bluuebunny/crossref_metadata_2025 huggingface dataset:
Near‐Infrared Free‐Radical and Free‐Radical‐Promoted Cationic Photopolymerizations by In‐Source Lighting Using Upconverting Glass
Authors: Kocaarslan Azra , Tabanli Sevcan , Eryurek Gonul , Yagci Yusuf
Published: September 2017

A method is presented for the initiation of free‐radical and free‐radical‐promoted cationic photopolymerizations by in‐source lighting in the near‐infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron‐transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free‐radical‐promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N‐vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved.
CsB4O6F: A Congruent‐Melting Deep‐Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units
Authors: Wang Xuefei , Wang Ying , Zhang Bingbing , Zhang Fangfang , Yang Zhihua , Pan Shilie
Published: September 2017

The discovery of new nonlinear optical (NLO) materials for coherent light generation in the deep‐ultraviolet (DUV, wavelength below 200 nm) region is essential for the development of laser technologies. Herein, we report a new material CsB4O6F (CBF), which combines the superior structural properties of two well‐known NLO materials, β‐BaB2O4 (BBO) and KBe2BO3F2 (KBBF). CBF exhibits excellent DUV optical properties including a short cutoff edge (155 nm), a large SHG response (≈1.9×KDP), and a suitable birefringence that enables frequency doubling down to 171.6 nm. Remarkably, CBF melts congruently and shows an improved growth habit. In addition, our rational design strategy will contribute to the discovery of DUV NLO materials.
Microwave responsive epoxy nanocomposites reinforced by carbon nanomaterials of different dimensions
Authors: Chen Lei , Liu Yanju , Leng Jinsong
Published: September 2017

This study fabricated nanocomposites consisting of epoxy‐based shape memory polymer (ESMP) matrix and carbon nanofillers. The nanofillers include zero‐dimensional carbon black, one‐dimensional multiwalled carbon nanotubes, two‐dimensional (2D) graphene nanoplatelets, and three‐dimensional (3D) functionalized graphene sheets, which are all efficient microwave‐absorbing materials that can transform microwaves into heat energy. As a result, the temperatures of the nanocomposites increased more rapidly than pristine ESMP in microwaves. The functionalized graphene sheets were found to transform the microwaves into heat more efficiently than the other nanofillers. Possible microwave propagation paths in the nanocomposites were proposed. Moreover, the nanocomposites displayed significantly higher mechanical strengths than pristine ESMP. The low cost and strong nanocomposites with fast microwave responses may be applied as actuators or deployable devices in medical treatments. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45676.
Enhanced Charpy impact strength of epoxy resin modified with vinyl‐terminated polydimethylsiloxane
Authors: Vilčáková Jarmila , Kutějová Lenka , Jurča Marek , Moučka Robert , Vícha Robert , Sedlačík Michal , Kovalcik Adriana , Machovský Michal , Kazantseva Natalia
Published: September 2017

This article deals with enhancement of the toughness of epoxy resin (ER) based on diglycidyl ether bisfenol A by either polydimethylsiloxane (PDMS) or vinyl‐terminated polydimethylsiloxane (VT‐PDMS). To improve the compatibility of these two phases, dicumylperoxide (DCP) was used as a compatibilizer. It was established that only specific composition of the components can lead to enhancement of ER toughness without significant reduction of storage modulus, Tg, and interphase adhesion. The highest impact strength was recorded for ER with VT‐PDMS (10 wt %) and DCP (2 wt %) due to increased interfacial compatibility between two phases, which was proved by 1H NMR and dielectric spectroscopy. Critical ductile brittle transition occurring between 10 and 15 wt % of rubber was observed by both morphological and dynamic mechanical analysis studies. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45720.
Why Improvement Can Trump Consistent Strong Performance: The Role of Effort Perceptions
Authors: Soliman Monica , Buehler Roger
Published: September 2017

How do evaluators form comparative judgments of improved versus consistently strong performance records with equivalent recent performance? We propose that evaluators judge those with improved records to be more deserving of future opportunities (e.g., a promotion) and that this can be explained – at least in part – by perceptions of effort investments. Specifically, evaluators rely on improvement to judge effort and hence devalue consistent strong performance. Five studies supported these propositions. Evaluators perceived greater effort investment and trait effort in individuals with improved profiles than those with consistent profiles and consequently thought that those with improved profiles were more deserving of future opportunities. We discuss implications of these results across various decision contexts. Copyright © 2017 John Wiley & Sons, Ltd.
Alternatives to Autopsy for Fetal and Early Neonatal (Perinatal) Deaths: Insights from the Wisconsin Stillbirth Service Program
Authors: McPherson Elspeth , Nestoridi Eirini , Heinke Dominique , Roberts Drucilla J. , Fretts Ruth , Yazdy Mahsa M. , Lin Angela E.
Published: September 2017

Background

Although autopsy is a key component of the etiologic evaluation following fetal and early neonatal death, and traditionally has been the preferred method to determine the cause of death, an alternative may be suitable when traditional autopsy by a perinatal pathologist is not available or declined.

Methods

Among 3137 cases evaluated through the Wisconsin Stillbirth Service Program (WiSSP), a community‐based program for etiologic evaluation of second trimester miscarriage, stillbirth, and early neonatal death, most diagnoses are based on multiple types of data including placental pathology, clinical examination, photographs, maternal records, radiographs, and laboratory testing.

Results

Cases in the WiSSP cohort without autopsy have nearly the same overall rate of diagnosis as those with traditional autopsy (56% vs. 58%). Review of the literature shows that although recent systematic protocols including autopsy, placental pathology and genetic studies yield a definite or probable diagnosis in 70% or more, both healthcare providers and families desire less invasive options. Several minimally invasive protocols substituting imaging, primarily MRI, for traditional autopsy have been proposed, but the numbers of deaths evaluated are still very small.

Conclusion

We join others who have promoted the benefits of a targeted or less invasive protocol to study perinatal deaths, and emphasize integration of clinical data, selective imaging, genetic testing, and parental counseling. Birth Defects Research 109:1430–1441, 2017.© 2017 Wiley Periodicals, Inc.
Wearable slot antenna at 2.45 GHz for off‐body radiation: Analysis of efficiency, frequency shift, and body absorption
Authors: Fernandez Marta , Espinosa Hugo G. , Thiel David V. , Arrinda Amaia
Published: September 2017

The interaction of body‐worn antennas with the human body causes a significant decrease in antenna efficiency and a shift in resonant frequency. A resonant slot in a small conductive box placed on the body has been shown to reduce these effects. The specific absorption rate is less than international health standards for most wearable antennas due to small transmitter power. This paper reports the linear relationship between power absorbed by biological tissues at different locations on the body and radiation efficiency based on numerical modeling (r = 0.99). While the −10 dB bandwidth of the antenna remained constant and equal to 12.5%, the maximum frequency shift occurred when the antenna was close to the elbow (6.61%) and on the thigh (5.86%). The smallest change was found on the torso (4.21%). Participants with body‐mass index (BMI) between 17 and 29 kg/m2 took part in experimental measurements, where the maximum frequency shift was 2.51%. Measurements showed better agreement with simulations on the upper arm. These experimental results demonstrate that the BMI for each individual had little effect on the performance of the antenna. Bioelectromagnetics. 39:25–34, 2018. © 2017 Wiley Periodicals, Inc.
Bayesian estimation of multivariate normal mixtures with covariate‐dependent mixing weights, with an application in antimicrobial resistance monitoring
Authors: Jaspers Stijn , Komárek Arnošt , Aerts Marc
Published: September 2017

Bacteria with a reduced susceptibility against antimicrobials pose a major threat to public health. Therefore, large programs have been set up to collect minimum inhibition concentration (MIC) values. These values can be used to monitor the distribution of the nonsusceptible isolates in the general population. Data are collected within several countries and over a number of years. In addition, the sampled bacterial isolates were not tested for susceptibility against one antimicrobial, but rather against an entire range of substances. Interest is therefore in the analysis of the joint distribution of MIC data on two or more antimicrobials, while accounting for a possible effect of covariates. In this regard, we present a Bayesian semiparametric density estimation routine, based on multivariate Gaussian mixtures. The mixing weights are allowed to depend on certain covariates, thereby allowing the user to detect certain changes over, for example, time. The new approach was applied to data collected in Europe in 2010, 2012, and 2013. We investigated the susceptibility of Escherichia coli isolates against ampicillin and trimethoprim, where we found that there seems to be a significant increase in the proportion of nonsusceptible isolates. In addition, a simulation study was carried out, showing the promising behavior of the proposed method in the field of antimicrobial resistance.
Consider the impact of regulations banning violent student‐athletes from teams
Authors: O'Brien Timothy
Published: September 2017

The cases of student‐athletes with a history of sexual violence — or who have been alleged to have engaged in such conduct — have garnered the attention of the entire college athletics community during the last several years.
Know the myths and facts in dealing with today's sports parents
Authors: McCarthy Claudine
Published: September 2017

Sometimes you find yourself wishing that those helicopter parents would just calm down and back off. But since you can't wish the problem away, you'll need a new game plan to address the challenges of parent relations.
Discover ways to do more with less to overcome budget restrictions
Authors: McCarthy Claudine
Published: September 2017

In this economy, any college athletics administrator can benefit from some fresh insight into how to accomplish more for their athletics department while spending less money.
Addition of teams, facilities boosts fundraising efforts
Authors: McCarthy Claudine
Published: September 2017

Trying to expand an athletics program at a small school on a tight budget brings plenty of challenges. Just ask Willis Pooler, M.B.A., director of athletics at Lindsey Wilson College in Kentucky. During his 14 years as AD, he's increased the student‐athlete population more than 70 percent; added football, wrestling, and men's and women's swimming; supervised the design of a new sports park and health/wellness center; and brought the athletics department's fundraising to an all‐time high.
Critical roles of hMAGEA2 in induced pluripotent stem cell pluripotency, proliferation, and differentiation
Authors: Park Song , Sung Yonghun , Jeong Jain , Choi Minjee , Lee Jinhee , Kwon Wookbong , Jang Soyoung , Park Si Jun , Kim Jae Young , Kim Sung Hyun , Yoon Duhak , Ryoo Zae Young , Kim Myoung Ok
Published: September 2017

Induced pluripotent stem (iPS) cells are important for clinical application and stem cell research. Although human melanoma‐associated antigen A2 (hMAGEA2) expression is known to affect differentiation in embryonic stem cells, its specific role in iPS cells remains unclear. To evaluate the function of hMAGEA2 and its characteristics in iPS cells, we produced hMAGEA2‐overexpressing iPS cells from hMAGEA2‐overexpressing transgenic mice. Although the iPS cells with overexpressed hMAGEA2 did not differ in morphology, their pluripotency, and self‐renewal related genes (Nanog, Oct3/4, Sox2, and Stat3), expression level was significantly upregulated. Moreover, hMAGEA2 contributed to the promotion of cell cycle progression, thereby accelerating cell proliferation. Through embryoid body formation in vitro and teratoma formation in vivo, we demonstrated that hMAGEA2 critically decreases the differentiation ability of iPS cells. These data indicate that hMAGEA2 intensifies the self‐renewal, pluripotency, and degree of proliferation of iPS cells, while significantly repressing their differentiation efficiency. Therefore, our findings prove that hMAGEA2 plays key roles in iPS cells.
Characterisation of the l‐Cystine β‐Lyase PatB from Phaeobacter inhibens: An Enzyme Involved in the Biosynthesis of the Marine Antibiotic Tropodithietic Acid
Authors: Dickschat Jeroen S. , Rinkel Jan , Klapschinski Tim , Petersen Jörn
Published: September 2017

The l‐cystine β‐lyase from Phaeobacter inhibens is involved in the biosynthesis of the sulfur‐containing antibiotic tropodithietic acid. The recombinant enzyme was obtained by heterologous expression in Escherichia coli and biochemically characterised by unambiguous chemical identification of the products formed from the substrate l‐cystine, investigation of the substrate spectrum, determination of the enzyme kinetics, sequence alignment with closely related homologues and site‐directed mutagenesis to identify a highly conserved lysine residue that is critical for functionality. PatB from P. inhibens is a new member of the small group of characterised l‐cystine β‐lyases and the first example of an enzyme with such an activity that is required for the biosynthesis of an antibiotic. A comparison of PatB to previously reported enzymes with l‐cystine β‐lyase activity from bacteria and plants is given.
Pathology of self‐expanding transcatheter aortic valves: Findings from the CoreValve US pivotal trials
Authors: Yahagi Kazuyuki , Torii Sho , Ladich Elena , Kutys Robert , Romero Maria E. , Mori Hiroyoshi , Kolodgie Frank D. , Popma Jeffrey J. , Virmani Renu , Finn Aloke V.
Published: September 2017

Background

Transcatheter aortic valve replacement (TAVR) has recently become an alternative to surgical aortic valve replacement for patients with severe aortic stenosis. However, paravalvular leaks, possible leaflet thrombosis, and device durability following TAVR remain unresolved issues.

Methods and Results

We conducted the first systematic microscopic and macroscopic pathologic analysis of self‐expanding CoreValve transcatheter aortic valves removed at autopsy or surgically from the U.S. pivotal trial of extreme‐ and high‐risk patients. Implants were evaluated for histopathologic changes in the valve frame and leaflets. Thrombus/neointima on the leaflets was graded depending on the leaflet thickness and the extent of leaflet involvement. Inflammation, calcification, and structural integrity were also assessed. A total of 21 cases (median age 86.0 years [IQR, 79.0–91.0]), with median duration of implant duration of 17.0 days ranged from 0 to 503 days were evaluated. No valve frame fracture was observed and severe paravalvular gaps were uncommon. Inflammation and thrombus in the valve frame was minimal, but neointimal growth increased overtime. Symptomatic valve thrombosis was observed in one case (5%) and subclinical moderate leaflet thrombus was observed in four additional cases (19%). Inflammation of the leaflets was mild, while structural changes were minimal, and one case had infective endocarditis. Pannus or leaflet calcification were not observed.

Conclusions

This first systematic macroscopic and microscopic pathologic analysis of self‐expanding transcatheter aortic valves demonstrates favorable short‐term pathologic findings. However, our finding of subclinical leaflet thrombus formation confirms prior observations and warrants further investigation.
Usefulness of the SYNTAX score II to validate 2‐year outcomes in patients with complex coronary artery disease undergoing percutaneous coronary intervention: A large single‐center study
Authors: Song Ying , Gao Zhan , Tang Xiaofang , Ma Yuanliang , Jiang Ping , Xu Jingjing , Yao Yi , Zhao Xueyan , Qiao Shubin , Yang Yuejin , Gao Runlin , Xu Bo , Yuan Jinqing
Published: September 2017

Objective

This study aimed to assess the prognostic ability of synergy between percutaneous coronary intervention with Taxus and cardiac surgery score II (SS‐II) in a large cohort of patients with complex coronary artery disease (CAD) undergoing percutaneous coronary intervention (PCI) in clinical practice.

Background

Few studies have explored the usefulness of SS‐II in nonrandomized clinical patients with complex CAD undergoing temporary PCI.

Methods

We prospectively enrolled 4398 consecutive patients undergoing three‐vessel and/or unprotected left main PCI in a single center from January 2013 to December 2013. Patients were stratified according to SS‐II for PCI tertiles as follows: SS‐II ≤ 20 (n = 1474); SS‐II 20–26 (n = 1462); and SS‐II > 26 (n = 1462). The predictive ability for 2‐year mortality was compared between angiographic scores and scores combining both angiographic and clinical variables.

Results

Mortality was significantly higher in the upper tertile than in the intermediate or lower tertiles during the 2‐year follow‐up (2.7% vs 1.7% vs 0.5%, respectively; P < 0.001). Multivariate analysis showed that SS‐II was an independent predictor of 2‐year mortality (hazard ratio: 1.66, 95% confidence interval: 1.03–2.68; P = 0.04). After adjusting for multivariable factors, SS‐II had better prediction of 2‐year mortality than baseline SS (C‐index: SS‐II = 0.740 vs baseline SS = 0.620; P < 0.001).

Conclusions

As a risk score combining both anatomical and clinical variables, SS‐II demonstrated superiority compared with the purely angiographic SS to predict 2‐year mortality in a clinical population of patients with severe CAD undergoing temporary PCI.
Complete filter‐based cerebral embolic protection with transcatheter aortic valve replacement
Authors: Van Gils Lennart , Kroon Herbert , Daemen Joost , Ren Claire , Maugenest Anne‐Marie , Schipper Marguerite , De Jaegere Peter P. , Van Mieghem Nicolas M.
Published: September 2017

Objectives

To evaluate the value of left vertebral artery filter protection in addition to the current filter‐based embolic protection technology to achieve complete cerebral protection during TAVR.

Background

The occurrence of cerebrovascular events after transcatheter aortic valve replacement (TAVR) has fueled concern for its potential application in younger patients with longer life expectancy. Transcatheter cerebral embolic protection (TCEP) devices may limit periprocedural cerebrovascular events by preventing macro and micro‐embolization to the brain. Conventional filter‐based TCEP devices cover three extracranial contributories to the brain, yet leave the left vertebral artery unprotected.

Methods

Patients underwent TAVR with complete TCEP. A dual‐filter system was deployed in the brachiocephalic trunk and left common carotid artery with an additional single filter in the left vertebral artery. After TAVR all filters were retrieved and sent for histopathological evaluation by an experienced pathologist.

Results

Eleven patients received a dual‐filter system and nine of them received an additional left vertebral filter. In the remaining two patients, the left vertebral filter could not be deployed. No periprocedural strokes occurred. We found debris in all filters, consisting of thrombus, tissue derived debris, and foreign body material. The left vertebral filter contained debris in an equal amount of patients as the Sentinel filters. The size of the captured particles was similar between all filters.

Conclusions

The left vertebral artery is an important entry route for embolic material to the brain during TAVR. Selective filter protection of the left vertebral artery revealed embolic debris in all patients. The clinical value of complete filter‐based TCEP during TAVR warrants further research.
Electrochemical Evaluation of Titanocenes in Ionic Liquids with Non‐coordinating and Coordinating Anions and Application for NH3 Synthesis
Authors: Katayama Akira , Inomata Tomohiko , Ozawa Tomohiro , Masuda Hideki
Published: September 2017

Redox behaviors of monomeric and dimeric titanocenes, [Cp2TiCl2] (1) and [(Cp2TiCl)2] (2), were investigated in two different types of ionic liquid (IL) with non‐coordinating and coordinating anions, 1‐butyl‐1‐methylpyrrolidinium tris(pentafluoroethyl)‐ trifluorophosphate (Pyr4FAP) and 1‐butyl‐1‐methylpyrrolidinium triflate (Pyr4OTf), respectively. UV‐vis/NIR spectra obtained during the electrochemical reduction of 1 revealed that it was converted to 2 in the ILs through the formation of [Cp2TiCl] (3). In Pyr4OTf, 3 was coordinated with the OTf anion in the η1‐O mode, during the electrochemical reductions of Ti(IV/III) process, whereas 3 was not coordinated by the FAP anion in Pyr4FAP. Additionally, electrochemical NH3 synthesis was carried out in a solid polymer electrolyte cell by using a gas diffusion electrode coated with Pyr4FAP or Pyr4OTf containing titanocenes. The electrochemical reduction using 2 in Pyr4FAP at −1.5 V (vs. Ag/AgCl) gave a high yield (34 % at 29.9 C) of NH3 per Ti ion. The electrochemical reduction using 1 in Pyr4OTf gave a 6.8 % yield of NH3 per Ti ion at 20 °C. These findings indicate that the use of an IL with a non‐coordinating anion such as FAP contributes to the coordination and reduction of N2 to titanocenes.
Bending Monolayer Artificial Muscle
Authors: Otero Toribio F. , Valero Laura
Published: September 2017

A bending electro‐chemo‐mechanical monolayer artificial muscle is presented and characterized. A transversal cross‐linking gradient attained during the film electropolymerization is proposed as the origin of the reaction‐driven muscular action. Each unit of charge consumed per unit of polymer weight gives the largest angular displacement described in the literature. This oversimplified polymeric motor for engineering applications saves extra energy required to bend and trail inactive layers from bilayer or multilayer classical structures.
Elucidation of the Reaction Behavior of Silicon Negative Electrodes in a Bis(fluorosulfonyl)amide‐Based Ionic Liquid Electrolyte
Authors: Yamaguchi Kazuki , Domi Yasuhiro , Usui Hiroyuki , Sakaguchi Hiroki
Published: September 2017

Excellent cycling performance of an electrode composed of silicon alone was achieved in a bis(fluorosulfonyl)amide (FSA)‐based electrolyte, with a high discharge capacity of 950 mA h g−1 observed even at the 500th cycle. To elucidate the reaction behavior of the Si electrode in an FSA‐based ionic liquid electrolyte, we investigated the change in the cross‐sectional morphology of the Si‐active material layer, the distribution of Li in the layer, and the crystallinity of Si on the electrode surface. By cross‐sectional scanning electron microscopy, we confirmed that the electrode thickness increased with the cycle number. The increase in thickness was less noticeable in the FSA‐based electrolyte than in an organic electrolyte. An elemental analysis of the electrode material revealed that a film derived from the electrolyte was formed not only on the surface but also inside of the electrode. Soft X‐ray emission spectroscopy demonstrated that the distribution of Li in the FSA‐based electrolyte was more uniform for the cross‐section of the cycled electrode compared to that in an organic electrolyte. The results of Raman spectroscopy indicated that domains of amorphous Si were homogeneously distributed on the electrode surface in the FSA‐based electrolyte. The uniform distribution of the lithiation−delithiation reaction should help to suppress disintegration of the active material layer.
Experimental and Computational Studies of the Structure of Sulfonimidoyl Vinyllithiums
Authors: Giesen Alexander Walter , Raabe Gerhard , Runsink Jan , Gais Hans‐Joachim
Published: September 2017

tBuCH=C(Li)S(O)(NSO2Tol)Ph⋅L (L=2THF, TMEDA) (1⋅L) in THF solution is a monomer with a C−Li bond according to NMR spectroscopy and cryoscopy. It was identified as CIP through the scalar 13C,6Li coupling and 6Li,{1H} NOE experiments. The CIP has a six‐membered C‐Li‐O‐S‐N‐S chelate ring structure. 6Li,1H FUCOUP and 6Li,1H HMQC NMR experiments of 1⋅TMEDA revealed a scalar 6Li,1H coupling across the Li−C=C−H bonds. According to the NMR data the π‐bond of 1⋅L is polarized by the negative charge of the anionic C atom. tBuCH=C(Li)S(O)(NMe)Ph (2⋅L) is most likely also a monomer with a C−Li bond. According to 6Li,{1H} NOE experiments it has a four‐membered C‐Li‐N‐S chelate ring structure. 13C NMR spectroscopy showed the C−Li bonds of 1⋅L and 2⋅L to be fluxional. 1H NMR spectroscopy and 1D TOCSY experiments of Ph2C=C(Li)S(O)(NSO2Tol)Ph revealed topomerization of the phenyl groups, which is attributed to a fast positional exchange of the Li atom and the sulfonimidoyl group. The fluxionality of the C−Li bond and the interchange of the Li atom and the sulfonimidoyl group at the anionic C atom of sulfonimidoyl vinyllithiums, which result in a low configurational stability, most likely involve the formation of O,Li and N,Li CIPs through heterolysis of the C−Li bond. Ab initio calculation of MeCH=C(Li)S(O)(NMe)Ph yielded an energy minimum structure with a C−Li bond, a four‐membered C‐Li‐N‐S chelate ring and a strongly expanded C=C−Li bond angle. According to calculation of MeCH=C(Li)S(O)(NMe)Ph, [MeCH=CS(O)(NMe)Ph]− and MeCH=C(H)S(O)(NMe)Ph deprotonation is not accompanied by a shortening of the C−S bond. Ab initio calculation of MeCH=C(Li)S(O)(NSO2Me)Ph gave a structure with a C−Li bond and a six‐membered C‐Li‐O‐S‐N‐S chelate ring. 6Li,1H NOE experiments and cryoscopy of LiCH2S(O)(NSO2Tol)Ph (3) revealed a monomeric CIP with a C−Li bond. The CIP has a six‐membered C‐Li‐O‐S‐N‐S chelate ring structure found in polymeric 3 in the crystal.
An Explosive Bomb‐Inspired Method to Prepare Collapsed and Ruptured Fe2O3/Nitrogen‐Doped Carbon Capsules as Catalyst Support
Authors: Wu Jie , Zhang Hui , Feng Yan , Zhang Xiao , Yao Tongjie , Lian Yongfu
Published: September 2017

Compared with integrated capsules, ruptured ones have better mass diffusion and transport properties due to large gaps in the shells. However, most studies focus on integrated capsules, whereas little attention has been paid to the ruptured counterparts. Herein, an explosive bomb‐inspired method was employed to prepare collapsed and ruptured Fe2O3/nitrogen‐doped carbon (CR‐Fe2O3/NC) capsules by using polystyrene (PS) nanoparticles (NPs) as a hard template, and polypyrrole (PPy) with embedded Prussian blue (PB) NPs as the shell. During pyrolysis, PB is converted into Fe2O3, and PPy is carbonized to form NC. Importantly, the PS core decomposes into gas molecules, leading to high pressure inside of the capsule, which explodes the thin shell into pieces. The roles of shell thickness and amount of Fe2O3 on determining the spherical or collapsed, and integrated or ruptured morphology were revealed. Taking advantage of structural merits, including large gaps, thin shells, low density, and high surface area, CR‐Fe2O3/NC capsules were used as supports for Pd NPs. These capsules exhibited better catalytic activity than that of integrated ones. Due to the magnetic properties, they could be reused at least five times.
Theoretical Evidence for the Utilization of Low‐Valent Main‐Group Complexes as Rare‐Synthon Equivalents
Authors: Benedek Zsolt , Orbán Balázs , Szilvási Tibor
Published: September 2017

We examine by the means of computational chemistry the ability of two phosphasilenes to transfer the phosphinidene moiety to four double bonded organic functional groups (>C=C<, ‐N=N‐, >C=O, and >C=S) in the presence of different bulky ligands. We show that large bulky groups in the reactants can sterically prohibit the otherwise favored association of reactants and phosphasilenes and instead a new phosphinidene transfer reaction can occur. We find that the transfer reaction mechanism is generally present independent from the functional group and by introducing large enough trimethylsilyl or tert‐butyl‐dimethylsilyl ligands it can be used to transfer phosphinidene to organic functional groups such as thioformaldehydes or diazenes, respectively. We propose that by exploiting the complex bonding nature of low‐valent main group complexes they can act as synthetic equivalents of hitherto unknown very reactive synthons. We encourage experimentalists to explore the reactivity of their main‐group complexes by varying the size of the bulky substituents on the reactants that can result in new unexpected chemistry.
Supramolecular Synthon Approach in Developing Anti‐Inflammatory Topical Gels for In Vivo Self‐Delivery
Authors: Roy Rajdip , Dastidar Parthasarathi
Published: September 2017

A new series of tertiary‐butyl ammonium (TBA) salts of various nonsteroidal anti‐inflammatory drugs (NSAIDs) have been synthesized and characterized. Nearly 90 % of the NSAID‐derived primary ammonium monocarboxylate (PAM) salts displayed remarkable gelation ability with various solvents including methyl salicylate. Single crystal X‐ray diffraction data (SXRD) revealed the existence of 1D PAM synthon in the gelator salts. Structure–property correlation studies based on SXRD and powder X‐ray diffraction (PXRD) data established the presence of the 1D PAM synthon in the bulk salts as well as in the corresponding xerogels. A parallel series of salts derived from TRIS (2‐amino‐2‐(hydroxymethyl)‐1,3‐propanediol) and the same set of NSAIDs displayed poor gelation ability; only 33 % of the salts in the series displayed gelation ability. A few selected gelator salts of both TBA and TRIS were found to be biocompatible (MTT assay with RAW 264.7 cell line) and two of the selected salts (FLR.TBA and FLR.TRIS) possessed anti‐inflammatory properties equal to the parent drug FLR (flurbiprofen). Finally a methyl salicylate topical gel derived from FLR.TRIS was successfully delivered in a self‐delivery fashion to treat inflamed skin conditions in the mice model. Histological studies of the dorsal tissues of the untreated and treated mice clearly demonstrated the effect of topical gels in such treatment.
Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers
Authors: Mosca Dario , Stopin Antoine , Wouters Johan , Demitri Nicola , Bonifazi Davide
Published: September 2017

Invited for the cover of this issue is the group of Bonifazi at the University of Cardiff and their collaborators from University of Namur (Belgium) and Elettra, Synchrotron Trieste (Italy). The image depicts the propeller‐like conformation of their newly synthesized molecular system that, thanks to the peculiar aromatic‐embracing folding, resembles the shape of the Sicilian Trinacria symbol, as demonstrated by its X‐ray single‐crystal structure. Read the full text of the article at 10.1002/chem.201702032.
Changes in parameters of right ventricular function with cardiac resynchronization therapy
Authors: Sharma Abhishek , Lavie Carl J. , Vallakati Ajay , Garg Akash , Goel Sunny , Lazar Jason , Fonarow Gregg C.
Published: September 2017

Background

Studies have shown that cardiac resynchronization therapy (CRT) significantly improves right ventricle (RV) size and function in patients with heart failure (HF).

Hypothesis

CRT does not lead to improvement in RV function independent of baseline clinical variables.

Methods

A systematic search of studies published between 1966 to August 31, 2015 was conducted using Pub Med, CINAHL, Cochrane CENTRAL and the Web of Science databases. Studies reporting tricuspid annular plane systolic excursion (TAPSE) or RV basal strain or RV long axis diameter or RV short axis diameter or RV fractional area change (FAC), before and after CRT, were identified. A meta‐analysis was performed using random effects with inverse variance method to determine the pooled mean difference in various parameters of RV function after CRT. Meta‐regression analysis was performed to test the relationship between change in various parameters of RV functions after CRT and covariates‐ age, QRS duration, and left ventricular ejection fraction (LVEF).

Results

Thirteen studies (N=1541) were selected for final analysis. CRT therapy led to statistically significant increases in TAPSE [1.21 (95% CI 0.55‐1.86; p<0.001)], RV FAC [2.26 (95% CI 0.50‐4.01; p<0.001)] and basal strain [2.82 (95% CI 0.59‐5.05; p<0.001)] and statistically significant decreases in mean RV long axis diameter [‐2.94 (95% CI ‐5.07‐ ‐0.82; p=0.005)] and short axis diameter [‐1.39 (95% CI ‐2.10‐ ‐0.67; p=0.876)] after a mean follow up period of 9 months. However, after meta‐regression analysis for age, QRS duration, and baseline LVEF as covariates, there was no significant improvement in any of the parameters of RV function after CRT.

Conclusion

There was a statistically significant improvement in TAPSE, RV basal strain, RV fractional area, RV long axis and short axis with CRT. However, improvement in these echocardiographic parameters of RV function after CRT was not independent of baseline clinical variables but statistically dependent on age, QRS duration and baseline LVEF.
Diagnostic accuracy of serum antibodies to human papillomavirus type 16 early antigens in the detection of human papillomavirus–related oropharyngeal cancer
Authors: Dahlstrom Kristina R. , Anderson Karen S. , Field Matthew S. , Chowell Diego , Ning Jing , Li Nan , Wei Qingyi , Li Guojun , Sturgis Erich M.
Published: September 2017

BACKGROUND

Because of the current epidemic of human papillomavirus (HPV)–related oropharyngeal cancer (OPC), a screening strategy is urgently needed. The presence of serum antibodies to HPV‐16 early (E) antigens is associated with an increased risk for OPC. The purpose of this study was to evaluate the diagnostic accuracy of antibodies to a panel of HPV‐16 E antigens in screening for OPC.

METHODS

This case‐control study included 378 patients with OPC, 153 patients with nonoropharyngeal head and neck cancer (non‐OPC), and 782 healthy control subjects. The tumor HPV status was determined with p16 immunohistochemistry and HPV in situ hybridization. HPV‐16 E antibody levels in serum were identified with an enzyme‐linked immunosorbent assay. A trained binary logistic regression model based on the combination of all E antigens was predefined and applied to the data set. The sensitivity and specificity of the assay for distinguishing HPV‐related OPC from controls were calculated. Logistic regression analysis was used to calculate odds ratios with 95% confidence intervals for the association of head and neck cancer with the antibody status.

RESULTS

Of the 378 patients with OPC, 348 had p16‐positive OPC. HPV‐16 E antibody levels were significantly higher among patients with p16‐positive OPC but not among patients with non‐OPC or among controls. Serology showed high sensitivity and specificity for HPV‐related OPC (binary classifier: 83% sensitivity and 99% specificity for p16‐positive OPC).

CONCLUSIONS

A trained binary classification algorithm that incorporates information about multiple E antibodies has high sensitivity and specificity and may be advantageous for risk stratification in future screening trials. Cancer 2017;123:4886‐94. © 2017 American Cancer Society.
Biomolecule‐Enabled Chiral Assembly of Plasmonic Nanostructures
Authors: Lee Hye‐Eun , Ahn Hyo‐Yong , Lee Jaehun , Nam Ki Tae
Published: September 2017

The field of chiral plasmonics has received increasing attention in various areas of nanoscience due to the unprecedented light‐matter interactions and promising optical applications. Chiral arrangement of nanoparticles is one of the strategies employed for fabrication of chiral nanostructures. These arrays exhibit collective chirality, where the chiroptical properties are governed by the geometrical parameters with nanometer precision. In this regard, the self‐assembly of biomolecules, such as peptides, DNA, and macromolecules, and their integration with plasmonic building blocks, can provide a route for the design and production of chiral plasmonic assemblies. In this Focus Review, we highlight biomolecule‐assisted methods for the chiral assembly of plasmonic nanostructures with emphasis on of the types of biomolecules and the geometry of the resulting assemblies. We present an overview of recent achievements in chiral plasmonic assemblies and provide perspectives for future directions in the field of chiral plasmonics.
Distinct seasonal migration patterns of Japanese native and non‐native genotypes of common carp estimated by environmental DNA
Authors: Uchii Kimiko , Doi Hideyuki , Yamanaka Hiroki , Minamoto Toshifumi
Published: September 2017

Understanding behavioral differences between intraspecific genotypes of aquatic animals is challenging because we cannot directly observe the animals underwater or visually distinguish morphologically similar counterparts. Here, we tested a new monitoring tool that uses environmental DNA (eDNA), an assemblage of DNA in environmental water, to specifically detect Japanese native and introduced non‐native genotypes of common carp (Cyprinus carpio) in Lake Biwa, Japan, and estimated differences between the two genotypes in the use of inland habitats. We monitored the ratios of native and non‐native single nucleotide polymorphism alleles of a mitochondrial locus of common carp in a lagoon connected to Lake Biwa for 3 years using eDNA. We observed seasonal dynamics in the allele frequency showing that the native genotype frequency peaked every spring, suggesting that native individuals migrated to the lagoon for spawning and then returned to the main lake, whereas non‐native individuals tended to stay in the lagoon. The estimated migration patterns corresponded with the estimates of a previous study, which were based on commercial fish catch data. Our findings suggest that eDNA‐based monitoring can be useful tool for addressing intraspecific behavioral differences underwater.
Frustrated Lewis Pair Chemistry with Magnesium Lewis Acids
Authors: Brand Steffen , Pahl Jürgen , Elsen Holger , Harder Sjoerd
Published: September 2017

Anilido imine–magnesium bromide complexes, (LHMgBr)2 and (LMeMgBr)2, have been prepared [LH = DIPP‐N(C6H4)C(H)N‐DIPP and LMe = DIPP‐N(C6H4)C(Me)N‐DIPP (DIPP = 2,6‐iPr2C6H3)]. Their dimeric crystal structures are compared to the dimer (DIPP‐nacnacMgBr)2 [DIPP‐nacnac = DIPP‐NC(Me)C(H)C(Me)N‐DIPP]. The anilido imine ligands show some degree of charge delocalization but are clearly more asymmetric than the DIPP‐nacnac complex: one of the N atoms has considerable anilido character, whereas the other one is close to an imine. Calculated natural population analysis (NPA) charges (B3PW91/6‐311++G**) and an atoms‐in‐molecules (AIM) study on model systems quantify the asymmetry in charge distribution. Quantification of the Lewis acidity of LHMgBr and LMeMgBr by the Gutmann–Beckett test gave acceptor numbers of 58.9 and 58.3, respectively. The complexes themselves are inert to a number of electrophiles; however, in combination with PPh3 the substrate 1‐butene oxide was ring‐opened. The resulting betaine‐type alkoxide complex is unstable and decomposes at room temperature through a Wittig‐type reaction. At higher temperatures also a reverse Wittig‐type decomposition is observed.
Optimization of Magnetic Relaxation and Isotopic Enrichment in Dimeric DyIII Single‐Molecule Magnets
Authors: Huang Gang , Yi Xiaohui , Jung Julie , Guillou Olivier , Cador Olivier , Pointillart Fabrice , Le Guennic Boris , Bernot Kevin
Published: September 2017

Single‐molecule magnet (SMM) behavior of dysprosium‐based dimers was optimized by substitution of a DyIII ancillary ligand (hfac– in the previously reported DyPyNO and tta– in Dy). A clear hysteresis opening is visible at 0.5 K for Dy that allows for the determination of an antiferromagnetic (AF) coupling of –2.92 cm–1 (S = 1/2, gz = 19.58) which was confirmed by ab initio calculations. Comparison with the results of DyPyNO shows that stronger AF coupling correlates with better SMM behavior. This is further demonstrated by diamagnetic substitution, and a Y–Dy species (YDy) highlights that the strong AF magnetic interaction in Dy significantly enhances magnetic relaxation at low temperature. This coupling is also expected to be at the origin of the unexpectedly weak isotopic effect observed for the isotopically pure parents of Dy, namely 161Dy and 164Dy.
AgII‐Mediated Synthesis of β‐Fluoroketones by Oxidative Cyclopropanol Opening
Authors: Deng Yuanlin , Kauser Nabeelah I. , Islam Shahidul M. , Mohr Justin T.
Published: September 2017

A regioselective synthesis of β‐fluorinated ketones by silver(II)‐mediated ring opening is described. Commercially available AgF2 serves as both an oxidant and fluorine‐atom source. A variety of β‐fluorinated ketones are efficiently prepared from tertiary cyclopropanol precursors, offering a straightforward approach for the introduction of a fluorine atom at a remote site. Selectivity is observed in the site of bond cleavage, which leads to fluorination at the more substituted site. A radical mediated sequential homolytic C–C bond cleavage and C–F bond formation is suggested.
Skin denervation does not alter cortical potentials to surface concentric electrode stimulation: A comparison with laser evoked potentials and contact heat evoked potentials
Authors: La Cesa S. , Di Stefano G. , Leone C. , Pepe A. , Galosi E. , Alu F. , Fasolino A. , Cruccu G. , Valeriani M. , Truini A.
Published: September 2017

Background

In the neurophysiological assessment of patients with neuropathic pain, laser evoked potentials (LEPs), contact heat evoked potentials (CHEPs) and the evoked potentials by the intraepidermal electrical stimulation via concentric needle electrode are widely agreed as nociceptive specific responses; conversely, the nociceptive specificity of evoked potentials by surface concentric electrode (SE‐PREPs) is still debated.

Methods

In this neurophysiological study we aimed at verifying the nociceptive specificity of SE‐PREPs. We recorded LEPs, CHEPs and SE‐PREPs in eleven healthy participants, before and after epidermal denervation produced by prolonged capsaicin application. We also used skin biopsy to verify the capsaicin‐induced nociceptive nerve fibre loss in the epidermis.

Results

We found that whereas LEPs and CHEPs were suppressed after capsaicin‐induced epidermal denervation, the surface concentric electrode stimulation of the same denervated skin area yielded unchanged SE‐PREPs.

Conclusion

The suppression of LEPs and CHEPs after nociceptive nerve fibre loss in the epidermis indicates that these techniques are selectively mediated by nociceptive system. Conversely, the lack of SE‐PREP changes suggests that SE‐PREPs do not provide selective information on nociceptive system function.

Significance

Capsaicin‐induced epidermal denervation abolishes laser evoked potentials (LEPs) and contact heat evoked potentials (CHEPs), but leaves unaffected pain‐related evoked potentials by surface concentric electrode (SE‐PREPs). These findings suggest that unlike LEPs and CHEPs, SE‐PREPs are not selectively mediated by nociceptive system.
Tapioca Biofilm Containing Nitrogen‐doped Titanium Dioxide Nanoparticles for Electrochemical Detection of 17‐β Estradiol
Authors: Mauruto de Oliveira Gabriela C. , P. de Palma Elisangela , Kunita Marcos H. , Antigo Medeiros Roberta , de Matos Roberto , Francisco Kelly Roberta , Janegitz Bruno C.
Published: September 2017

A novel sensor architecture based on thin film of tapioca decorated within nitrogen‐doped titanium dioxide (N‐TiO2) nanoparticles is reported. The nanostructures were characterized by scanning electron microscope, transmission electron microscope, X‐rays diffraction and voltammetric techniques. The proposed electrode was used for detection of low concentrations of 17‐β estradiol in without purification step, which was investigated by using linear sweep adsorptive stripping voltammetry. Under optimal conditions, the analytical curve was linear over a 17β‐estradiol concentration range of 9.9×10−6 to 1.4×10−5 mol L−1, with a detection limit of 1.7×10−7 mol L−1. The tapioca and N‐TiO2 nanoparticles homogeneous film was applied for detection of 17‐β‐estradiol in tap water and synthetic urine samples, which presented satisfactory results.
Microcolumn studies of dye biosorption from textile effluent on to dead biomass of Rhizopusarrhizus NCIM 997
Authors: Saraf Sukhada , Vaidya Varsha K.
Published: September 2017

Adsorption behavior of remazol reactive dyes from textile effluent was investigated using Rhizopus arrhizus as a biosorbent in up‐flow fixed‐bed micro column. The characteristics of mass transfer zone (MTZ), where adsorption in column occurs, were affected by bed depth and flow rate. The height of mass transfer zone (HMTZ), the rate of mass transfer zone (RMTZ), the effluent volume (Veff) and the column capacity at exhaustion (qcolumn) were estimated for the removal of dyes by the biosorbent. Thomas and Yoon–Nelson models were applied to the experimental data to predict the “S” shaped breakthrough curves and to determine the biosorption capacity of the column. Both the models were found suitable for describing the whole dynamic behavior of the column with respect to flow rate and bed depth. Hutchins BDST model showed that the variation of the service time with the bed depth was highly linear, thus, indicating its validity when applied to the continuous microcolumn studies. The empty bed residence time model (EBRT) indicated that the biosorbent exhaustion rate decreased with increasing EBRT. The results of this study indicated the applicability of fixed‐bed micro column for removing remazol reactive dyes from the textile effluent. © 2017 American Institute of Chemical Engineers Environ Prog, 37: 355–366, 2018
A pediatric structural MRI analysis of healthy brain development from newborns to young adults
Authors: Levman Jacob , MacDonald Patrick , Lim Ashley Ruyan , Forgeron Cynthia , Takahashi Emi
Published: September 2017

Assessment of healthy brain maturation can be useful toward better understanding natural patterns of brain growth and toward the characterization of a variety of neurodevelopmental disorders as deviations from normal growth trajectories. Structural magnetic resonance imaging (MRI) provides excellent soft‐tissue contrast, which allows for the assessment of gray and white matter in the developing brain. We performed a large‐scale retrospective analysis of 993 pediatric structural brain MRI examinations of healthy subjects (n = 988, aged 0–32 years) imaged clinically at 3 T, and extracted a wide variety of measurements such as white matter volumes, cortical thickness, and gyral curvature localized to subregions of the brain. All extracted structural biomarkers were tested for their correlation with subject age at time of imaging, providing measurements that may assist in the assessment of neurological maturation. Additional analyses were also performed to assess gender‐based differences in the brain at a variety of developmental stages, and to assess hemispheric asymmetries. Results add to the literature by analyzing a realistic distribution of healthy participants imaged clinically, a useful cohort toward the investigation and creation of diagnostic tests for a variety of pathologies as aberrations from healthy growth trajectories. The next generation of diagnostic tests will be responsible for identifying pathological conditions from populations of healthy clinically imaged individuals. Hum Brain Mapp 38:5931–5942, 2017. © 2017 Wiley Periodicals, Inc.