSA) and inorganic sulphuric acid (SA) in this Ni‐MOF and observed high proton conductivity of 5.28×10−2 S cm−1 at 90 °C and 98% relative humidity for the SA‐doped material. Enhancement of proton conductivity by proton doping under humid conditions suggested a very promising feature of this Ni‐MOF.
LC–MS/MS method for determination of seneciphylline and its metabolite, seneciphylline N‐oxide in rat plasma, and its application to a rat pharmacokinetic study
Authors: Long Feng , Ji Jie , Wang Xin , Wang Lili , Chen Ting 
Published: April 2021

AbstractA rapid and sensitive ultra‐performance liquid chromatography‐tandem electrospray ionization mass spectrometry (UPLC‐ESI/MS) method was established and validated for simultaneous determination of seneciphylline and its main metabolite in rat plasma. The plasma sample was prepared by simple methanol‐mediated precipitation. Chromatographic separation was achieved within 3 min by gradient elution using acetonitrile and water containing 0.1% formic acid as mobile phase on a Waters ACQUITY BEH C18 column (100 × 2.1 mm, i.d. 1.7  μm). Quantitation was conducted in a positive multiple reaction monitoring mode. The linearity of the method was over the range of 1–1,000 ng/mL, with the lower limit of quantification of 1 ng/mL. The intra‐ and inter‐day precision and accuracy, extraction recovery, and matrix effect of analytes were within the acceptable limit. The analytes were stable during the process of sample collection, preparation, and analysis. The validated method was further applied to a pharmacokinetic study of seneciphylline in rats after oral and intravenous administration. The results revealed that seneciphylline was quickly absorbed into plasma (Tmax, 0.23–0.32 h) and reached the maximum concentration of 0.82–1.75 μg/mL after oral administration. Both seneciphylline and seneciphylline N‐oxide were eliminated from plasma quickly. The low system exposure (oral bioavailability, 5.43–10.31%) was related to the extensive metabolism in the liver and microflora.
Development of NanoBRET‐Binding Assays for FKBP‐Ligand Profiling in Living Cells
Authors: Gnatzy Monika T. , Geiger Thomas M. , Kuehn Angela , Gutfreund Niklas , Walz Michael , Kolos Jürgen M. , Hausch Felix 
Published: April 2021

AbstractFK506‐binding proteins (FKBPs) are promising targets for a variety of disorders and infectious diseases. High FKBP occupancy is thought to be necessary for ligands to effectively compete with the endogenous intracellular functions of FKBPs. Here, we report the development of NanoBRET assays for the most prominent cytosolic FKBPs, FKBP12, 12.6, 51 and 52. These assays allowed rapid profiling of FKBP ligands for target engagement and selectivity in living cells. These assays confirmed the selectivity of SAFit‐type ligands for FKBP51 over FKBP52 but revealed a substantial offset for the intracellular activity of these ligands compared to bicyclic ligands or natural products. Our results stress the importance to control for intracellular FKBP occupancy and provide the assays to guide further FKBP ligand optimization.
Incorporation of yellow pea flour into white pan bread
Authors: Paladugula Moorti Prabhakara , Smith Brennan , Morris Craig F. , Kiszonas Alecia 
Published: April 2021

AbstractBackground and objectivesWith growing trends in health‐conscious consumers, pea flour has been investigated for incorporation into baked products. The objective of this study was to understand the effect of pea flour incorporation (0, 1, 2, 5, 10, and 20%) milled with a Miag Multomat mill into white pan bread. Bread and sensory quality were assessed.FindingsBread loaf volume was reduced with higher levels of pea flour incorporation. Texture, specific volume, and height were not significantly different between treatments until ≥10% w/w pea flour addition. Bread crust color was not affected by pea flour incorporation. Bread crumb color was redder, more yellow and slightly darker with pea flour addition. Crumb gas cell structure was indicative of gas cell coalescence with larger cells and thicker cell walls. Bread quality was assessed with a consumer sensory panel comprised of 60 individuals. Consumers could perceive differences between the control and pea flour containing breads. However, there were no major differences in overall acceptability between pea flour containing treatments. Even with 20% pea flour addition, pea flour can be used in conjunction with wheat to make a sensorially acceptable bread.ConclusionsA high‐quality pea flour containing wheat bread can be made. At 20% pea flour incorporation, quality as defined by instrumental analyses decreases, while sensory analysis showed few differences between treatments.Significance and noveltyNutrient dense pea flour can be incorporated into wheat breads at a level of 20% with little effect on consumer acceptance.
Extraction of Chlorophylls and Carotenoids from Microalgae: COSMO‐SAC‐Assisted Solvent Screening
Authors: Valcareggi Morcelli Allan , da Silva Andrade Willian , Frankenberg Claudio Luis Crescente , Rech Rosane , Marcílio Nilson Romeu 
Published: April 2021

AbstractEfficient pigment extraction is a key factor influencing the economic feasibility of microalgal biorefineries. Ethanol, acetone, ethyl acetate, and hexane were evaluated for the batch extraction of chlorophyll a, chlorophyll b, and carotenoids from Chlorella sorokiniana and Heterochlorella luteoviridis. Solvent‐to‐biomass ratios did not affect extraction results in most cases. Ethanol showed the highest efficiency in the recovery of chlorophylls, presenting high extraction yields. Acetone was among the most efficient solvents to extract violaxanthin, lutein, zeaxanthin, and carotene from both microalgae, proving to be generally suitable to this application. Conductor‐like screening model for real solvent segment activity (COSMO‐SAC) corroborated experimental results, proving to be an important tool in the screening of solvents for extraction processes.
Interplay Between Charge Accumulation and Oxygen Reduction Catalysis in Nanostructured TiO2 Electrodes Functionalized with a Molecular Catalyst
Authors: Kim Yee‐Seul , Kriegel Sébastien , Bessmertnykh‐Lemeune Alla , Harris Kenneth D. , Limoges Benoît , Balland Véronique 
Published: April 2021

AbstractThe catalytic reduction of O2 by a manganese(III) porphyrin immobilized in a nanostructured semiconductive transparent TiO2 electrode is here investigated by UV‐Vis spectroelectrochemistry in an aqueous buffered medium. Analysis of the operando spectroelectrochemical data, collected for both the immobilized catalyst and the TiO2 matrix, demonstrates the coexistence of two faradaic electrochemical processes, namely (i) irreversible interfacial electron transfer from TiO2 to the immobilized porphyrin triggering the catalytic reduction of O2, and (ii) reversible proton‐coupled electrochemical reduction of TiO2 leading to the accumulation of electrons in the TiO2 bulk. The competition between these two processes is modulated by the local concentration of O2, which itself varies with the rate of the catalysis. Indeed, when O2 is locally strongly depleted by catalysis, the process switches from catalysis to charge storage, like a battery. As a result, the electrons stored in TiO2 were observed to pursue the catalysis even after the electrode polarization was switched‐off (i. e., under open circuit). This is an overlooked phenomenon that we believe is important to consider in applications relying on metal oxide‐based photoelectrodes operating in aqueous media.
Low‐Temperature H2 Reduction of Copper Oxide Subnanoparticles
Authors: Sonobe Kazutaka , Tanabe Makoto , Imaoka Takane , Chun Wang‐Jae , Yamamoto Kimihisa 
Published: April 2021

AbstractSubnanoparticles (SNPs) with sizes of approximately 1 nm are attractive for enhancing the catalytic performance of transition metals and their oxides. Such SNPs are of particular interest as redox‐active catalysts in selective oxidation reactions. However, the electronic states and oxophilicity of copper oxide SNPs are still a subject of debate in terms of their redox properties during oxidation reactions for hydrocarbons. In this work, in situ X‐ray absorption fine structure (XAFS) measurements of Cu28Ox SNPs, which were prepared by using a dendritic phenylazomethine template, during temperature‐programmed reduction (TPR) with H2 achieved lowering of the temperature (T50=138 °C) reported thus far for the CuII→CuI reduction reaction because of Cu−O bond elongation in the ultrasmall copper oxide particles.
A Rapid and Mild Sulfation Strategy Reveals Conformational Preferences in Therapeutically Relevant Sulfated Xylooligosaccharides
Authors: Vo Yen , Schwartz Brett D. , Onagi Hideki , Ward Jas S. , Gardiner Michael G. , Banwell Martin G. , Nelms Keats , Malins Lara R. 
Published: April 2021

AbstractAlthough sulfated xylooligosaccharides are promising therapeutic leads for a multitude of afflictions, the structural complexity and heterogeneity of commercially deployed forms (e. g. Pentosan polysulfate 1) complicates their path to further clinical development. We describe herein the synthesis of the largest homogeneous persulfated xylooligomers prepared to date, comprising up to eight xylose residues, as standards for biological studies. Near quantitative sulfation was accomplished using a remarkably mild and operationally simple protocol which avoids the need for high temperatures and a large excess of the sulfating reagent. Moreover, the sulfated xylooligomer standards so obtained enabled definitive identification of a pyridinium contaminant in a sample of a commercially prepared Pentosan drug and provided significant insights into the conformational preferences of the constituent persulfated monosaccharide residues. As the spatial distribution of sulfates is a key determinant of the binding of sulfated oligosaccharides to endogenous targets, these findings have broad implications for the advancement of Pentosan‐based treatments.
Comprehensive Characterization of the Self‐Folding Cavitand Dynamics
Authors: López‐Coll Ricard , Álvarez‐Yebra Rubén , Feixas Ferran , Lledó Agustí 
Published: April 2021

AbstractThe conformational equilibria and guest exchange process of a resorcin[4]arene derived self‐folding cavitand receptor have been characterized in detail by molecular dynamics simulations (MD) and 1H EXSY NMR experiments. A multi‐timescale strategy for exploring the fluxional behaviour of this system has been constructed, exploiting conventional MD and accelerated MD (aMD) techniques. The use of aMD allows the reconstruction of the folding/unfolding process of the receptor by sampling high‐energy barrier processes unattainable by conventional MD simulations. We obtained MD trajectories sampling events occurring at different timescales from ns to s: 1) rearrangement of the directional hydrogen bond seam stabilizing the receptor, 2) folding/unfolding of the structure transiting partially open intermediates, and 3) guest departure from different folding stages. Most remarkably, reweighing of the biased aMD simulations provided kinetic barriers that are in very good agreement with those determined experimentally by 1H NMR. These results constitute the first comprehensive characterization of the complex dynamic features of cavitand receptors. Our approach emerges as a valuable rational design tool for synthetic host‐guest systems
Rhodium‐Mediated Stoichiometric Synthesis of Mono‐, Bi‐, and Bis‐1,2‐Azaborinines: 1‐Rhoda‐3,2‐azaboroles as Reactive Precursors
Authors: Heß Merlin , Krummenacher Ivo , Dellermann Theresa , Braunschweig Holger 
Published: April 2021

AbstractA series of highly substituted 1,2‐azaborinines, including a phenylene‐bridged bis‐1,2‐azaborinine, was synthesized from the reaction of 1,2‐azaborete rhodium complexes with variously substituted alkynes. 1‐Rhoda‐3,2‐azaborole complexes, which are accessible by phosphine addition to the corresponding 1,2‐azaborete complexes, were also found to be suitable precursors for the synthesis of 1,2‐azaborinines and readily reacted with alkynyl‐substituted 1,2‐azaborinines to generate new regioisomers of bi‐1,2‐azaborinines, which feature directly connected aromatic rings. Their molecular structures, which can be viewed as boron‐nitrogen isosteres of biphenyls, show nearly perpendicular 1,2‐azaborinine rings. The new method using rhodacycles instead of 1,2‐azaborete complexes as precursors is shown to be more effective, allowing the synthesis of a wider range of 1,2‐azaborinines.
Trifaceted Mickey Mouse Amphiphiles for Programmable Self‐Assembly, DNA Complexation and Organ‐Selective Gene Delivery
Authors: Carbajo‐Gordillo Ana I. , González‐Cuesta Manuel , Jiménez Blanco José L. , Benito Juan M. , Santana‐Armas María L. , Carmona Thais , Di Giorgio Christophe , Przybylski Cédric , Ortiz Mellet Carmen , Tros de Ilarduya Conchita , Mendicuti Francisco , García Fernández José M. 
Published: April 2021

AbstractInstilling segregated cationic and lipophilic domains with an angular disposition in a trehalose‐based trifaceted macrocyclic scaffold allows engineering patchy molecular nanoparticles leveraging directional interactions that emulate those controlling self‐assembling processes in viral capsids. The resulting trilobular amphiphilic derivatives, featuring a Mickey Mouse architecture, can electrostatically interact with plasmid DNA (pDNA) and further engage in hydrophobic contacts to promote condensation into transfectious nanocomplexes. Notably, the topology and internal structure of the cyclooligosaccharide/pDNA co‐assemblies can be molded by fine‐tuning the valency and characteristics of the cationic and lipophilic patches, which strongly impacts the transfection efficacy in vitro and in vivo. Outstanding organ selectivities can then be programmed with no need of incorporating a biorecognizable motif in the formulation. The results provide a versatile strategy for the construction of fully synthetic and perfectly monodisperse nonviral gene delivery systems uniquely suited for optimization schemes by making cyclooligosaccharide patchiness the focus.
Optimizing Fe‐Based Metal‐Organic Frameworks through Ligand Conformation Regulation for Efficient Dye Adsorption and C2H2/CO2 Separation
Authors: Zhang Xiurong , Fan Weidong , Jiang Weifeng , Li Yue , Wang Yutong , Fu Mingyue , Sun Daofeng 
Published: April 2021

AbstractRegulating the structure of metal‐organic frameworks (MOFs) by adjusting the ligands reasonably is expected to enhance the interaction of MOFs on special molecules/ions, which has significant application value for the selective adsorption of guest molecules. Herein, two tricarboxylic ligands H3L−Cl and H3L−NH2 were designed and synthesized based on the ligand H3TTCA by replacing part of the benzene rings with C=C bonds and modifying the chlorine and amino groups on the 4‐position of the benzene ring. Two 3D Fe‐MOFs (UPC‐60‐Cl and UPC‐60‐NH2) with the new topology types were constructed. As the C=C bonds of the ligands have flexible torsion angles, UPC‐60‐Cl features three types of irregular 2D channels, while UPC‐60‐NH2 has a cage with two types of windows on the surface. The synergistic effect of unique channels and modification of functional groups endows UPC‐60‐Cl and UPC‐60‐NH2 with high adsorption capacity for organic dyes. Compound UPC‐60‐Cl shows high adsorption capacity for CV (147.2 mg g−1), RHB (100.3 mg g−1), and MO (220.9 mg g−1), whereas UPC‐60‐NH2 exhibits selective adsorption of MO (158.7 mg g−1). Meanwhile, based on the diverse pore structure and modification of active sites, UPC‐60‐Cl and UPC‐60‐NH2 show the selective separation of equimolar C2H2/CO2. Therefore, reasonable regulation of organic ligands plays a significant role in guiding the structure diversification and performance improvement of MOFs.