bluuebunny/crossref_metadata_2025_split huggingface dataset:
Brief Report: Drugs Implicated in Systemic Autoimmunity Modulate Neutrophil Extracellular Trap Formation
Authors: Irizarry‐Caro Jorge A. , Carmona‐Rivera Carmelo , Schwartz Daniella M. , Khaznadar Sami S. , Kaplan Mariana J. , Grayson Peter C. 
Published: November 2017

ObjectiveAberrant neutrophil extracellular trap (NET) formation has been implicated as a mechanism to induce autoreactivity in individuals at risk of autoimmune diseases. The objective of this study was to assess whether medications implicated in cases of drug‐induced autoimmunity (hydralazine and procainamide) and medications less commonly associated with drug‐induced autoimmunity (minocycline and clozapine) induce NET formation and/or prevent NET degradation.MethodsHuman neutrophils were incubated with the drugs of interest and resultant NET formation was quantified by fluorescent microscopy. The ability of these drugs to interfere with NET degradation by serum nuclei was assessed. Pathways of drug‐induced NET formation were studied with pharmacologic inhibitors of reactive oxygen species (ROS), peptidylarginine deiminases (PADs), and muscarinic receptors, and by assessment of intracellular calcium levels by flow cytometry. To determine if NET protein cargo varies by drug stimulus and/or neutrophil source, proteomic analysis of NET lysates induced by specific medications was compared using neutrophils from healthy donors and from patients with autoimmune diseases.ResultsHydralazine and procainamide significantly induced NET formation while minocycline and clozapine did not. None of the medications significantly impaired NET degradation. NETosis induced by these drugs required NADPH oxidase and PAD4 activation. Procainamide triggered NETs via muscarinic receptor engagement on neutrophils, while hydralazine modulated calcium release from intracellular stores. Differences in protein cargo, particularly histone content, were observed in NETs induced by hydralazine and procainamide.ConclusionMedications commonly implicated in drug‐induced autoimmunity trigger NET formation displaying distinct protein cargo, via common and specific pathways. NETosis may play a role in the pathogenesis of drug‐induced autoimmunity.
In Vitro, In Silico Elucidation of Antiurease Activity, Kinetic Mechanism and COX‐2 Inhibitory Efficacy of Coagulansin A of Withania coagulans
Authors: Phull Abdul Rehman , Hassan Mubshir , Abbas Qamar , Raza Hussain , Haq Ihsan ul , Seo Sung Yum , Kim Song Ja 
Published: November 2017

Urease enzyme plays a crucial role in the survival of Helicobacter pylori that contributes to different diseases, including peptic ulcer (gastric and duodenal ulcers). Coagulansin A is the steroidal lactone (withanolide) found in plants of solanaceae family such Withania coagulans. The current study was carried out to examine the in vitro urease, COX‐2 inhibitory activity and effect on type II collagen expression of coagulansin A. Moreover, we investigated cytotoxic effects on rabbit articular chondrocytes through MTT assay. COX‐2 and type II collagen expressions were determined through a Western blot method. Molecular docking and simulation studies of urease (PDBID 4H9M) and COX‐2 (PDBID 5F1A) proteins were also performed as an in silico approach. Results showed that COX‐2 expression was decreased dose dependably, significantly higher expression of type II collagen was observed at higher doses. In the current study, coagulansin A was found as non‐toxic, and showed notable urease inhibitory activity in non‐competitive manner with IC50 23.14 μm in comparison to reference drug thiourea 17.81 μm. Significant decrease in COX‐2 expression (40%) and increase in type II collagen (20%) were observed as compared to control. In silico results unveiled the strong binding affinities of coagulansin A with both of these urease and COX‐2 proteins. Therefore, herein we proposed the significant antiurease potential of this compound that could be used in treating different diseases such as ulcers. Moreover, detailed in vivo studies and molecular mechanism based studies are suggested.
Enzymes as Enhancers for the Biodegradation of Synthetic Polymers in Wastewater
Authors: Haernvall Karolina , Zitzenbacher Sabine , Biundo Antonino , Yamamoto Motonori , Schick Michael Bernhard , Ribitsch Doris , Guebitz Georg M. 
Published: November 2017

AbstractSynthetic polyesters are today the second‐largest class of ingredients in household products and are entering wastewater treatment plants (WWTPs) after product utilization. One approach to improve polymer biodegradation in wastewater would be to complement current processes with polyester‐hydrolyzing enzymes and their microbial producers. In this study, the hydrolysis of poly(oxyethylene terephthalate) polymer by hydrolases from wastewater microorganisms was investigated in vitro and under realistic WWTP conditions. An esterase and a cutinase from Pseudomonas pseudoalcaligenes and a lipase from Pseudomonas pelagia were heterologously expressed in Escherichia coli BL21‐Gold(DE3) and were purified by a C‐terminal His6 tag. The hydrolases were proven to hydrolyze the polymer effectively, which is a prerequisite for further biodegradation. The hydrolases maintained high activity up to 50 % upon lowering the temperature from 28 to 15 °C to mimic WWTP conditions. The hydrolases were also not inhibited by the wastewater matrix. Polyester‐hydrolyzing enzymes active under WWTP conditions and their microbial producers thus have the potential to improve biological treatment of wastewater rich in synthetic polymers.
Simultaneous laparoscopic cholecystectomy and transabdominal preperitoneal hernioplasty: two case reports evaluate the safety and surgical complications
Authors: Arafat Shawqi , Alsabek Mhd Belal 
Published: November 2017

Key Clinical MessageThe safety of combining transabdominal preperitoneal (TAPP) hernioplasty and cholecystectomy in one laparoscopic surgery is still for many years questionable. We report two cases describing the safety and discussing the main concerns regarding the complications. As there are only few cases discuss this kind of combination, we aim to further clarify this subject to provide the best practice for our patients.
Ambient Pressure Photoelectron Spectroscopy: Opportunities in Catalysis from Solids to Liquids and Introducing Time Resolution
Authors: Roy Kanak , Artiglia Luca , van Bokhoven Jeroen A. 
Published: November 2017

AbstractPhotoelectron spectroscopy is an excellent technique to explore chemically complex systems in catalysis. However, due to a small mean free path of photoelectrons in gas, liquid, and solid media, the study of the gas–solid, liquid–gas, solid–liquid interfaces, as well as liquid homogeneous systems are a serious challenge. With differentially pumped analyzers this limitation ceases to exist and no longer restricts photoelectron spectroscopy only to ultra‐high vacuum conditions. Presently, photoemission studies at tens of mbar of pressure are possible. To reach atmospheric pressure and even higher, membrane‐covered closed cells have been developed. Graphene membranes are impermeable to molecules and almost transparent to photoelectrons. They are used as a pressure barrier between the enclosed cell at atmospheric pressure and the electron analyzer at vacuum while allowing transmission of photoelectrons. By accessing to atmospheric pressure range, with this kind of cell, photoemission studies will become a versatile in situ and operando tool for catalysis. Studies involving liquids in static conditions are an important aspect in this direction, which can be extended to homogeneous catalytic systems. Liquids are presently accessible using micro‐jets. Another aspect which is of paramount interest to investigate catalysts is time resolution. By improving the time resolution of photoemission measurements to the sub‐second regime it is possible to follow the kinetic changes that are crucial of a catalytic reaction, the changes that occur during catalyst pretreatment and activation, and notably to differentiate active species from spectator ones, which may be the dominating species in a classical experiment.
Pd‐Catalyzed versus Uncatalyzed, PhI(OAc)2‐Mediated Cyclization Reactions of N6‐([1,1′‐Biaryl]‐2‐yl)Adenine Nucleosides
Authors: Satishkumar Sakilam , Poudapally Suresh , Vuram Prasanna K. , Gurram Venkateshwarlu , Pottabathini Narender , Sebastian Dellamol , Yang Lijia , Pradhan Padmanava , Lakshman Mahesh K. 
Published: November 2017

AbstractThe front cover artwork for Issue 21/2017 is provided by the Lakshman Group at The City College of New York (USA). The image shows the beautifully delicate architecture of Hawa Mahal, in Jaipur, as a symbol of the delicate balance of various factors in the described C−N bond formation of N6‐([1,1′‐biaryl]‐2‐yl)adenine nucleosides promoted by PhI(OAc)2 under both Pd‐mediated and uncatalyzed reaction conditions, which ultimately leads to relatively complex product structures. See the Full Paper itself at https://doi.org/10.1002/cctc.201700918.
Reduced Shuttle Effect of Lithium−sulfur Batteries by using a Simple Graphite‐Modified Separator with a Preformed SEI Film
Authors: Zeng Pan , Huang Liwu , Han Yamiao , Zhang Xinling , Zhang Ruixue , Chen Yungui 
Published: November 2017

AbstractLithium−sulfur (Li−S) batteries, which possess a high theoretical capacity of 1675 mAh g−1 and energy density of 2600 Wh kg−1, are regarded as appealing candidates for next‐generation power storage systems. However, poor electrochemical performance, mainly attributed to polysulfide diffusion, obstructs their practical application. Herein, a simple graphite‐modified separator with a preformed solid electrolyte interphase (SEI) is first fabricated to suppress the polysulfide shuttle. Particularly, the formed SEI film on the graphite surface inhibits the graphite exfoliation caused by co‐intercalation of solvents. Thus, the stable graphite layer with a preformed SEI can function as an effective physical barrier to suppress the polysulfide shuttle and enhance the utilization of the trapped active material. As a result, the cell using the graphite‐modified separator exhibits a high capacity of 698 mAh g−1 (0.2 C) after 100 cycles with a low capacity decay of 0.13 % per cycle. Even under relatively high sulfur loading (2.5 mg cm−2), it shows a reversible capacity of 519 mAh g−1 after 200 cycles.
Simultaneous Electrospinning and Electrospraying: Fabrication of a Carbon Nanofibre/MnO/Reduced Graphene Oxide Thin Film as a High‐Performance Anode for Lithium‐Ion Batteries
Authors: Wang Fan , Cai Jianxin , Yu Ji , Li Chao , Yang Zhenyu 
Published: November 2017

AbstractRational fabrication of flexible thin‐film electrodes with superior electrochemical performance is challenging now in consumer electronics miniaturization. In this work, we combine electrospinning with electrospraying in a simultaneous process to achieve the CNFs/MnO/rGO composite film electrodes (CNFs=carbon nanofibres; rGO=reduced graphene oxide) for lithium‐ion batteries. For the as‐obtained thin‐film electrode, the 2D reduced graphene sheets are dispersed on each of the 1D CNFs/MnO composite filaments, in which the nanofibres and rGO nanosheets can form interconnected morphologies simultaneously. The thin‐film electrodes with enhanced electrical conductivity and flexibility could efficiently accommodate the volume changes of MnO particles by the very elastic buffer space. As expected, the composite electrode exhibits a high discharge capacity of 1118 mAh g−1 at 0.1 A g−1, and then back to 0.1 A g−1 after 80 cycles, the capacity retention is still up to 98 %; at high rates (e. g. 5 A g−1), the composite is still able to maintain a high reversible capacity of 574 mAh g−1 after 3000 cycles with a significant Coulombic efficiency of 99 %. This is the best specific capacity at 5 A g−1 and longest cycling life reported for MnO thin‐film anodes. In addition, the technique provides a facile path to combine 1D fibres/2D nanosheets layer‐by‐layer in a composite film with tunable fibre diameter. This is the first time that the fabrication of 1D CNFs/MnO fibres and 2D rGO sheet network film electrodes via simultaneous electrospinning and electrospraying methods has been reported.
Quantitative structure‐property relationship modeling of small organic molecules for solar cells applications
Authors: Tortorella Sara , De Angelis Filippo , Cruciani Gabriele 
Published: November 2017

AbstractDespite the need of a reliable technology for solar energy harvesting, research on new materials for third generation photovoltaics is slowed down by the diffuse use of trial and error rather than rational material design approaches. The proposed study investigates the use of alternative strategies to material discovery inspired by drug design and molecular modeling. In particular, training set and test set (for validation purposes) comprising well‐known small molecule‐bulk heterojunction organic photovoltaics were built. Molecules were characterized by semiempirical calculated and 3D molecular interaction fields–based descriptors. Then partial least squares algorithm was applied to rationalize structure‐photovoltaic activity relationships, and coefficients were investigated to clarify contributions played by the different molecular properties to the final performance. In addition, a photovoltaic desirability function (PhotD) was also proposed as alternative and versatile novel tool for ranking potential candidates. The partial least squares model and PhotD function were both internally and externally validated demonstrating their ability in estimating new candidates performances. The proposed approach demonstrates that, in the context of computational materials science, chemometrics and molecular modeling tools could effectively boost the discovery of novel promising candidates for photovoltaic application.
Automated data mining of secondary ion mass spectrometry spectra
Authors: Tuccitto Nunzio 
Published: November 2017

AbstractTime of flight secondary ion mass spectrometry (ToF‐SIMS) allows the reliable analytical determination of organic and polymeric materials. Since a typical raw data may contain thousands of peaks, the amount of information to deal with is accordingly large, so that data reduction techniques become indispensable for extracting the most significant information from the given dataset. Here, the use of the wavelet‐principal component analysis–based signal processing of giant raw data acquired during ToF‐SIMS experiments is presented. The proposed procedure provides a straightforwardly “manageable” dataset without any binning procedure neither detailed integration. By studying the principal component analysis results, detailed and reliable information about the chemical composition of polymeric samples have been gathered.
Phosphorescence Tuning through Heavy Atom Placement in Unsymmetrical Difluoroboron β‐Diketonate Materials
Authors: Liu Tiandong , Zhang Guoqing , Evans Ruffin E. , Trindle Carl O. , Altun Zikri , DeRosa Christopher A. , Wang Fang , Zhuang Meng , Fraser Cassandra L. 
Published: November 2017

AbstractDifluoroboron β‐diketonates (BF2bdks) show both fluorescence (F) and room‐temperature phosphorescence (RTP) when confined to a rigid matrix, such as poly(lactic acid). These materials have been utilized as optical oxygen sensors (e.g., in tumors, wounds, and cells). Spectral features include charge transfer (CT) from the major aromatic donor to the dioxaborine acceptor. A series of naphthyl–phenyl dyes (BF2nbm) (1–6) were prepared to test heavy‐atom placement effects. The BF2nbm dye (1) was substituted with Br on naphthyl (2), phenyl (3), or both rings (4) to tailor the fluorescence/phosphorescence ratio and RTP lifetime—important features for designing O2 sensing dyes by means of the heavy atom effect. Computational studies identify the naphthyl ring as the major donor. Thus, Br substitution on the naphthyl ring produced greater effects on the optical properties, such as increased RTP intensity and decreased RTP lifetime compared to phenyl substitution. However, for electron‐donating piperidyl‐phenyl dyes (5), the phenyl aromatic is the major donor. As a result, Br substitution on the naphthyl ring (6) did not alter the optical properties significantly. Experimental data and computational modeling show the importance of Br position. The S1 and T1 states are described by two singly occupied MOs (SOMOs). When both of these SOMOs have substantial amplitude on the heavy atom, passage from S1 to T1 and emission from T1 to S0 are both favored. This shortens the excited‐state lifetimes and enhances phosphorescence.
Efficient endo Cycloisomerization of Terminal Alkynols Catalyzed by a New Ruthenium Complex with 8‐(Diphenylphosphino)quinoline Ligand and Mechanistic Investigation
Authors: Cai Tao , Yang Yu , Li Wei‐Wei , Qin Wen‐Bing , Wen Ting‐Bin 
Published: November 2017

AbstractSeveral new ruthenium complexes supported by the P,N‐donor ligand 8‐(diphenylphosphino)quinoline (DPPQ) were synthesized, including [RuCl2(DPPQ)2] (1), [Ru(μ‐Cl)(DPPQ)2]2(BPh4)2 (2), and [RuCl(DPPQ)2Py](BF4) (3). Complex 2, with only 1 mol % loading, was found to be catalytically active for the endo cycloisomerization of various terminal alkynols to endo‐cyclic enol ethers in moderate to excellent yields. In particular, the 7‐ and 8‐endo heterocyclization can be achieved efficiently to give the seven‐membered 3‐benzoxepine and eight‐membered 3‐benzo[d]oxocine derivatives. The stoichiometric reactions of 2 with various alkynol substrates have been carried out to investigate the mechanism, which led to a series of seven‐, six‐, and five‐membered oxacyclocarbene ruthenium complexes including [RuCl(DPPQ)2{=CCH2C6H4CH2CH2O}](BPh4) (12) and [RuCl(DPPQ)2{=CCH2(CH2)nCH2O}](BPh4) (n=3, 12′; n=2, 13; n=1, 14). The quantitative transformation of oxacyclocarbene 12 into catalyst 2 and 3‐benzoxepine 5 a as well as the efficient catalytic activity of 12 for the endo‐cyclization of 2‐(2‐ethynylphenyl)ethanol (4 a) demonstrated that 12 is a key intermediate involved in the catalytic cycle. Moreover, comparative studies on the modeling reactions and catalytic activity of the series of oxacyclocarbene complexes indicated that the different catalytic activity of 2 for the endo‐cycloisomerization of different types of alkynols can be related to the reactivity of the respective ruthenium oxacyclocarbene intermediates.
Well‐Defined Chiral Copper NHC Complex in the Asymmetric Conjugated β‐Borylation and One‐Pot Metathesis‐Asymmetric β‐Borylation Reactions
Authors: Jana Anupam , Trzybiński Damian , Woźniak Krzysztof , Grela Karol 
Published: November 2017

AbstractHighly stereoselective conjugate β‐borylation, using a new chiral NHC‐based copper catalyst, has been achieved. The chiral NHC copper complex was prepared in gram scale and showed high enantioselectivity and activity (up to 10 000 turnovers at 100 ppm of catalyst loading). This method was employed in the synthesis of a chiral β‐borylated ester from simple unconjugated alkenes though an unprecedented one‐pot cross metathesis‐asymmetric borylation sequence.
Preparation and Characterization of P2BCh Ring Systems (Ch=S, Se) and Their Reactivity with N‐Heterocyclic Carbenes
Authors: Graham Cameron M. E. , Millet Clément R. P. , Price Amy N. , Valjus Juuso , Cowley Michael J. , Tuononen Heikki M. , Ragogna Paul J. 
Published: November 2017

AbstractFour‐membered rings with a P2BCh core (Ch=S, Se) have been synthesized by the reaction of phosphinidene chalcogenide (Ar*P=Ch) and phosphaborene (Mes*P=BNR2). The mechanistic pathways towards these rings are explained by detailed computational work that confirmed the preference for the formation of P−P, not P−B, bonded systems, which seems counterintuitive given that both phosphorus atoms contain bulky ligands. The reactivity of the newly synthesized heterocycles, as well as that of the known (RPCh)n rings (n=2, 3), was probed by the addition of N‐heterocyclic carbenes, which revealed that all investigated compounds can act as sources of low‐coordinate phosphorus species.
A Magic Ratio Rule for Beginners: A Chemist's Guide to Quantum Interference in Molecules
Authors: Lambert Colin J. , Liu Shi‐Xia 
Published: November 2017

AbstractThis Concept article will give a glimpse into chemical design principles for exploiting quantum interference (QI) effects in molecular‐scale devices. Direct observation of room temperature QI in single‐molecule junctions has stimulated growing interest in fabrication of tailor‐made molecular electronic devices. Herein, we outline a new conceptual advance in the scientific understanding and technological know‐how necessary to control QI effects in single molecules by chemical modification. We start by discussing QI from a chemical viewpoint and then describe a new magic ratio rule (MRR), which captures a minimal description of connectivity‐driven charge transport and provides a useful starting point for chemists to design appropriate molecules for molecular electronics with desired functions. The MRR predicts conductance ratios, which are solely determined by QI within the core of polycyclic aromatic hydrocarbons (PAHs). The manifestations of QI and related quantum circuit rules for materials discovery are direct consequences of the key concepts of weak coupling, locality, connectivity, mid‐gap transport and phase coherence in single‐molecule junctions.
Construction of Zeolite‐Like Cluster Organic Frameworks from 3 d–4 d/3 d–3 d Heterometallic Supertetrahedral Secondary Building Units: Syntheses, Structures, and Properties
Authors: Lin Li‐Dan , Deng Chu‐Chu , Zhao D. , Li Xin‐Xiong , Zheng Shou‐Tian 
Published: November 2017

AbstractTwo zeolite‐like cluster organic frameworks based on Cd‐Cu/Mn‐Cu heterometallic supertetrahedral secondary building units have been successfully constructed under solvothermal conditions, namely, Cu[Cd4Cu6(L)4(H2O)18](Ac)9⋅DMA⋅3 H2O (1), and Cu[Mn4Cu6(L)4(Ac)3(H2O)12](Ac)6⋅CH3CN⋅13 H2O (2), where H3L=2‐(hydroxymethyl)‐2‐(pyridin‐4‐yl)‐1,3‐propanediol, Ac=CH3COO−, DMA=N,N′‐dimethylacetamide. Single‐crystal X‐ray structural analysis reveals that both 1 and 2 exhibit 3‐dimensional zeolite‐like architectures with similar 4‐connected components, but possess definitely different topologies of diamondoid (dia) and uncommon lonsdaleite (lon), respectively. 1 and 2 represent the first cases of zeolite‐like cluster organic frameworks containing Cd‐Cu/Mn‐Cu heterometallic supertetrahedral secondary building units. Furthermore, the magnetic properties and porous nature of 1 and 2 were also studied.
Exponential Activation of Carbonic Anhydrase by Encapsulation in Dynameric Host Matrices with Chiral Discrimination
Authors: Zhang Yan , Supuran Claudiu T. , Barboiu Mihail 
Published: November 2017

AbstractHerein an unexpected exponential activation of bovine carbonic anhydrase (bCA) in aqueous solutions in the presence of dynameric host matrices is reported. Successive experiments confirmed the important role of dynamic imine exchange within the dynameric host structures for direct enzyme activation. This allows for optimal encapsulation of the guest enzyme, whereas the presence of external proton‐sponge amino groups is less important. Non‐exchanging polymeric sec‐amine congeners formed from imine reduction of dynameric structures show no obvious activation on bCA. Although the dynamers synthesized from diamino chiral‐pair precursors displayed similar activation constants toward bCA, different activation delay times were observed from these two dynamers of opposite optical activity. The circular dichroism (CD) spectra demonstrate selective structural changes in the secondary structure of bCA upon dynameric encapsulation in aqueous solution. The different interaction molds observed in CD spectra for the dynamers with opposite chirality explain the longer activation time required for one of the dynamers.