bluuebunny/crossref_metadata_2025 huggingface dataset:
Concussion in adolescence and risk of multiple sclerosis
Authors: Montgomery Scott , Hiyoshi Ayako , Burkill Sarah , Alfredsson Lars , Bahmanyar Shahram , Olsson Tomas
Published: September 2017

Objective

To assess whether concussion in childhood or adolescence is associated with subsequent multiple sclerosis (MS) risk. Previous research suggests an association, but methodological limitations included retrospective data collection and small study populations.

Methods

The national Swedish Patient Register (hospital diagnoses) and MS Register were used to identify all MS diagnoses up to 2012 among people born since 1964, when the Patient Register was established. The 7,292 patients with MS were matched individually with 10 people without MS by sex, year of birth, age/vital status at MS diagnosis, and region of residence (county), resulting in a study population of 80,212. Diagnoses of concussion and control diagnoses of broken limb bones were identified using the Patient Register from birth to age 10 years or from age 11 to 20 years. Conditional logistic regression was used to examine associations with MS.

Results

Concussion in adolescence was associated with a raised risk of MS, producing adjusted odds ratios (95% confidence intervals) of 1.22 (1.05–1.42, p = 0.008) and 2.33 (1.35–4.04, p = 0.002) for 1 diagnosis of concussion and >1 diagnosis of concussion, respectively, compared with none. No notable association with MS was observed for concussion in childhood, or broken limb bones in childhood and adolescence.

Interpretation

Head trauma in adolescence, particularly if repeated, is associated with a raised risk of future MS, possibly due to initiation of an autoimmune process in the central nervous system. This further emphasizes the importance of protecting young people from head injuries. Ann Neurol 2017;82:554–561
Helicity Multiplexed Spin‐Orbit Interaction in Metasurface for Colorized and Encrypted Holographic Display
Authors: Zhang Xiaohu , Pu Mingbo , Jin Jinjin , Li Xiong , Gao Ping , Ma Xiaoliang , Wang Changtao , Luo Xiangang
Published: September 2017

The photonic spin‐orbit interaction (PSOI) in inhomogeneous anisotropic metasurface has drawn much attentions recently due to its superior ability to manipulate light wave in the deep‐subwavelength scale. Traditional methods involving PSOI are limited to operational spectral bandwidth owing to the intrinsic dispersion of the constitutive materials. In this paper, a helicity‐multiplexing scheme is proposed to achieve independent control of the PSOI in both the spectral and spatial domains by combining the broadband characteristic with polarization dependence of the metasurface. Two simultaneous functions of multicolor holographic display and polarization encryption are experimentally demonstrated with a single metasurface perforated with nanoholes. Although the optical response of the nanoholes themselves are almost independent of the light wavelength, the obtained image can have abundant spectral information. The approach proposed here is promising for realizing multifunction optical device, multicolor display, optical storage and information encryption.
Repairing Nanoparticle Surface Defects
Authors: Marino Emanuele , Kodger Thomas E. , Crisp Ryan W. , Timmerman Dolf , MacArthur Katherine E. , Heggen Marc , Schall Peter
Published: September 2017

Solar devices based on semiconductor nanoparticles require the use of conductive ligands; however, replacing the native, insulating ligands with conductive metal chalcogenide complexes introduces structural defects within the crystalline nanostructure that act as traps for charge carriers. We utilized atomically thin semiconductor nanoplatelets as a convenient platform for studying, both microscopically and spectroscopically, the development of defects during ligand exchange with the conductive ligands Na4SnS4 and (NH4)4Sn2S6. These defects can be repaired via mild chemical or thermal routes, through the addition of L‐type ligands or wet annealing, respectively. This results in a higher‐quality, conductive, colloidally stable nanomaterial that may be used as the active film in optoelectronic devices.
Selective C−H Bond Cleavage in Methane by Small Gold Clusters
Authors: Lang Sandra M. , Bernhardt Thorsten M. , Chernyy Valeriy , Bakker Joost M. , Barnett Robert N. , Landman Uzi
Published: September 2017

Methane represents the major constituent of natural gas. It is primarily used only as a source of energy by means of combustion, but could also serve as an abundant hydrocarbon feedstock for high quality chemicals. One of the major challenges in catalysis research nowadays is therefore the development of materials that selectively cleave one of the four C−H bonds of methane and thus make it amenable for further chemical conversion into valuable compounds. By employing infrared spectroscopy and first‐principles calculations it is uncovered herein that the interaction of methane with small gold cluster cations leads to selective C−H bond dissociation and the formation of hydrido methyl complexes, H‐Aux+‐CH3. The distinctive selectivity offered by these gold clusters originates from a fine interplay between the closed‐shell nature of the d states and relativistic effects in gold. Such fine balance in fundamental interactions could prove to be a tunable feature in the rational design of a catalyst.
Phosphate Transfer in Activated Protein Complexes Reveals Interaction Sites
Authors: Tamara Sem , Scheltema Richard A. , Heck Albert J. R. , Leney Aneika C.
Published: September 2017

For many proteins, phosphorylation regulates their interaction with other biomolecules. Herein, we describe an unexpected phenomenon whereby phosphate groups are transferred non‐enzymatically from one interaction partner to the other within a binding interface upon activation in the gas phase. Providing that a high affinity exists between the donor and acceptor sites, this phosphate transfer is very efficient and the phosphate groups only ligate to sites in proximity to the binding region. Consequently, such phosphate‐transfer reactions may define with high precision the binding site between a phosphoprotein and its binding partner, as well as reveal that the binding site in this system is retained in the phase transfer from solution to the gas phase.
Columnar Lithium Metal Anodes
Authors: Zhang Xue‐Qiang , Chen Xiang , Xu Rui , Cheng Xin‐Bing , Peng Hong‐Jie , Zhang Rui , Huang Jia‐Qi , Zhang Qiang
Published: September 2017

The rechargeable lithium metal anode is of utmost importance for high‐energy‐density batteries. Regulating the deposition/dissolution characteristics of Li metal is critical in both fundamental researches and practical applications. In contrast to gray Li deposits featured with dendritic and mossy morphologies, columnar and uniform Li is herein plated on lithium‐fluoride (LiF)‐protected copper (Cu) current collectors. The electrochemical properties strongly depended on the microscale morphologies of deposited Li, which were further embodied as macroscale colors. The as‐obtained ultrathin and columnar Li anodes contributed to stable cycling in working batteries with a dendrite‐free feature. This work deepens the fundamental understanding of the role of LiF in the nucleation/growth of Li and provides emerging approaches to stabilize rechargeable Li metal anodes.
Spin Changes Accompany Ultrafast Structural Interconversion in the Ground State of a Cobalt Nitrosyl Complex
Authors: Marroux Hugo J. B. , Curchod Basile F. E. , Faradji Charly A. , Shuttleworth Timothy A. , Sparkes Hazel A. , Pringle Paul G. , Orr‐Ewing Andrew J.
Published: September 2017

Ultrafast, reversible intersystem crossing (ISC) is reported under ambient conditions for the electronic ground state of the pentacoordinate cobalt nitrosyl complexes, [CoX2(NO)(PMePh2)2] (X=Cl, Br), in solution. ISCs on such short timescales are more typically observed in electronically excited states reached by absorption of ultraviolet or visible light. Singlet and triplet electron spin states of the complex, corresponding to two different isomers, are populated at room temperature, and the two isomers exchange on a timescale of a few picoseconds. Ultrafast two‐dimensional infrared spectroscopy observes the change in wavenumber of the NO ligand band accompanying the isomerization and associated ISC on the (spin) adiabatic ground potential energy surface. Comparison of the dynamics of the chloro‐ and bromo‐complexes shows that inertial effects of the ligand motion have a greater effect than spin–orbit coupling on determining the forward and reverse isomerization and ISC rates.
Organocatalytic Intramolecular [4+2] Cycloaddition between In Situ Generated Vinylidene ortho‐Quinone Methides and Benzofurans
Authors: Wu Xiaoyan , Xue Lu , Li Dongmei , Jia Shiqi , Ao Jun , Deng Jun , Yan Hailong
Published: September 2017

Described herein is the enantioselective construction of oxygen‐containing [5‐6‐5] tricyclic heterocycles by an organocatalyzed asymmetric [4+2] cycloaddition of vinylidene ortho‐quinone methides and benzofurans. According to this methodology, a series of oxygen‐containing [5‐6‐5] tricyclic heterocycles with various functional groups were synthesized in excellent enantio‐ and diastereoselectivities (>99 % ee, >20:1 d.r.). Furthermore, the deuterium‐labeling experiments and high‐resolution mass spectroscopy demonstrated that a vinylidene ortho‐quinone methide intermediate was involved and possibly resulted from a prototropic rearrangement of 2‐ethynylphenol. Remarkably, a catalyst loading as low as 0.1 mol %, and a gram‐scale synthesis were achieved for this transformation.
Reductive Coupling of Acrylates with Ketones and Ketimines by a Nickel‐Catalyzed Transfer‐Hydrogenative Strategy
Authors: Buxton Craig S. , Blakemore David C. , Bower John F.
Published: September 2017

Nickel‐catalyzed coupling of benzyl acrylates with activated ketones and imines provides γ‐butyrolactones and lactams, respectively. The benzyl alcohol byproduct released during the lactonization/lactamization event is relayed to the next cycle where it serves as the reductant for C−C bond formation. This strategy represents a conceptually unique approach to transfer‐hydrogenative C−C bond formation, thus providing examples of reductive heterocyclizations where hydrogen embedded within an alcohol leaving group facilitates turnover.
Hydrosulfonylation Reaction with Arenesulfonyl Chlorides and Tetrahydrofuran: Conversion of Terminal Alkynes into Cyclopentylmethyl Sulfones
Authors: Gloor Christian Simon , Dénès Fabrice , Renaud Philippe
Published: September 2017

An efficient and simple radical chain reaction to convert terminal alkynes into arenesulfonylmethylcyclopentanes is described. The reaction involves a radical addition–translocation–cyclization process and necessitates solely the use of readily available arenesulfonyl chlorides in tetrahydrofuran. Interestingly, this radical‐mediated C−H activation process took place with a high level of retention of configuration when an enantiomerically pure starting material was used.
Near‐ultraviolet transit photometry of HAT‐P‐32 b with the Large Binocular Telescope: Silicate aerosols in the planetary atmosphere
Authors: Mallonn Matthias , Wakeford Hannah R.
Published: September 2017

Broad‐band exoplanet transit photometry can characterize the planetary atmosphere when observed at multiple selected filters. This observing technique can reveal gradients in the spectra of extrasolar planets, for example, the slope of decreasing opacity from short to long optical wavelengths caused by aerosol scattering. In this work, we observed a transit of the hot Jupiter HAT‐P‐32 b in the shortest wavelength possible from the ground using the Large Binocular Telescope (LBT). The data comprise the best quality ground‐based U‐band measurement taken so far of an exoplanet transit. Compared to broad‐band observations of intermediate and long optical wavelengths published previously, a clear scattering slope in the planetary transmission spectrum is revealed. Most likely, the scattering particles are magnesium silicate aerosols larger than 0.1 µm. We define a spectral index to compare this scattering feature of HAT‐P‐32 b with published results of other exoplanets. It turns out to be very typical in amplitude within the compared sample. Furthermore, we searched for correlation in this sample of the spectral index with planetary equilibrium temperature, surface acceleration, and stellar activity indicator, but could not find any.
Constructing arabinofuranosidases for dual arabinoxylan debranching activity
Authors: Wang Weijun , Andric Nikola , Sarch Cody , Silva Bruno T. , Tenkanen Maija , Master Emma R.
Published: September 2017

Enzymatic conversion of arabinoxylan requires α‐L‐arabinofuranosidases able to remove α‐L‐arabinofuranosyl residues (α‐L‐Araf) from both mono‐ and double‐substituted D‐xylopyranosyl residues (Xylp) in xylan (i.e., AXH‐m and AXH‐d activity). Herein, SthAbf62A (a family GH62 α‐L‐arabinofuranosidase with AXH‐m activity) and BadAbf43A (a family GH43 α‐L‐arabinofuranosidase with AXH‐d3 activity), were fused to create SthAbf62A_BadAbf43A and BadAbf43A_SthAbf62A. Both fusion enzymes displayed dual AXH‐m,d and synergistic activity toward native, highly branched wheat arabinoxylan (WAX). When using a customized arabinoxylan substrate comprising mainly α‐(1 → 3)‐L‐Arafand α‐(1 → 2)‐L‐Arafsubstituents attached to disubstituted Xylp(d‐2,3‐WAX), the specific activity of the fusion enzymes was twice that of enzymes added as separate proteins. Moreover, the SthAbf62A_BadAbf43A fusion removed 83% of all α‐L‐Araffrom WAX after a 20 hr treatment.1H NMR analyses further revealed differences in SthAbf62A_BadAbf43 rate of removal of specific α‐L‐Araf substituents from WAX, where 9.4 times higher activity was observed toward d‐α‐(1 → 3)‐L‐Arafcompared to m‐α‐(1 → 3)‐L‐Arafpositions.
Metabonomic analysis of serum reveals antifatigue effects of Yi Guan Jian on fatigue mice using gas chromatography coupled to mass spectrometry
Authors: Shui Sufang , Cai Xiaorong , Huang Rongqing , Xiao Bingkun , Yang Jianyun
Published: September 2017

Yi Guan Jian (YGJ), one of the most commonly used traditional Chinese medicines, has been reported to possess significant antifatigue effects. However, the mechanisms underlying its antifatigue effects remain largely unresolved. In this study, a metabonomics approach, involving gas chromatography coupled to mass spectrometry and a multivariate statistical technique, was developed to estimate the extent to which YGJ alleviated the exhausting swimming‐induced fatigue of mice. High‐dose treatment with YGJ significantly extended the swimming time of fatigued mice. Significant alterations of metabolites involving amino acids, organic acids and carbohydrates were observed in the serum of fatigued mice, which were reversed by YGJ treatment while biochemical indexes returned to normal. These metabolic changes suggest that the antifatigue effect of YGJ is associated with the impairement of amino acid, organic acids and carbohydrates. It also appears that YGJ can induce significant metabolic alterations independent of the exhausting swimming‐induced metabolic changes. The significantly altered metabolites induced by YGJ intervention include l‐2‐amino‐acetoacetate, taurine, fumaric acid, malic acid, oxoadipic acid and l‐aspartate, all of which are associated with antifatigue properties. This suggests that YGJ exerts chemopreventive effects via antifatigue mechanisms.
Exploring the mechanism of Jieduquyuziyin prescription on systemic lupus erythematosus by GC–MS‐based urine metabolomics
Authors: Wei Jing , Gao Jun , Ding Xinghong
Published: September 2017

A urine metabolomics method based on gas chromatography–mass spectrometry was developed in order to investigate the metabolite characteristics of systemic lupus erythematosus (SLE) and the therapeutic effects of Jieduquyuziyin prescription. The urinary metabolic profiles in urine specimens of the SLE model mice (MRL/lpr) group, prednisone acetate‐treated SLE mouse group, Jieduquyuziyin prescription‐treated SLE mouse group, and control group (C57BL/6 J) after the administration were analyzed by gas chromatography–mass spectrometry. These metabolic profiles were then processed by multivariate analysis, in particular Mass Profiler Professional, SIMCA‐P and partial least‐squares discriminant analysis. According to the partial least‐squares discriminant analysis results, the SLE model group and the control group were obviously separated, indicating that the incidence of SLE had a greater impact on the metabolic network, and the SLE model group had significant difference compared with the control group in urine metabolites. Eleven differential metabolites were identified to be related to SLE, and the results of differential metabolite identification showed that the metabolites were mainly related to energy metabolism and amino acid metabolism pathway. These results can provide an experimental basis for further exploring the mechanism of traditional Chinese medicine in the treatment of SLE.
Chromatographic approaches for the characterization and quality control of therapeutic oligonucleotide impurities
Authors: El Zahar N. M. , Magdy N. , El‐Kosasy A. M. , Bartlett Michael G.
Published: September 2017

Phosphorothioate (PS) oligonucleotides are a rapidly rising class of drugs with significant therapeutic applications. However, owing to their complex structure and multistep synthesis and purification processes, generation of low‐level impurities and degradation products are common. Therefore, they require significant investment in quality control and impurity identification. This requires the development of advanced methods for analysis, characterization and quantitation. In addition, the presence of the PS linkage leads to the formation of chiral centers which can affect their biological properties and therapeutic efficiency. In this review, the different types of oligonucleotide impurities and degradation products, with an emphasis on their origin, mechanism of formation and methods to reduce, prevent or even eliminate their production, will be extensively discussed. This review will focus mainly on the application of chromatographic techniques to determine these impurities but will also discuss other approaches such as mass spectrometry, capillary electrophoresis and nuclear magnetic resonance spectroscopy. Finally, the chirality and formation of diastereomer mixtures of PS oligonucleotides will be covered as well as approaches used for their characterization and the application for the development of stereochemically‐controlled PS oligonucleotides.
An educational software to reinforce the comprehensive learning of materials selection
Authors: Rodríguez‐Prieto Alvaro , Camacho Ana M. , Merayo David , Sebastián Miguel A.
Published: September 2017

An educational software, called CalSev 1.0.2, has been developed for supporting the teaching in materials selection seminars. As a case study, a selection of materials for nuclear reactor pressure vessels has been chosen, because it is a representative example of the relationship between chemical composition, mechanical properties, and in‐service behavior. This software has been developed to improve the students’ understanding of the materials selection tasks, providing an interactive user‐friendly platform that allows to modify—in real time—the content of chemical elements and mechanical requirements to obtain a materials performance evaluation. Due to its versatility, this informatics tool represents a great value for educational purposes, with special impact in blended and distance learning, by simplifying the arduous task of materials selection for a wide range of applications and promoting a collaborative working environment by easing the creation of small groups analyzing different study cases. Finally, to evaluate the functionality, interest, user‐friendliness and the educational characteristics of CalSev 1.0.2, a survey among 36 undergraduate students has been carried out.
Correctness assessment of a crowdcoding project in a computer programming introductory course
Authors: Ferrán Sebastián , Beghelli Alejandra , Huerta‐Cánepa Gonzalo , Jensen Federico
Published: September 2017

Crowdcoding is a programming model that outsources a software project implementation to the crowd. As educators, we think that crowdcoding could be leveraged as part of the learning path of engineering students from a computer programming introductory course to solve local community problems. The benefits are twofold: on the one hand the students practice the concepts learned in class and, on the other hand, they participate in real‐life problems. Nevertheless, several challenges arise when developing a crowdcoding platform, the first one being how to check the correctness of student's code without giving an extra burden to the professors in the course. To overcome this issue, we propose a novel system that does not resort to expert review; neither requires knowing the right answers beforehand. The proposed scheme automatically clusters the student's codes based solely on the output they produce. Our initial results show that the largest cluster contains the same codes selected as correct by the automated and human testing, as long as some conditions apply.
IMECE—Implementation of mathematical, experimental, and computer‐based education: A special application of fluid mechanics for civil and environmental engineering students
Authors: Yetilmezsoy Kaan
Published: September 2017

A novel educational methodology, Implementation of Mathematical, Experimental, and Computer‐based Education (IMECE), where its name was derived from the letters of the word “imece” (a Turkish tradition) by taking into account the integrative meaning of this cultural concept, was proposed to explore the synergistic effect of the conventional mathematical solution procedure, visual application, and MATLAB‐based simulation on the perceptions and learning quality of the engineering students. Within the scope the present research carried out both at the state university (undergraduate and graduate levels) and at the foundation university (undergraduate level), water discharge problem (a special case of the Bernoulli's principle/Toricelli's law) was chosen as an example application. In the study, the experimental results of three different tank models (vertical cylindrical, conical, and spherical) and the solution algorithms written in MATLAB were presented in detail, and new empirical equations were also developed for each laboratory scale system depending on the experimental data. The effectiveness of the proposed IMECE method was evaluated statistically within the framework of both “Student Survey” and “Student Assessment” conducted with the participation of 84 students. Based on the mean scores obtained for all participating students, the results of the statistical tests indicated that the quantitative performance (or effectiveness) of the applied IMECE methodology was determined as 97.73%, 67.36%, and 82.55% for the perception/satisfaction section, the learning section, and the overall evaluation category, respectively.
‘This is Not Just About History…’ Addressing the Disconnect in Historic (Non‐Recent) Child Abuse Investigations
Authors: Aldridge Jo
Published: September 2017

Key Practitioner Messages:

Historic (non‐recent) child abuse investigations need to consider the effects of investigative processes on victims and survivors.

Such investigations include those undertaken by the police and by the Independent Inquiry into Child Sexual Abuse (IICSA).

Victim and survivor accounts need to be taken seriously and investigated thoroughly in order for victims/survivors not to feel let down by, and disconnected from, criminal justice and IICSA processes.

‘Historic (non‐recent) child abuse investigations need to consider the effects of investigative processes on victims and survivors’
Substrate Recognition by a Dual‐Function P450 Monooxygenase GfsF Involved in FD‐891 Biosynthesis
Authors: Miyanaga Akimasa , Takayanagi Ryuichi , Furuya Takashi , Kawamata Ayano , Itagaki Tomohiro , Iwabuchi Yoshiharu , Kanoh Naoki , Kudo Fumitaka , Eguchi Tadashi
Published: September 2017

GfsF is a multifunctional P450 monooxygenase that catalyzes epoxidation and subsequent hydroxylation in the biosynthesis of macrolide polyketide FD‐891. Here, we describe the biochemical and structural analysis of GfsF. To obtain the structural basis of a dual‐function reaction, we determined the crystal structure of ligand‐free GfsF, which revealed GfsF to have a predominantly hydrophobic substrate binding pocket. The docking models, in conjunction with the results of the enzymatic assay with substrate analogues and site‐directed mutagenesis suggested two distinct substrate binding modes for epoxidation and hydroxylation reactions, which explained how GfsF regulates the order of two oxidative reactions. These findings provide new insights into the reaction mechanism of multifunctional P450 monooxygenases.
Identification of Chimeric αβγ Diterpene Synthases Possessing both Type II Terpene Cyclase and Prenyltransferase Activities
Authors: Mitsuhashi Takaaki , Okada Masahiro , Abe Ikuro
Published: September 2017

Two unusual diterpene synthases composed of three domains (α, β, and γ) were identified from fungal Penicillium species. They are the first enzymes found to possess both type II terpene cyclase (TC) and prenyltransferase (PT) activities. These enzymes were characterized by heterologous expression in Aspergillus oryzae and in vitro experiments with wild‐type, mutated, and truncated enzymes. The results revealed that the α domain in the C‐terminal region of these enzymes was responsible for the PT activity, whereas the βγ domains in the N‐terminal region composed the type II TC, and formed copalyl diphosphate (2). Additionally, between the α and βγ domains, there is a characteristic linker region, in which minimal secondary structure is predicted. This linker does not exist in the characterized three‐domain (αβγ) terpene synthases known as monofunctional type I or type II TCs, or bifunctional type I and type II TC enzymes. Therefore, both the catalytic activities and protein architecture substantially differentiate these new enzymes from the previously characterized terpene synthases.
Achieving Gender Equity for Women Leaders in Community Colleges Through Better Communication
Authors: Edwards Amy Fara
Published: September 2017

This chapter provides an action plan to help achieve gender equity by better understanding the role of gender, leadership, and communication in higher education administration.
“Good” Places to Work: Women Faculty, Community Colleges, Academic Work, and Family Integration
Authors: Ward Kelly , Wolf‐Wendel Lisa
Published: September 2017

This chapter draws on a longitudinal study about women faculty, work–family, and career advancement in community colleges. The study found that the participants, though highly satisfied with their careers and qualified for administration, are largely uninterested in moving to more senior administrative positions.
From Boots to Suits: Women Veterans Transitioning to Community College Students
Authors: Heineman Judie A.
Published: September 2017

This chapter explores the unique needs of women student–veterans and highlights the ways that community college leaders can support women student–veterans on their college campuses.
Looking Forward—Strategies for Inclusivity
Authors: Eddy Pamela L.
Published: September 2017

This final chapter draws together the ways in which intersectionality occurs for a range of stakeholders regarding constructions of gender in community colleges and provides tactics for increasing equity.
Five‐year follow‐up of the endothelial progenitor cell capturing stent versus the paxlitaxel‐eluting stent in de novo coronary lesions with a high risk of coronary restenosis
Authors: Woudstra Pier , Kalkman Deborah N. , Beijk Marcel A. , Klomp Margo , Damman Peter , Koch Karel T. , Henriques Jose P. S. , Baan Jan , Vis Marije M. , Piek Jan J. , Tijssen Jan G. P. , de Winter Robbert J.
Published: September 2017

Objectives

To assess the long‐term safety and clinical efficacy of the Genous endothelial progenitor cell capturing stent (ECS) compared with the TAXUS Liberté paclitaxel‐eluting stent (PES) in lesions with a high risk of restenosis.

Background

Instead of the use of cytotoxic or cytostatic drugs in drug‐eluting stents, a “pro‐healing” approach in ECS may overcome impeded healing response due to delayed functional endothelialization of the stent struts.

Methods

In the prospective, randomized TRIAS pilot study 193 patients with coronary artery lesions carrying a high risk of restenosis were included (ECS: n = 98, PES: n = 95). The primary focus of this analysis was target vessel failure (TVF) at 5 years. Dual antiplatelet therapy was prescribed for ≥1 month after ECS and for ≥6 months after PES.

Results

At 5 years follow‐up, no significant differences were found in TVF (ECS 24% vs. PES 29%, risk difference 95% confidence interval (RDCI) −17.3% to 7.4%). Between 2 and 5 years after the index procedure, low numbers of TVF were observed in ECS compared with PES (ECS 4% vs. PES 16%, RDCI −20.8% to −2.3%). There was no definite stent thrombosis in ECS compared with four patients in the PES group.

Conclusion

This is the first randomized study providing very long‐term clinical efficacy and safety of the ECS in lesions carrying a high risk of restenosis. At 5 years follow‐up, TVF rates in ECS group are numerically lower compared with PES due to an increase of events between 2 and 5 years after the index procedure.
Importance of the Reducing Agent in Direct Reductive Heck Reactions
Authors: Raoufmoghaddam Saeed , Mannathan Subramaniyan , Minnaard Adriaan J. , de Vries Johannes G. , de Bruin Bas , Reek Joost N. H.
Published: September 2017

The role of the reductant in the palladium N‐heterocyclic carbene (NHC) catalyzed reductive Heck reaction and its effect on the mechanism of the reaction is reported. For the first time in this type of transformation, the palladium‐NHC‐catalyzed reductive Heck reaction was shown to proceed in the presence of LiOMe and iPrOH even at 10 °C to give the products very efficiently in excellent yields and with exceptional chemoselectivities. This study shows that the reaction proceeds through two distinct mechanisms that depend on the nature of the reducing agent. In the presence of a protic solvent or acidic medium the reaction undergoes protonation to yield the reduced product, whereas in the absence of proton source, it proceeds through the insertion of the reductant followed by reductive elimination. The kinetic data reveal that the oxidative addition is the rate‐determining step in the reaction. The reaction profiles show first‐order kinetics in aryl iodide and Pd and zero‐order kinetics in LiOMe, benzylideneacetone, and the excess amount of NHC ligand. In addition, the reaction progress kinetic analysis shows that neither catalyst decomposition nor product inhibition occurs during the reaction. DFT calculations of the key steps confirm that the oxidative addition step is the rate‐determining step in the reaction. Deuterium‐labeling experiments indicate that the product is formed by the protonation of the Pd−Calkyl bond of the intermediate formed after enone insertion into the Pd−CAr bond. Application of chiral NHC ligands in the asymmetric reductive Heck reaction only results in poor enantioselectivities (enantiomeric excess up to 20 %) and is also substrate specific. DFT calculations suggest that the migration of the aryl group to the alkene of the substrate is the enantioselectivity‐determining step of the reaction. It is further shown that if the steric bulk at the enone is small (a methyl group), the two transition state barriers from [PdII(L2)(ArI)(enone)] species Cre and Csi, which have the re and si face of the enone substrate coordinated to Pd, are very similar, in line with the experimental results. With a slightly larger group (an isopropyl substituent) a significant difference in energy barriers is calculated (2.6 kcal mol−1), and in the experiment this product is formed with a modest enantiomeric excess (up to 20 %).
Support Interaction Effect of Platinum Nanoparticles on Non‐, Y‐, Ce‐Doped Anatase and Its Implication on the ORR in Acid and Alkaline Media
Authors: Estudillo‐Wong Luis Alberto , Ramos‐Sanchez Guadalupe , Calvillo Laura , Granozzi Gaetano , Alonso‐Vante Nicolas
Published: September 2017

Platinum nanoparticles (Pt NPs) were prepared by using the photo‐assisted method and supported onto oxide‐carbon composites synthesized through a modified sol‐gel route (M : TiO2‐C, with M=Y and Ce). The physicochemical properties of these materials were investigated by transmission electron microscopy (TEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). Rietveld refinement was used to identify existing phases of electrocatalysts and to determine the crystallite size. Micro‐strain and intrinsic stacking fault increased and decreased, respectively, as a function of crystallite size. Molecular probing via CO‐stripping analyses assessed the selectively deposition of Pt NPs onto oxide domains of M : TiO2‐C (M=Y and Ce) supports. This phenomenon can be associated with the formation of the covalent bond at the heterojunction interface between Pt and oxide sites. As confirmed by DFT simulation, this phenomenon was related to the adsorption energy between Pt NPs and Y‐ or Ce‐doped TiO2. Turnover frequency evaluation revealed that, in acid medium, the strong Pt/oxide interaction promotes the oxygen reduction reaction activity by 1.7‐fold, as compared to alkaline medium.
Cooperative Adsorption by Porous Frameworks: Diffraction Experiment and Phenomenological Theory
Authors: Dovgaliuk Iurii , Nouar Farid , Serre Christian , Filinchuk Yaroslav , Chernyshov Dmitry
Published: September 2017

Materials science of metal open frameworks is a state‐of‐the‐art field for numerous applications, such as gas storage, sensors, and medicine. Two nanoporous frameworks, γ‐Mg(BH4)2 and MIL‐91(Ti), with different levels of structural flexibility, were examined with in situ X‐ray diffraction guest adsorption–desorption experiments. Both frameworks exhibit a cooperative guest adsorption correlated with a lattice deformation. This cooperativity originates from the long‐range interactions between guest molecules, mediated by elastic response of the host porous structure. The observed experimental scenarios are rationalized with a mean field Gorsky–Bragg–Williams (GBW) approach for the lattice‐gas Ising model. The adjusted GBW model, in combination with in situ synchrotron powder diffraction, demonstrates an efficient experimental and phenomenological approach to characterize thermodynamics of the adsorption in MOFs not only for the total uptake but also for every specific guest site.
Ratiometric Fluorescence Detection of Phosphorylated Amino Acids Through Excited‐State Proton Transfer by Using Molecularly Imprinted Polymer (MIP) Recognition Nanolayers
Authors: Wan Wei , Descalzo Ana B. , Shinde Sudhirkumar , Weißhoff Hardy , Orellana Guillermo , Sellergren Börje , Rurack Knut
Published: September 2017

A 2,3‐diaminophenazine bis‐urea fluorescent probe monomer (1) was developed. It responds to phenylphosphate and phosphorylated amino acids in a ratiometric fashion with enhanced fluorescence accompanied by the development of a redshifted emission band arising from an excited‐state proton transfer (ESPT) process in the hydrogen‐bonded probe/analyte complex. The two urea groups of 1 form a cleft‐like binding pocket (Kb>1010 L2 mol−2 for 1:2 complex). Imprinting of 1 in presence of ethyl ester‐ and fluorenylmethyloxycarbonyl (Fmoc)‐protected phosphorylated tyrosine (Fmoc‐pTyr‐OEt) as the template, methacrylamide as co‐monomer, and ethyleneglycol dimethacrylate as cross‐linker gave few‐nanometer‐thick molecularly imprinted polymer (MIP) shells on silica core microparticles with excellent selectivity for the template in a buffered biphasic assay. The supramolecular recognition features were established by spectroscopic and NMR studies. Rational screening of co‐monomers and cross‐linkers allowed to single out the best performing MIP components, giving significant imprinting factors (IF>3.5) while retaining ESPT emission and the ratiometric response in the thin polymer shell. Combination of the bead‐based detection scheme with the phase‐transfer assay dramatically improved the IF to 15.9, allowing sensitive determination of the analyte directly in aqueous media.
Synthesis and Magnetic Properties of Trioxytriphenylamine Dimers in their Di(radical cationic) States
Authors: Suzuki Shuichi , Tanaka Nobuaki , Kozaki Masatoshi , Shiomi Daisuke , Sato Kazunobu , Takui Takeji , Okada Keiji
Published: September 2017

Three structural isomers of trioxytriphenylamine (TOT) dimers, 4,4′′′‐bis(2,2′:6′,2“:6”,6‐trioxytriphenylamine) (4), 3,3′′′‐bis(2,2′:6′,2“:6”,6‐trioxytriphenylamine) (5), and 3,4′′′‐bis(2,2′:6′,2“:6”,6‐trioxytriphenylamine) (6), have been prepared and their electronic and magnetic properties in their di(radical cationic) states have been investigated. These di(radical cationic) species can be handled under ambient conditions because of their high stability under aerated conditions even in solution. The X‐ray crystal structure analysis demonstrated that the TOT moieties of all the di(radical cation)s have planar structures similar to that of the parent TOT radical cation 3+. The UV/Vis spectra of the di(radical cation)s show characteristic absorptions depending on the connecting pattern. Thus, in the long‐wavelength region (600–900 nm), 42+ exhibits strong and broad characteristic absorptions, whereas compounds 52+ and 62+ exhibit weak absorptions. Notably, in the 450–600 nm region, 52+ displays very similar absorptions (with twice the intensity) to 3+, whereas small differences were observed for 62+. Finally, we investigated in detail the magnetic properties of the corresponding di(radical cation)s by electron spin resonance spectroscopy and magnetic susceptibility measurements, which indicated intramolecular exchange interactions with a singlet ground state and a large singlet–triplet (S–T) gap for 42+, a singlet ground state and a small S–T gap for 52+, and a triplet ground state for 62+.
Formation of Palladium η2‐Bound Chalcogenoketones across a Pd+−C− Bond
Authors: Rothstein Patrick E. , Comanescu Cezar C. , Iluc Vlad M.
Published: September 2017

A series of chalcogen analogues encompassing a ketone and chalcogenoketones [{PC(=E)P}Pd(PMe3)] (E=O, S, Se, Te) was generated from a nucleophilic palladium carbene compound, [{PC(sp2)P}Pd(PMe3)] ([PC(sp3)HP]=bis[2‐(diisopropylphosphino)‐phenyl]methyl, iPr2P‐C6H4‐CH‐C6H4‐PiPr2). The thio‐, seleno‐, and telluroketone were all synthesized by means of an atom transfer from the respective chalcogens. The ketone analogue, however, required the use of nitrobenzene or nitrosobenzene as the oxygen‐atom transfer agent.
The 1,6,7,12‐Tetraazaperylene Bridging Ligand as an Electron Reservoir and Its Disulfonato Derivative as Redox Mediator in an Enzyme–Electrode Process
Authors: Brietzke Thomas , Dietz Thomas , Kelling Alexandra , Schilde Uwe , Bois Julianae , Kelm Harald , Reh Manuel , Schmitz Markus , Körzdörfer Thomas , Leimkühler Silke , Wollenberger Ulla , Krüger Hans‐Jörg , Holdt Hans‐Jürgen
Published: September 2017

The homodinuclear ruthenium(II) complex [{Ru(l‐N4Me2)}2(μ‐tape)](PF6)4 {[1](PF6)4} (l‐N4Me2=N,N′‐dimethyl‐2,11‐diaza[3.3](2,6)‐pyridinophane, tape=1,6,7,12‐tetraazaperylene) can store one or two electrons in the energetically low‐lying π* orbital of the bridging ligand tape. The corresponding singly and doubly reduced complexes [{Ru(l‐N4Me2)}2(μ‐tape.−)](PF6)3 {[2](PF6)3} and [{Ru(l‐N4Me2)}2(μ‐tape2−)](PF6)2 {[3](PF6)2}, respectively, were electrochemically generated, successfully isolated and fully characterized by single‐crystal X‐ray crystallography, spectroscopic methods and magnetic susceptibility measurements. The singly reduced complex [2](PF6)3 contains the π‐radical tape.− and the doubly reduced [3](PF6)2 the diamagnetic dianion tape2− as bridging ligand, respectively. Nucleophilic aromatic substitution at the bridging tape in [1]4+ by two sulfite units gave the complex [{Ru(l‐N4Me2)}2{μ‐tape‐(SO3)2}]2+ ([4]2+). Complex dication [4]2+ was exploited as a redox mediator between an anaerobic homogenous reaction solution of an enzyme system (sulfite/sulfite oxidase) and the electrode via participation of the low‐energy π*‐orbital of the disulfonato‐substituted bridging ligand tape–(SO3)22− (Ered1=−0.1 V versus Ag/AgCl/1 m KCl in water).
Adhesive Stalks of DiatomDidymosphenia geminataas a Novel Biological Adsorbent for Hazardous Metals Removal
Authors: Wysokowski Marcin , Bartczak Przemysław , Żółtowska‐Aksamitowska Sonia , Chudzińska Agata , Piasecki Adam , Langer Enrico , Bazhenov Vasilii V. , Petrenko Iaroslav , Noga Teresa , Stelling Allison L. , Ehrlich Hermann , Jesionowski Teofil
Published: September 2017

The application of biomass derived from the nuisance fresh‐water diatom speciesDidymosphenia geminatatoward the adsorption and removal of heavy‐metal ions from water is reported. The cell‐free polysaccharide‐based stalks of these diatoms are used as adsorbents to remove harmful metal ions: Pb(II), Ni(II), and Cd(II). Detailed analyses of the adsorption kinetics using both pseudo‐first‐order model and pseudo‐second‐order models are performed. The results show a strong correspondence to a pseudo‐second‐order kinetic model. The Langmuir and Freundlich models are used to describe the adsorption isotherms. The correlation coefficients (r2) of the Langmuir model are equal to 0.994 (Pb2+), 0.995 (Cd2+), and 0.995 (Ni2+), and ther2for the Freundlich model are equal to 0.991 (Pb2+), 0.991 (Cd2+), and 0.987 (Ni2+). The experimental data for all metal ions strongly support the Langmuir isotherm model. It is shown that stalks ofD. geminataexhibit exceptional sorption capacity (qm) for Pb(II) ions of 175.48 mg g−1. Additionally, a high sorption capacity for Cd(II) (145.86 mg g−1), and Ni(II) (130.27 mg g−1) is observed. The thermodynamic aspects of the adsorption process of selected metal ions are also discussed. Preliminary tests investigating applications ofD. geminatastalks for sewage purification from galvanic industry and battery and accumulator production were performed. These comprehensive studies show thatD. geminatacan be robustly applied for the removal of harmful metal ions from wastewater.
Multi‐wavelength excitation method for measuring FWA‐treated paper
Authors: Imura Kenji , Nagai Yoshiroh
Published: September 2017

Colorimetric properties of fluorescent materials depend on the SPD of the illumination. That is why most standards for evaluating them specify the illuminations, which are often hard‐to‐realize daylight illuminants. The presented method using commercially available LEDs enables accurate enough colorimetric measurements of FWA‐treated papers or prints on them illuminated by the specified illuminant. The total spectral radiance factor of a fluorescent specimen, from which most colorimetric values are derived, consists of the luminescent spectral radiance factor and the spectral reflectance factor. This method separately estimates those of FWA‐treated paper to add up to the total spectral radiance factor. The luminescent spectral radiance factor is obtained by estimating the SPD of luminescence excited by the specified illuminant as the weighted sum of the multiple SPDs of luminescence excited by the respective narrow band LED emissions at different wavelengths. The LEDs and their weights are determined optimally for generally used papers. The spectral reflectance factor is derived from the estimated SPD of the radiation with fluorescence excluded from the paper illuminated by visible illumination. The method was applied with five different illumination systems each using two or three narrow band LEDs in the excitation range. They were evaluated by measuring the total spectral radiance factors by D50 of seven FWA‐treated papers and CMYK prints on four papers. The derived colorimetric values were compared to the respective references by the ideal D50.
High Photoluminescence Quantum Yields in Organic Semiconductor–Perovskite Composite Thin Films
Authors: Longo Giulia , La‐Placa Maria‐Grazia , Sessolo Michele , Bolink Henk J.
Published: September 2017

One of the obstacles towards efficient radiative recombination in hybrid perovskites is a low exciton binding energy, typically in the orders of tens of meV. It has been shown that the use of electron‐donor additives can lead to a substantial reduction of the non‐radiative recombination in perovskite films. Herein, the approach using small molecules with semiconducting properties, which are candidates to be implemented in future optoelectronic devices, is presented. In particular, highly luminescent perovskite–organic semiconductor composite thin films have been developed, which can be processed from solution in a simple coating step. By tuning the relative concentration of methylammonium lead bromide (MAPbBr3) and 9,9spirobifluoren‐2‐yl‐diphenyl‐phosphine oxide (SPPO1), it is possible to achieve photoluminescent quantum yields (PLQYs) as high as 85 %. This is attributed to the dual functions of SPPO1 that limit the grain growth while passivating the perovskite surface. The electroluminescence of these materials was investigated by fabricating multilayer LEDs, where charge injection and transport was found to be severely hindered for the perovskite/SPPO1 material. This was alleviated by partially substituting SPPO1 with a hole‐transporting material, 1,3‐bis(N‐carbazolyl)benzene (mCP), leading to bright electroluminescence. The potential of combining perovskite and organic semiconductors to prepare materials with improved properties opens new avenues for the preparation of simple lightemitting devices using perovskites as the emitter.
Modulating Crystallinity of Graphitic Carbon Nitride for Photocatalytic Oxidation of Alcohols
Authors: Zhou Min , Yang Pengju , Yuan Rusheng , Asiri Abdullah M. , Wakeel Muhammad , Wang Xinchen
Published: September 2017

Exploiting efficient photocatalysts with strengthened structure for solar‐driven alcohol oxidation is of great significance. The photocatalytic performance of graphitic carbon nitrides can be considerably promoted by modulating its crystallinity. Results confirmed that a high crystallinity accelerates the separation and transfer of photogenerated charge carriers, thus providing more free charges for photoredox reactions. More importantly, the high crystallinity facilitated the adsorption of benzyl alcohol and desorption of benzaldehyde and simultaneously lowered the energy barrier for O2 activation. As a result, the crystalline carbon nitride exhibited a roughly twelvefold promotion with respect to the normal carbon nitride. The remarkable enhancement of activity can be attributed to the synergistic effects of increased electron–hole separation and increased surface reaction kinetics. These findings will open up new opportunities to modulate the structure of polymers for a wide variety of organic reactions.