bluuebunny/crossref_metadata_2025_split huggingface dataset:
Robust Hydroxyapatite Coating by Laser‐Induced Hydrothermal Synthesis
Authors: Um Seung‐Hoon , Chung Yong‐Woo , Seo Youngmin , Seo Hyunseon , Ok Myoung‐Ryul , Kim Yu‐Chan , Han Hyung‐Seop , Chung Justin J. , Edwards James R. , Jeon Hojeong 
Published: September 2020

AbstractOwing to enhanced biocompatibility and osseointegration, hydroxyapatite (HAp) coatings are often applied to biomedical devices that are implanted directly on the bone. Although various HAp coating techniques have been developed, they are restricted due to the time‐consuming HAp synthesis and additional coating processes. Herein, the development of a rapid single‐step method for simultaneous synthesis and coating of HAp via nanosecond laser surface treatment is described. In the conventional HAp‐coating method, the resulting interface between the HAp layer and the base material is clearly distinguished. However, in this method, HAp synthesis and coating occur simultaneously via the melting of the base material (i.e., titanium, polyetheretherketone, and polycaprolactone) to form a gradient HAp‐base material composite coating layer. The resultant coating layer on a titanium surface exhibits a binding force of 31.7–47.2 N, which is sufficient for medical implant applications. Changing the laser irradiation conditions provides quantitative adjustment of the HAp formation process and coating layer thickness. Furthermore, the resulting HAp coating layer better facilitates the attachment of bone cells. These results offer a breakthrough in the surface treatment of bone‐bonding sites of metal and polymer biomedical devices.
Rational Design of Multifunctional Integrated Host Configuration with Lithiophilicity‐Sulfiphilicity toward High‐Performance Li–S Full Batteries
Authors: Wei Yunhong , Wang Boya , Zhang Yin , Zhang Mi , Wang Qian , Zhang Yun , Wu Hao 
Published: September 2020

AbstractHigh‐energy‐density Li–S batteries are considered one of the next‐generation energy storage systems, but the uncontrolled Li‐dendrite growth in Li metal anodes and the shuttling of polysulfides in S cathode severely impede the commercial development of Li–S batteries. Herein, a conductive composite architecture that is made up of bio‐derived N‐doped porous carbon fiber bundles (N‐PCFs) with co‐imbedded cobalt and niobium carbide nanoparticles is employed as a multifunctional integrated host for simultaneously addressing the challenges in both Li anodes and S cathodes. The implantation of Co and NbC nanoparticles bestows the N‐PCFs matrix with synergistically enhanced degree of graphitization, electrical conductivity, hierarchical porosity, and surface polarization. Theoretical calculations and experimental results show that NbC with specific lithiophilic and sulfiphilic features can synchronously regulate the Li and S electrochemistry by realizing homogeneous lithium deposition with suppressed Li‐dendrite growth and exerting catalytic effects for promoting the polysulfide conversion together with fast Li2S nucleation. Hence, the assembled Li–S full batteries exhibit a superb rate capability (704 mAh g−1 at 5 C) and cycling life (≈82.3% capacity retention after 500 cycles) at a sulfur loading over 3.0 mg cm−2, as well as high reversible areal capacity (>6.0 mAh cm−2) even at a higher sulfur loading of 6.7 mg cm−2.
Enhanced Electrocaloric Response of Vinylidene Fluoride–Based Polymers via One‐Step Molecular Engineering
Authors: Le Goupil Florian , Kallitsis Konstantinos , Tencé‐Girault Sylvie , Pouriamanesh Naser , Brochon Cyril , Cloutet Eric , Soulestin Thibaut , Domingue Dos Santos Fabrice , Stingelin Natalie , Hadziioannou Georges 
Published: September 2020

AbstractElectrocaloric refrigeration is one of the most promising environmentally‐friendly technologies to replace current cooling platforms—if a notable electrocaloric effect (ECE) is realized around room temperature where the highest need is. Here, a straight‐forward, one‐pot chemical modification of P(VDF‐ter‐TrFE‐ter‐CTFE) is reported through the controlled introduction of small fractions of double bonds within the backbone that, very uniquely, decreases the lamellar crystalline thickness while, simultaneously, enlarging the crystalline coherence along the a‐b plane. This increases the polarizability and polarization without affecting the degree of crystallinity or amending the crystal unit cell—undesirable effects observed with other approaches. Specifically, the permittivity increases by >35%, from 52 to 71 at 1 kHz, and ECE improves by >60% at moderate electric fields. At 40 °C, an adiabatic temperature change >2 K is realized at 60 MV m−1 (>5.5 K at 192 MV m−1), compared to ≈1.3 K for pristine P(VDF‐ter‐TrFE‐ter‐CTFE), highlighting the promise of a simple, versatile approach that allows direct film deposition without requiring any post‐treatment such as mechanical stretching or high‐temperature annealing for achieving the desired performance.
Emergent Interfacial Ferromagnetism and Exchange Bias Effect in Paramagnetic/Ferromagnetic Oxide Heterostructures
Authors: Bhatt Harsh , Kumar Yogesh , Prajapat Champa Lal , Kinane Christy J. , Caruana Andrew , Langridge Sean , Basu Saibal , Singh Surendra 
Published: September 2020

AbstractThe experimental evidence of the exchange bias (EB) effect in epitaxial heterostructures of ferromagnetic La0.67Sr0.33MnO3 (LSMO) and paramagnetic LaNiO3 (LNO) grown on MgO(001) substrates is reported. The macroscopic magnetization measurements show a clear indication of EB in LNO/LSMO and LSMO/LNO/LSMO heterostructures. The strength of the exchange coupling rapidly reduces as the temperature is increased and almost vanishes above 50 K. Using spin dependent polarized neutron reflectometry (PNR) detailed depth dependent magnetization profiles of the heterostructures are investigated to understand the role of interface magnetism in the observed EB. PNR results establish the emergence of the interfacial ferromagnetic LNO layer of thickness ≈22–35 Å (≈6–9 unit cell) and magnetization ≈80 emu cc−1 at the LNO/LSMO interface for T < 100 K. The PNR results also show both ferromagnetic and anti‐ferromagnetic coupling between the LSMO and interfacial LNO layers, which may be dependent on the stacking order. The emergence of ferromagnetism in the interfacial paramagnetic LNO layer with unexpected EB in these heterostructures suggests a promising platform toward the effective realization of magnetic devices.
Palladium‐Catalyzed Regioselective Domino Spirocyclization of Carbamoyl Chlorides with Alkynes and Benzynes
Authors: Wang Chenchen , Zhao Wenyu , Wu Xianqing , Qu Jingping , Chen Yifeng 
Published: September 2020

AbstractA palladium‐catalyzed domino spiro‐cyclization of carbamoyl chlorides with alkynes and benzynes, involving intramolecular C−H activation to afford valuable oxindole scaffolds bearing spiro quaternary stereocenters, has been developed. This one‐step synthesis of spirooxindole is both step‐ and atom‐economic, proceeding with high regioselectivity in moderate to excellent yields.magnified image
Equilibrium analysis of CH4, CO, CO2, H2O, H2, C mixtures in C–H–O atom space using Gibbs free energy global minimization
Authors: Chaconas Demetrios , Pichardo Patricia , Manousiouthakis Ioannis V. , Manousiouthakis Vasilios I. 
Published: September 2020

AbstractGibbs free energy minimization is employed to carry out thermodynamic equilibrium analysis studies of mixtures containing methane, carbon monoxide, carbon dioxide, water, and hydrogen ideal gases, and possibly solid carbon. The employed global minimization approach represents a general, unifying, conceptual framework that allows reaction and phase equilibrium analysis to be simultaneously carried out in the atom‐mol fraction space (aH, aO), thus capturing in a comprehensive manner the equilibrium behavior of a number of industrially important processes, such as methane reforming (steam, dry, energetically enhanced), and methanation. Two theorems are presented, establishing necessary and sufficient (necessary) feasibility and regularity (optimality) conditions for the aforementioned minimization problem. The equilibrium results obtained through application of these theorems are guaranteed to be globally optimal. They quantify in (aH, aO) space, the feasible region, the carbon formation region, and all species mole over total atom‐mol normalized ratios, for a range of temperatures and pressures.
Inducible DNA Polymerase Chain Reaction Triggered by Oxidative Species
Authors: Wang Sheng , Zhao Jizhong , Wang Li , Zhang Jingwen , Hu Hongmei , Yu Ping , Wang Rui 
Published: September 2020

AbstractWe report here a chemically synthetic method to introduce a PinB‐modified thymidine into well‐defined DNA first. The modification was designed to disturb the T−A base‐pairing, thus regulate the DNA activity for PCR amplification. By treatment with small molecules, i. e., reactive oxygen species, the DNA polymerase activity was successfully restored. Due to tight temporal regulation and cell‐membrane permeability, our approach could lead to application potential in live cell.
An image analysis protocol for the quantification of interglobular dentine in anthropological tooth sections
Authors: Snoddy Anne Marie E. , Miszkiewicz Justyna J. , Loch Carolina , Tromp Monica , Buckley Hallie R. 
Published: September 2020

AbstractThe histological identification of interglobular dentine (IGD) in archeological human remains with macroscopic evidence of rickets has opened a promising new avenue for the investigation of metabolic disease in the past. Recent paleopathological studies have shown that histological analysis of archeological human teeth may allow the identification of periods of vitamin D deficiency occurring within very narrow developmental  windows, yielding new information on the seasonality or even maternal‐fetal transmission of this disease. However, currently available techniques for recording IGD rely on subjective scoring systems or visual estimations, potentially leaving them open to inter and intra‐observer error and rendering comparisons of datasets difficult. Here we describe a new imaging protocol that utilizes open access software and may yield more objective and quantitative data on the amount of IGD present within a dentinal region of interest. We demonstrate that grayscale histograms in FIJI®/ImageJ® might be used to provide less subjective estimates of the percentage of a region of interest affected by IGD. Application of this technique may enable more accurate comparison of datasets between researchers.
Azithromycin in high‐risk, refractory chronic rhinosinusitus after endoscopic sinus surgery and corticosteroid irrigations: a double‐blind, randomized, placebo‐controlled trial
Authors: Maniakas Anastasios , Asmar Marc‐Henri , Renteria Axel Eluid , Nayan Smriti , Alromaih Saud , Endam Leandra Mfuna , Sampalis John Sam , Desrosiers Martin 
Published: September 2020

BackgroundRefractory chronic rhinosinusitis (CRS) remains a significant burden for patients, often leaving them with few therapeutic options that provide low‐morbidity, long‐term, and meaningful symptomatologic and endoscopic disease improvement. Macrolides have long been thought to offer both an immunomodulatory and antimicrobial effect. Our objective was to evaluate the efficacy of low‐dose, long‐term azithromycin in a carefully selected high‐risk population failing appropriate medical therapy of budesonide nasal irrigations (BNIs) and endoscopic sinus surgery (ESS).MethodsA double‐blind, randomized, placebo‐controlled trial was completed in a single tertiary‐care center assessing the addition of 250 mg azithromycin, 3 times per week for 16 weeks, in adults failing ESS and high‐volume BNIs. Associated comorbidities, as well as symptomatologic, microbiologic, and serologic values, were systematically collected.ResultsA total of 128 patients were enrolled and underwent ESS followed by BNI. At the 4‐month post‐ESS visit, 48 patients showed disease persistence and were randomized to azithromycin or placebo. Overall, azithromycin, when compared with placebo, did not show a statistically significant difference in disease clearance (54% vs 33%, respectively; p = 0.146), although patients with disease clearance who were on azithromycin showed significantly better 22‐item Sino‐Nasal Outcome Test score improvements than patients on placebo (18 vs −0.9, respectively; p = 0.046). In a subgroup analysis excluding aspirin‐exacerbated respiratory disease (AERD) patients, azithromycin significantly improved disease clearance when compared with placebo (71% vs 35%, respectively; p = 0.031), with a number needed to treat of 3 (2.8).ConclusionLow‐dose azithromycin is a therapeutic option with few side effects. Its use can show favorable clinical outcomes in this difficult‐to‐treat population, especially if patients are AERD‐negative.
Quantitative Protein Corona Composition and Dynamics on Carbon Nanotubes in Biological Environments
Authors: Pinals Rebecca L. , Yang Darwin , Rosenberg Daniel J. , Chaudhary Tanya , Crothers Andrew R. , Iavarone Anthony T. , Hammel Michal , Landry Markita P. 
Published: September 2020

AbstractWhen nanoparticles enter biological environments, proteins adsorb to form the “protein corona” which alters nanoparticle biodistribution and toxicity. Herein, we measure protein corona formation on DNA‐functionalized single‐walled carbon nanotubes (ssDNA‐SWCNTs), a nanoparticle used widely for sensing and delivery, in blood plasma and cerebrospinal fluid. We characterize corona composition by mass spectrometry, revealing high‐abundance corona proteins involved in lipid binding, complement activation, and coagulation. We investigate roles of electrostatic and entropic interactions driving selective corona formation. Lastly, we study real‐time protein binding on ssDNA‐SWCNTs, obtaining agreement between enriched proteins binding strongly and depleted proteins binding marginally, while highlighting cooperative adsorption mechanisms. Knowledge of protein corona composition, formation mechanisms, and dynamics informs nanoparticle translation from in vitro design to in vivo application.
A Versatile Method for Kinetic Resolution of Protecting‐Group‐Free BINAMs and NOBINs through Chiral Phosphoric Acid Catalyzed Triazane Formation
Authors: Liu Wei , Jiang Qianwen , Yang Xiaoyu 
Published: September 2020

AbstractA versatile kinetic resolution of protecting‐group‐free BINAMs and NOBINs has been realized through chiral phosphoric acid catalyzed triazane formation with azodicarboxylates. A series of mono‐N‐protected and unprotected BINAMs, diphenyl diamines and NOBIN derivatives could be kinetically resolved with excellent performances (with s factor up to 420). The gram‐scale reactions and facile derivatizations of the chiral products demonstrate the potential of these methods in the asymmetric synthesis of chiral catalysts and ligands.
Co‐Assembly between Fmoc Diphenylalanine and Diphenylalanine within a 3D Fibrous Viscous Network Confers Atypical Curvature and Branching
Authors: Chakraborty Priyadarshi , Tang Yiming , Guterman Tom , Arnon Zohar A. , Yao Yifei , Wei Guanghong , Gazit Ehud 
Published: September 2020

AbstractSupramolecular polymer co‐assembly is a useful approach to modulate peptide nanostructures. However, the co‐assembly scenario where one of the peptide building blocks simultaneously forms a hydrogel is yet to be studied. Herein, we investigate the co‐assembly formation of diphenylalanine (FF), and Fmoc‐diphenylalanine (FmocFF) within the 3D network of FmocFF hydrogel. The overlapping peptide sequence between the two building blocks leads to their co‐assembly within the gel state modulating the nature of the FF crystals. We observe the formation of branched microcrystalline aggregates with an atypical curvature, in contrast to the FF assemblies obtained from aqueous solution. Optical microscopy reveal the sigmoidal kinetic growth profile of these aggregates. Microfluidics and ToF‐SIMS experiments exhibit the presence of co‐assembled structures of FF and FmocFF in the crystalline aggregates. Molecular dynamics simulation was used to decipher the mechanism of co‐assembly formation.
Fluorescent Self‐Threaded Peptide Probes for Biological Imaging
Authors: Zhai Canjia , Schreiber Cynthia L. , Padilla‐Coley Sasha , Oliver Allen G. , Smith Bradley D. 
Published: September 2020

AbstractA general synthetic method creates a new class of covalently connected, self‐threaded, fluorescent molecular probes with figure‐eight topology, an encapsulated deep‐red fluorophore, and two peripheral peptide loops. The globular molecular shape and rigidified peptide loops enhance imaging performance by promoting water solubility, eliminating probe self‐aggregation, and increasing probe stability. Moreover, the peptide loops determine the affinity and selectivity for targets within complex biological samples such as cell culture, tissue histology slices, or living subjects. For example, a probe with cell‐penetrating peptide loops targets the surface of cell plasma membranes, whereas, a probe with bone‐targeting peptide loops selectively stains the skeleton within a living mouse. The unique combination of bright deep‐red fluorescence, high stability, and predictable peptide‐based targeting is ideal for photon intense fluorescence microscopy and biological imaging.
Concise Total Synthesis of Tronocarpine
Authors: Nakayama Atsushi , Nakamura Tenta , Zaima Toshihiro , Fujimoto Saho , Karanjit Sangita , Namba Kosuke 
Published: September 2020

AbstractA concise total synthesis of tronocarpine, a chippiine‐type indole alkaloid, was accomplished. The key feature of this total synthesis is a one‐pot construction of the pentacyclic skeleton containing an azabicyclo[3.3.1]nonane core by tandem cyclization from an indole derivative with all carbon side chains and functional groups. This tandem cyclization consists of α,β‐unsaturated aldehyde formation, intramolecular aldol reaction, six‐membered lactamization, azide reduction, and seven‐membered lactamization. The stereochemical outcome in this tandem cyclization is controlled by the stereocenter at the C14 position. This strategy can be utilized to synthesize other chippiine‐type alkaloids with azabicyclo[3.3.1]nonane skeletons.
Frustrated Radical Pairs: Insights from EPR Spectroscopy
Authors: Dasgupta Ayan , Richards Emma , Melen Rebecca L. 
Published: September 2020

AbstractProgress in frustrated Lewis pair (FLP) chemistry has revealed the importance of the main group elements in catalysis, opening new avenues in synthetic chemistry. Recently, new reactivities of frustrated Lewis pairs have been uncovered that disclose that certain combinations of Lewis acids and bases undergo single‐electron transfer (SET) processes. Here an electron can be transferred from the Lewis basic donor to a Lewis acidic acceptor to generate a reactive frustrated radical pair (FRP). This minireview aims to showcase the recent advancements in this emerging field covering the synthesis and reactivities of frustrated radical pairs, with extensive highlights of the results from Electron Paramagnetic Resonance (EPR) spectroscopy to explain the nature and stability of the different radical species observed.
Face‐Directed Assembly of Molecular Cubes: In Situ Substitution of a Predetermined Concave Cluster
Authors: Gong Yaru , Qin Chao , Zhang Yuteng , Sun Chunyi , Pan Qinhe , Wang Xinlong , Su Zhongmin 
Published: September 2020

AbstractSystematic design and self‐assembly of metal–organic polyhedra with predictable configurations has been a long‐standing challenge in crystal engineering. Herein a concave polyoxovanadate cluster, [V6O6(OCH3)9(SO4)4]5−, which can be generated in situ under specific reaction conditions, is reported. Based on this cluster, a potential trivalent molecular building block, [V6O6(OCH3)9(SO4)(CO2)3]2−, can be obtained by the bridging‐ligand‐substitution strategy and it possesses appropriate angle information for the design of molecular cubes. Utilizing the face‐directed assembly of the trivalent molecular building block and a diverse set of tetratopic carboxylate linkers, a series of metal–organic cubes (VMOC‐1–VMOC‐5) with the same topology but different functionalities and dimensions were designed and constructed. An inclusion study using VMOC‐3 shows that they are potential molecular receptors for selective capture of size‐matching polycyclic aromatic hydrocarbon guest molecules.
A Hydrogen‐Bonded yet Hydrophobic Porous Molecular Crystal for Molecular‐Sieving‐like Separation of Butane and Isobutane
Authors: Ye Zi‐Ming , Zhang Xue‐Wen , Liao Pei‐Qin , Xie Yi , Xu Yan‐Tong , Zhang Xue‐Feng , Wang Chao , Liu De‐Xuan , Huang Ning‐Yu , Qiu Ze‐Hao , Zhou Dong‐Dong , He Chun‐Ting , Zhang Jie‐Peng 
Published: September 2020

AbstractPorous molecular crystals sustained by hydrogen bonds and/or weaker connections are an intriguing type of adsorbents, but they rarely demonstrate efficient adsorptive separation because of poor structural robustness and tailorability. Herein, we report a porous molecular crystal based on hydrogen‐bonded cyclic dinuclear AgI complex, which exhibits exceptional hydrophobicity with a water contact angle of 134°, and high chemical stability in water at pH 2–13. The seemingly rigid adsorbent shows a pore‐opening or nonporous‐to‐porous type butane adsorption isotherm and complete exclusion of isobutane, indicating potential molecular sieving. Quantitative column breakthrough experiments show slight co‐adsorption of isobutane with an experimental butane/isobutane selectivity of 23, and isobutane can be purified more efficiently than for butane. In situ powder/single‐crystal X‐ray diffraction and computational simulations reveal that a trivial guest‐induced structural transformation plays a critical role.
Toward Flexible Zinc‐Ion Hybrid Capacitors with Superhigh Energy Density and Ultralong Cycling Life: The Pivotal Role of ZnCl2 Salt‐Based Electrolytes
Authors: Wang Cheng , Pei Zengxia , Meng Qiangqiang , Zhang Chunmei , Sui Xiao , Yuan Ziwen , Wang Sijie , Chen Yuan 
Published: September 2020

AbstractZinc ion hybrid capacitors (ZIHCs) are promising energy storage devices for emerging flexible electronics, but they still suffer from trade‐off in energy density and cycling life. Herein, we show that such a dilemma can be well‐addressed by deploying ZnCl2 based electrolytes. Combining experimental studies and density functional theory (DFT) calculations, for the first time, we demonstrate an intriguing chloride ion (Cl−) facilitated desolvation mechanism in hydrated [ZnCl]+(H2O)n−1 (with n=1–6) clusters. Based on this mechanism, a water‐in‐salt type hydrogel electrolyte filled with ZnCl2 was developed to concurrently improve the energy storage capacity of porous carbon materials and the reversibility of Zn metal electrode. The resulting ZIHCs deliver a battery‐level energy density up to 217 Wh kg−1 at a power density of 450 W kg−1, an unprecedented cycling life of 100 000 cycles, together with excellent low‐temperature adaptability and mechanical flexibility.
Cobalt‐Catalyzed Markovnikov‐Type Selective Hydroboration of Terminal Alkynes
Authors: Chen Jieping , Shen Xuzhong , Lu Zhan 
Published: September 2020

AbstractA cobalt‐catalyzed Markovnikov‐type hydroboration of terminal alkynes with HBpin to access α‐alkenyl boronates with good regioselectivity and atom economy is reported. A new ligand has been developed for the cobalt hydride catalyst that has been used for a unique Markovnikov selective insertion of terminal alkynes into metal hydride bond. This operationally simple protocol exhibits excellent functional group tolerance to deliver valuable alkene derivatives.