bluuebunny/crossref_metadata_2025 huggingface dataset:
Correlating Glycoforms of DC‐SIGN with Stability Using a Combination of Enzymatic Digestion and Ion Mobility Mass Spectrometry
Authors: Yen Hsin‐Yung , Liko Idlir , Gault Joseph , Wu Di , Struwe Weston B. , Robinson Carol V.
Published: July 2020

The immune scavenger protein DC‐SIGN interacts with glycosylated proteins and has a putative role in facilitating viral infection. How these recognition events take place with different viruses is not clear and the effects of glycosylation on the folding and stability of DC‐SIGN have not been reported. Herein, we report the development and application of a mass‐spectrometry‐based approach to both uncover and characterise the effects of O‐glycans on the stability of DC‐SIGN. We first quantify the Core 1 and 2 O‐glycan structures on the carbohydrate recognition and extracellular domains of the protein using sequential exoglycosidase sequencing. Using ion mobility mass spectrometry, we show how specific O‐glycans, and/or single monosaccharide substitutions, alter both the overall collision cross section and the gas‐phase stability of the DC‐SIGN isoforms. We find that rather than the mass or length of glycoprotein modifications, the stability of DC‐SIGN is better correlated with the number of glycosylation sites.
A Boosted Critical Temperature of 166 K in Superconducting D3S Synthesized from Elemental Sulfur and Hydrogen
Authors: Minkov Vasily S. , Prakapenka Vitali B. , Greenberg Eran , Eremets Mikhail I.
Published: July 2020

The discovery of superconductivity in H3S at 203 K marked an advance towards room‐temperature superconductivity and demonstrated the potential of H‐dominated compounds to possess a high critical temperature (Tc). There have been numerous reports of the H‐S system over the last five years, but important questions remain unanswered. It is crucial to verify whether the Tc was determined correctly for samples prepared from compressed H2S, since they are inevitably contaminated with H‐depleted byproducts. Here, we prepare stoichiometric H3S by direct in situ synthesis from elemental S and excess H2. The Im
m phase of D3S samples exhibits a Tc significantly higher than previously reported values (ca. 150 K), reaching a maximum Tc of 166 K at 157 GPa. Furthermore, we confirm that the sharp decrease in Tc below 150 GPa is accompanied by continuous rhombohedral structural distortions and demonstrate that the Cccm phase is non‐metallic, with molecular H2 units in the crystal structure.
Enantio‐ and Site‐Selective α‐Fluorination of N‐Acyl 3,5‐Dimethylpyrazoles Catalyzed by Chiral π–CuII Complexes
Authors: Ishihara Kazuaki , Nishimura Kazuki , Yamakawa Katsuya
Published: July 2020

Catalytic enantioselective α‐fluorination reactions of carbonyl compounds are among the most powerful and efficient synthetic methods for constructing optically active α‐fluorinated carbonyl compounds. Nevertheless, α‐fluorination of α‐nonbranched carboxylic acid derivatives is still a big challenge because of relatively high pKa values of their α‐hydrogen atoms and difficulty of subsequent synthetic transformation without epimerization. Herein we show that chiral copper(II) complexes of 3‐(2‐naphthyl)‐l‐alanine‐derived amides are highly effective catalysts for the enantio‐ and site‐selective α‐fluorination of N‐(α‐arylacetyl) and N‐(α‐alkylacetyl) 3,5‐dimethylpyrazoles. The substrate scope of the transformation is very broad (25 examples including a quaternary α‐fluorinated α‐amino acid derivative). α‐Fluorinated products were converted into the corresponding esters, secondary amides, tertiary amides, ketones, and alcohols with almost no epimerization in high yield.
Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion
Authors: Costil Romain , Sterling Alistair J. , Duarte Fernanda , Clayden Jonathan
Published: July 2020

In common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the structural requirement for atropisomerism in structurally simpler secondary and acyclic diarylamines. In this paper we describe a systematic study of a series of acyclic secondary diarylamines, and we quantify the degree of steric hindrance in the ortho positions that is required for atropisomerism to result. Through a detailed experimental and computational analysis, the role of each ortho‐substituent on the mechanism and rate of conformational interconversion is rationalised. We also present a simple predictive model for the design of configurationally stable secondary diarylamines.
Engineered Anisotropic Fluids of Rare‐Earth Nanomaterials
Authors: Shao Baiqi , Wan Sikang , Yang Chenjing , Shen Jianlei , Li Yiwen , You Hongpeng , Chen Dong , Fan Chunhai , Liu Kai , Zhang Hongjie
Published: July 2020

The self‐assembly of inorganic nanoparticles into well‐ordered structures in the absence of solvents is generally hindered by van der Waals forces, leading to random aggregates between them. To address the problem, we functionalized rigid rare‐earth (RE) nanoparticles with a layer of flexible polymers by electrostatic complexation. Consequently, an ordered and solvent‐free liquid crystal (LC) state of RE nanoparticles was realized. The RE nanomaterials including nanospheres, nanorods, nanodiscs, microprisms, and nanowires all show a typical nematic LC phase with one‐dimensional orientational order, while their microstructures strongly depend on the particles’ shape and size. Interestingly, the solvent‐free thermotropic LCs possess an extremely wide temperature range from −40 °C to 200 °C. The intrinsic ordering and fluidity endow anisotropic luminescence properties in the system of shearing‐aligned RE LCs, offering potential applications in anisotropic optical micro‐devices.
Stable Ti3+ Defects in Oriented Mesoporous Titania Frameworks for Efficient Photocatalysis
Authors: Lan Kun , Wang Ruicong , Wei Qiulong , Wang Yanxiang , Hong Anh , Feng Pingyun , Zhao Dongyuan
Published: July 2020

By introducing a compatible reducing agent (2‐ethylimidazole) into a mono‐micelle assembly process, we present a type of ordered mesoporous TiO2 microspheres that combines radially aligned mesostructure with Ti3+ defects in mesoporous frameworks. Such reductant acts as a building block of mesostructured frameworks and reduces Ti4+ in situ to generate defects during calcination, giving rise to the coexistence of bulk Ti3+ defects and an ordered mesostructure. The mesoporous TiO2 has both excellent mesoporosity (a high surface area of 106 m2 g−1, a mean pore size of 18.4 nm) and stable defects with an extended photoresponse. Such integration of unique mesoscopic architecture and atomic vacancies provide both effective mass transportation and enhanced light utilization, leading to a remarkable increase in H2 generation rate. A maximum H2 evolution rate of 19.8 mmol g−1 h−1 can be achieved, along with outstanding stability under solar light.
Protonenvermittelter Ringschluss eines negativ photochromen, Azulen‐basierten Diarylethens
Authors: Hou Ian Cheng‐Yi , Berger Fabian , Narita Akimitsu , Müllen Klaus , Hecht Stefan
Published: July 2020

Auf Protonen ansprechende photochrome Moleküle sind aufgrund ihrer Fähigkeit, auf nicht‐invasive schnelle optische Stimuli zu reagieren, und wegen der ubiquitären Bedeutung von Protonierungs‐ und Deprotonierungsprozessen, sehr interessant. Üblicherweise befinden sich die sauren/basischen Stellen dieser Moleküle an Heteroatomen, die orthogonal zum photoaktiven π‐Zentrum ausgerichtet sind. In dieser Arbeit wird Azulen, ein protonensensitiver reiner Kohlenwasserstoff, in das Gerüst eines Diarylethen‐Photoschalters eingebaut. Dieser zeigt einen bisher ungekannten, protonenvermittelten, negativ photochromen Ringschluss. Veränderungen seiner optischen Eigenschaften durch Protonierung, sowohl in der offenen, als auch in der geschlossenen Form, sind viel ausgeprägter als die von Diarylethen‐Photoschaltern mit Säure/Base‐Gruppen auf Heteroatombasis. Das einzigartige Verhalten des neuen Photoschalters kann auf die direkte Protonierung seines π‐Systems zurückgeführt werden, was sowohl durch 1H‐NMR als auch durch theoretische Berechnungen belegt wird. Unsere Ergebnisse zeigen das große Potenzial der Einbindung nicht‐alternierender Kohlenwasserstoffe in photochrome Systeme für die Entwicklung von molekularen Schaltern, die auf unterschiedliche Stimuli reagieren.
Polyoxometalate‐Based Compounds for Photo‐ and Electrocatalytic Applications
Authors: Li Ning , Liu Jiang , Dong Bao‐Xia , Lan Ya‐Qian
Published: July 2020

Photo/electrocatalysis of water (H2O) splitting and CO2 reduction reactions is a promising strategy to alleviate the energy crisis and excessive CO2 emissions. For the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and CO2 reduction reaction (CO2RR) involved, the development of effective photo/electrocatalysts is critical to reduce the activation energy and accelerate the sluggish dynamics. Polyoxometalate (POM)‐based compounds with tunable compositions and diverse structures are emerging as unique photo/electrocatalysts for these reactions as they offer unparalleled advantages such as outstanding solution and redox stability, quasi‐semiconductor behaviour, etc. This Minireview provides a basic introduction related to photo/electrocatalytic HER, OER and CO2RR, followed by the classification of pristine POM‐based compounds toward different catalytic reactions. Recent breakthroughs in engineering POM‐based compounds as efficient photo/electrocatalysts are highlighted. Finally, the advantages, challenges, strategies and outlooks of POM‐based compounds on improving photo/electrocatalytic performance are discussed.
Detailed Visualization of Aromaticity Using Isotropic Magnetic Shielding
Authors: Lampkin Bryan J. , Karadakov Peter B. , VanVeller Brett
Published: July 2020

For many years, Clar's aromatic sextet theory has served as a qualitative method for assessing the aromatic character of polycyclic aromatic hydrocarbons. A new approach, based on the calculation of isotropic magnetic shielding (IMS) contour plots, is shown to provide a feature‐rich picture of aromaticity that is both quantitative yet still easily interpreted. Chemists are visual creatures who are adept at discerning reactivity and chemical behavior from molecular structures. To quote Roald Hoffmann, “People like pictures. Chemists live off them.” Thus, the detailed image analysis we present simultaneously provides quantitative assessment of electronic structure, which is still easy‐to‐understand through visual inspection, embedded in an aesthetically appealing and intuitive picture that draws the reader in. We provide novel computed IMS contour plots for a representative selection of aromatic molecules. Where Clar's static drawings capture only a partial sketch of the electronic properties of a molecule, IMS contour plots present a detailed, global landscape of a molecule that sums all possible resonance structures. This novel analysis allows us to correct certain drawbacks of Clar's analysis with respect to polycyclic aromatics and quantitatively assess the bonding and electronic structure of acene hydrocarbons.
Synthesis of Robust MOFs@COFs Porous Hybrid Materials via an Aza‐Diels–Alder Reaction: Towards High‐Performance Supercapacitor Materials
Authors: Peng Haijun , Raya Jésus , Richard Fanny , Baaziz Walid , Ersen Ovidiu , Ciesielski Artur , Samorì Paolo
Published: July 2020

Metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have attracted enormous attention in recent years. Recently, MOF@COF are emerging as hybrid architectures combining the unique features of the individual components to enable the generation of materials displaying novel physicochemical properties. Herein we report an unprecedented use of aza‐Diels–Alder cycloaddition reaction as post‐synthetic modification of MOF@COF‐LZU1, to generate aza‐MOFs@COFs hybrid porous materials with extended π‐delocalization. A a proof‐of‐concept, the obtained aza‐MOFs@COFs is used as electrode in supercapacitors displaying specific capacitance of 20.35 μF cm−2 and high volumetric energy density of 1.16 F cm−3. Our approach of post‐synthetic modification of MOFs@COFs hybrids implement rational design for the synthesis of functional porous materials and expands the plethora of promising application of MOFs@COFs hybrid porous materials in energy storage applications.
124I Radiolabeling of a AuIII‐NHC Complex for In Vivo Biodistribution Studies
Authors: Guarra Federica , Terenzi Alessio , Pirker Christine , Passannante Rossana , Baier Dina , Zangrando Ennio , Gómez‐Vallejo Vanessa , Biver Tarita , Gabbiani Chiara , Berger Walter , Llop Jordi , Salassa Luca
Published: July 2020

AuIII complexes with N‐heterocyclic carbene (NHC) ligands have shown remarkable potential as anticancer agents, yet their fate in vivo has not been thoroughly examined and understood. Reported herein is the synthesis of new AuIII‐NHC complexes by direct oxidation with radioactive [124I]I2 as a valuable strategy to monitor the in vivo biodistribution of this class of compounds using positron emission tomography (PET). While in vitro analyses provide direct evidence for the importance of AuIII‐to‐AuI reduction to achieve full anticancer activity, in vivo studies reveal that a fraction of the AuIII‐NHC prodrug is not immediately reduced after administration but able to reach the major organs before metabolic activation.
Synthesis and antimicrobial evaluation of coordination compounds containing 2,2′‐bis(3‐aminopyridyl) diselenide as ligand
Authors: Dias Renne de Sousa , Cervo Rodrigo , Siqueira Fallon dos Santos , de Campos Marli Matiko Anraku , Lang Ernesto Schulz , Tirloni Bárbara , Schumacher Ricardo Frederico , Cargnelutti Roberta
Published: July 2020

The reaction between 2,2′‐bis(3‐aminopyridyl) diselenide (L) and metal transition salts results in the formation of molecular or cluster complexes. The structural elucidation of the synthesized complexes [CuCl2(L)] (1), [Cu(3‐NH2PySeO2)2]·2H2O (2), [Cu4(3‐NH2PySe)4]·dimethylformamide (3), [CoCl2(L)] (4), [ZnCl2(L)] (5), and [Ag6(3‐NH2PySe)6] (6) demonstrates the coordination of nitrogen atoms to CuII, CoII, and ZnII, and that of the selenium atoms to CuIand AgI, which agrees with Pearson’s hard and soft acids and bases (HSAB) theory. Furthermore, the oxidation of selenium with the formation of 3‐aminopyridylseleninate [3‐NH2PySeO2]−bonded to the copper atom was observed in complex2. The antimicrobial action of complexes1,2,4, and5was evaluated againstMycobacterium fortuitum,Mycobacterium massiliense, andMycobacterium abscessus.It was observed that all these complexes have potential antimicrobial activity compared with the free ligand and metal salts used in the synthesis.
Sandwiched meshes with superwettability for oil/water separation and heavy metal ion absorption
Authors: Dong Wei , Yang Ling , Qian Fuping , Lv Zhong , Wu Chunhua , Xiang Tengfei , Chen Depeng
Published: July 2020

Oil/water separation and heavy metal ion adsorptions have become a worldwide challenge due to the global industrial development and its indiscriminate discharge. Large numbers of methods have been developed to solve the problems, among which using superwettability material to selective separation is one of an efficient approach. However, this method cannot adsorb the heavy metal ions from water. Herein, we developed superwettability meshes that can not only separate oil/water after modification but also adsorb heavy metal ions before modification, which is just sandwiching an adsorbent layer between the meshes. The results showed that this method can separate most of oil/water mixtures with high efficiency (higher than 95%) as well as favorable recyclability. Besides, it can separate oil/water emulsion easily. In addition, the carbon layer between the meshes can adsorb heavy metal ions such as Ni(II), Cr(VI) (in the form of Cr2O72−), and Cd(II) with high adsorption efficiency. More importantly, the carbon layer can be replaced by any other powers such as metal–organic frameworks (MOFs) and magnetic particle to extend the applications. We believe that such a novel and simple approach can provide some new perspectives to settle the environmental problems.
The role of structural evolution of polyacrylonitrile fibers during thermal oxidative stabilization on mechanical properties
Authors: Ge Yuan , Fu Zhongyu , Zhang Mingyao , Zhang Huixuan
Published: July 2020

The effects of chemical and physical structural evolution of polyacrylonitrile (PAN)‐based carbon fibers precursor during thermal oxidative stabilization (TOS) on the mechanical properties of stabilized fibers were systematically studied. The results of Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, and density gradient column showed that the PAN fibers treated with high temperature and for long time have higher extent of cyclization, oxygen content, and crosslinking content. The crystallinity and crystallite size decreased with the increase of TOS time and temperature, whereas the bulk density of the stabilized fibers increased. The mechanical property results indicated that the decrease in tensile strength was inseparable from the formation of the cyclic structure and the amorphization transition of the crystal structure. The fibers have better structural stability when the extent of cyclization was 80–83%, the crystallinity was 34–45%, and the bulk density of stabilized fibers was 1.33–1.35 g/cm3, but exceeding these ranges, a serious skin‐core structure appeared.
Variable infrared emissivity based on polyaniline electrochromic device influenced by porous substrate
Authors: Lu Feifei , Tan Peiyu , Han Yuge
Published: July 2020

Polyaniline (PANI) films and its electrochromic devices based on various porous substrates were obtained by electrochemical deposition. The pore size distribution of the porous substrate has shown important influence on the infrared emissivity variation (∆ε) of the device. Morphology and structure of PANI were characterized by scan electronic microscopy (SEM) images and Fourier transform infrared spectra (FTIR). SEM images present the morphology difference of PANI on different substrates, which suggest that large pores will prevent PANI particles from forming orderly and compactly films. FTIR spectrum indicates that pore size of substrates affects the orientation of PANI chains. Furthermore, electrochemical properties and stability of PANI films were analyzed by cyclic voltammetry (CV) curves. And the CV curve revealed that the generation of irreversible degradation products is the reason for poor stability of PANI films. Finally, greatly improved ∆ε of 0.559 in 3–5 μm waveband and 0.39 in 8–14 μm waveband is achieved by choosing a small pore substrate.
A Macrocyclic Peptide Library with a Structurally Constrained Cyclopropane‐containing Building Block Leads to Thiol‐independent Inhibitors of Phosphoglycerate Mutase
Authors: Okuma Rika , Kuwahara Tomoki , Yoshikane Takafumi , Watanabe Mizuki , Dranchak Patricia , Inglese James , Shuto Satoshi , Goto Yuki , Suga Hiroaki
Published: July 2020

Here we report the construction of an mRNA‐encoded library of thioether‐closed macrocyclic peptides by using an N‐chloroacetyl‐cyclopropane‐containing exotic initiator whose structure is more constrained than the ordinary N‐chloroacetyl‐α‐amino acid initiators. The use of such an initiator has led to a macrocycle library with significantly suppressed population of lariat‐shaped species compared with the conventional libraries. We previously used a conventional library and identified a small lariat thioether‐macrocycle with a tail peptide with a C‐terminal free Cys whose sidechain plays an essential role in potent inhibitory activity against a parasitic model enzyme, phosphoglycerate mutase. On the other hand, the cyclopropane‐containing macrocycle library has yielded a larger thioether‐macrocycle lacking a free Cys residue, which exhibits potent inhibitory activity to the same enzyme with a different mode of action. This result indicates that such a cyclopropane‐containing macrocycle library would allow us to access mechanistically distinct macrocycles.
Nutrient Sensing by Histone Marks: Reading the Metabolic Histone Code Using Tracing, Omics, and Modeling
Authors: Campit Scott E. , Meliki Alia , Youngson Neil A. , Chandrasekaran Sriram
Published: July 2020

Several metabolites serve as substrates for histone modifications and communicate changes in the metabolic environment to the epigenome. Technologies such as metabolomics and proteomics have allowed us to reconstruct the interactions between metabolic pathways and histones. These technologies have shed light on how nutrient availability can have a dramatic effect on various histone modifications. This metabolism–epigenome cross talk plays a fundamental role in development, immune function, and diseases like cancer. Yet, major challenges remain in understanding the interactions between cellular metabolism and the epigenome. How the levels and fluxes of various metabolites impact epigenetic marks is still unclear. Discussed herein are recent applications and the potential of systems biology methods such as flux tracing and metabolic modeling to address these challenges and to uncover new metabolic–epigenetic interactions. These systems approaches can ultimately help elucidate how nutrients shape the epigenome of microbes and mammalian cells.
Some actions for behavior analyst licensing bodies to consider in response to the COVID‐19 pandemic
Authors: Fronapfel Brighid H. , Dubuque Erick M. , Milyko Kerri , Fuller Christine M. , Green Gina
Published: July 2020

The COVID‐19 global pandemic has had a significant impact on the practice of applied behavior analysis (ABA). Practitioners and caregivers have had to adapt quickly as physical distancing, stay‐at‐home orders, and shelter‐in‐place directives have become commonplace. As the field copes with the changes produced by the COVID‐19 outbreak, many behavior analytic practitioners are seeking guidance from regulatory bodies to ensure they are practicing legally and ethically. This article outlines some actions that the regulatory bodies that manage state behavior analyst licensure programs may consider to assist ABA practitioners and consumers during this unprecedented time. Additionally, suggestions are offered as to how state licensing bodies might prepare to support the practice of licensees during future events that present challenges similar to the current pandemic.
Simultaneous determination of FL118 and W34 in rat Blood by LC–MS/MS: Application to pharmacokinetic studies
Authors: Feng Kun , Zhang Jiayuan , Zhang Yixuan , Jiang Tao , Lv Zhihua , Yu Mingming
Published: July 2020

W34 is a prodrug of FL118, and it can be converted to FL118 via a hydrolysis reaction. In this report, a highly sensitive LC–MS/MS method using a C18 column was validated and used for the simultaneous determination of W34 and FL118 in rat blood. A stepwise gradient elution with 0.1% formic acid in water and acetonitrile was employed. The assays were linear over a concentration range of 0.50–50.0 ng/ml for both W34 and FL118. The accuracy of the validation method ranged from 89.74 to 98.94% for W34 and from 88.61 to 94.60% for FL118. The precision was within 7.15% for W34 and 9.63% for FL118. Extraction recoveries of W34 were 94.56–100.49 and 87.67–106.32% for FL118. No significant matrix effects for both W34 and FL118 were observed in blood. The assay has been successfully applied to biological samples obtained from a stability and pharmacokinetic study of W34 and FL118.
Applicability of two violence risk assessment tools in a psychiatric prison hospital population
Authors: Krebs Julia , Negatsch Vincent , Berg Christine , Aigner Annette , Opitz‐Welke Annette , Seidel Peter , Konrad Norbert , Voulgaris Alexander
Published: July 2020

The risk of violent behavior is known to be higher for patients who suffer from a severe mental disorder. However, specific prediction tools for clinical work in prison psychiatry are lacking. In this single‐center study, two violence risk assessment tools (Forensic Psychiatry and Violence Tool, “FoVOx,” and Mental Illness and Violence Tool, “OxMIV”) were applied to a prison hospital population with a primary psychotic or bipolar disorder and subsequently compared. The required information on all items of both tools was obtained retrospectively for a total of 339 patients by evaluation of available patient files. We obtained the median and inter‐quartile range for both FoVOx and OxMIV, and their rank correlation coefficient along with 95% confidence intervals (CIs)—for the full cohort, as well as for cohort subgroups. The two risk assessment tools were strongly positively correlated (Spearman correlation = 0.83; 95% CI = 0.80–0.86). Such a high correlation was independent of nationality, country of origin, type of detention, schizophrenia‐spectrum disorder, previous violent crime and alcohol use disorder, where correlations were above 0.8. A lower correlation was seen with patients who were 30 years old or more, married, with affective disorder and with self‐harm behavior, and also in patients without aggressive behavior and without drug use disorder. Both risk assessment tools are applicable as an adjunct to clinical decision making in prison psychiatry.
Bioprosthetic valve oversizing is associated with increased risk of valve thrombosis following TAVR
Authors: Simpson Timothy F. , Tuohy Craig V. , Rajotte Katherine , Golwala Harsh , Fuss Cristina , Song Howard K. , Zahr Firas , Chadderdon Scott M.
Published: July 2020

Background

Hypoattenuating leaflet thickening (HALT), the radiographic manifestation of transcatheter heart valve thrombosis, is commonly identified following transcatheter aortic valve replacement (TAVR) and associated with increased risk of stroke and structural valve deterioration. While anticoagulation effectively resolves HALT, routine use remains controversial. We aimed to identify hemodynamic, anatomic, and comorbid predictors of HALT.

Methods

We evaluated consecutive patients with severe aortic stenosis who underwent TAVR with Edwards SAPIEN 3 bioprosthesis at a single center between June 1, 2018 and October 30, 2019. Patients on anticoagulation and those receiving valve‐in‐valve were excluded. Clinically driven computed tomography (CT) imaging was performed to assess for HALT at the discretion of the treating valve team.

Results

A total of 78 patients with a mean age of 78 ± 10 years and STS risk score 5.5 ± 3.3% were analyzed. HALT was identified in 11 (14.1%) patients. Compared to controls, those with HALT had smaller annular areas, 435 ± 57 mm2 vs. 489 ± 79 mm2 (p = .032), but received comparable size valves. In multivariate regression, valve oversizing by more than 20% was associated with increased risk of HALT, OR 23.5, 95% CI 2.5–223, (p = .006). After initiation of anticoagulation, patients with HALT had similar rates of stroke, major bleeding, and all‐cause mortality out to an average of 243 days.

Conclusions

In this pragmatic study of patients undergoing TAVR with SAPIEN 3 valves, we report the novel finding that oversizing by more than 20% was independently associated with increased risk of HALT. These findings warrant confirmation in larger and prospective trials.
A case report of rare intraperitoneal cholesteatoma diagnosed and treated through multidisciplinary collaboration
Authors: Jiang Jie , Chu Guang , Chen Gang , Liao Hongyun , Yu Lu , Yu Hongjun , Liu Jie , Hu Zongqiang
Published: July 2020

55‐year‐old female patient with abdominal distension and poor appetite for 3 months was diagnosed as intraperitoneal cholesteatoma by imaging findings and histological tests. Patient has received surgical resection and recovered well after operation.
Kinetic and mechanistic study of CO oxidation over nanocomposite Cu−Fe−Al oxide catalysts
Authors: Fedorov Aleksandr , Saraev Andrey , Kremneva Anna , Selivanova Aleksandra , Vorokhta Mykhailo , Šmíd Bretislav , Bulavchenko Olga , Yakovlev Vadim , Kaichev Vasily
Published: July 2020

The oxidation of CO has been studied over Fe−Al and Cu−Fe−Al oxide nanocomposite catalysts prepared by melting of copper, iron, and aluminum nitrates. It was shown that the addition of copper significantly increases the catalytic activity of the Fe−Al nanocomposites. The catalysts were characterized by low‐temperature nitrogen adsorption, X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS). It was found that the catalysts contain Fe2O3 with the hematite structure modified by aluminum. Copper in the three‐component catalyst is in the Cu2+ state, forming CuO and CuFeOx clusters on the catalyst surface. An increase in the copper content leads to the formation of a CuxAlyFe3‐x‐yO4 spinel phase. In situ XPS study showed that a treatment of the catalysts in a CO flow leads to the reduction of both copper and iron cations into the metallic state. In contrast, a treatment in a CO/O2 flow leads only to partial reduction of Cu2+ to Cu1+, while Fe3+ are not reduced. The tests of catalytic activity performed in a flow fixed bed reactor using a CO pulse technique showed that the light‐off temperature in the oxidation of CO over the Cu−Fe−Al nanocomposite catalysts depends on the copper content. The minimal light‐off temperature was achieved over the catalyst containing 5 wt% CuO. In addition, we performed kinetic measurements in a differential reactor and obtained the activation energy and the reaction orders with respect to the reactants. The reaction mechanism of the catalytic oxidation of CO and the origin of active species are discussed.
Electrochemical Performance of B‐Type Vanadium Dioxide as a Sodium‐Ion Battery Cathode: A Combined Experimental and Theoretical Study
Authors: Koch Daniel , Petnikota Shaikshavali , Yang Zhou , Srinivasan Madhavi , Manzhos Sergei
Published: July 2020

B‐type vanadium dioxide is a frequently investigated lithium‐ion battery material because of its appreciable gravimetric capacity, energy density, rate capability and cycling stability, but investigations of its performance with sodium working metal are scarce. We present a combined experimental‐theoretical study exploring the underlying mechanism of the electrochemical sodiation of B‐type vanadium dioxide. We find agreement between theoretical and experimental results, which complement each other and map out a detailed mechanistic picture. We are able to identify the sluggish diffusion of sodium ions in the vanadium dioxide host material, especially at low concentrations, as a key obstacle to the utilization of the pristine material as a high‐performance cathode for sodium‐ion batteries. Our findings provide context for previously reported results and can be used for a more targeted vanadium dioxide electrode design in the future.
In Situ Spectroelectrochemical Investigation of Potential‐Dependent Changes in an Amphiphilic Imidazolium‐Based Ionic Liquid Film on the Au(111) Electrode Surface
Authors: Sieling Thorben , Brand Izabella
Published: July 2020

Invited for this month's cover picture are Thorben Sieling and Izabella Brand from the University of Oldenburg (Germany). The cover picture shows molecular‐scale changes of an amphiphilic imidazolium‐based ionic liquid in a monolayer film on the Au(111) electrode. Read the full text of the Article at 10.1002/celc.202000385.
Biocatalytic Micro‐ and Nanomotors
Authors: Hermanová Soňa , Pumera Martin
Published: July 2020

Enzyme‐powered micro‐ and nanomotors are tiny devices inspired by nature that utilize enzyme‐triggered chemical conversion to release energy stored in the chemical bonds of a substrate (fuel) to actuate it into active motion. Compared with conventional chemical micro‐/nanomotors, these devices are particularly attractive because they self‐propel by utilizing biocompatible fuels, such as glucose, urea, glycerides, and peptides. They have been designed with functional material constituents to efficiently perform tasks related to active targeting, drug delivery and release, biosensing, water remediation, and environmental monitoring. Because only a small number of enzymes have been exploited as bioengines to date, a new generation of multifunctional, enzyme‐powered nanorobots will emerge in the near future to selectively search for and utilize water contaminants or disease‐related metabolites as fuels. This Minireview highlights recent progress in enzyme‐powered micro‐ and nanomachines.
Impact of optimizing diagnostic workup and reducing the time to treatment in head and neck cancer
Authors: Schutte Henrieke W. , van den Broek Guido B. , Steens Stefan C. A. , Hermens Rosella P. M. G. , Honings Jimmie , Marres Henri A. M. , Merkx Matthias A. W. , Weijs Willem L. J. , Arens Anne I. J. , van Engen–van Grunsven Adriana C. H. , van Herpen Carla M. L. , Kaanders Johannes H. A. M. , van den Hoogen Frank J. A. , Takes Robert P.
Published: July 2020

Background

Timely and efficient diagnostic workup of patients with head and neck cancer (HNC) is challenging. This observational study describes the implementation of an optimized multidisciplinary oncological diagnostic workup for patients with HNC and its impact on diagnostic and treatment intervals, survival, costs, and patient satisfaction.

Methods

All patients with newly diagnosed HNC who underwent staging and treatment at the Radboud University Medical Center were included. Conventional workup (CW) in 2009 was compared with the fast‐track, multidisciplinary, integrated care program, that is, optimized workup (OW), as implemented in 2014.

Results

The study included 486 patients with HNC (218 with CW and 268 with OW). The time‐to‐treatment interval was significantly lower in the OW cohort than the CW cohort (21 vs 34 days; P < .0001). The 3‐year overall survival rate was 12% higher after OW (72% in the CW cohort vs 84% in the OW cohort; P = .002). After correction for confounders, the 3‐year risk of death remained significantly lower in the OW cohort (hazard ratio, 1.73; 95% confidence interval, 1.14‐2.63; P = .010). Total diagnostic costs were comparable in the 2 cohorts. The general satisfaction score, as measured with the Consumer Quality Index for Oncological Care, was significantly better in a matched OW group than the CW group (9.1 vs 8.5; P = .007).

Conclusions

After the implementation of a fast‐track, multidisciplinary, integrated care program, the time‐to‐treatment interval was significantly reduced. Overall survival and patient satisfaction increased significantly, whereas costs did not change. This demonstrates the impact and improved quality of care achieved by efficiently organizing the diagnostic phase of HNC management.
CFD analysis on the effect of combining positive and negative pressure during the irrigation of artificial isthmuses
Authors: Loroño Gaizka , Zaldívar J.M.R. , Jimenez‐Octavio J.R. , Dorado Saul , Arias Ana , Cisneros Rafael
Published: July 2020

Fluid dynamics generated by irrigation needles have not been deeply analyzed in root canal irregularities such as apical ramifications or isthmus where the cleaning capacity of irrigants might be compromised and hence the treatment outcome. The goal of this study was to compare the key irrigation parameters (flow pattern, irrigant velocity, apical pressure, and shear stress) between two irrigation needles and the additional effect of aspiration cannulas through computational fluid dynamics. A 3D‐model consisting of two canals linked by an isthmus was modeled. The abovementioned needles irrigated the primary canal, whereas an aspiration cannula was located inside the secondary canal. Both the geometry definition and spatial discretization were carried out with ANSYS 16.2, through which six different simulations were performed: lateral exit (LE) needle, frontal exit (FE) needle, LE and cannula in crown (LEC), FE and cannula in crown (FEC), LE and cannula in middle third (LEM), FE and cannula in middle third (FEM). FE and FEM showed that the irrigation flow only passes through the isthmus in the most apical section (maximum irrigant velocity / shear stress = 8.44 m/s / 1628.44 Pa and 8.63 m/s / 1185.69 Pa, respectively). However, the remaining simulations showed the irrigation flow passing through the isthmus twice, through the most apical section first and through the upper part of the isthmus later (maximum irrigant velocity / shear stress = 8.48 m/s / 1298.24 Pa (LE), 8.61 m/s / 1261.36 Pa (LEM), 8.61 m/s / 1355.24 Pa (LEC), 8.59 m/s / 1256.87 Pa (FEC)). Furthermore, the highest velocity values were detected when aspiration cannulas were added.
2H QUOSY 2D‐NMR Experiments in Weakly Aligning Systems: From the Conventional to the Ultrafast Approach
Authors: Gouilleux Boris , Meddour Abdelkrim , Lesot Philippe
Published: July 2020

We describe three anisotropic ultrafast (UF) QUadrupolar Ordered SpectroscopY (QUOSY) 2D‐NMR experiments (referred to as ADUF 2D NMR spectroscopy) designed for recording the 2H homonuclear 2D spectra of weakly aligned (deuterated) solutes in sub‐second experiment times. These new ADUF 2D experiments derive from the Q‐COSY, Q‐resolved and Q‐DQ 2D pulse sequences (J. Am. Chem. Soc. 1999, 121, 5249) and allow the correlation between the two components of each quadrupolar doublet, and then their assignment on the basis of 2H chemical shifts. The UF 2D pulse sequences are analyzed by using the Cartesian spin‐operator formalism for spin I=1 nuclei with a small quadrupolar moment. The optimal experimental/practical conditions as well as the resolution, sensitivity and quantification issues of these ADUF 2D experiments are discussed on comparison to their conventional 2D counterparts and their analytical potentialities. Illustrative ADUF 2D experiments using deuterated achiral/prochiral/chiral solutes in poly‐γ‐benzyl‐L‐glutamate based chiral liquid crystals are presented, as well as the first examples of natural abundance deuterium (ANADUF) 2D spectrum using 14.1 T magnetic field and a basic gradient unit (53 G.cm−1) in oriented solvents.
Design and Derivation of Multi‐Reporter Pluripotent Stem Cell Lines via CRISPR/Cas9n‐Mediated Homology‐Directed Repair
Authors: Dettmer Rabea , Naujok Ortwin
Published: July 2020

During the past decade, RNA‐guided Cas9 nuclease from microbial clustered regularly interspaced short palindromic repeats (CRISPR/Cas9) has become a powerful tool for gene editing of human pluripotent stem cells (PSCs). Using paired CRISPR/Cas9 nickases (CRISPR/Cas9n) it is furthermore possible to reduce off‐target effects that may typically occur with traditional CRISPR/Cas9 systems while maintaining high on‐target efficiencies. With this technology and a well‐designed homology‐directed repair vector (HDR), we are now able to integrate transgenes into specific gene loci of PSCs in an allele conserving way. In this protocol we describe CRISPR/Cas9n design and homology directed repair vector design, transfection of human pluripotent stem cells and selection and expansion of generated cell clones. © 2020 The Authors.

Basic Protocol 1: Repair template design and CRISPR/Cas9n construction

Basic Protocol 2: Transfection of human pluripotent stem cells by electroporation

Basic Protocol 3: Genotyping of generated cell clones
Robust FCS Parsing: Exploring 211,359 Public Files
Authors: Bras Anne E. , van der Velden Vincent H. J.
Published: July 2020

When it comes to data storage, the field of flow cytometry is fairly standardized, thanks to the flow cytometry standard (FCS) file format. The structure of FCS files is described in the FCS specification. Software that strictly complies with the FCS specification is guaranteed to be interoperable (in terms of exchange via FCS files). Nowadays, software interoperability is crucial for eco system, as FCS files are frequently shared, and workflows rely on more than one piece of software (e.g., acquisition and analysis software). Ideally, software developers strictly follow the FCS specification. Unfortunately, this is not always the case, which resulted in various nonconformant FCS files being generated over time. Therefore, robust FCS parsers must be developed, which can handle a wide variety of nonconformant FCS files, from different resources. Development of robust FCS parsers would greatly benefit from a fully fledged set of testing files. In this study, readability of 211,359 public FCS files was evaluated. Each FCS file was checked for conformance with the FCS specification. For each data set, within each FCS file, validated parse results were obtained for the TEXT segment. Highly space efficient testing files were generated. FlowCore was benchmarked in depth, by using the validated parse results, the generated testing files, and the original FCS files. Robustness of FlowCore (as measured by testing against 211,359 files) was improved by re‐implementing the TEXT segment parser. Altogether, this study provides a comprehensive resource for FCS parser development, an in‐depth benchmark of FlowCore, and a concrete proposal for improving FlowCore. © 2020 The Authors. Cytometry Part A published by Wiley Periodicals LLC on behalf of International Society for Advancement of Cytometry.
Large intelligent surfaces: Random waypoint mobility and two‐way relaying
Authors: Pillay Narushan , Xu Hongjun
Published: July 2020

In this paper, we first investigate the effect of mobility via the random waypoint (RWP) mobility model on the performance of nonaccess point (non‐AP) or AP large intelligent surfaces (LISs). The theoretical average bit error probability (ABEP) for each of these LISs under mobility is formulated. The presented formulation is complicated to solve; hence, the trapezoidal approximation is employed. Simulation results serve to validate the ABEP. Second, we investigate a two‐way relaying (TWR) network assisted by non‐AP or AP LISs. A network with two source/destination nodes with a single relay node employing decode‐and‐forward placed between these nodes is considered. The transmission interval is broken into two transmission phases. In the first phase, the two source nodes transmit information blocks to the relay node assisted by LISs. On receiving these information blocks, the relay node decodes the two information blocks and encodes these into a single information block via the use of network coding. In the second phase, the relay node forwards the network‐coded information block to the destination nodes assisted by LISs, where the intended information block is decoded via network coding. The theoretical ABEP is formulated for the proposed non‐AP and AP LIS‐assisted TWR schemes and is validated by simulation results. RWP mobility is also demonstrated for the proposed TWR schemes.
The Milan system for reporting salivary gland cytopathology: A comprehensive review of the literature
Authors: Jalaly Jalal B. , Farahani Sahar J. , Baloch Zubair W.
Published: July 2020

Background

The Milan system for Reporting Salivary Gland Cytopathology (MSRSGC) was published in 2018. Since then, many authors have published their institutional experience by retrospectively assigning salivary gland fine‐needle aspiration cases to each of the MSRSGC categories and calculated their risk of malignancy (ROM) accordingly.

Methods

We reviewed all published articles available online in English that used the MSRSGC since or near its publication. We calculated the risk of neoplasm and ROM for each diagnostic category. In addition, the false‐negative and false‐positive rates from all studies were examined.

Results

Thirty‐seven articles were identified in the English literature; 2 were published in 2017, 14 in 2018, 18 in 2019, and 3 in 2020. The total number of cases was 16 394, and 8 468 had surgical follow‐up. The mean ROM was 16.9% for category I, 10.5% for category II, 39.3% for category III, 2.9% for category IVa, 39.4% for category IVb, 84.2% for category V, and 97.5% for category VI. The mean false‐negative rate for MSRSGC categories II and IVa was 4.5%. Similarly, the mean false‐positive rate for MSRSGC categories V and VI was 5.1%.

Conclusion

A tiered classification scheme of MSRSGC is helpful in effectively guiding clinical management of patients with salivary gland lesions. The reported mean ROM for each category in most studies is within the recommended range published by the MSRSGC.
Revisiting potential druggable targets against SARS‐CoV‐2 and repurposing therapeutics under preclinical study and clinical trials: A comprehensive review
Authors: Sohag Abdullah Al Mamun , Hannan Md Abdul , Rahman Sadaqur , Hossain Motaher , Hasan Mahmudul , Khan Md Kawsar , Khatun Amena , Dash Raju , Uddin Md Jamal
Published: July 2020

Coronavirus disease‐19 (COVID‐19), caused by severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2), is one of the most contagious diseases in human history that has already affected millions of lives worldwide. To date, no vaccines or effective therapeutics have been discovered yet that may successfully treat COVID‐19 patients or contain the transmission of the virus. Scientific communities across the globe responded rapidly and have been working relentlessly to develop drugs and vaccines, which may require considerable time. In this uncertainty, repurposing the existing antiviral drugs could be the best strategy to speed up the discovery of effective therapeutics against SARS‐CoV‐2. Moreover, drug repurposing may leave some vital information on druggable targets that could be capitalized in target‐based drug discovery. Information on possible drug targets and the progress on therapeutic and vaccine development also needs to be updated. In this review, we revisited the druggable targets that may hold promise in the development of the anti‐SARS‐CoV‐2 agent. Progresses on the development of potential therapeutics and vaccines that are under the preclinical studies and clinical trials have been highlighted. We anticipate that this review will provide valuable information that would help to accelerate the development of therapeutics and vaccines against SARS‐CoV‐2 infection.
Increasing engagement in pharmacology and pharmacogenetics education using games and online resources: The PharmacoloGenius mobile app
Authors: Zammarchi Gianpaolo , Del Zompo Maria , Squassina Alessio , Pisanu Claudia
Published: July 2020

Mobile applications represent useful instruments to convey information and engage the users even during traveling, thanks to the wide diffusion of smartphones, tablets, smartwatches, and similar devices. As such, they have high potential as learning tools that can act complementary to traditional teaching approaches. In the field of pharmacology, mobile applications are increasingly being used to improve adherence of patients or to help them report suspect adverse drug reactions. However, they have been scarcely applied to pharmacology education. In this article, we present PharmacoloGenius, a free Android mobile application integrating resources useful for students as well as healthcare professionals or researchers to expand knowledge on pharmacological topics. We gave particular emphasis to pharmacogenetics, as it is a fundamental tool to achieve personalized treatment. The application offers original games such as pharmacological trivia based on textbooks or special “journal club” trivia based on research articles conveying the state of the art on specific topics. Additionally, the app offers a curated list of online resources to study pharmacology and pharmacogenetics (e.g., free online courses, videos, and databases) as well as updated news on conferences, grants, and opportunities for pharmacologists. In conclusion, PharmacoloGenius aims to be a useful instrument for people interested in expanding their knowledge on pharmacology in an engaging way.