bluuebunny/crossref_metadata_2025 huggingface dataset:
Tm3Fe5O12/Pt Heterostructures with Perpendicular Magnetic Anisotropy for Spintronic Applications
Authors: Quindeau Andy , Avci Can O. , Liu Wenqing , Sun Congli , Mann Maxwell , Tang Astera S. , Onbasli Mehmet C. , Bono David , Voyles Paul M. , Xu Yongbing , Robinson Jason , Beach Geoffrey S. D. , Ross Caroline A.
Published: December 2016

With recent developments in the field of spintronics, ferromagnetic insulator (FMI) thin films have emerged as an important component of spintronic devices. Ferrimagnetic yttrium iron garnet in particular is an excellent insulator with low Gilbert damping and a Curie temperature well above room temperature, and has been incorporated into heterostructures that exhibit a plethora of spintronic phenomena including spin pumping, spin Seebeck, and proximity effects. However, it has been a challenge to develop high quality sub‐10 nm thickness FMI garnet films with perpendicular magnetic anisotropy (PMA) and PMA garnet/heavy metal heterostructures to facilitate advances in spin‐current and anomalous Hall phenomena. Here, robust PMA in ultrathin thulium iron garnet (TmIG) films of high structural quality down to a thickness of 5.6 nm are demonstrated, which retain a saturation magnetization close to bulk. It is shown that TmIG/Pt bilayers exhibit a large spin Hall magnetoresistance (SMR) and SMR‐driven anomalous Hall effect, which indicates efficient spin transmission across the TmIG/Pt interface. These measurements are used to quantify the interfacial spin mixing conductance in TmIG/Pt and the temperature‐dependent PMA of the TmIG thin film.
Dual‐Functional N Dopants in Edges and Basal Plane of MoS2 Nanosheets Toward Efficient and Durable Hydrogen Evolution
Authors: Xiao Wen , Liu Peitao , Zhang Jingyan , Song Wendong , Feng Yuan Ping , Gao Daqiang , Ding Jun
Published: December 2016

Herein, the authors explicitly reveal the dual‐functions of N dopants in molybdenum disulfide (MoS2) catalyst through a combined experimental and first‐principles approach. The authors achieve an economical, ecofriendly, and most efficient MoS2‐based hydrogen evolution reaction (HER) catalyst of N‐doped MoS2 nanosheets, exhibiting an onset overpotential of 35 mV, an overpotential of 121 mV at 100 mA cm−2 and a Tafel slope of 41 mV dec−1. The dual‐functions of N dopants are (1) activating the HER catalytic activity of MoS2 S‐edge and (2) enhancing the conductivity of MoS2 basal plane to promote rapid charge transfer. Comprehensive electrochemical measurements prove that both the amount of active HER sites and the conductivity of N‐doped MoS2 increase as a result of doping N. Systematic first‐principles calculations identify the active HER sites in N‐doped MoS2 edges and also illustrate the conducting charges spreading over N‐doped basal plane induced by strong Mo 3d–S 2p–N 2p hybridizations at Fermi level. The experimental and theoretical research on the efficient HER catalysis of N‐doped MoS2 nanosheets possesses great potential for future sustainable hydrogen production via water electrolysis and will stimulate further development on nonmetal‐doped MoS2 systems to bring about novel high‐performance HER catalysts.
Die Methyltransferase‐gesteuerte Markierung von Biomolekülen und ihre Anwendungen
Authors: Deen Jochem , Vranken Charlotte , Leen Volker , Neely Robert K. , Janssen Kris P. F. , Hofkens Johan
Published: December 2016

Methyltransferasen (MTasen) bilden eine große Familie von Enzymen, die vielfältige Zielstrukturen methylieren, von DNA, RNA und Proteinen bis zu niedermolekularen Verbindungen. Die meisten MTasen nutzen S‐Adenosyl‐l‐methionin (AdoMet) als Methylquelle. In den letzten Jahren wurde intensiv an der Entwicklung von AdoMet‐Analoga gearbeitet, mit dem Ziel, andere Einheiten als einfache Methylgruppen zu übertragen. Derzeit gibt es zwei Hauptklassen von AdoMet‐Analoga – doppelt aktivierte Moleküle und Moleküle auf Aziridinbasis – die jeweils einen anderen Ansatz zur Transalkylierung des Zielmoleküls verfolgen. Dieser Aufsatz erörtert die Methoden zur Markierung und Funktionalisierung von Biomolekülen unter Verwendung von AdoMet‐abhängigen MTasen und AdoMet‐Analoga. Er behandelt die Synthesewege hin zu AdoMet‐Analoga, die Stabilität von AdoMet‐Analoga in biologischen Umgebungen und ihre Anwendung in Transalkylierungen. Schließlich werden einige Perspektiven für die Anwendung von AdoMet‐Analoga in der biologischen Forschung, Genetik oder Epigenetik und Nanotechnologie aufgezeigt.
Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Efficient Tool for Olefin Metathesis
Authors: Gawin Rafał , Kozakiewicz Anna , Guńka Piotr A. , Dąbrowski Paweł , Skowerski Krzysztof
Published: December 2016

The state‐of‐the‐art in olefin metathesis is application of N‐heterocyclic carbene (NHC)‐containing ruthenium alkylidenes for the formation of internal C=C bonds and of cyclic alkyl amino carbene (CAAC)‐containing ruthenium benzylidenes in the production of terminal olefins. A straightforward synthesis of bis(CAAC)Ru indenylidene complexes, which are highly effective in the formation of both terminal and internal C=C bonds at loadings as low as 1 ppm, is now reported.
Methyltransferase‐Directed Labeling of Biomolecules and its Applications
Authors: Deen Jochem , Vranken Charlotte , Leen Volker , Neely Robert K. , Janssen Kris P. F. , Hofkens Johan
Published: December 2016

Methyltransferases (MTases) form a large family of enzymes that methylate a diverse set of targets, ranging from the three major biopolymers to small molecules. Most of these MTases use the cofactor S‐adenosyl‐l‐Methionine (AdoMet) as a methyl source. In recent years, there have been significant efforts toward the development of AdoMet analogues with the aim of transferring moieties other than simple methyl groups. Two major classes of AdoMet analogues currently exist: doubly‐activated molecules and aziridine based molecules, each of which employs a different approach to achieve transalkylation rather than transmethylation. In this review, we discuss the various strategies for labelling and functionalizing biomolecules using AdoMet‐dependent MTases and AdoMet analogues. We cover the synthetic routes to AdoMet analogues, their stability in biological environments and their application in transalkylation reactions. Finally, some perspectives are presented for the potential use of AdoMet analogues in biology research, (epi)genetics and nanotechnology.
Ionic iron(III) complexes bearing a dialkylbenzimidazolium cation: Efficient catalysts for magnesium‐mediated cross‐couplings of aryl phosphates with alkyl bromides
Authors: Li Zhuang , Lu Bing , Sun Hongmei , Shen Qi , Zhang Yong
Published: December 2016

A series of ionic iron(III) complexes of general formula [HLn][FeX4] (HL1 = 1,3‐dibenzylbenzimidazolium cation, X = Cl, 1; HL1, X = Br, 2; HL2 = 1,3‐dibutylbenzimidazolium cation, X = Br, 3; HL3 = 1,3‐bis(diphenylmethyl)benzimidazolium cation, X = Br, 4) were easily prepared in high yields by the direct reaction of FeX3 with 1 equiv. of [HLn]X under mild conditions. All of them were characterized using elemental analysis, Raman spectroscopy and electrospray ionization mass spectrometry, and X‐ray crystallography for 1 and 4. In the presence of magnesium turnings and LiCl, these air‐ and moisture‐insensitive complexes showed high catalytic activities in direct cross‐couplings of aryl phosphates with primary and secondary alkyl bromides with broad substrate scope, wherein complex 4 was the most effective.
A comparison of scanning methods and the vertical control implications for scanning probe microscopy
Authors: Teo Yik R. , Yong Yuen , Fleming Andrew J.
Published: December 2016

This article compares the imaging performance of non‐traditional scanning patterns for scanning probe microscopy including sinusoidal raster, spiral, and Lissajous patterns. The metrics under consideration include the probe velocity, scanning frequency, and required sampling rate. The probe velocity is investigated in detail as this quantity is proportional to the required bandwidth of the vertical feedback loop and has a major impact on image quality. By considering a sample with an impulsive Fourier transform, the effect of scanning trajectories on imaging quality can be observed and quantified. The non‐linear trajectories are found to spread the topography signal bandwidth which has important implications for both low and high‐speed imaging. These effects are studied analytically and demonstrated experimentally with a periodic calibration grating.
Stabilization of Coupled ODE‐PDE System with Intermediate Point and Spatially Varying Effects Interconnection
Authors: Yuan Yuanlong , Shen Zhengwei , Liao Fucheng
Published: December 2016

In this paper, the stabilization analysis problem of a bi‐directional coupled ODE‐PDE system is proposed. The spatially varying coefficient and the intermediate point interaction between the subsystems makes the coupled system more representative. An invertible infinite‐dimensional backstepping transformation is introducted to bring the original system into an exponentially stable target system. By employing the backstepping method, the kernel functions in the transformations are worked out under some assumptions of the spatially varying coefficient. Then, an explicit state‐feedback law is designed and the exponential stability of the transformed closed‐loop system has been also discussed. Finally, numerical simulation is provided to illustrate the effectiveness of the proposed design.
Integrated optimization of bus priority operations in connected vehicle environment
Authors: Wu Wei , Ma Wanjing , Long Kejun , Wang Yinhai
Published: December 2016

Most previous works associated with transit signal priority merely focus on the optimization of signal timings, ignoring both bus speed and dwell time at bus stops. This paper presents a novel approach to optimize the holding time at bus stops, signal timings, and bus speed to provide priority to buses at isolated intersections. The objective of the proposed model is to minimize the weighted average vehicle delays of the intersection, which includes both bus delay and impact on nearby intersection traffic, ensuring that buses clear these intersections without being stopped by a red light. A set of formulations are developed to explicitly capture the interaction between bus speed, bus holding time, and transit priority signal timings. Experimental analysis is used to show that the proposed model has minimal negative impacts on general traffic and outperforms the no priority, signal priority only, and signal priority with holding control strategies (no bus speed adjustment) in terms of reducing average bus delays and stops. A sensitivity analysis further demonstrates the potential of the proposed approach to be applied to bus priority control systems in real‐time under different traffic demands, bus stop locations, and maximum speed limits. Copyright © 2016 John Wiley & Sons, Ltd.
Experience of disadvantage: The influence of identity on engagement in working class students’ educational trajectories to an elite university
Authors: Thiele Tamara , Pope Daniel , Singleton Alexander , Snape Darlene , Stanistreet Debbi
Published: December 2016

Pervasive socio‐economic differences in relation to participation in higher education in the United Kingdom are particularly prominent in the most prestigious institutions. This study provides insight into why some individuals from disadvantaged backgrounds are successful in being admitted into one of these institutions. Underpinned by phenomenology, semi‐structured interviews were carried out to examine the lived experiences of high‐achieving students from socio‐economically disadvantaged backgrounds throughout their educational trajectories from primary school to a Russell Group university. Two main themes emerged from the data: identity and educational engagement. Various sources of disadvantage associated with material hardship, socio‐cultural and interpersonal factors were strongly linked to identity and students’ perceptions of their own social status. In turn, these factors and identity‐related constructs associated with peer‐group memberships, low expectations and negative group stereotypes affected how individuals engaged with education, contributing, for instance, to their lack of active involvement at school/college and poor attendance. However, identity‐related factors were also found to influence individuals’ educational engagement positively, including their motivations for overcoming obstacles, achieving high grades and pursuing HE. The barriers and facilitators discussed by these individuals have important implications for widening access to HE and thus require further consideration.
Academic and Career Development of Undocumented College Students: The American Dream?
Authors: Kantamneni Neeta , Shada Nichole , Conley Morgan R. , Hellwege Mary A. , Tate Jessica M. , Wang Sherry C.
Published: December 2016

Little is known about the academic and career decision‐making process for college students with undocumented status. This study used a multiple case study approach to explore how academic and work‐related decisions were made for 2 college students with undocumented citizenship status. Participants responded to a series of questions about their academic and career development. Data collected from these interviews were analyzed by a research team. After cross‐case analysis, 6 themes emerged: (a) barriers; (b) emotional impact; (c) resiliency, supports, and coping; (d) discrimination; (e) familial and cultural influences; and (f) academic, work, and career factors. Findings suggest that counseling professionals should attend to systemic, academic, and work‐related barriers that directly affect the educational and career decisions of students with undocumented citizenship status. Future research could expand on the present study by further exploring systemic and contextual factors that influence how undocumented students make academic and career choices using varied qualitative and quantitative methodologies.
Career Decision Self‐Efficacy of Transgender People: Pre‐ and Posttransition
Authors: dickey lore m. , Walinsky Daniel , Rofkahr Crystal , Richardson‐Cline Kara , Juntunen Cindy
Published: December 2016

Transgender people often make the decision to change jobs before, during, or after making a social or medical transition. This study explores reported self‐efficacy from an online sample of transgender people. Results indicate that there are differences in self‐efficacy based on one's gender identity, transition status, and education level. This study offers insight into the important and often overlooked vocational experiences of transgender people. Results suggest ways in which the transition process may interact with career decision self‐efficacy.
Career Experiences of Women With Major Financial Barriers
Authors: Clark Madeline E. , Bower Jamie D.
Published: December 2016

The career experiences of women facing major financial barriers are unique and varied. To better understand and assist such women, the authors interviewed 10 women twice to explore their lived career experiences, using photographs in one interview as stimuli to increase participants' voice and triangulate data. Participants' responses were grouped into 20 themes across 4 domains: career as privilege, reasons for engaging in work, supports, and barriers. Women with major financial barriers appear to understand career as a privilege while experiencing significant obstacles to successfully obtaining work. Participants expressed resiliency and self‐motivation to transcend and mitigate these obstacles. This study indicates a need for increased focus on the career development and engagement of marginalized populations in career counseling theory, assessment, and practice while suggesting practical interventions.
Perceptions of Professional Identity Development From Counselor Educators in Leadership Positions
Authors: Woo Hongryun , Storlie Cassandra A. , Baltrinic Eric R.
Published: December 2016

The perceptions of professional identity development from 10 counseling leaders were examined through consensual qualitative research methodology. Themes and implications include the (a) intersection of being counselor educators and leaders in the counseling field and (b) the development and strengthening of professional identity over time.
Most Likely to Succeed: Exploring Predictor Variables for the Counselor Preparation Comprehensive Examination
Authors: Hartwig Elizabeth Kjellstrand , Van Overschelde James P.
Published: December 2016

The authors investigated predictor variables for the Counselor Preparation Comprehensive Examination (CPCE) to examine whether academic variables, demographic variables, and test version were associated with graduate counseling students' CPCE scores. Multiple regression analyses revealed all 3 variables were statistically significant predictors of CPCE total scores and subtest scores.
A New Kind of Fireproof, Flexible, Inorganic, Nanocomposite Paper and Its Application to the Protection Layer in Flame‐Retardant Fiber‐Optic Cables
Authors: Dong Li‐Ying , Zhu Ying‐Jie
Published: December 2016

An innovative method for making a new kind of highly flexible, fireproof, inorganic, nanocomposite paper made from glass fibers (GFs) coated with network‐structured hydroxyapatite ultralong nanowires (NS‐HANWs) is reported. The NS‐HANW/GF paper is fireproof, high‐temperature resistant, highly flexible, highly exquisite, and smooth, which is comparable to high‐quality advanced coated paper. The most incredible characteristic of the NS‐HANW/GF paper is its incombustibility. The as‐prepared NS‐HANW/GF paper, with the addition of optimized inorganic additives, has high mechanical properties (tensile strength ≈16 MPa) and the tensile strength is nearly 15 times that of GF paper. In addition, the NS‐HANW/GF paper exhibits a high biocompatibility, owing to the coating effect of NS‐HANWs on GFs. Thermal analysis indicates that the NS‐HANW/GF paper has high thermal stability at high temperatures up to 1000 °C. Competitive to conventional insulation materials, the NS‐HANW/GF paper exhibits a low thermal conductivity and excellent heat insulation performance. Experiments show that the NS‐HANW/GF paper is promising for application in the protection layer of fire‐retardant fiber‐optic cable. The NS‐HANW/GF paper can also be used as printing, copying, or writing paper; nonflammable China paper; fire‐retardant wallpaper; specialty fireproof paper; and so on.
Divergent Reactivity of In Situ Generated Metal Azides: Reaction with N,N‐Bis(oxy)enamines as a Case Study
Authors: Zhmurov Petr A. , Khoroshutina Yulia A. , Novikov Roman A. , Golovanov Ivan S. , Sukhorukov Alexey Yu. , Ioffe Sema L.
Published: December 2016

Metal azides generated in situ by ion exchange exhibit divergent reactivity in reaction with cyclic N‐alkoxy,N‐siloxy‐enamines. Depending on the nature of metal and the [M]/N3− ratio, addition of the azide ion to the C,C‐double bond proceeds with regioselective cleavage of either exo‐ or endo‐cyclic N−O bond leading to cyclic or open‐chain α‐azidooxime derivatives, respectively. Mechanistic studies in combination with solvent state FTIR spectroscopy and DFT calculations revealed that covalently bound metal azides (Co, Cu, Zn) transfer N3− anion to the C,C‐double bond through a Lewis acid‐assisted SN′ substitution of trialkylsilyloxy‐group. More ionic metal azides (N1, Mg, Al, Sc, Ni, Yb) tend to react by initial nucleophilic attack of N3− anion on the silicon atom generating conjugated nitrosoalkenes. α‐Azidooxime derivatives prepared by using the designed protocols were stereoselectively reduced to valuable 1,2‐diaminoalcohols bearing up to four contiguous stereogenic centers. By reducing the α‐azidooxime fragment in a stepwise manner site‐selective protection and reductive amination of each of the emerging primary amino groups was achieved.
Heteromultimetallic Complexes with Redox‐Active Mesoionic Carbenes: Control of Donor Properties and Redox‐Induced Catalysis
Authors: Hettmanczyk Lara , Suntrup Lisa , Klenk Sinja , Hoyer Carolin , Sarkar Biprajit
Published: December 2016

Invited for the cover of this issue is the group of Biprajit Sarkar at the Free University Berlin. The image depicts a gold mesoionic carbene complex that is inactive in the reduced form and is an active catalyst in the oxidized form. Read the full text of the article at 10.1002/chem.201604615.
Chitosan/sericin blend membranes for adsorption of bovine serum albumin
Authors: Du Jennifer Runhong , Su Xiao , Feng Xianshe
Published: December 2016

Chitosan/sericin blend membranes for adsorption of bovine serum albumin (BSA) were investigated. A preliminary screening test was carried out to identify a suitable chitosan/sericin blend ratio. The blend membrane with a chitosan/sericin mass ratio of 4:1 was found to have a maximum adsorption capacity (qm) of 25.3 g/m2, which is 45 % greater than the maximum adsorption capacity of the pure chitosan membrane. The adsorption‐desorption cycle studies showed that the chitosan/sericin blend affinity membrane could be reused, and over 80 % of the original adsorption capacity was retained after regeneration. Compared to other affinity membranes for BSA adsorption, the chitosan/sericin membrane exhibited a significantly high adsorption capacity with a comparable adsorption rate.
Testing the Social Innovation Construct: An Empirical Approach to Align Socially Oriented Objectives, Stakeholder Engagement, and Environmental Sustainability
Authors: Segarra‐Oña Marival , Peiró‐Signes Angel , Albors‐Garrigós José , Miguel‐Molina Blanca De
Published: December 2016

Innovation is not just an economic and or technological tool; it is also a social phenomenon. This paper draws together the concepts of creating shared value, the stakeholder theory, and socially oriented innovation to research companies' decisions on asserting socially related objectives when innovating. We examine the extent to which this decision process is bounded by constraints related to information and the characteristics of innovation. To perform this study we used a dataset that monitors the innovation activities of companies. This study offers an empirical analysis of the influence on firms' social innovation orientation. The empirical analysis supports the theoretical framework and identifies the firm's community links as key factors in developing new innovations, process and product‐oriented, which have an impact on the social‐innovation orientation of the firm. Additionally, it shows how the setting up of social goals when innovating is affected by the information source and the innovation mode being developed. Copyright © 2016 John Wiley & Sons, Ltd and ERP Environment
Covalent Surface Modification of Gallium Arsenide Photocathodes for Water Splitting in Highly Acidic Electrolyte
Authors: Garner Logan E. , Steirer K. Xerxes , Young James L. , Anderson Nicholas C. , Miller Elisa M. , Tinkham Jonathan S. , Deutsch Todd G. , Sellinger Alan , Turner John A. , Neale Nathan R.
Published: December 2016

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water‐oxidation and proton‐reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p‐GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p‐GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Results indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH −0.5 electrolyte under 1 Sun (1000 W m−2) illumination resulting from the covalently bound surface dipole. Though X‐ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p‐GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of −20.5 mA cm−2 within −0.5 V of the reversible hydrogen electrode.
Production of p‐Methylstyrene and p‐Divinylbenzene from Furanic Compounds
Authors: Koehle Maura , Saraçi Erisa , Dauenhauer Paul , Lobo Raul F.
Published: December 2016

A four‐step catalytic process was developed to produce p‐methylstyrene from methylfuran, a biomass‐derived species. First, methylfuran was acylated over zeolite H‐Beta with acetic anhydride. Second, the acetyl group was reduced to an ethyl group with hydrogen over copper chromite. Third, p‐ethyltoluene was formed through Diels–Alder cycloaddition and dehydration of 2‐ethyl‐5‐methyl‐furan with ethylene over zeolite H‐Beta. Dehydrogenation of p‐ethyltoluene to yield p‐methylstyrene completes the synthesis but was not investigated because it is a known process. The first two steps were accomplished in high yield (>88 %) and the Diels–Alder step resulted in a 67 % yield of p‐ethyltoluene with a 99.5 % selectivity to the para isomer (final yield of 53.5 %). The methodology was also used for the preparation of p‐divinylbenzene. It is shown that acylation of furans over H‐Beta zeolites is a highly selective and high‐yield reaction that could be used to produce other valuable molecules from biomass‐derived furans.
Synthesis, Properties, and Structures of Low‐Melting Tetraisocyanatocobaltate(II)‐Based Ionic Liquids
Authors: Peppel Tim , Hinz Alexander , Thiele Philipp , Geppert‐Rybczyńska Monika , Lehmann Jochen K. , Köckerling Martin
Published: December 2016

A series of new ionic liquids of the formula Ax[CoII(NCO)4] with the [CoII(NCO)4]2– anion and nitrogen‐based organic cations (A) were synthesized. The single‐crystal structures of all of the compounds were determined by X‐ray diffraction, and the presence of discrete ions was revealed for all cases. At room temperature, these compounds exhibit paramagnetic behavior owing to the presence of high‐spin tetrahedrally coordinated CoII ions. The melting points or glass‐transition temperatures are in the range for ionic liquids for some of the compounds with singly charged cations and above 100 °C for all compounds with doubly charged cations and the bis(triphenylphosphine)iminium ([PPN]+) salt. Each compound was characterized by elemental analysis as well as NMR, IR, and UV/Vis spectroscopy. Measurements of the density, dynamic viscosity, conductivity, and surface tension of the low‐melting substance [EMIm]2[Co(NCO)4] ([EMIm]+ = 1‐ethyl‐3‐methylimidazolium) show that they differ slightly to the corresponding values for the isothiocyanato complexes but are generally comparable.
Surprising Outcomes of Classic Ring‐Expansion Conditions Applied to Octaethyloxochlorin, 1. Baeyer–Villiger‐Oxidation Conditions
Authors: Li Ruoshi , Zeller Matthias , Brückner Christian
Published: December 2016

The conversion of synthetic porphyrins to derivatives that contain a nonpyrrolic building block is an appealing method to generate porphyrinoids with functional groups at their periphery for sensing applications or chromophores with fine‐tuned electronic properties for a number of technical and biomedical applications. Baeyer–Villiger oxidations are potentially suited to generate such pyrrole‐expanded porphyrinoids from known octaethyloxochlorin. However, the application of different Baeyer–Villiger‐oxidation conditions to this ketone merely led to the formation of novel and known compounds, such as porphyrinic meso‐OH and N‐oxide derivatives. This work demonstrates how the extraordinary structural stability of the porphyrin macrocycle redirects the reactivity patterns of classic ring‐expansion reactions, which outlines some limits of the methods to convert a pyrrole in porphyrins into a nonpyrrolic building block.
Surprising Outcomes of Classic Ring‐Expansion Conditions Applied to Octaethyloxochlorin, 3. Schmidt‐Reaction Conditions
Authors: Li Ruoshi , Zeller Mathias , Bruhn Torsten , Brückner Christian
Published: December 2016

The Schmidt reaction (treatment of a ketone with sodium azide and a mineral acid) is an alternative to the Beckmann rearrangement to expand a cyclic ketone to a lactam. However, when applied toward the conversion of a synthetic porphyrin into a derivative containing a nonpyrrolic building block, this approach failed to generate the expected lactam. Instead, by using sulfuric acid as a catalyst, a novel heptaethyl‐2‐hydroxy‐chlorin‐3‐one was formed, structurally characterized, and its mechanism of formation deduced. The work demonstrates how the extraordinary structural stability of the porphyrin macrocycle redirects the reactivity patterns of classic ring‐expansion reactions. By using hydrochloric acid as a catalyst, a somewhat regioselective chlorination of the meso‐positions of the oxochlorin was observed. The halogenation sites were determined spectroscopically and by X‐ray crystallography of selected derivatives. The regioselectivity of the halogenation was computationally rationalized. This method is superior to alternative halogenation methods for the regioselective generation of 5‐chloro‐, 10‐chloro‐, and 5,10‐dichlorooxochlorins.
Surprising Outcomes of Classic Ring‐Expansion Conditions Applied to Octaethyloxochlorin, 2. Beckmann‐Rearrangement Conditions
Authors: Li Ruoshi , Meehan Eileen , Zeller Mathias , Brückner Christian
Published: December 2016

The step‐wise conversion of synthetic porphyrins to derivatives that contain a non‐pyrrolic building block is an appealing method to generate functionalized porphyrinoids. Applied to octaethyloxochlorin oxime, a Beckmann rearrangement is potentially suited to generate a nitrogen‐expanded porphyrinoid. Unexpectedly, this reaction led to a ring‐expansion by an oxygen atom. The mechanism – an abnormal Beckmann reaction, followed by an intramolecular ring‐closing reaction and hydrolysis – was conclusively derived by trapping and structural characterization of the key secochlorin intermediate. The structural and UV/Vis spectral changes observed upon ring‐expansion of the oxochlorin are discussed. Other Beckmann‐rearrangement conditions failed to produce ring‐expanded products altogether. This work demonstrates in many ways how the extraordinary structural stability of the porphyrin macrocycle redirects the reactivity patterns of classic ring‐expansion reactions, which outlines the limits of the “breaking and mending of porphyrins” approach toward pyrrole‐modified porphyrins.
Stereoselective Synthesis of Functionalized Bicyclic Scaffolds by Passerini 3‐Center‐2‐Component Reactions of Cyclic Ketoacids
Authors: Cioc Răzvan C. , Estévez Verónica , van der Niet Daan J. , Vande Velde Christophe M. L. , Turrini Nikolaus G. , Hall Mélanie , Faber Kurt , Ruijter Eelco , Orru Romano V. A.
Published: December 2016

We report the use of bifunctional starting materials (ketoacids) in a diastereoselective Passerini three‐center‐two‐component reaction. Study of the reaction scope revealed the required structural features for stereoselectivity in the isocyanide addition. In this system, an interesting isomerization of the primary Passerini product – the α‐carboxamido lactone – into an atypical product, an α‐hydroxy imide, was found to occur under acidic conditions. Furthermore, enantioenriched Passerini products can be generated from an enantioenriched ketoacid obtained by chemoenzymatic synthesis.
Ultrasensitive Electrochemiluminescence Biosensor for mRNA Based on Polymerase Assisted Signal Amplification
Authors: Zhou F. Y. , Hai H. , Yuan Y. L. , Li J. P.
Published: December 2016

A novel biosensor for ultra‐trace mRNA sensing was constructed based on isothermal circular strand‐replacement polymerization (CSRP) to amplify the electrochmeiluminescence (ECL) signal by combining quantum dots (CdTe) as luminophore. After the hairpin‐like capture DNA was opened by hybridization with target mRNA, the additive primer (DNA1) was able to get access to its complementary sequence which is partially belong to the stem part and triggered a polymerization of DNA strand, leading to the release of target mRNA and another polymerization cycle. The remaining sequence of the stem part continued to hybridize with QDs labeled DNA, accomplishing ECL signal amplification. Target mRNA could be specifically assayed with a linear relationship between the signal intensity and the logarithm of concentrations of target DNA in the range of 1.0×10−14∼5.0×10−10 M, with a low detection limit of 1.4×10−15 M. The signal could discriminate perfect matched target mRNA from 1‐base mismatch sequence. This proposed ECL biosensor exhibited an efficient performance in serum sample, opening new opportunities for genetic target analysis in diagnostic and clinic biomedical fields.
Silver nanoparticles and dissolved silver activate contrasting immune responses and stress-induced heat shock protein expression in sea urchin
Authors: Magesky Adriano , de Oliveira Ribeiro Ciro A. , Beaulieu Lucie , Pelletier Émilien
Published: December 2016

Using immune cells of sea urchin Strongylocentrotus droebachiensis in early development as a model, the cellular protective mechanisms against ionic and poly(allylamine)-coated silver nanoparticle (AgNPs; 14 ± 6 nm) treatments at 100 μg L−1 were investigated. Oxidative stress, heat shock protein expression, and pigment production by spherulocytes were determined as well as AgNP translocation pathways and their multiple effects on circulating coelomocytes. Sea urchins showed an increasing resilience to Ag over time because ionic Ag is accumulated in a steady way, although nanoAg levels dropped between 48 h and 96 h. A clotting reaction emerged on tissues injured by dissolved Ag (present as chloro-complexes in seawater) between 12 h and 48 h. Silver contamination and nutritional state influenced the production of reactive oxygen species. After passing through coelomic sinuses and gut, AgNPs were found in coelomocytes. Inside blood vessels, apoptosis-like processes appeared in coelomocytes highly contaminated by poly(allylamine)-coated AgNPs. Increasing levels of Ag accumulated by urchins once exposed to AgNPs pointed to a Trojan-horse mechanism operating over 12-d exposure. However, under short-term treatments, physical interactions of poly(allylamine)-coated AgNPs with cell structures might be, at some point, predominant and responsible for the highest levels of stress-related proteins detected. The present study is the first report detailing nano-translocation in a marine organism and multiple mechanisms by which sea urchin cells can deal with toxic AgNPs. Environ Toxicol Chem 2017;36:1872–1886. © 2016 SETAC
Assessing data quality in citizen science
Authors: Kosmala Margaret , Wiggins Andrea , Swanson Alexandra , Simmons Brooke
Published: December 2016

Ecological and environmental citizen‐science projects have enormous potential to advance scientific knowledge, influence policy, and guide resource management by producing datasets that would otherwise be infeasible to generate. However, this potential can only be realized if the datasets are of high quality. While scientists are often skeptical of the ability of unpaid volunteers to produce accurate datasets, a growing body of publications clearly shows that diverse types of citizen‐science projects can produce data with accuracy equal to or surpassing that of professionals. Successful projects rely on a suite of methods to boost data accuracy and account for bias, including iterative project development, volunteer training and testing, expert validation, replication across volunteers, and statistical modeling of systematic error. Each citizen‐science dataset should therefore be judged individually, according to project design and application, and not assumed to be substandard simply because volunteers generated it.
A review of ecological risk assessment methods for amphibians: Comparative assessment of testing methodologies and available data
Authors: Johnson Mark S , Aubee Catherine , Salice Christopher J , Leigh Katrina B , Liu Elissa , Pott Ute , Pillard David
Published: December 2016

Historically, ecological risk assessments have rarely included amphibian species, focusing preferentially on other aquatic (fish, invertebrates, algae) and terrestrial wildlife (birds and mammal) species. Often this lack of consideration is due to a paucity of toxicity data, significant variation in study design, uncertainty with regard to exposure, or a combination of all three. Productive risk assessments for amphibians are particularly challenging, given variations in complex life history strategies. Further consideration is needed for the development of useful laboratory animal models and appropriate experimental test procedures that can be effectively applied to the examination of biological response patterns. Using these standardized techniques, risk estimates can be more accurately defined to ensure adequate protection of amphibians from a variety of stress agents. Patterns in toxicity may help to ascertain whether test results from 1 amphibian group (e.g., Urodela) could be sufficiently protective of another (e.g., Anura) and/or whether some nonamphibian aquatic taxonomic groups (e.g., fish or aquatic invertebrates) may be representative of aquatic amphibian life stages. This scope is intended to be a guide in the development of methods that would yield data appropriate for ecological risk decisions applicable to amphibians. Integr Environ Assess Manag 2017;13:601–613. © 2016 SETAC

Key Points

Amphibians have complex life histories that add levels of complexity in the evaluation of risk at contaminated sites. Life histories for amphibians include exposures to contaminated water, soil, and potentially sediments. Aquatic surrogates (e.g., fish) are only partially useful in predicting effects to a single life stage for some amphibian species. More research is needed to understand the relative importance of exposure to terrestrial life stages in estimating risk.
Secretory phospholipase A2 in the pathogenesis of acute dengue infection
Authors: Jeewandara Chandima , Gomes Laksiri , Udari Sukhitha , Paranavitane S.A. , Shyamali N.L.A. , Ogg Graham S. , Malavige Gathsaurie Neelika
Published: December 2016

Introduction

Platelet activating factor (PAF) is an important mediator of vascular leak in acute dengue. Phospholipase A2s (PLA2) are inflammatory lipid enzymes that generate and regulate PAF and other mediators associated with mast cells. We sought to investigate if mast cell activation and increases in secretory sPLA2s are associated with an increase in PAF and occurrence of dengue haemorrhagic fever (DHF).

Methods

The changes in the levels of mast cell tryptase, PAF and the activity of sPLA2 were determined throughout the course of illness in 13 adult patients with DHF, and 30 patients with dengue fever (DF).

Results

We found that sPLA2 activity was significantly higher in patients with DHF when compared to those with DF, during the first 120 h of clinical illness. sPLA2 activity was significantly associated with PAF levels, which were also significantly higher in patients with DHF. Although levels of mast cell tryptase were higher in patients with DHF, the difference was not significant, and the levels were not above the reference ranges. sPLA2 activity significantly correlated with the degree of viraemia in patients with DHF but not in those with DF.

Conclusion

sPLA2 appears to play an important role in the pathogenesis of dengue. Since its activity is significantly increased during the early phase of infection in patients with DHF, this suggests that understanding the underlying mechanisms may provide opportunities for early intervention.
War and disaster in Sri Lanka: Implications for widows' family adjustment and perception of self‐efficacy in caring for one's family
Authors: Witting Alyssa Banford , Lambert Jessica , Wickrama Thulitha
Published: December 2016

The data for this study were collected in 2014 from widows in Eastern Sri Lanka whose spouses died in the civil war, tsunami, or from health‐related problems. Conservation of resources (COR) theory was used as a lens to examine the extent to which war and tsunami‐related damages and family problems predict variation in social support, family adjustment and a perception of self‐efficacy in caring for one's family as reported by widowed women. We also investigated whether social support from the community and social support from family and friends mediated those relationships. Results of a path model fit to the data suggested variation in family adjustment to be negatively predicted by war‐related family problems and positively predicted by the social support of friends and family. Additionally, a sense of self‐efficacy in caring for one's family was found to be inversely predicted by war‐related family problems and tsunami damages. Clinical, social and theoretical implications are discussed as well as directions for further research.
Obstetrics
Authors: Held E.
Published: December 2016

Obstetrics by J.P. Greenhill, published by W.B. Saunders, 13th Edition, Philadelphia and London, 1965.
Neonatal Practice
Authors: Bamatter Fred
Published: December 2016

Neonatal Practice, by Prof. Lucien Michon, Introduction by Prof. B. Jamain. L'Expansion Scientifique Francaise, Paris, 1965, pp. 231.
Clinical endocrine cytology
Authors: Pundel J. Paul
Published: December 2016

Clinical endocrine cytology, by Jacoba C. de Neef, Hoeber Medidical Division ‐ New York, 1965 ‐ 310 pp. vol. with 205 illustrations, 185 in color.
Female Hormones and Woman's Health
Authors: Swyer G.I.M.
Published: December 2016

Female Hormones and Woman's Health, by Lyle Bachman, 145 pages. Printed by Mid‐Pacific Press, Honolulu, 1967.
Type 2 Diabetes Mellitus Is Associated With Better Bone Microarchitecture But Lower Bone Material Strength and Poorer Physical Function in Elderly Women: A Population-Based Study
Authors: Nilsson Anna G , Sundh Daniel , Johansson Lisa , Nilsson Martin , Mellström Dan , Rudäng Robert , Zoulakis Michail , Wallander Märit , Darelid Anna , Lorentzon Mattias
Published: December 2016

Type 2 diabetes mellitus (T2DM) is associated with an increased risk of fractures according to several studies. The underlying mechanisms remain unclear, although small case-control studies indicate poor quality of the cortical bone. We have studied a population-based sample of women aged 75 to 80 years in Gothenburg, randomly invited from the population register. Areal bone mineral density (aBMD) was measured by dual-energy X-ray absorptiometry (Hologic Discovery A), bone microarchitecture by high-resolution peripheral quantitative computed tomography (HR-pQCT; ExtremeCT from Scanco Medical AG), and reference point indentation was performed with Osteoprobe (Active Life Scientific). Women with T2DM (n = 99) had higher aBMD compared to controls (n = 954). Ultradistal tibial and radial trabecular bone volume fraction (+11% and +15%, respectively), distal cortical volumetric BMD (+1.6% and +1.7%), cortical area (+11.5% and +9.3%), and failure load (+7.7% and +12.9%) were higher in diabetics than in controls. Cortical porosity was lower (mean ± SD: 1.5% ± 1.1% versus 2.0% ± 1.7%, p = 0.001) in T2DM in the distal radius but not in the ultradistal radius or the tibia. Adjustment for covariates (age, body mass index, glucocorticoid treatment, smoking, physical activity, calcium intake, bone-active drugs) eliminated the differences in aBMD but not in HR-pQCT bone variables. However, bone material strength index (BMSi) by reference point indentation was lower in T2DM (74.6 ± 7.6 versus 78.2 ± 7.5, p < 0.01), also after adjustment, and women with T2DM performed clearly worse in measures of physical function (one leg standing: –26%, 30-s chair-stand test: –7%, timed up and go: +12%, walking speed: +8%; p < 0.05-0.001) compared to controls. In conclusion, we observed a more favorable bone microarchitecture but no difference in adjusted aBMD in elderly women with T2DM in the population compared to nondiabetics. Reduced BMSi and impaired physical function may explain the increased fracture risk in T2DM. © 2016 American Society for Bone and Mineral Research.
BMI-1 Mediates Estrogen-Deficiency–Induced Bone Loss by Inhibiting Reactive Oxygen Species Accumulation and T Cell Activation
Authors: Li Jinbo , Wang Qian , Yang Renlei , Zhang Jiaqi , Li Xing , Zhou Xichao , Miao Dengshun
Published: December 2016

Previous studies have shown that estrogen regulates bone homeostasis through regulatory effects on oxidative stress. However, it is unclear how estrogen deficiency triggers reactive oxygen species (ROS) accumulation. Recent studies provide evidence that the B lymphoma Mo-MLV insertion region 1 (BMI-1) plays a critical role in protection against oxidative stress and that this gene is directly regulated by estrogen via estrogen receptor (ER) at the transcriptional level. In this study, ovariectomized mice were given drinking water with/without antioxidant N-acetyl-cysteine (NAC, 1 mg/mL) supplementation, and compared with each other and with sham mice. Results showed that ovariectomy resulted in bone loss with increased osteoclast surface, increased ROS levels, T cell activation, and increased TNF and RANKL levels in serum and in CD4 T cells; NAC supplementation largely prevented these alterations. BMI-1 expression levels were dramatically downregulated in CD4 T cells from ovariectomized mice. We supplemented drinking water to BMI-1–deficient mice with/without NAC and compared them with each other and with wild-type (WT) mice. We found that BMI-1 deficiency mimicked alterations observed in ovariectomy whereas NAC supplementation reversed all alterations induced by BMI-1 deficiency. Because T cells are critical in mediating ovariectomy-induced bone loss, we further assessed whether BMI-1 overexpression in lymphocytes can protect against estrogen deficiency–induced osteoclastogenesis and bone loss by inhibiting oxidative stress, T cell activation, and RANKL production. When WT and Eμ-BMI-1 transgenic mice with BMI-1 specifically overexpressed in lymphocytes were ovariectomized and compared with each other and with WT sham mice, we found that BMI-1 overexpression in lymphocytes clearly reversed all alterations induced by ovariectomy. Results from this study indicate that estrogen deficiency downregulates BMI-1 and subsequently increases ROS, T cell activation, and RANKL production in T cells, thus enhancing osteoclastogenesis and accelerating bone loss. This study clarifies a novel mechanism regulating estrogen deficiency–induced bone loss. © 2016 American Society for Bone and Mineral Research.
First isolation of a new type of human adenovirus (genotype 79), species Human mastadenovirus B (B2) from sewage water in Japan
Authors: Yoshitomi Hideaki , Sera Nobuyuki , Gonzalez Gabriel , Hanaoka Nozomu , Fujimoto Tsuguto
Published: December 2016

Human mastadenoviruses (HAdVs) are highly infectious viral pathogens that survive for prolonged periods in environmental waters. We monitored the presence of HAdVs in sewage waters between April 2014 and March 2015. A total of 27 adenoviral strains were detected in 75% (18/24 in occasion‐base) of 24 wastewater collected samples. We identified the types of the strains as HAdV‐C2 (n = 5), HAdV‐A31 (5), HAdV‐C1 (4), HAdV‐B3 (4), HAdV‐C5 (4), HAdV‐B11 (2), P11H34F11 (2), and HAdV‐D56 (1). The complete genome sequence of one P11H34F11 (strain T150125) was determined by next‐generation sequencing and compared to other genome sequences of HAdV‐B strains. The comparisons revealed evidence of a recombination event with breaking point in the hexon encoding region, which evidenced high similarity to HAdV‐B34, while half of the rest of the genome showed similarity to HAdV‐B11, including regions encoding fiber and E3 region proteins. The penton base encoding region seemed to be a recombinant product of HAdV‐B14, ‐34; however, it was evidenced to be divergent to both as a novel type despite showing low bootstrap to support a new clade. We propose T150125 (P11H34F11) is a strain of a novel genotype, HAdV‐79. These results support the usefulness of environmental surveillance approaches to monitor circulating HAdVs including novel types.