bluuebunny/crossref_metadata_2025 huggingface dataset:
A Silica Bilayer Supported on Ru(0001): Following the Crystalline‐to Vitreous Transformation in Real Time with Spectro‐microscopy
Authors: Klemm Hagen W. , Prieto Mauricio J. , Xiong Feng , Hassine Ghada B. , Heyde Markus , Menzel Dietrich , Sierka Marek , Schmidt Thomas , Freund Hans‐Joachim
Published: March 2020

The crystalline‐to‐vitreous phase transformation of a SiO2 bilayer supported on Ru(0001) was studied by time‐dependent LEED, local XPS, and DFT calculations. The silica bilayer system has parallels to 3D silica glass and can be used to understand the mechanism of the disorder transition. DFT simulations show that the formation of a Stone–Wales‐type of defect follows a complex mechanism, where the two layers show decoupled behavior in terms of chemical bond rearrangements. The calculated activation energy of the rate‐determining step for the formation of a Stone—Wales‐type of defect (4.3 eV) agrees with the experimental value. Charge transfer between SiO2 bilayer and Ru(0001) support lowers the activation energy for breaking the Si−O bond compared to the unsupported film. Pre‐exponential factors obtained in UHV and in O2 atmospheres differ significantly, suggesting that the interfacial ORu underneath the SiO2 bilayer plays a role on how the disordering propagates within the film.
Stereospecific Asymmetric Synthesis of Tertiary Allylic Alcohol Derivatives by Catalytic [2,3]‐Meisenheimer Rearrangements
Authors: Yu Xin , Wannenmacher Nick , Peters René
Published: March 2020

Chiral acyclic tertiary allylic alcohols are very important synthetic building blocks, but their enantioselective synthesis is often challenging. A major limitation in catalytic asymmetric 1,2‐addition approaches to ketones is the enantioface differentiation by steric distinction of both ketone residues. Herein we report the development of a catalytic asymmetric Meisenheimer rearrangement to overcome this problem, as it proceeds in a stereospecific manner. This allows for high enantioselectivity also for the formation of products in which the residues at the generated tetrasubstituted stereocenter display a similar steric demand. Low catalyst loadings were found to be sufficient and the reaction conditions were mild enough to tolerate even highly reactive functional groups, such as an enolizable aldehyde, a primary tosylate, or an epoxide. Our investigations suggest an intramolecular rearrangement pathway.
Solvent‐Free Self‐Assembly for Scalable Preparation of Highly Crystalline Mesoporous Metal Oxides
Authors: Xiong Hailong , Zhou Hongru , Sun Ge , Liu Zhilin , Zhang Liangliang , Zhang Ling , Du Fei , Qiao Zhen‐An , Dai Sheng
Published: March 2020

Mesoporous metal oxides (MMOs) have been demonstrated great potential in various applications. Up to now, the direct synthesis of MMOs is still limited to the solvent induced inorganic‐organic self‐assembly process. Here, we develop a facile, general, and high throughput solvent‐free self‐assembly strategy to synthesize a series of MMOs including single‐component MMOs and multi‐component MMOs (e.g., doped MMOs, composite MMOs, and polymetallic oxide) with high crystallinity and remarkable porous properties by grinding and heating raw materials. Compared with the traditional solution self‐assembly process, the avoidance of solvents in this method not only greatly increases the yield of target products and synthesis efficiency, but also reduces the environmental pollution and the consumption of cost and energy. We believe the presented approach will pave a new avenue for scalable production of advanced mesoporous materials for various applications.
Chemical anisotropy of the cosmic microwave background radiation
Authors: Chyla W. T.
Published: March 2020

It is shown how the large‐scale inhomogeneous distribution of chemical elements in the primordial medium contributes to temperature fluctuations of the cosmic microwave background radiation (CMB). The magnitude of the chemical anisotropy of the CMB, which is sensitive to the absolute and relative abundance of chemical elements at the time of decoupling, is compared with the primary Sachs‐Wolfe anisotropy of the CMB in the baryon acoustic oscillations scale, which shows that the two effects are of similar importance.
Probeinstandsetzung einer Wehrpfeilerdecke am Eidersperrwerk
Authors: Dridiger Wladimir , Walz Marcus
Published: March 2020

Die Arbeiten am größten deutschen Küstenschutzbauwerk stellten für das ausführende Unternehmen ZÜBLIN eine große Herausforderung dar. Die Decken aller vier Wehrpfeiler des Eidersperrwerks müssen instand gesetzt werden. Zur Beurteilung des tatsächlichen Schädigungsgrads sowie des Arbeitsaufwands und die Optimierung des Instandsetzungskonzepts wurde die Decke des Wehrpfeilers 2 probeweise instand gesetzt. Durch hohe Anforderungen hinsichtlich der Qualität und des Bauablaufs war eine bis ins kleinste Detail ausgearbeitete Terminplanung notwendig. Zudem erschwerten die aufgrund der geografischen Lage vorhandenen äußeren Rahmenbedingungen die Bauarbeiten. Wind und Wetter, die Begrenzung der Bauzeit durch den Einbruch der Sturmflutsaison und die Aufrechterhaltung des Betriebs sowie der Zugänglichkeit des Bauwerks erforderten verstärkte Schutzmaßnahmen und eine enge Abstimmung aller Beteiligten. Der unerwartete Fund von oberflächennahen Spanngliedern und Spannglocken bedurfte eine umfassende Anpassung der geplanten Bauverfahren. Die vollständige Umplanung der Dehnfugenkonstruktion sowie der Einsatz von auf diesen speziellen Anwendungsfall optimal abgestimmten Materialien ermöglichten einen erfolgreichen Abschluss des Bauvorhabens.
3D Periodic Ion Transport Channel to Suppress Top Deposition toward Stable Lithium Metal Anode
Authors: Pan Linhai , Wang Jian , Luo Zhifu , Zhao Zehua , Li Yanyan , Egun Ishioma , He Haiyong
Published: March 2020

3D structures have been widely used to suppress dendritic growth for stabilizing lithium metal anode. Unfortunately, it is hard to avoid lithium metal depositing on top of the framework, causing framework to lose its function. Here, we constructed a 3D periodic TiO2 framework (3D‐TiO2) on copper foil using polystyrene beads as template. The poor conductivity of TiO2 makes metallic lithium to nucleate on copper surface under framework. Combining with 3D periodic channels for fast ion transport, lithium metal gradually filled the whole space of framework. No lithium metal appeared on surface of 3D‐TiO2 electrode before filling up inner space. Meanwhile, large space provided by interconnected framework can ensure high loading of lithium, thereby suppressing the volume fluctuation during cycling. Additionally, batteries assembled by 3D‐TiO2 electrode exhibited excellent rate capability, owning to the fast ion transport supplied by 3D periodic structure. We believe that the combination of high capacity and frequency response in lithium metal anode could meet the challenge of the currently available devices.
„Trotz mancher Schwierigkeiten“. Zu den Auslandsreisen deutscher Geisteswissenschaftler zwischen 1933 und 1945
Authors: Albrecht Andrea , Klausnitzer Ralf
Published: March 2020

In the years of National Socialism, and even during World War II, German scientists traveled abroad extensively. While international travels by natural scientists were studied in some detail, travels by scholars in the humanities have been studied to a much lesser degree, even though travel documents offer valuable insights into the regulated internationality of National Socialism. – We provide a first overview of international travels of scholars in the humanities between 1933 and 1945. The examples demonstrate how travelling academics dealt with conflicting expectations, justified their intentions, articulated disappointment, offered pragmatic advice for the further shaping of contacts abroad, and in this way became active participants of the resource ensemble of academia and politics. The study is based on extensive material from the political archive of the Auswärtiges Amt and the archive of the Reichsministerium für Wissenschaft, Erziehung und Volksbildung from the Bundesarchiv which to this date have been hardly explored.
On a class of non‐linear transformation cure rate models
Authors: Balakrishnan Narayanaswamy , Milienos Fotios S.
Published: March 2020

In this paper, we propose a generalization of the mixture (binary) cure rate model, motivated by the existence of a zero‐modified (inflation or deflation) distribution, on the initial number of causes, under a competing cause scenario. This non‐linear transformation cure rate model is in the same form of models studied in the past; however, following our approach, we are able to give a realistic interpretation to a specific class of proper transformation functions, for the cure rate modeling. The estimation of the parameters is then carried out using the maximum likelihood method along with a profile approach. A simulation study examines the accuracy of the proposed estimation method and the model discrimination based on the likelihood ratio test. For illustrative purposes, analysis of two real life data‐sets, one on recidivism and another on cutaneous melanoma, is also carried out.
Engineering d‐Lactate Dehydrogenase to Favor an Non‐natural Cofactor Nicotinamide Cytosine Dinucleotide
Authors: Liu Yuxue , Li Qing , Wang Lei , Guo Xiaojia , Wang Junting , Wang Qian , Zhao Zongbao K.
Published: March 2020

Synthetic nicotinamide adenine dinucleotide (NAD) analogues are of great scientific and biotechnological interest. One such analogue, nicotinamide cytosine dinucleotide (NCD), has been successfully applied to creating bioorthogonal redox systems. Yet, only a few redox enzymes have been devised to favor NCD. We have engineered Lactobacillus helveticus‐derived NAD‐dependent d‐lactate dehydrogenase (LhDLDH) to favor NCD by semirational design. Sequence alignment and structural analysis revealed that amino acid residues I177 and N213 form a “gate” guarding the NAD adenine moiety binding cavity. Saturated mutagenesis libraries were constructed by using the mutant LhDLDH‐V152R as the parental sequence. Mutants were obtained with good catalytic efficiency, and NCD preference increased by up to 940‐fold. Experiments showed that Escherichia coli cells expressing mutants with higher NCD preference afforded much less d‐lactate, thus suggesting the potential to construct NCD‐mediated orthogonal metabolism.
β‐Diketonate versus β‐Ketoiminate: The Importance of a Ferrocenyl Moiety in Improving the Anticancer Potency
Authors: Allison Matthew , Wilson Daniel , Pask Christopher M. , McGowan Patrick C. , Lord Rianne M.
Published: March 2020

Herein we present a library of fully characterized β‐diketonate and β‐ketoiminate compounds that are functionalized with a ferrocenyl moiety. Their cytotoxic potential has been determined by screening against human breast adenocarcinomas (MCF‐7 and MDA‐MB‐231), human colorectal carcinoma p53 wild type (HCT116 p53+/+) and normal human prostate (PNT2) cell lines. The ferrocenyl β‐diketonate compounds are more than 18 times more cytotoxic than the ferrocenyl β‐ketoiminate analogues. Against MCF‐7, compounds functionalized at the meta position are up to nine times more cytotoxic than when functionalized at the para position. The ferrocenyl β‐diketonate compounds have increased selectivity towards MCF‐7 and MDA‐MB‐231, with several complexes having selectivity index (SI) values that are more than nine times (MCF‐7) and more than six times (MDA‐MB‐231) that of carboplatin. The stability of these compounds in dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) has been assessed by NMR spectroscopy and mass spectrometry studies, and the compounds show no oxidation of the iron center from FeII to FeIII. Cytotoxicity screening was performed in both DMSO and DMF, with no significant differences observedin their potency.
Aggregation‐Induced Improvement of Catalytic Activity by Inner‐Aggregate Electronic Communication of Metal‐Fullerene‐Based Surfactants
Authors: Kunkel Marius , Bitter Stefan , Sailer Frank , Winter Rainer F. , Polarz Sebastian
Published: March 2020

A paradigm for active constituents in (homogeneous) catalysis is that optimum performance requires maximum dispersion. Generally, aggregation results in a decline. This is a different case in supramolecular catalysis. A new concept based on surfactants equipped with functional heads is presented, which becomes a more active catalyst itself upon aggregation. The head group of the surfactants is composed of a diethylenetriamine‐functionalized fullerene capable of coordinating to catalytically active metals like CoII. The improvement of catalytic properties upon aggregation is demonstrated via electrocatalytic water‐splitting reaction as a model system. Detailed electrochemistry studies were performed at concentrations below and above the critical aggregation concentration (cac). While isolated surfactant molecules represent only moderately active catalysts, drastic improvement of efficiency in the hydrogen evolution (HER) as well as in the oxygen evolution reactions (OER) were detected, once vesicular structures have formed. Self‐organization of the surfactants leads to an increase in turnover frequencies of up to 1300 % (HER). The strongly beneficial effect of aggregation arises from the favorable alignment of individual molecules, thus, facilitating intermolecular charge transfer processes in the vesicles.
An Overview of Recent Electroanalytical Applications Utilizing Screen‐Printed Electrodes Within Flow Systems
Authors: Squissato André L. , Munoz Rodrigo A. A. , Banks Craig E. , Richter Eduardo M.
Published: March 2020

This review addresses the use of screen‐printed electrodes (SPEs) coupled to flow systems such as flow injection analysis (FIA), batch injection analysis (BIA), and high‐performance liquid chromatography (HPLC) systems over the last six years (since 2014). The combination of SPEs and flow systems is a powerful synergy to increase the throughput of measurements, improve electrode lifetime, and reduce reagent consumption and waste generation. Recently, commercial flow cells for SPEs were made available by different companies and potential new users that are unable to construct homemade electrochemical flow cells have been attracted to work in the area. This overview aims to show both trends and future potential for the development of new methods useful for modern electroanalysis and/or portable applications.
Habits in organizational contexts: Information systems routines, cues, and rewards
Authors: Khatib Rima , Barki Henri
Published: March 2020

The objective of the present paper is to identify and develop a framework of IS habits that individuals tend to develop in organizational contexts. Based on Duhigg's (2012) framework of habit, the paper develops a new conceptualization of IS habit as a cue–routine–reward loop. The key difference between the proposed conceptualization and those that have been used in past research is its consideration of rewards as an essential element of habit. Based on the results of an exploratory study, the proposed framework of habits incorporates several categories of IS routines, cues, and rewards, as well as five propositions that explain how individual usage behaviours develop into IS habits. The paper's findings are also likely to help improve employee task performances.
Experimental methods in chemical engineering: Rheometry
Authors: Ghanbari Abbas , Mousavi Zeinab , Heuzey Marie‐Claude , Patience Gregory S. , Carreau Pierre J.
Published: March 2020

Rheometry is an experimental technique that measures the relationship between stresses, strains, and their derivatives of fluids and deformable materials. Capillary and Couette viscometers were among the first instruments used to study rheology but now sophisticated shear and extensional rheometers are widely available for quality control, research, and product development. Here, we introduce the basics of rheology, define material functions, and describe conventional instruments, physical principles, applications, and uncertainties. In 2016 and 2017, the Web of Science indexed 8400 articles that mention rheometry and a bibliometric map assigned the keywords into five clusters of research: behaviour and viscosity, mechanical properties and morphology, rheological properties and microstructure, polymers and nano‐particles, and visco‐elastic properties and mixtures. Journal of Rheology, Construction Building Materials, Food Hydrocolloids, Soft Matter, Rheologica Acta, and Journal of Applied Polymer Science publish at least 80 articles per year that mention rheometry.
Additional postdilatation using noncompliant balloons after everolimus‐eluting stent implantation: Results of the PRESS trial
Authors: Park Gyung‐Min , Lee Jae‐Hwan , Choi Si Wan , Jeong Jin‐Ok , Shin Eun‐Seok , Bae Jang‐Whan , Yoon Hyuck‐Jun , Jung Kyung Tae , Baek Ju Yeol , Choi Woong Gil , Choi Rak Kyeong , Her Sung‐Ho , Lee Jin Bae , Suh Jon , Lee Jae Beom , Lee Se‐Whan , Chae In‐Ho , Choi So‐Yeon , Seong In‐Whan
Published: March 2020

Background

There are limited data on the clinical value of routine postdilatation using noncompliant balloons after contemporary drug‐eluting stent implantation.

Hypothesis

Additional postdilatation using noncompliant balloons after everolimus‐eluting stent implantation could provide better clinical outcomes.

Methods

We randomly assigned 1774 patients with coronary artery disease to undergo additional high‐pressure postdilatation using noncompliant balloons and moderate‐pressure dilatation using stent balloons after everolimus‐eluting stent implantation. The primary endpoint was a composite of death, myocardial infarction (MI), stent thrombosis, and target vessel revascularization (TVR) 2 years after randomization.

Results

The study was discontinued early owing to slow enrollment. In total, 810 patients (406 patients in the high pressure group and 404 in the moderate pressure group) were finally enrolled. At 2 years, the primary endpoint occurred in 3.6% of patients in the high pressure group and in 4.4% of those in the moderate pressure group (P = .537). In addition, no significant differences were observed between the two groups in the occurrence of an individual end point of death (0.8% in the high pressure group vs 1.5% in the moderate group, P = .304), MI (0.2% vs 0.5%, P = .554), stent thrombosis (0% vs 0.2%, P = .316), or TVR (2.8% vs 2.6%, P = .880).

Conclusions

The strategy of routine postdilatation using noncompliant balloons after everolimus‐eluting stent implantation did not provide incremental clinical benefits.
An evolutionary framework for treating pediatric sarcomas
Authors: Reed Damon R. , Metts Jonathan , Pressley Mariyah , Fridley Brooke L. , Hayashi Masanori , Isakoff Michael S. , Loeb David M. , Makanji Rikesh , Roberts Ryan D. , Trucco Matteo , Wagner Lars M. , Alexandrow Mark G. , Gatenby Robert A. , Brown Joel S.
Published: March 2020

Lessons from extinction can be used in trials designed to pursue a cure for cancer. When cancer cannot be cured, similar strategies may be unwise, and strategies that leverage the adaptations of cancer to therapy should be considered.
Cationic Biphotonic Lanthanide Luminescent Bioprobes Based on Functionalized Cross‐Bridged Cyclam Macrocycles
Authors: Mendy Jonathan , Thy Bui Anh , Roux Amandine , Mulatier Jean‐Christophe , Curton Damien , Duperray Alain , Grichine Alexei , Guyot Yannick , Brasselet Sophie , Riobé François , Andraud Chantal , Le Guennic Boris , Patinec Véronique , Tripier Pr. Raphael , Beyler Maryline , Maury Olivier
Published: March 2020

Cationic lanthanide complexes are generally able to spontaneously internalize into living cells. Following our previous works based on a diMe‐cyclen framework, a second generation of cationic water‐soluble lanthanide complexes based on a constrained cross‐bridged cyclam macrocycle functionalized with donor‐π‐conjugated picolinate antennas was prepared with europium(III) and ytterbium(III). Their spectroscopic properties were thoroughly investigated in various solvents and rationalized with the help of DFT calculations. A significant improvement was observed in the case of the Eu3+ complex, while the Yb3+ analogue conserved photophysical properties in aqueous solvent. Two‐photon (2P) microscopy imaging experiments on living T24 human cancer cells confirmed the spontaneous internalization of the probes and images with good signal‐to‐noise ratio were obtained in the classic NIR‐to‐visible configuration with the Eu3+ luminescent bioprobe and in the NIR‐to‐NIR with the Yb3+ one.
Kinetic Isotope Effect as a Tool To Investigate the Oxygen Reduction Reaction on Pt‐based Electrocatalysts – Part I: High‐loading Pt/C and Pt Extended Surface
Authors: George Thomas Y. , Asset Tristan , Avid Arezoo , Atanassov Plamen , Zenyuk Iryna V.
Published: March 2020

The front cover artwork is provided by the groups of Prof. Atanassov and Prof. Zenyuk (University of California Irvine, USA). The image shows rate‐determining step of oxygen reduction reaction on platinum nanoparticle supported by carbon, which requires electron transfer but no proton. Read the full text of the Article at 10.1002/cphc.201901091.
Knowledge representation and data sharing to unlock crop variation for nutritional food security
Authors: Andrés‐Hernández Liliana , Baten Abdul , Azman Halimi Razlin , Walls Ramona , King Graham J.
Published: March 2020

Meeting the challenge of food and nutritional security requires ongoing innovation, particularly in managing dietary nutritional information for pre‐breeding analysis, selection, and cultivation of specific food crops and cultivars. At present, the ability to compare the relative nutritional value of crops is limited, with data management systems for most crops often inconsistent and poorly integrated. Here, we review generic efforts to standardize the description and management of crop trait data and discuss several issues currently constraining their exchange and comparison, with a focus on knowledge representation related to dietary nutrition. These issues include lack of consistency within or between crop specific databases, as well as limited data standardization and interoperability. At present, the use of common descriptors or controlled vocabularies between crops is fragmentary, with only partial implementation or uptake of formal ontologies, particularly for dietary nutritional composition. Although development of the existing Crop Ontology (CO) system has improved data sharing and reuse, it represents only a limited set of trait classes and crops. We identify the need for more robust and generic ontologies, particularly those that may address crop contributions to human dietary nutrition. We propose development of a Crop Dietary Nutrition Ontology (CDNO) as a robust structured controlled vocabulary for dietary nutritional composition and function, and provide examples of specific use cases and different end users who would benefit from using CDNO terms in their database searches. This development is likely to transform the way in which crops may be compared in terms of optimal dietary nutritional values.
Selective Electroreduction of Carbon Dioxide over SnO2‐Nanodot Catalysts
Authors: Hu Congling , Li Lulu , Deng Wanyu , Zhang Gong , Zhu Wenjin , Yuan Xintong , Zhang Lei , Zhao Zhi‐Jian , Gong Jinlong
Published: March 2020

The development of electrochemical CO2conversion allows green carbon utilization. Formate and syngas are two typical products of electrochemical CO2reduction, and the coproduction of these two products will maximize the energy efficiency of CO2conversion. However, few works have successfully achieved the cogeneration of formate and syngas. This paper describes a novel strategy to maximize the efficiency of CO2conversion through coproduction of formate and syngas on ultrasmall SnO2nanodots (NDs) homogeneously anchored on carbon nanotubes (CNT#SnO2NDs) electrodes. The CNT#SnO2NDs not only decreased the adsorption energy of *OCHO but also reduced the adsorption energy difference of *COOH and *H. High energy efficiency toward formate and adjustable H2/CO ratio were obtained over a broad potential window with long‐term stability. In addition, CNT#SnO2NDs and Ir foil were coupled together to construct an electrolyzer for electrochemical CO2reduction reaction and oxygen evolution reaction (CO2ERR–OER), which also produced formate and syngas with 24 h stability. A promising approach is presented for the electrochemical CO2conversion in fuel production.
Effectiveness of revascularisation of the ulcerated foot in patients with diabetes and peripheral artery disease: A systematic review
Authors: Forsythe Rachael O. , Apelqvist Jan , Boyko Edward J. , Fitridge Robert , Hong Joon P. , Katsanos Konstantinos , Mills Joseph L. , Nikol Sigrid , Reekers Jim , Venermo Maarit , Zierler R. Eugene , Hinchliffe Robert J. , Schaper Nicolaas C.
Published: March 2020

In patients with diabetes, foot ulceration and peripheral artery disease (PAD), it is often difficult to determine whether, when and how to revascularise the affected lower extremity. The presence of PAD is a major risk factor for non‐healing and yet clinical outcomes of revascularisation are not necessarily related to technical success. The International Working Group of the Diabetic Foot updated systematic review on the effectiveness of revascularisation of the ulcerated foot in patients with diabetes and PAD is comprised of 64 studies describing >13 000 patients. Amongst 60 case series and 4 non‐randomised controlled studies, we summarised clinically relevant outcomes and found them to be broadly similar between patients treated with open vs endovascular therapy. Following endovascular revascularisation, the 1 year and 2 year limb salvage rates were 80% (IQR 78‐82%) and 78% (IQR 75‐83%), whereas open therapy was associated with rates of 85% (IQR 80‐90%) at 1 year and 87% (IQR 85‐88%) at 2 years, however these results were based on a varying combination of studies and cannot therefore be interpreted as cumulative. Overall, wound healing was achieved in a median of 60% of patients (IQR 50‐69%) at 1 year in those treated by endovascular or surgical therapy, and the major amputation rate of endovascular vs open therapy was 2% vs 5% at 30 days, 10% vs 9% at 1 year and 13% vs 9% at 2 years. For both strategies, overall mortality was found to be high, with 2% (1‐6%) perioperative (or 30 day) mortality, rising sharply to 13% (9‐23%) at 1 year, 29% (19‐48%) at 2 years and 47% (39‐71%) at 5 years. Both the angiosome concept (revascularisation directly to the area of tissue loss via its main feeding artery) or indirect revascularisation through collaterals, appear to be equally effective strategies for restoring perfusion. Overall, the available data do not allow us to recommend one method of revascularisation over the other and more studies are required to determine the best revascularisation approach in diabetic foot ulceration.
Aldimine‐Thioether‐Phenolate Based Mono‐ and Bimetallic Zinc Complexes as Catalysts for the Reaction of CO2 with Cyclohexene Oxide
Authors: Cozzolino Mariachiara , Melchionno Flavia , Santulli Federica , Mazzeo Mina , Lamberti Marina
Published: March 2020

A synthetic strategy for the preparation of a new class of ligands is introduced. The bis(aldimine‐thioether‐phenolate) ligands bear two anionic oxygen donors from phenolate moieties, two neutral sulfur donors and two neutral nitrogen donors belonging, respectively, to thioether and aldimine functionalities. The so designed OSNNSO ligands show two coordinative pockets and thus should be able to host two metallic centers. Instead, the aldimine‐thioether‐phenolate OSN ligands are tridentate ligands which may form monometallic complexes. Two OSNNSO and one OSN ligands of this class, have been synthesized. Satisfyingly, by direct reaction of the ligands with one or two equivalents of the zinc precursor, the corresponding bimetallic Zn(II) complexes were prepared from the bis(aldimine‐thioether‐phenolate) ligands, while the monometallic zinc complex was prepared from the tridentate ligand. These zinc amido complexes act as single component catalysts in the reaction of CO2 with cyclohexene oxide by furnishing polycyclohexene carbonate, while adding PPNCl as cocatalyst to the reaction medium, cyclohexene carbonates were obtained as the main products.
Diels‐Alder Reaction of β‐Fluoro‐β‐nitrostyrenes. Synthesis of Mono‐fluorinated Six‐Membered Derivatives
Authors: Larkovich Roman V. , Ponomarev Savva A. , Aldoshin Alexander S. , Tabolin Andrey A. , Ioffe Sema L. , Nenajdenko Valentine G.
Published: March 2020

The Diels‐Alder reaction of β‐fluoro‐β nitrostyrenes with some linear dienes was investigated. A number of monofluorinated [4+2]‐cycloadducts was prepared in up to 90 % yield. The kinetics of [4+2]‐cycloaddition to 2,3‐dimethyl‐1,3‐butadiene was studied in detail to reveal substituent effect and activation parameters of the reaction. It was demonstrated that base‐induced elimination of nitrous acid followed by oxidative aromatization can be used for the preparation of mono‐fluorinated biphenyls in up to 92 % isolated yield.
Palladium‐Catalyzed Cyanation of Aryl Halides Using Formamide and Cyanuric Chloride as a New “CN” Source
Authors: Niknam Esmaeil , Panahi Farhad , Khalafi‐Nezhad Ali
Published: March 2020

A new source of “CN” employing formamide and cyanuric chloride is introduced for the cyanation reactions. The treatment of formamide and 2,4,6‐trichloro‐1,3,5‐triazine (TCT; cyanuric chloride) afforded an efficient cyanating agent which it can be used as a nontoxic, readily available, and non‐expensive reagent in the cyanation transformations. In this study, palladium‐catalyzed cyanation of aryl halides was successfully accomplished using this new “CN” source in high yields.
Detection of dairy fouling by cyclic voltammetry and square wave voltammetry
Authors: Fysun Olga , Khorshid Sara , Rauschnabel Johannes , Langowski Horst‐Christian
Published: March 2020

Fouling in food processing environment can cause the increase of production costs due to additional cleaning steps and risk of contamination of food products. There is a demand to introduce advanced techniques to detect fouling in food processing equipment. Cyclic voltammetry (CV) and square wave voltammetry (SWV) were probed in this work to detect the dairy fouling and the reconstructed dairy emulsion by platinum‐based interdigitated microelectrodes. The results demonstrated that both methods can potentially be used for the fouling detection, since the attachment of fouling to the microelectrode surface leads to lower current responses compared to the clean microelectrodes.
Lipoprotein‐Like Nanoparticle Carrying Small Interfering RNA Against Spalt‐Like Transcription Factor 4 Effectively Targets Hepatocellular Carcinoma Cells and Decreases Tumor Burden
Authors: Cruz William , Huang Huang , Barber Brian , Pasini Elisa , Ding Lili , Zheng Gang , Chen Juan , Bhat Mamatha
Published: March 2020

Patients with advanced hepatocellular carcinoma (HCC) are often unable to tolerate chemotherapy due to liver dysfunction in the setting of cirrhosis. We investigate high‐density lipoprotein (HDL)‐mimicking peptide phospholipid scaffold (HPPS), which are nanoparticles that capitalize on normal lipoprotein metabolism and transport, as a solution for directed delivery of small interfering RNA (siRNA) cargo into HCC cells. Spalt‐like transcription factor 4 (SALL4), a fetal oncoprotein expressed in aggressive HCCs, is specifically targeted as a case study to evaluate the efficacy of HPPS carrying siRNA cargo. HPPS containing different formulations of siRNA therapy against SALL4 were generated specifically for HCC cells. These were investigated both in vitro and in vivo using fluorescence imaging. HPPS‐SALL4 effectively bound to scavenger receptor, class B type 1 (SR‐BI) and delivered the siRNA cargo into HCC cells, as seen in vitro. HPPS‐SALL4 effectively inhibited HCC tumor growth (P < 0.05) and induced a 3‐fold increase in apoptosis of the cancer cells in vivo compared to HPPS‐scramble. Additionally, there was no immunogenicity associated with HPPS‐SALL4 as measured by cytokine production. Conclusion: We have developed unique HDL‐like nanoparticles that directly deliver RNA interference (RNAi) therapy against SALL4 into the cytosol of HCC cells, effectively inhibiting HCC tumor growth without any systemic immunogenicity. This therapeutic modality avoids the need for hepatic metabolism in this cancer, which develops in the setting of cirrhosis and liver dysfunction. These natural lipoprotein‐like nanoparticles with RNAi therapy are a promising therapeutic strategy for HCC.
Posttraumatic growth among combat veterans and their siblings: A dyadic approach
Authors: Zerach Gadi
Published: March 2020

Objectives

We aimed to use a dyadic approach to assess the effects of veterans' posttraumatic stress disorder symptoms (PTSS) and siblings' secondary PTSS, as well as veterans' and siblings' relationship quality, on primary and secondary posttraumatic growth (PTG).

Method

A volunteers' sample of 106 dyads of Israeli combat veterans and their close‐in‐age siblings responded to self‐report questionnaires in a cross‐sectional, dyadic design study.

Results

Veterans' primary PTG was positively associated with siblings' secondary PTG. Veterans' PTSS and siblings' secondary PTSS were associated with higher levels of primary and secondary PTG, respectively. Furthermore, among veterans, warmth in siblings' relationships was associated with higher levels of primary PTG. However, among siblings, rivalry in sibling relationships was associated with lower levels of secondary PTG.

Conclusions

Both veterans' and siblings' PTSS are only related to their own PTG. Moreover, perception of siblings' relationship quality might have a differential effect on PTG among veterans and their siblings.
Examining attitudes towards mental health treatment and experiences with trauma: Understanding the needs of trauma‐exposed middle‐aged and older adults
Authors: Hansen Marissa C. , Ghafoori Bita , Diaz Melanie
Published: March 2020

Middle‐aged and older adults who have been exposed to traumatic events may have specific developmental needs with respect to engagement in mental health treatment. The current study examined factors that potentially facilitate or inhibit attitudes towards mental health service use (ATMHSU) in a trauma‐exposed sample of treatment‐seeking adults of age 50 years and older. In this mixed‐methods study, quantitative data (N =  165) were analyzed to examine relationships with trauma exposure, posttraumatic stress disorder, quality of life (QOL), and ATMHSU. Semi‐structured interviews were conducted assessing similar constructs with a subsample of the data (n = 12). Regression analysis revealed higher QOL‐environmental well‐being as associated with more positive ATMHSU and higher QOL‐social support with more negative ATMHSU. Qualitative themes emerged around perceived distress in managing lifelong traumas due to challenges with functioning, coping, and accessing services. Emphasizing resources to help manage the impact of distress on daily life needs may support aging trauma‐exposed populations.
A multicenter study comparing the outcome of catheter ablation of atrial fibrillation between cryoballoon and radiofrequency ablation in patients with heart failure (CRABL‐HF): Study design
Authors: Miyamoto Koji , Hasegawa Kanae , Takahashi Hiroki , Masue Yoh , Kataoka Naoya , Fukuzawa Koji , Ashikaga Keiichi , Noda Takashi , Satomi Kazuhiro , Tada Hiroshi , Takagi Masahiko , Yasuda Satoshi , Kusano Kengo
Published: March 2020

Background

Catheter ablation of atrial fibrillation (AF) is increasingly performed worldwide in patients with heart failure (HF). However, it has been recently emphasized that AF ablation in patients with HF is associated with increased risks of procedure‐related complications and mortality. There are little data about the differences in the efficacy and safety between cryoballoon (CB) and radiofrequency (RF) ablation of AF in patients with HF.

Methods

The CRABL‐HF study is designed as a prospective, multicenter, open‐label, controlled, and randomized clinical trial comparing the efficacy and safety of AF ablation between CB and RF ablation in patients with HF (LVEF ≤40%) (UMIN Clinical Trials Registry UMIN000032433). The CRABL‐HF study will consist of 110 patients at multicenter in Japan. The patients will be registered and randomly assigned to either the CB ablation or RF ablation group with a 1:1 allocation. The primary endpoint of this study is the occurrence of atrial tachyarrhythmias (ATs) at 1 year with a blanking period of 90 days after ablation. Key secondary endpoints are the success rate of the pulmonary vein isolation, total procedural time, left atrial dwelling time, total fluoroscopy time, radiation exposure, complication rate, composite of all‐cause mortality or HF hospitalizations, cardiovascular events, change in left ventricular ejection fraction, and change in quality of life.

Results

The results of this study are currently under investigation.

Conclusion

The CRABL‐HF study is being conducted to compare the efficacy and safety of catheter ablation of AF between CB and RF ablation in patients with HF.
Increasing the pixel density for VR displays with a polarization grating
Authors: Zou Junyu , Zhan Tao , Xiong Jianghao , Wu Shin‐Tson
Published: March 2020

An optical approach to increase the pixel density by using a Pancharatnam‐Berry deflector (PBD), which generates two virtual shifted‐pixel grids based on polarization multiplexing, is demonstrated. A three‐layer multi‐twist PBD is fabricated, which can achieve high diffraction efficiency, broad bandwidth, and large incident angle in the visible spectral region.
Observation of Local Symmetry in a Photonic System
Authors: Schmitt Nora , Weimann Steffen , Morfonios Christian V. , Röntgen Malte , Heinrich Matthias , Schmelcher Peter , Szameit Alexander
Published: March 2020

The concept of local symmetry has been shown to be a powerful tool in predicting and designing complex transport phenomena in stationary scattering off aperiodic media, in terms of symmetry‐adapted nonlocal currents. For time‐evolving wavepackets, the spatiotemporal correlations caused by local symmetries are more challenging to reveal. A recent formalism‐based nonlocal continuity equation shows how local symmetries are encoded into the dynamics of light propagation in discrete waveguide arrays governed by a Schrödinger equation. However, the experimental demonstration is elusive so far. Representative examples of locally symmetric, globally symmetric, and fully nonsymmetric configurations are fabricated in fs laser‐written photonic arrays and their dynamics are probed. The approach allows to distinguish all three types of structures.
On the Herbrand functional interpretation
Authors: Oliva Paulo , Xu Chuangjie
Published: March 2020

We show that the types of the witnesses in the Herbrand functional interpretation can be simplified, avoiding the use of “sets of functionals” in the interpretation of implication and universal quantification. This is done by presenting an alternative formulation of the Herbrand functional interpretation, which we show to be equivalent to the original presentation. As a result of this investigation we also strengthen the monotonicity property of the original presentation, and prove a monotonicity property for our alternative definition.
A continuation principle for Fredholm maps II: application to homoclinic solutions
Authors: Pötzsche Christian , Skiba Robert
Published: March 2020

When studying the behavior of autonomous ordinary differential equations under time‐dependent perturbations vanishing for , their equilibria generically persist locally as homoclinic solutions. Using an abstract and flexible continuation theorem, we find even global branches of such homoclinic solutions for parametrized nonautonomous ordinary differential equations. Our approach is based on degree‐theoretical arguments. In particular, Landesman–Lazer conditions are proposed to obtain the existence of homoclinic solutions by means of a nonzero degree.
On the Borisov–Nuer conjecture and the image of the Enriques‐to‐K3 map
Authors: Aprodu Marian , Kim Yeongrak
Published: March 2020

We discuss the Borisov–Nuer conjecture in connection with the canonical maps from the moduli spaces of polarized Enriques surfaces with fixed to the moduli space of polarized K3 surfaces of genus g with , and we exhibit a naturally defined locus . One direct consequence of the Borisov–Nuer conjecture is that would be contained in a particular Noether–Lefschetz divisor in , which we call the Borisov–Nuer divisor and we denote by . In this short note, we prove that is non‐empty whenever is divisible by 4. To this end, we construct polarized Enriques surfaces , with divisible by 4, which verify the conjecture. In particular, when we consider the moduli space of (numerically) polarized Enriques surfaces which contains such , the conjecture also holds for any other polarized Enriques surface contained in the same moduli.
Eigenvalues of non‐Hermitian matrices: A dynamical and an iterative approach—Application to a truncated Swanson model
Authors: Bagarello Fabio , Gargano Francesco
Published: March 2020

We propose two different strategies to find eigenvalues and eigenvectors of a given, not necessarily Hermitian, matrix
. Our methods apply also to the case of complex eigenvalues, making the strategies interesting for applications to physics and to pseudo‐Hermitian quantum mechanics in particular. We first consider a dynamical approach, based on a pair of ordinary differential equations defined in terms of the matrix
and of its adjoint
. Then, we consider an extension of the so‐called power method, for which we prove a fixed point theorem for
useful in the determination of the eigenvalues of
and
. The two strategies are applied to some explicit problems. In particular, we compute the eigenvalues and the eigenvectors of the matrix arising from a recently proposed quantum mechanical system, the truncated Swanson model, and we check some asymptotic features of the Hessenberg matrix.
Large‐scale magnetic resonance simulations: A tutorial
Authors: Concilio Maria Grazia
Published: March 2020

Computational modeling is becoming an essential tool in magnetic resonance to design and optimize experiments, test the performance of theoretical models, and interpret experimental data. Recent theoretical research and software development made possible simulations of large spin systems, for example, proteins with thousands of spins, in reasonable time. In the last few years, the Fokker–Planck formalism also re‐emerged due to its ability to handle spatial dynamics. The purpose of this tutorial is to describe advantages and disadvantages of the most common formalisms, the latest developments and strategies to improve the computational efficiency, and to guide users in the setting up of a simulation using theSpinachsoftware.
Time estimation in a case of Tourette's syndrome: Effect of antipsychotic medications
Authors: Inagawa Takuma , Ueda Natsuki , Nakagome Kazuyuki , Sumiyoshi Tomiki
Published: March 2020

Aims

Dopamine (DA) hyperactivity causes overestimation of time, whereas DA hypoactivity produces its underestimation. DA activity also provides neurochemical substrates pertinent to several psychiatric conditions, such as schizophrenia and Tourette's syndrome. The overestimation of time sometimes exists in patients with Tourette's syndrome, but no reports have addressed time perception in relation to antipsychotic medications which typically act as DA receptor antagonists. We herein report a case of Tourette's syndrome, in which time estimation was differentially affected by risperidone (a DA antagonist) and aripiprazole (a DA partial agonist).

Case

A 27‐year‐old man who suffered from verbal and motor tics was treated with risperidone. His tic symptoms disappeared; however, he began to experience a strange feeling that “time is going too fast.” For example, “people walk more quickly compared to a normal pace.” These complaints were thought to represent underestimation of time. Then, risperidone was switched to oral aripiprazole to optimize DA transmissions, which resulted in the amelioration of these subjective feelings.

Conclusion

Our observations indicate that the underestimation of time may occur in patients with Tourette's syndrome who receive antipsychotic drugs with high DA D2 receptor blocking potency. This may support the concept that the estimation of time is influenced by DA activity.
Mediating role of body‐related shame and guilt in the relationship between weight perceptions and lifestyle behaviours
Authors: Lucibello K. M. , Sabiston C. M. , O'Loughlin E. K. , O'Loughlin J. L.
Published: March 2020

Introduction

A substantial proportion of individuals with overweight or obesity perceive themselves as ‘too heavy’ relative to ‘about right’. Perceiving one's weight as ‘too heavy’ is associated with lower levels of physical activity and higher levels of sedentary behaviour. However, the mechanisms underpinning the associations between weight perception and lifestyle behaviours have not been identified. Based on theoretical tenets and empirical evidence, the self‐conscious emotions of shame and guilt may mediate these associations.

Methods

Participants were young adults (n = 618, Mage = 24.0 ± .6 years) who provided data on weight, weight perception, body‐related shame and guilt, physical activity and screen time.

Results

Mediation analyses using the PROCESS macro indicated that shame and guilt significantly mediated the relationships between weight perception and physical activity and shame significantly mediated the relationship between weight perception and screen time.

Conclusions

These findings provide preliminary evidence that self‐conscious emotions may be mechanisms by which weight perception influences physical activity and sedentary behaviour in young adults. However, longitudinal investigations of this mechanism are needed.
Longitudinal Experience–Wide Association Studies—A Framework for Studying Personality Change
Authors: Bleidorn Wiebke , Hopwood Christopher J. , Back Mitja D. , Denissen Jaap J.A. , Hennecke Marie , Jokela Markus , Kandler Christian , Lucas Richard E. , Luhmann Maike , Orth Ulrich , Roberts Brent W. , Wagner Jenny , Wrzus Cornelia , Zimmermann Johannes
Published: March 2020

The importance of personality for predicting life outcomes in the domains of love, work, and health is well established, as is evidence that personality traits, while relatively stable, can change. However, little is known about the sources and processes that drive changes in personality traits and how such changes might impact important life outcomes. In this paper, we make the case that the research paradigms and methodological approaches commonly used in personality psychology need to be revised to advance our understanding of the sources and processes of personality change. We propose Longitudinal Experience–Wide Association Studies as a framework for studying personality change that can address the limitations of current methods, and we discuss strategies for overcoming some of the challenges associated with Longitudinal Experience–Wide Association Studies. © 2020 European Association of Personality Psychology