bluuebunny/crossref_metadata_2025 huggingface dataset:
Graphene/Half‐Metallic Heusler Alloy: A Novel Heterostructure toward High‐Performance Graphene Spintronic Devices
Authors: Li Songtian , Larionov Konstantin V. , Popov Zakhar I. , Watanabe Takahiro , Amemiya Kenta , Entani Shiro , Avramov Pavel V. , Sakuraba Yuya , Naramoto Hiroshi , Sorokin Pavel B. , Sakai Seiji
Published: December 2019

Graphene‐based vertical spin valves (SVs) are expected to offer a large magnetoresistance effect without impairing the electrical conductivity, which can pave the way for the next generation of high‐speed and low‐power‐consumption storage and memory technologies. However, the graphene‐based vertical SV has failed to prove its competence due to the lack of a graphene/ferromagnet heterostructure, which can provide highly efficient spin transport. Herein, the synthesis and spin‐dependent electronic properties of a novel heterostructure consisting of single‐layer graphene (SLG) and a half‐metallic Co2Fe(Ge0.5Ga0.5) (CFGG) Heusler alloy ferromagnet are reported. The growth of high‐quality SLG with complete coverage by ultrahigh‐vacuum chemical vapor deposition on a magnetron‐sputtered single‐crystalline CFGG thin film is demonstrated. The quasi‐free‐standing nature of SLG and robust magnetism of CFGG at the SLG/CFGG interface are revealed through depth‐resolved X‐ray magnetic circular dichroism spectroscopy. Density functional theory (DFT) calculation results indicate that the inherent electronic properties of SLG and CFGG such as the linear Dirac band and half‐metallic band structure are preserved in the vicinity of the interface. These exciting findings suggest that the SLG/CFGG heterostructure possesses distinctive advantages over other reported graphene/ferromagnet heterostructures, for realizing effective transport of highly spin‐polarized electrons in graphene‐based vertical SV and other advanced spintronic devices.
Fast, 3D Isotropic Imaging of Whole Mouse Brain Using Multiangle‐Resolved Subvoxel SPIM
Authors: Nie Jun , Liu Sa , Yu Tingting , Li Yusha , Ping Junyu , Wan Peng , Zhao Fang , Huang Yujie , Mei Wei , Zeng Shaoqun , Zhu Dan , Fei Peng
Published: December 2019

The recent integration of light‐sheet microscopy and tissue‐clearing has facilitated an important alternative to conventional histological imaging approaches. However, the in toto cellular mapping of neural circuits throughout an intact mouse brain remains highly challenging, requiring complicated mechanical stitching, and suffering from anisotropic resolution insufficient for high‐quality reconstruction in 3D. Here, the use of a multiangle‐resolved subvoxel selective plane illumination microscope (Mars‐SPIM) is proposed to achieve high‐throughput imaging of whole mouse brain at isotropic cellular resolution. This light‐sheet imaging technique can computationally improve the spatial resolution over six times under a large field of view, eliminating the use of slow tile stitching. Furthermore, it can recover complete structural information of the sample from images subject to thick‐tissue scattering/attenuation. With Mars‐SPIM, a digital atlas of a cleared whole mouse brain (≈7 mm × 9.5 mm × 5 mm) can readily be obtained with an isotropic resolution of ≈2 µm (1 µm voxel) and a short acquisition time of 30 min. It provides an efficient way to implement system‐level cellular analysis, such as the mapping of different neuron populations and tracing of long‐distance neural projections over the entire brain. Mars‐SPIM is thus well suited for high‐throughput cell‐profiling phenotyping of brain and other mammalian organs.
A Multifunctional Nanocomposite Hydrogel for Endoscopic Tracking and Manipulation
Authors: Augurio Adriana , Cortelletti Paolo , Tognato Riccardo , Rios Anne , Levato Riccardo , Malda Jos , Alini Mauro , Eglin David , Giancane Gabriele , Speghini Adolfo , Serra Tiziano
Published: December 2019

Herein, the fabrication of multi‐responsive and hierarchically organized nanomaterial using core‐shell SrF2 upconverting nanoparticles, doped with Yb3+, Tm3+, Nd3+ incorporated into gelatin methacryloyl matrix, is reported. Upon 800 nm excitation, deep monitoring of 3D‐printed constructs is demonstrated. Addition of magnetic self‐assembly of iron oxide nanoparticles within the hydrogel provides anisotropic structuration from the nano‐ to the macro‐scale and magnetic responsiveness permitting remote manipulation. The present study provides a new strategy for the fabrication of a novel highly organized multi‐responsive material using additive manufacturing, which can have important implications in biomedicine.
An Optoneuronic Device with Realistic Retinal Expressions for Bioinspired Machine Vision
Authors: Berco Dan , Ang Diing Shenp , Zhang Hai Zhong
Published: December 2019

Machine vision systems rely on communication between cameras and processor modules to capture and analyze visual information. This arrangement renders them as bulky and inefficient in terms of speed and power dissipation for futuristic big data applications that involve artificial intelligence algorithms. An apparatus able to imitate the operation of biologic eyes and function as a standalone platform would therefore present the next evolutional step in machine visual perception. Neuromorphic computing is an alternative approach to the Von Neumann architecture that carries the potential for implementing such intelligent cameras. In this regard, artificial synaptic devices have been widely used in recent years to construct hardware‐based neural networks mainly due to their adjustable electric parameters. Herein, a bioinspired, hybrid electrophotonic responsive neuronic device that mimics the combined functionality of retinal cones and bipolar cells is demonstrated. Under illumination, it features a hyperpolarization‐like current response in an OFF state and a complementary depolarized reaction when toggled to an ON state. Furthermore, electrical pulsing done in conjunction with light stimulation can emulate the horizontal cell neurotransmitter release in center‐surround biologic configurations. These devices may thus serve as building blocks for advanced visual systems, integrating self‐healing sensory and neuromorphic computing into an artificial cognitive retina.
Human height preferences as a function of population size in the Cook Islands and Norway
Authors: Sorokowski Piotr , Oleszkiewicz Anna , Sorokowska Agnieszka , Pisanski Katarzyna
Published: December 2019

Objectives

Height preferences and mating patterns related to body size vary across cultures yet it remains unclear why such between‐population differences exist. Here, we test a hypothesis that nonrandom assortative mating is negative (mating with nonsimilar partners) in small isolated populations, and positive (mating with similar partners) in larger populations.

Methods

We compared preferences for sexual dimorphism in stature (SDS, male height/female height) among men and women living in small isolated communities (as few as 60 inhabitants) vs larger urban areas (as many as 70 000 inhabitants). To increase generalizability, data were collected from heterogeneous populations in the South Pacific (Rarotonga vs Palmerston, Cook Islands) and Northern Europe (capital city of Tromsø vs villages in the Troms County of Norway).

Results

Norwegians preferred a significantly larger difference in height between partners (median SDS ratio of 1.14) than did Cook Islanders (median SDS ratios of 1‐1.04). Indeed, while 30% of Cook Island men and women preferred a partner of the exact same height, this preference was observed among less than 3% of Norwegian men and 7% of Norwegian women. Critically, distributions in SDS preferences did not differ by sex or population size. Thus, rural and urban dwellers within both countries showed similar positive assortative preferences for height, wherein own height explained up to 62% of the variability in preferred partner height.

Conclusions

Our results do not support negative assortative preferences in small‐scale communities, and further indicate that the “male‐taller norm,” while weaker among Cook Islanders than Europeans, is observed to some extent in the South Pacific.
Metastable Chiral Azobenzenes Stabilized in a Double Racemate
Authors: Mohan Amalu , Sasikumar Devika , Bhat Vinayak , Hariharan Mahesh
Published: December 2019

The self‐assembly of chiral organic chromophores is gaining huge significance due to the abundance of supramolecular chirality found in natural systems. We report an interdigitated molecular assembly involving axially chiral octabrominated perylenediimide (OBPDI) which transfers chiral information to achiral aromatic moieties. The crystalline two‐component assemblies of OBPDI and electron‐rich aromatic units were facilitated through π‐hole⋅⋅⋅π donor–acceptor interactions, and the charge‐transfer characteristics in the ground and excited states of the OBPDI cocrystals were established through spectroscopic and theoretical techniques. The OBPDI cocrystals entail a remarkable homochiral segregation of P and M enantiomers of both molecular entities in the same crystal system, leading to twisted double‐racemic arrangements. Synergistically engendered cavities with the stored chiral information of the twisted OBPDI stabilize higher‐energy P/M enantiomers oftrans‐azobenzene through non‐covalent interactions.
Isotopically Labeled Desthiobiotin Azide (isoDTB) Tags Enable Global Profiling of the Bacterial Cysteinome
Authors: Zanon Patrick R. A. , Lewald Lisa , Hacker Stephan M.
Published: November 2019

Rapid development of bacterial resistance has led to an urgent need to find new druggable targets for antibiotics. In this context, residue‐specific chemoproteomic approaches enable proteome‐wide identification of binding sites for covalent inhibitors. Described here are easily synthesized isotopically labeled desthiobiotin azide (isoDTB) tags that shortened the chemoproteomic workflow and allowed an increased coverage of cysteines in bacterial systems. They were used to quantify 59 % of all cysteines in essential proteins in Staphylococcus aureus and enabled the discovery of 88 cysteines that showed high reactivity, which correlates with functional importance. Furthermore, 268 cysteines that are engaged by covalent ligands were identified. Inhibition of HMG‐CoA synthase was verified and will allow addressing the bacterial mevalonate pathway through a new target. Overall, a broad map of the bacterial cysteinome was obtained, which will facilitate the development of antibiotics with novel modes‐of‐action.
Heterobifunctional Rotaxanes for Asymmetric Catalysis
Authors: Pairault Noël , Zhu Hui , Jansen Dennis , Huber Alexander , Daniliuc Constantin G. , Grimme Stefan , Niemeyer Jochen
Published: December 2019

Heterobifunctional rotaxanes serve as efficient catalysts for the addition of malonates to Michael acceptors. We report a series of four different heterobifunctional rotaxanes, featuring an amine‐based thread and a chiral 1,1′‐binaphthyl‐phosphoric‐acid‐based macrocycle. High‐level DFT calculations provided mechanistic insights and enabled rational catalyst improvements, leading to interlocked catalysts that surpass their non‐interlocked counterparts in terms of reaction rates and stereoselectivities.
Single‐Crystal X‐Ray Diffraction Study of Pressure and Temperature‐Induced Spin Trapping in a Bistable Iron(II) Hofmann Framework
Authors: Turner Gemma F. , Campbell Fallyn , Moggach Stephen A. , Parsons Simon , Goeta Andrés E. , Muñoz M. Carmen , Real José A.
Published: November 2019

High‐pressure single‐crystal X‐ray diffraction has been used to trap both the low‐spin (LS) and high‐spin (HS) states of the iron(II) Hofmann spin crossover framework, [FeII(pdm)(H2O)[Ag(CN)2]2⋅H2O, under identical experimental conditions, allowing the structural changes arising from the spin‐transition to be deconvoluted from previously reported thermal effects.
Electrochemical Access to Aza‐Polycyclic Aromatic Hydrocarbons: Rhoda‐Electrocatalyzed Domino Alkyne Annulations
Authors: Kong Wei‐Jun , Shen Zhigao , Finger Lars H. , Ackermann Lutz
Published: December 2019

Nitrogen‐doped polycyclic aromatic hydrocarbons (aza‐PAHs) have found broad applications in material sciences. Herein, a modular electrochemical synthesis of aza‐PAHs was developed via a rhodium‐catalyzed cascade C−H activation and alkyne annulation. A multifunctional O‐methylamidoxime enabled the high chemo‐ and regioselectivity. The isolation of two key rhodacyclic intermediates made it possible to delineate the exact order of three C−H activation steps. In addition, the metalla‐electrocatalyzed multiple C−H transformation is characterized by unique functional group tolerance, including highly reactive iodo and azido groups.
Effect of functionalized graphene oxide with phosphaphenanthrene and isocyanurate on flammability, mechanical properties, and thermal stability of epoxy composites
Authors: Shao Zhiheng , Wang Hongchao , Li Meng , Chen Ting , Xu Yiting , Yuan Conghui , Zeng Birong , Dai Lizong
Published: December 2019

Maleic anhydride, 9, 10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide, and 1, 3, 5‐triglycidyl isocyanurate functionalized graphene oxide (GO) was prepared in this paper. The resultant phosphorus‐nitrogen functionalized GO called GOMT was homogeneously dispersed and incorporated into diglycidyl ether of bisphenol A to prepare composites. The char residue of GOMT/EP composites increased and its LOI value increased to 28.1% with UL‐94 V‐1 rating.Tgof composite containing 1 phr GOMT increases to 165.6 °C, and the storage modulus of the sample with 3 phr GOMT was increased by 19% compared with pure EP. Furthermore, the elastic modulus and flexural strength of epoxy composite with 5 phr GOMT were increased by 17.9 and 26.7% at room temperature, respectively. Besides, the incorporation of GOMT into EP significantly reduces the PHRR and THR of the matrix. Therefore, the as‐designed GOMT not just obviously enhances the flame retardancy with low loading but raises the mechanical behavior and thermal stability of epoxy resins. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2020,137, 48761.
Retouched, rejuvenated, recycled and occasionally hafted as projectiles: stone points of Holocene Australia
Authors: MALONEY TIM RYAN
Published: December 2019

Macroscopic evidence for projectile use of stone points across the Kimberley region of northern Australia is examined using archaeological assemblages from the mid to late Holocene. There is scant evidence to support more than occasional projectile use. High rates of rejuvenation, recycling and continuous resharpening contribute to the low frequency of impact damage. The extent and location of edge damage, interpreted as probable use‐wear, is demonstrated to have distribution patterns consistent with multipurpose functions. Projectile use was merely one, albeit infrequent function of these versatile tools. This study uses use‐wear data to engage with technological organisation theory and discusses rates of use, resharpening, rejuvenation and recycling. Standardisation and an emphasis on maintainability provide the best explanation as to why people produced these tools during the Holocene.
The 2019 American College of Rheumatology/European League Against Rheumatism Classification Criteria for IgG4‐Related Disease
Authors: Wallace Zachary S. , Naden Ray P. , Chari Suresh , Choi Hyon , Della‐Torre Emanuel , Dicaire Jean‐Francois , Hart Phil A. , Inoue Dai , Kawano Mitsuhiro , Khosroshahi Arezou , Kubota Kensuke , Lanzillotta Marco , Okazaki Kazuichi , Perugino Cory A. , Sharma Amita , Saeki Takako , Sekiguchi Hiroshi , Schleinitz Nicolas , Stone James R. , Takahashi Naoki , Umehara Hisanori , Webster George , Zen Yoh , Stone John H. ,   for the American College of Rheumatology/European League Against Rheumatism IgG4‐Related Disease Classification Criteria Working Group
Published: December 2019

Objective

IgG4‐related disease (IgG4‐RD) can cause fibroinflammatory lesions in nearly any organ. Correlation among clinical, serologic, radiologic, and pathologic data is required for diagnosis. This work was undertaken to develop and validate an international set of classification criteria for IgG4‐RD.

Methods

An international multispecialty group of 86 physicians was assembled by the American College of Rheumatology (ACR) and the European League Against Rheumatism (EULAR). Investigators used consensus exercises, existing literature, derivation and validation cohorts of 1,879 subjects (1,086 cases, 793 mimickers), and multicriterion decision analysis to identify, weight, and test potential classification criteria. Two independent validation cohorts were included.

Results

A 3‐step classification process was developed. First, it must be demonstrated that a potential IgG4‐RD case has involvement of at least 1 of 11 possible organs in a manner consistent with IgG4‐RD. Second, exclusion criteria consisting of a total of 32 clinical, serologic, radiologic, and pathologic items must be applied; the presence of any of these criteria eliminates the patient from IgG4‐RD classification. Third, 8 weighted inclusion criteria domains, addressing clinical findings, serologic results, radiology assessments, and pathology interpretations, are applied. In the first validation cohort, a threshold of 20 points had a specificity of 99.2% (95% confidence interval [95% CI] 97.2–99.8%) and a sensitivity of 85.5% (95% CI 81.9–88.5%). In the second, the specificity was 97.8% (95% CI 93.7–99.2%) and the sensitivity was 82.0% (95% CI 77.0–86.1%). The criteria were shown to have robust test characteristics over a wide range of thresholds.

Conclusion

ACR/EULAR classification criteria for IgG4‐RD have been developed and validated in a large cohort of patients. These criteria demonstrate excellent test performance and should contribute substantially to future clinical, epidemiologic, and basic science investigations.
Automatisierte AKR‐Prüfung im 60 °C‐Betonversuch
Authors: Krütt Enno , Wallau Wilma , Meng Birgit , Greim Markus , Pirskawetz Stephan
Published: November 2019

Der 60 °C‐Betonversuch ist eine in Deutschland und international verbreitete Methode, um die Empfindlichkeit von Gesteinskörnungen und Betonen hinsichtlich einer Alkali‐Kieselsäure‐Reaktion (AKR) zu prüfen. Dieser Beitrag stellt eine neu entwickelte, automatisierte Variante der Prüfmethode in einem Minireaktor vor. Dabei werden die Dehnungen von Betonprismen nicht wie beim konventionellen Test manuell, sondern automatisch in entsprechend ausgerüsteten Prüfbehältern gemessen. Neben einer Reduzierung des Messaufwands bringt die automatisierte Prüfung im Minireaktor weitere Vorteile. Die Dehnungssignale werden, anders als bei der konventionellen Messung, quasi kontinuierlich aufgezeichnet und bilden das Expansionsverhalten der Prismen detailliert ab. Außerdem bleiben Unterbrechungen der AKR‐provozierenden Lagerung aus, die bei der konventionellen Prüfung notwendig sind. Im Beitrag werden die automatisierte und konventionelle Prüfung anhand der Dehnungen von Prismen zweier Gesteinskörnungen verglichen. In Übereinstimmung mit vorhergehenden Untersuchungen sind im Minireaktor gemessene Dehnungen systematisch kleiner als manuell gemessene. Als mögliche Ursache werden Unterschiede im Auslaugverhalten experimentell untersucht. Zur Überprüfung der Einstufung der zwei Gesteinskörnungen erfolgen außerdem Referenzprüfungen in der Nebelkammerlagerung bei 40 °C.
Entwicklung und Anwendung der Ultraschalltechnik zur Qualitätssicherung von Beton
Authors: Große Christian U.
Published: November 2019

Aus Anlass des 80. Geburtstags von Hans‐Wolf Reinhardt wird in diesem Beitrag eines der wichtigsten Messverfahren dargestellt, an dessen Entwicklung er maßgeblich beteiligt war – der Einsatz der Ultraschalltechnik zur Analyse von Frischbeton und zur Qualitätssicherung von Mörtel, Beton und Betonwaren. Zur Hervorhebung der Verdienste von Prof. Reinhardt wird die Entwicklung an der Universität Stuttgart zusammengefasst und einige unter seiner Leitung mit den entwickelten Messgeräten gewonnenen Ergebnisse präsentiert.

Der Artikel zeigt zudem die Leistungsfähigkeit des Verfahrens und präsentiert einige neuere Anwendungsbeispiele. Ein Abschnitt ist dem internationalen Stand hinsichtlich Zusammenarbeit auf dem Gebiet gewidmet. Der Autor hofft, mit diesem Artikel weitere Wissenschaftler und Anwender für die Thematik zu interessieren, damit noch stärker als bisher das Verfahren Eingang in die Baupraxis erhält.
Convergence in Cold War Physics: Coinventing the Maser in the Postwar Soviet Union
Authors: da Silva Neto Climério Paulo , Kojevnikov Alexei
Published: December 2019

At the height of the Cold War, in the 1950s, the process of parallel invention of masers and lasers took place on the opposing sides of the Iron Curtain. While the American part of the story has been investigated by historians in much penetrating detail, comparable Soviet developments were described more superficially. This study aims at, to some extent, repairing this discrepancy by analyzing the Soviet path towards the maser from a comparative angle. It identifies, on the one hand, significant differences between the two projects regarding their heuristics, the relationship between theory and experiment, grounding in different academic cultures, and the resulting conceptualization of the maser principle. At the same time, the case also illustrates more fundamental transformations in the practices of postwar research that can be characterized as a convergence between the Soviet and the American science of the period.
Photo‐crosslinking: An Emerging Chemical Tool for Investigating Molecular Networks in Live Cells
Authors: Mishra Pratyush Kumar , Yoo Chang‐Mo , Hong Eunmi , Rhee Hyun Woo
Published: December 2019

Studying protein–protein interactions (PPIs) is useful for understanding cellular functions and mechanisms. Evaluating these PPIs under conditions as similar as possible to native conditions can be achieved using photo‐crosslinking methods because of their on‐demand ability to generate reactive species in situ by irradiation with UV light. Various fusion tag, metabolic incorporation, and amber codon suppression approaches using various crosslinkers containing aryl azide, benzophenone, and diazirines have been applied in live cells. Mass spectrometry and immunological techniques are used to identify crosslinked proteins based on their capture transient and context‐dependent interactions. Herein we discuss various incorporation methods and crosslinkers that have been used for interactome mapping in live cells.
Intrathoracic complications associated with trans‐femoral transcatheter aortic valve replacement: Implications for emergency surgical preparedness
Authors: Hodson Robert W. , Jin Ruyun , Ring Michael E. , Gafoor Sameer , Verburg Shawnna , Lehr Eric J. , Spinelli Kateri J.
Published: December 2019

Background

Intrathoracic complications (ITC) requiring emergency surgical intervention occur during transcatheter aortic valve replacement (TAVR).

Objectives

Characterize the incidence, outcomes and predictors of ITC in a large cohort of transfemoral (TF) TAVR cases over a 5 year period.

Methods

Retrospective registry and chart review of all nonclinical trial TF‐TAVR patients from seven centers within one hospital system from 2012–2016. ITC were defined as cardiac perforation, new or worsening pericardial effusion/tamponade, annular rupture, thoracic aortic injury, aortic valve dislodgement, and coronary artery occlusion. Procedural and 30‐day outcomes and 1‐year mortality were compared between ITC and no ITC patients. Multivariable logistic regression was used to identify predictors of ITC.

Results

Over the study period, 1,581 patients had TF‐TAVR and 68 ITC occurred in 46 patients (2.9%). The most common ITCs were pericardial effusion/tamponade (59%), cardiac perforation (33%), and valve dislodgement (33%). ITC rate did not decline over time (rate (95% confidence interval) for 2012 = 0% (0–8.8%), 2013 = 1.3% (0–7.2%), 2014 = 4.4% (2.2–8.0%), 2015 = 3.5% (2.0–5.6%), and 2016 = 2.4% (1.5–3.8%)). ITC patients had worse 1‐year survival (ITC: 60.7% (45.1–73.1%), no ITC: 88.7% (87.0–90.3%); p < .001). The majority of ITC patient deaths occurred within the first 30 days. Multivariable models to predict ITC were not successful.

Conclusions

ITC did not decline over time in our cohort. Predictors of ITC could not be identified. While these events are rare, they are associated with worse procedural outcomes and mortality. Heart teams should continue to be prepared for emergency intervention.
Reduced radiation exposure in the cardiac catheterization laboratory with a novel vertical radiation shield
Authors: Panetta Carmelo J. , Galbraith Erin M. , Yanavitski Marat , Koller Patrick K. , Shah Binita , Iqbal Sohah , Cigarroa Joaquin E. , Gordon Gregory , Rao Sunil V.
Published: December 2019

Objectives

Investigation of novel vertical radiation shield (VRS) in reducing operator radiation exposure.

Background

Radiation exposure to the operator remains an occupational health hazard in the cardiac catheterization laboratory (CCL).

Methods

A mannequin simulating an operator was placed near a computational phantom, simulating a patient. Measurement of dose equivalent and Air Kerma located the angle with the highest radiation, followed by a common magnification (8 in.) and comparison of horizontal radiation absorbing pads (HRAP) with or without VRS with two different: CCL, phantoms, and dosimeters. Physician exposure was subsequently measured prospectively with or without VRS during clinical procedures.

Results

Dose equivalent and Air Kerma to the mannequin was highest at left anterior oblique (LAO)‐caudal angle (p < .005). Eight‐inch magnification increased mGray by 86.5% and μSv/min by 12.2% compared to 10‐in. (p < .005). Moving 40 cm from the access site lowered μSv/min by 30% (p < .005). With LAO‐caudal angle and 8‐in. magnification, VRS reduced μSv/min by 59%, (p < .005) in one CCL and μSv by 100% (p = .016) in second CCL in addition to HRAP. Prospective study of 177 procedures with HRAP, found VRS lowered μSv by 41.9% (μSv: 15.2 ± 13.4 vs. 26.2 ± 31.4, p = .001) with no difference in mGray. The difference was significant after multivariate adjustment for specified variables (p < .001).

Conclusions

Operator radiation exposure is significantly reduced utilizing a novel VRS, HRAP, and distance from the X‐ray tube, and consideration of lower magnification and avoiding LAO‐caudal angles to lower radiation for both operator and patient.
Successful treatment of a paravalvular leak with balloon cracking and valve‐in‐valve TAVR
Authors: Ruge Hendrik , Erlebach Magdalena , Lieberknecht Eveline , Lange Rüdiger
Published: December 2019

Transcatheter heart valve implantation into degenerated bioprosthetic valves (ViV‐THV implantation) has become an established procedure for high risk patients. In general, paravalvular leak (PVL) is a contraindication for valve‐in‐valve‐TAVR (ViV‐TAVR). Herein, we report on a 81‐year‐old patient presenting with acute heart failure for a failing aortic bioprosthesis (Medtronic Mosaic 27 mm). Intraoperative transesophageal echocardiography during urgent ViV‐TAVR revealed a PVL previously not detected. After transfemoral implantation of a 26 mm‐Evolut‐R, balloon‐fracturing of the bioprosthetic ring was performed using a 24 mm True Dilatation balloon for treatment of the PVL. Afterward, left ventricular to aortic peak‐to‐peak pressure gradient measured 2–4mmHg. Transesophageal echocardiography merely revealed trace PVL. Aortic root angiography showed no PVL. At discharge, echocardiography measured a transprosthetic mean gradient of 5mmHg detecting no PVL. Intentional ring‐fracturing of an aortic valve prostheses may prove not only to be effective in lowering transvalvular gradients after valve‐in‐valve‐TAVR, but may also be a tool to treat PVL alongside degenerated surgical aortic bioprostheses in certain patients.
Highly Stable Copper(I)–Thiacalix[4]arene‐Based Frameworks for Highly Efficient Catalysis of Click Reactions in Water
Authors: Wang Xue‐Xia , Yang Jin , Xu Xianxiu , Ma Jian‐Fang
Published: December 2019

Environmentally friendly metal–organic frameworks (MOFs) have gained considerable attention for their potential use as heterogeneous catalysts. Herein, two CuI‐based MOFs, namely, [Cu4Cl4L]⋅CH3OH⋅1.5 H2O (1‐Cl) and [Cu4Br4L]⋅DMF⋅0.5 H2O (1‐Br), were assembled with new functionalized thiacalix[4]arenes (L) and halogen anions X− (X=Cl and Br) under solvothermal conditions. Remarkably, catalysts 1‐Cl and 1‐Br exhibit great stability in aqueous solutions over a wide pH range. Significantly, MOFs 1‐Cl and 1‐Br, as recycled heterogeneous catalysts, are capable of highly efficient catalysis for click reactions in water. The MOF structures, especially the exposed active CuI sites and 1D channels, play a key role in the improved catalytic activities. In particular, their catalytic activities in water are greatly superior to those in organic solvents or even in mixed solvents. This work proposes an attractive route for the design and self‐assembly of environmentally friendly MOFs with high catalytic activity and reusability in water.
Hollow PtFe Alloy Nanoparticles Derived from Pt‐Fe3O4 Dimers through a Silica‐Protection Reduction Strategy as Efficient Oxygen Reduction Electrocatalysts
Authors: Yang Zhaojun , Shang Lu , Xiong Xuyang , Shi Run , Waterhouse Geoffrey I. N. , Zhang Tierui
Published: November 2019

The development of efficient and stable electrocatalysts for the oxygen reduction reaction (ORR) is critical for the large‐scale production of fuel cells. Platinum (Pt) nanoparticle catalysts show excellent performance for ORR, though the high cost of Pt is a limiting factor that directly impacts fuel cell production costs. Alloying Pt with other transition metals is an effective strategy to reduce Pt utilization whilst maintaining good ORR performance. In this work, novel hollow PtFe alloy catalysts were successfully synthesized by high‐temperature pyrolysis of SiO2‐coated Pt‐Fe3O4 nanoparticle dimers supported on carbon at 900 °C, followed by SiO2 shell removal and partial dealloying of the PtFe nanoparticles formed using HF. The obtained hollow PtFe nanoparticle catalysts (denoted herein as PtFe‐900) showed a 2.3‐fold enhancement in ORR mass activity compared to PtFe nanoparticles synthesized without SiO2 protection, and a remarkable 7.8‐fold enhancement relative to a commercial Pt/C catalyst. Further, after 10 000 potential cycles, the ORR mass activity of PtFe‐900 remained very high (90.9 % of the initial mass activity). The outstanding ORR performance of PtFe‐900 can be attributed to the modification of Pt lattice and electronic structure by alloying with Fe at high temperature under the protection of the SiO2 coating. This work guides the development of improved, highly dispersed Pt‐based alloy nanoparticle catalysts for ORR and fuel cell applications.
The Effect of Guest Metal Ions on the Reduction Potentials of Uranium(VI) Complexes: Experimental and Theoretical Investigations
Authors: Ghosh Tanmoy Kumar , Mahapatra Prithwish , Drew Michael G. B. , Franconetti Antonio , Frontera Antonio , Ghosh Ashutosh
Published: December 2019

Two mononuclear uranyl complexes, [UO2L1] (1) and [UO2L2]⋅0.5 CH3CN⋅0.25 CH3OH (2), have been synthesized from two multidentate N3O4 donor ligands, N,N′‐bis(5‐methoxysalicylidene)diethylenetriamine (H2L1) and N,N′‐bis(3‐methoxysalicylidene)diethylenetriamine (H2L2), respectively, and have been structurally characterized. Both complexes 1 and 2 showed a reversible UVI/UV couple at −1.571 and −1.519 V, respectively, in cyclic voltammetry. The reduction potential of the UVI/UV couple shifted towards more positive potential on addition of Li+, Na+, K+, and Ag+ metal ions to acetonitrile solutions of complex 2, and the resulting potential was correlated with the Lewis acidity of the metal ions and was also justified by theoretical DFT calculations. No such shift in reduction potential was observed for complex 1. All four bimetallic products, [UO2L2Li0.5](ClO4)0.5 (3), [UO2L2Na(ClO4)]2 (4), [UO2L2Ag(NO3)(H2O)] (5), and [(UO2L2)2K(H2O)2]PF6 (6), formed on addition of the Li+, Na+, Ag+, and K+ metal ions, respectively, to acetonitrile solutions of complex 2, were isolated in the solid state and structurally characterized by single‐crystal X‐ray diffraction. In all the species, the inner N3O2 donor set of the ligand encompasses the equatorial plane of the uranyl ion and the outer open compartment with O2O′2 donor sites hosts the second metal ion.
Synthetic Strategies for Artificial Lipidation of Functional Proteins
Authors: Takahara Mari , Kamiya Noriho
Published: December 2019

Biosynthesis of natural lipidated proteins is linked to important signal pathways, and therefore analyzing protein lipidation is crucial for understanding cellular functions. Artificial lipidation of proteins has attracted attention in recent decades as it allows modulation of the amphiphilic nature of the protein of interest, and is used in the design of drug‐delivery systems containing antibodies anchored on a lipid bilayer carrier. However, the intrinsic hydrophobicity of lipids makes the synthesis of lipid–protein conjugates challenging with respect to the yield and selectivity of the lipidation. In this Minireview, the development of chemical and enzymatic synthetic strategies for the preparation of a range of lipid–protein conjugates that do not compromise the functions of the proteins are discussed as well as applications of the conjugates.
Efficient Screening for Ternary Molecular Ionic Cocrystals Using a Complementary Mechanosynthesis and Computational Structure Prediction Approach
Authors: Shunnar Abeer F. , Dhokale Bhausaheb , Karothu Durga Prasad , Bowskill David H. , Sugden Isaac J. , Hernandez Hector H. , Naumov Panče , Mohamed Sharmarke
Published: December 2019

The discovery of molecular ionic cocrystals (ICCs) of active pharmaceutical ingredients (APIs) widens the opportunities for optimizing the physicochemical properties of APIs whilst facilitating the delivery of multiple therapeutic agents. However, ICCs are often observed serendipitously in crystallization screens and the factors dictating their crystallization are poorly understood. We demonstrate here that mechanochemical ball milling is a versatile technique for the reproducible synthesis of ternary molecular ICCs in less than 30 min of grinding with or without solvent. Computational crystal structure prediction (CSP) calculations have been performed on ternary molecular ICCs for the first time and the observed crystal structures of all the ICCs were correctly predicted. Periodic dispersion‐corrected DFT calculations revealed that all the ICCs are thermodynamically stable (mean stabilization energy=−2 kJ mol−1) relative to the crystallization of a physical mixture of the binary salt and acid. The results suggest that a combined mechanosynthesis and CSP approach could be used to target the synthesis of higher‐order molecular ICCs with functional properties.
Double Chalcogen Bonds: Crystal Engineering Stratagems via Diffraction and Multinuclear Solid‐State Magnetic Resonance Spectroscopy
Authors: Kumar Vijith , Xu Yijue , Bryce David L.
Published: December 2019

Group 16 chalcogens potentially provide Lewis‐acidic σ‐holes, which are able to form attractive supramolecular interactions with electron rich partners through chalcogen bonds. Here, a multifaceted experimental and computational study of a large series of novel chalcogen‐bonded cocrystals, prepared using the principles of crystal engineering, is presented. Single‐crystal X‐ray diffraction studies reveal that dicyanoselenadiazole and dicyanotelluradiazole derivatives work as promising supramolecular synthons with the ability to form double chalcogen bonds with a wide range of electron donors including halides and oxygen‐ and nitrogen‐containing heterocycles. Extensive 77Se and 125Te solid‐state nuclear magnetic resonance spectroscopic investigations of cocrystals establish correlations between the NMR parameters of selenium and tellurium and the local chalcogen bonding geometry. The relationships between the electronic environment of the chalcogen bond and the 77Se and 125Te chemical shift tensors were elucidated through a natural localized molecular orbital density functional theory analysis. This systematic study of chalcogen‐bond‐based crystal engineering lays the foundations for the preparation of the various multicomponent systems and establishes solid‐state NMR protocols to detect these interactions in powdered materials.
Synthesis and Chiroptical Properties of Chiral Carbazole‐Based BODIPYs
Authors: Maeda Chihiro , Suka Keita , Nagahata Keiji , Takaishi Kazuto , Ema Tadashi
Published: December 2019

A series of carbazole‐based boron dipyrromethenes (BODIPYs) 2 a–g bearing binaphthyl units have been synthesized by the Et2AlCl‐mediated reaction of the corresponding BODIPY difluorides 1 a–g with 1,1′‐binaphthalene‐2,2′‐diol. Substituents such as halogen, nitrile, and amino groups were tolerated under the reaction conditions, and the reaction of the phenylethynyl‐substituted 1 h gave (R,R)‐3 h bearing two binaphthyl units. The chiroptical properties of these dyes with different substituents were investigated by UV/Vis, CD, fluorescence, and circularly polarized luminescence (CPL) spectroscopy. The CD spectra showed Cotton effects in the absorption region of the BODIPY moieties. In addition, they showed CPL both in solution and in the solid state. Interestingly, several dyes recorded higher glum values in the solid state, probably due to intermolecular interactions. Because (R,R)‐3 h recorded relatively low glum values, the diastereomer (R,S)‐3 h was prepared. The (R,S) diastereomer showed intense CPL, which suggests a synergetic effect of the two binaphthyl groups. Finally, chiral carbazole‐based BODIPY dimers have been synthesized for the first time and their chiroptical properties were investigated. They showed redshifted fluorescence and CPL, which reached the near‐IR (NIR) region in the solid state.
Site‐Selective N‐Methylation of 5,15‐Diazaporphyrins: Reactive Cationic Porphyrinoids that Provide Isoporphyrin Analogues
Authors: Chia Wen Xi , Nishijo Mayu , Kang Seongsoo , Oh Juwon , Nishimura Tsubasa , Omori Hiroto , Longevial Jean‐François , Miyake Yoshihiro , Kim Dongho , Shinokubo Hiroshi
Published: December 2019

N‐Alkylation significantly changes the electronic and optical properties, as well as the reactivity of nitrogen‐containing π‐conjugated molecules. In this study, it is found that treating 5,15‐diazaporphyrins with methyl triflate selectively affords the corresponding N‐methyl‐5,15‐diazaporphyrinium cations in good yield. N‐Methylation substantially alters the electronic properties and reactivity of diazaporphyrins. The electron‐accepting properties of the N‐methyl‐5,15‐diazaporphyrinium cations are enhanced due to their lowered LUMO level. Stabilization of the LUMO energy enables regio‐ and stereoselective Diels–Alder reactions of the cationic diazaporphyrin with cyclopentadiene. N‐Methylation also enhances the acidity of the inner NH protons, and thus, allows facile deprotonation to provide nitrogen‐substituted isoporphyrin analogues with only one NH group in the central cavity.
Treatment of recurrent epithelial ovarian cancer
Authors: Pignata Sandro , Pisano Carmela , Di Napoli Marilena , Cecere Sabrina Chiara , Tambaro Rosa , Attademo Laura
Published: December 2019

The majority of patients with advanced ovarian cancer progress after first‐line therapy and require further treatment. Tumor biology, prior chemotherapy, responses to previous therapy, performance status, and toxicity are the characteristics that influence treatment choice. These criteria have been linked to the time between relapse and last platinum therapy: the platinum‐free interval. Today, patients are classified as either those who are eligible for a new platinum‐based therapy or those for whom platinum is not an option. A nonplatinum regimen should be administered to patients who are not candidates for platinum re‐treatment. This group includes patients with early relapse after, or progression during, previous platinum‐based chemotherapy and patients with platinum intolerability. A single agent such as weekly paclitaxel, pegylated liposomal doxorubicin (PLD), gemcitabine, or topotecan represents the standard. For patients not treated with bevacizumab in the first line, this drug should be added to chemotherapy. For patients for whom platinum rechallenge is an option (because they are potentially platinum‐responsive), different strategies are available with the incorporation of biological drugs targeting angiogenesis or the mechanisms of DNA repair. A BRCA mutation status predicts a better response to platinum and poly(adenosine diphosphate–ribose) polymerase (PARP) inhibition. PARP inhibitors and antiangiogenic drugs have proven efficacy as maintenance therapy after chemotherapy and concurrently with chemotherapy, respectively. These agents have changed current practice, although few biomarkers are available to guide decisions. Patients potentially responsive to platinum who cannot receive the drug again can be treated with a combination of trabectedin and PLD, the most active nonplatinum therapy in this setting.
Hyperthermic intraperitoneal chemotherapy for ovarian cancer: The heat is on
Authors: Koole Simone N. , van Driel Willemien J. , Sonke Gabe S.
Published: December 2019

Patients with advanced epithelial ovarian cancer have a high incidence of peritoneal disease recurrence despite maximal efforts to surgically remove all visible tumor plus intravenous chemotherapy. The administration of intraperitoneal chemotherapy that specifically targets the peritoneal surface has been investigated in previous trials, but questions about the design of these studies has prevented this treatment from being widely adopted in clinical practice. Hyperthermic intraperitoneal chemotherapy (HIPEC) is a single intraoperative approach that also targets the peritoneal surface. A randomized phase 3 trial showed significant benefit in recurrence‐free and overall survival when HIPEC was added to interval cytoreductive surgery (CRS) in patients who were not eligible for primary surgery because of the extent of their disease (OVHIPEC trial; NCT00426257). The trial showed no important differences in toxicity or patient‐reported outcomes between the study groups. The extent of surgery and the number of bowel resections were also similar between the 2 study groups, and the effect of HIPEC was homogeneous across the levels of predefined and post hoc subgroups. Nevertheless, the design and the results of the OVHIPEC trial were critically assessed, and this resembles the reluctance to adopt the positive results of the earlier intraperitoneal chemotherapy studies. This overview discusses the design and results of the OVHIPEC trial. The evidence that is currently available points to a clinically relevant and cost‐effective benefit of HIPEC added to interval CRS for patients with stage III ovarian cancer who are not eligible for primary surgery. Ongoing collaborative research will provide further evidence regarding the role of HIPEC in ovarian cancer.
Biomarkers in ovarian cancer: To be or not to be
Authors: Arend Rebecca , Martinez Alba , Szul Tomasz , Birrer Michael J.
Published: December 2019

Biomarkers are becoming increasingly important in the treatment of epithelial ovarian cancer. Recent work from many laboratories has begun to provide clinically meaningful biomarkers. This review summarizes the state of the science regarding biomarkers for stratifying early‐stage patients into those who benefit from adjuvant treatment, primary debulking versus interval debulking, and specific targeted therapy. In addition, new molecular imaging technologies have been developed to allow the surgeon to resect subvisible tumor deposits. These efforts should increase clinical effectiveness while minimizing toxicities for patients.
A Preorganized Hydrogen‐Bonding Motif for the Molecular Recognition of Carbohydrates
Authors: Francesconi Oscar , Cicero Federico , Nativi Cristina , Roelens Stefano
Published: December 2019

The choice between adaptive and preorganized architectures, or of the most effective hydrogen bonding groups to be selected, are dilemmas that supramolecular chemists must address in designing synthetic receptors for such a challenging guest as carbohydrates. In this paper, structurally related architectures featuring two alternative hydrogen bonding motifs were compared to ascertain the structural and functional origin of their binding differences and the advantages that can be expected in monosaccharide recognition. A set of structurally related macrocyclic receptors were prepared, and their binding properties were measured by NMR and ITC techniques in chloroform vs a common saccharidic target, namely, the β‐octyl glycoside of D‐glucose. Results showed that the diaminocarbazolic motif, recently reported as the constituting unit of highly effective receptors for saccharides in water, is a superior hydrogen bonding motif compared to the previously described diaminopyrrolic motif, which was successfully employed in molecular recognition of carbohydrates in polar organic solvents, due to intrinsic structural and functional factors, rather than to hydrophobic contributions. In addition, the occurrence of a rare example of a thermodynamic template effect exerted by the beta‐glucoside has been ascertained, enhancing the synthesis outcome of the otherwise low yielding preparation of the described macrocyclic receptors.
Expression and function of DNAM‐1 on human B‐lineage cells
Authors: Nagayama‐Hasegawa Yuko , Honda Shin‐ichiro , Shibuya Akira , Shibuya Kazuko
Published: November 2019

Background

Although DNAM‐1 is an activating receptor constitutively expressed on the majority of NK cells, CD8+ T cells, CD4+ T cells, monocytes, and platelets in human, several evidences demonstrated that a small population in B‐lineage cells also expressed DNAM‐1. However, the expression profile of DNAM‐1 on B‐lineage cells and its function remain obscure. Previous reports revealed that a considerable number of leukocytes including B cells in the peripheral blood conjugated to platelet. Thus, the proportion of DNAM‐1+ B‐lineage cells determined by flow cytometry analysis in the previous reports might be overestimated.

Methods

We examined whether platelets conjugate B cells and then analyzed the expression of DNAM‐1 on the subpopulations of B‐lineage cells according to their maturation stages after exclusion of platelet‐conjugated B cells. We also assessed the involvement of DNAM‐1 in IL‐10 and antibody production from cultured B‐lineage cells stimulated with CpG‐ODN.

Results

Approximately 10% of human DNAM‐1+ CD19+ B cells in the peripheral blood conjugated to platelets, resulting in the overestimation of the proportion of DNAM‐1+ B cells. After exclusion of platelet‐conjugating B cells, we show that DNAM‐1 expression was detected on subpopulations of memory B cells, plasmablasts, and plasma cells and upregulated by stimulation with CpG‐ODN. Moreover, DNAM‐1 was involved in IL‐10 and antibody productions by B cells after CpG‐ODN stimulation.

Conclusions

DNAM‐1 may be involved in B‐lineage cell‐mediated immune responses.