bluuebunny/crossref_metadata_2025 huggingface dataset:
α‐Carbonylkationen in Sulfoxid‐vermittelten oxidativen Cyclisierungen
Authors: Stopka Tobias , Niggemann Meike , Maulide Nuno
Published: August 2017

Ausgehend von einfachen disubstituierten Alkinen gelang die selektive metallfreie Erzeugung von α‐Carbonylkationen durch Addition eines Sulfoxids an ein Vinylkation. Die hohe Reaktivität dieser α‐Carbonylkationen konnte genutzt werden, um Hydrid‐ und Kohlenstoff‐Verschiebungen mit ungewöhnlicher Selektivität zu ermöglichen. Hierdurch konnten, basierend auf einfachen Vorläuferverbindungen, in einem Schritt komplexe und sterisch gehinderte tertiäre und vollständig substituierte, quartäre Kohlenstoffzentren aufgebaut werden. Mechanistische Untersuchungen stützen das Auftreten des Schlüsselintermediats und erlauben einfache Vorhersagen über die Wanderungstendenz unterschiedlicher Substituenten.
Photosalient Phenomena that Mimic Impatiens Are Observed in Hollow Crystals of Diarylethene with a Perfluorocyclohexene Ring
Authors: Hatano Eri , Morimoto Masakazu , Imai Takahito , Hyodo Kengo , Fujimoto Ayako , Nishimura Ryo , Sekine Akiko , Yasuda Nobuhiro , Yokojima Satoshi , Nakamura Shinichiro , Uchida Kingo
Published: August 2017

A diarylethene with a perfluorocyclohexene ring formed hollow crystals by sublimation under normal pressure. Upon UV irradiation of the crystals, they showed remarkable photosalient phenomena and scattered into small pieces. The speed of the flying debris released from the crystal by UV irradiation exceeded several meters per second. To clearly show a photosalient effect resembling the scattering behavior of Impatiens on a smaller scale, small fluorescent beads (1‐μm diameter) were inserted into the hollow crystal. Consequently, scattering of the beads was observed as UV irradiation caused deformation and bursting of the hollow structure. This phenomenon is unique to hollow crystals, and the ability to effectively induce remarkable photosalient phenomena is similar to the behavior of hollow‐structured Impatiens in nature.
α‐Carbonyl Cations in Sulfoxide‐Driven Oxidative Cyclizations
Authors: Stopka Tobias , Niggemann Meike , Maulide Nuno
Published: August 2017

The selective, metal‐free generation of α‐carbonyl cations from simple internal alkynes was accomplished by the addition of a sulfoxide to a densely substituted vinyl cation. The high reactivity of the α‐carbonyl cations was found to efficiently induce hydrogen and even carbon shift reactions with unusual selecivities. Complex compounds with highly congested tertiary and all‐carbon‐substituted quartenary carbon centers can thus be accessed in a single step from simple precursors. Mechanistic analysis strongly supports the intermediacy of the title compounds and provides a simple predictive scheme for the migratory aptitude of different substituents.
From Precursor Powders to CsPbX3 Perovskite Nanowires: One‐Pot Synthesis, Growth Mechanism, and Oriented Self‐Assembly
Authors: Tong Yu , Bohn Bernhard J. , Bladt Eva , Wang Kun , Müller‐Buschbaum Peter , Bals Sara , Urban Alexander S. , Polavarapu Lakshminarayana , Feldmann Jochen
Published: August 2017

The colloidal synthesis and assembly of semiconductor nanowires continues to attract a great deal of interest. Herein, we describe the single‐step ligand‐mediated synthesis of single‐crystalline CsPbBr3 perovskite nanowires (NWs) directly from the precursor powders. Studies of the reaction process and the morphological evolution revealed that the initially formed CsPbBr3 nanocubes are transformed into NWs through an oriented‐attachment mechanism. The optical properties of the NWs can be tuned across the entire visible range by varying the halide (Cl, Br, and I) composition through subsequent halide ion exchange. Single‐particle studies showed that these NWs exhibit strongly polarized emission with a polarization anisotropy of 0.36. More importantly, the NWs can self‐assemble in a quasi‐oriented fashion at an air/liquid interface. This process should also be easily applicable to perovskite nanocrystals of different morphologies for their integration into nanoscale optoelectronic devices.
Determination of twisting angle of electrospun nanofiber bundle for continuous electrospinning system
Authors: Lee Jung Hun , Gim Yeonghyeon , Bae Seonghyun , Oh Changeun , Ko Han Seo , Baik Seunghyun , Oh Tae Sik , Yoo Ji Beom
Published: August 2017

Electrospinning continuously produced twisted nanofibers with a convergence coil and a rotating ring collector. The positively charged nozzle was used in the electrospinning process to deposit electrospun fibers of polyacrylonitrile onto a rotating ring collector. By withdrawing the electrospun fibers from the rotating ring collector, it was possible to spin the electrospun fibers yarn. In this study, theoretical approaches and numerical simulations were used to determine the twisting angle of the yarn. Using the equations developed in this study, we performed numerical simulations and compared the experimental results with the numerical simulation results. Mechanical properties of the fiber bundle were analyzed for twisting angle. It was confirmed the relationship among the winding drum, the ring collector, and flux of the fibers mass per time during electrospinning in the developed system. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45528.
The impact of pollen consumption on honey bee (Apis mellifera) digestive physiology and carbohydrate metabolism
Authors: Ricigliano Vincent A. , Fitz William , Copeland Duan C. , Mott Brendon M. , Maes Patrick , Floyd Amy S. , Dockstader Arnold , Anderson Kirk E.
Published: August 2017

Carbohydrate‐active enzymes play an important role in the honey bee (Apis mellifera) due to its dietary specialization on plant‐based nutrition. Secretory glycoside hydrolases (GHs) produced in worker head glands aid in the processing of floral nectar into honey and are expressed in accordance with age‐based division of labor. Pollen utilization by the honey bee has been investigated in considerable detail, but little is known about the metabolic fate of indigestible carbohydrates and glycosides in pollen biomass. Here, we demonstrate that pollen consumption stimulates the hydrolysis of sugars that are toxic to the bee (xylose, arabinose, mannose). GHs produced in the head accumulate in the midgut and persist in the hindgut that harbors a core microbial community composed of approximately 108 bacterial cells. Pollen consumption significantly impacted total and specific bacterial abundance in the digestive tract. Bacterial isolates representing major fermentative gut phylotypes exhibited primarily membrane‐bound GH activities that may function in tandem with soluble host enzymes retained in the hindgut. Additionally, we found that plant‐originating β‐galactosidase activity in pollen may be sufficient, in some cases, for probable physiological activity in the gut. These findings emphasize the potential relative contributions of host, bacteria, and pollen enzyme activities to carbohydrate breakdown, which may be tied to gut microbiome dynamics and associated host nutrition.
A Multiple Structure‐Design Strategy towards Ultrathin Niobate Perovskite Nanosheets with Thickness‐Dependent Photocatalytic Hydrogen‐Evolution Performance
Authors: Zhou Yannan , Wen Ting , Zhang Xiaofan , Chang Binbin , Kong Weiqian , Guo Yanzhen , Yang Baocheng , Wang Yonggang
Published: August 2017

Hydrogen production by catalytic water splitting using sunlight holds great promise for clean and sustainable energy source. Despite the efforts made in the past decades, challenges still exist in pursuing solid catalysts with light‐harvesting capacity, large surface areas and efficient utilities of the photogenerated carrier, at the same time. Here, a multiple structure design strategy leading to highly enhanced photocatalytic performance on hydrogen production from water splitting in Dion–Jacobson perovskites KCa2Nan‐3NbnO3n+1 is described. Specifically, chemical doping (N/Nb4+) of the parent oxides via ammoniation improved the ability of sunlight harvesting efficiently; subsequent liquid exfoliation of the doped perovskites yielded ultrathin [Ca2Nan‐3NbnO3n+1]− nanosheets with greatly increased surface areas. Significantly, the maximum hydrogen evolution appears in the n=4 nanosheets, which suggests the most favorable thickness for charge separation in such perovskite‐type catalysts. The optimized black N/Nb4+‐[Ca2NaNb4O13]− nanosheets show greatly enhanced photocatalytic performance, as high as 973 μmol h−1 with Pt loading, on hydrogen evolution from water splitting. As a proof‐of‐concept, this work highlights the feasibility of combining various chemical strategies towards better catalysts and precise thickness control of two‐dimensional materials.
A comparison of group prediction approaches in longitudinal discriminant analysis
Authors: Hughes David M. , El Saeiti Riham , García‐Fiñana Marta
Published: August 2017

Longitudinal discriminant analysis (LoDA) can be used to classify patients into prognostic groups based on their clinical history, which often involves longitudinal measurements of various clinically relevant markers. Patients' longitudinal data is first modelled using multivariate generalised linear mixed models, allowing markers of different types (e.g. continuous, binary, counts) to be modelled simultaneously. We describe three approaches to calculating a patient's posterior group membership probabilities which have been outlined in previous studies, based on the marginal distribution of the longitudinal markers, conditional distribution and distribution of the random effects. Here we compare the three approaches, first using data from the Mayo Primary Biliary Cirrhosis study and then by way of simulation study to explore in which situations each of the three approaches is expected to give the best prediction. We demonstrate situations in which the marginal or random‐effects approach perform well, but find that the conditional approach offers little extra information to the random‐effects and marginal approaches.
Synthesis, Biological Evaluation, and Molecular Docking Studies of Novel 4‐[4‐Arylpyridin‐1(4H)‐yl]benzoic Acid Derivatives as Anti‐HIV‐1 Agents
Authors: Sepehri Saghi , Soleymani Sepehr , Zabihollahi Rezvan , Aghasadeghi Mohammad R. , Sadat Mehdi , Saghaie Lotfollah , Fassihi Afshin
Published: August 2017

The structural similarities between N1 substituted 1,4‐dihydropyridines and the known gp41 inhibitors, NB‐2 and NB‐64, were considered in the current research for the design of some novel anti‐HIV‐1 agents. A series of novel 4‐[4‐arylpyridin‐1(4H)‐yl]benzoic acid derivatives were synthesized and after a comprehensive structural elucidation were screened for in vitro anti‐HIV‐1 activity. Most of the tested compounds displayed moderate to good inhibitory activity against HIV‐1 growth and were evaluated for in vitro cytotoxic activity using XTT assay at the concentration of 100 μm. Among the tested compounds, 1c, 1d and 1e showed potent anti‐HIV‐1 activity against P24 expression at 100 μm with inhibition percentage of 84.00%, 76.42% and 80.50%, respectively. All the studied compounds possessed no significant cytotoxicity on MT‐2 cell line. The binding modes of these compounds to gp41 binding site were determined through molecular docking study. Docking studies proved 1a as the most potent compound and binding maps exhibited that the activities might be attributed to the electrostatic and hydrophobic interactions and additional H‐bonds with the gp41 binding site. The Lipinski's ‘rule of five’ and drug‐likeness criteria were also calculated for the studied compounds. All derivatives obeyed the Lipinski's ‘rule of five’ and had drug‐like features. The findings of this study suggest that novel 4‐[4‐arylpyridin‐1(4H)‐yl]benzoic acid might be a promising scaffold for the discovery and development of novel anti‐HIV‐1 agents.
DMSO Chemically Alters Cell Membranes to Slow Exocytosis and Increase the Fraction of Partial Transmitter Released
Authors: Majdi Soodabeh , Najafinobar Neda , Dunevall Johan , Lovric Jelena , Ewing Andrew G.
Published: August 2017

Dimethyl sulfoxide (DMSO) is frequently used as a solvent in biological studies and as a vehicle for drug therapy; but the side effects of DMSO, especially on the cell environment, are not well understood, and controls with DMSO are not neutral at higher concentrations. Herein, electrochemical measurement techniques are applied to show that DMSO increases exocytotic neurotransmitter release, while leaving vesicular contents unchanged. In addition, the kinetics of release from DMSO‐treated cells are faster than that of untreated ones. The results suggest that DMSO has a significant influence on the chemistry of the cell membrane, leading to alteration of exocytosis. A speculative chemical mechanism of the effect on the fusion pore during exocytosis is presented.
Deconstructing Quinoline‐Class Antimalarials to Identify Fundamental Physicochemical Properties of Beta‐Hematin Crystal Growth Inhibitors
Authors: Olafson Katy N. , Nguyen Tam Q. , Vekilov Peter G. , Rimer Jeffrey D.
Published: August 2017

A versatile approach to control crystallization involves the use of modifiers, which are additives that interact with crystal surfaces and alter their growth rates. Elucidating a modifier's binding specificity to anisotropic crystal surfaces is a ubiquitous challenge that is critical to their design. In this study, we select hematin, a byproduct of malaria parasites, as a model system to examine the complementarity of modifiers (i.e., antimalarial drugs) to β‐hematin crystal surfaces. We divide two antimalarials, chloroquine and amodiaquine, into segments consisting of a quinoline base, common to both drugs, and side chains that differentiate their modes of action. Using a combination of scanning probe microscopy, bulk crystallization, and analytical techniques, we show that the base and side chain work synergistically to reduce the rate of hematin crystallization. In contrast to general observations that modifiers retain their function upon segmentation, we show that the constituents do not act as modifiers. A systematic study of quinoline isomers and analogues shows how subtle rearrangement and removal of functional moieties can create effective constituents from previously ineffective modifiers, along with tuning their inhibitory modes of action. These findings highlight the importance of specific functional moieties in drug compounds, leading to an improved understanding of modifier–crystal interactions that could prove to be applicable to the design of new antimalarials.
Home monitoring after ambulatory implanted primary cardiac implantable electronic devices: The home ambulance pilot study
Authors: Parahuleva Mariana S. , Soydan Nedim , Divchev Dimitar , Lüsebrink Ulrich , Schieffer Bernhard , Erdogan Ali
Published: August 2017

Background

The Home Monitoring (HM) system of cardiac implantable electronic devices (CIEDs) permits early detection of arrhythmias or device system failures. The aim of this pilot study was to examine how the safety and efficacy of the HM system in patients after ambulatory implanted primary CIEDs compare to patients with a standard procedure and hospitalization.

Hypothesis

We hypothesized that HM and their modifications would be a useful extension of the present concepts for ambulatory implanted CIEDs.

Methods

This retrospective analysis evaluates telemetric data obtained from 364 patients in an ambulatory single center over 6 years. Patients were assigned to an active group (n = 217), consisting of those who were discharged early on the day of implantation of the primary CIED, or to a control group (n = 147), consisting of those discharged and followed up with the HM system according to usual medical practices.

Results

The mean duration of hospitalization was 73.2% shorter in the active group than in the control group, corresponding to 20.5 ± 13 fewer hours (95% confidence interval [CI]: 6.3‐29.5; P < 0.01) spent in the hospital (7.5 ± 1.5 vs 28 ± 4.5 h). This shorter mean hospital stay was attributable to a 78.8% shorter postoperative period in the active group. The proportion of patients with treatment‐related adverse events was 11% (n = 23) in the active group and 17% (n = 25) in the control group (95% CI: 5.5‐8.3; P = 0.061). This 6% absolute risk reduction (95% CI: 3.3‐9.1; P = 0.789) confirmed the noninferiority of the ambulatory implanted CIED when compared with standard management of these patients.

Conclusions

Early discharge with the HM system after ambulatory CIED implantation was safe and not inferior to the classic medical procedure. Thus, together with lower costs, HM and its modifications would be a useful extension of the present concepts for ambulatory implanted CIEDs.
A pattern‐based risk‐stratification scheme for salivary gland cytology: A multi‐institutional, interobserver variability study to determine applicability
Authors: Griffith Christopher C. , Schmitt Alessandra C. , Pantanowitz Liron , Monaco Sara E.
Published: August 2017

BACKGROUND

Salivary gland aspiration cytology is useful in the preoperative management of patients but remains challenging, because of the extensive morphologic overlap of some tumors limits the ability to always determine the presence of malignancy. In response to this challenge, there has been increasing drive to develop a risk‐based categorization scheme for salivary gland aspirates. Herein, the authors examine the interobserver variability of 1 such pattern and risk‐based system.

METHODS

Select smears and cell‐block sections of 50 salivary gland aspirates from 2 large academic centers were digitally imaged. These scanned slides were independently and blindly reviewed by 4 cytopathologists, and each aspirate was assigned to 1 of the proposed pattern‐based categories if it was considered neoplastic by the observer. Interobserver agreement was scored and aggregated risks of malignancy were calculated for cases with available surgical follow‐up.

RESULTS

In total, 42 samples (84%) were considered neoplastic by at least 2 observers and were scored for interobserver agreement: 10 of 42 (23.8%) had uniform agreement, 14 of 42 (33.3%) had majority agreement, and 5 of 42 (11.9%) had divided agreement. Only 9 of 42 samples (21.4%) had minimal agreement, and 4 of 42 (9.5%) had no agreement. Condensation of similar categories was able to improve interobserver agreement and still maintain stratified risk of malignancy.

CONCLUSIONS

The proposed pattern‐based risk‐stratification scheme, which could be implemented with the forthcoming Milan System, has good overall interobserver agreement and successfully stratifies the risk of malignancy. Some simplification is possible to make the system easier to use and improve interobserver agreement while maintaining stratification of risk. Cancer Cytopathol 2017;125:776‐85. © 2017 American Cancer Society.
Probing Laser‐Induced Heterogeneous Microenvironment Changes in Room‐Temperature Ionic Liquids
Authors: Ma Renjun , Wang Xian , Jie Jialong , Yan Linyin , Kuang Zhuoran , Guo Qianjin , Li Boxuan , Xia Andong
Published: August 2017

Modulating the heterogeneous microenvironment in room‐temperature ionic liquids (RTILs) by external stimuli is an important approach for understanding and designing external field‐induced chemical reactions in natural and applied systems. Here, we report for the first time the redistribution of oxygen molecules related to microstructure changes in RTILs induced by an external laser field, which is probed simultaneously by the triplet‐state dynamics of porphyrin. A remarkably long‐lived triplet state of porphyrin is observed with changes of microstructures after irradiation, suggesting that charge‐shifted O2 molecules are induced by the external field and/or rearranged intrinsic ions move from nonpolar domains into the polar domains of RTILs through electrostatic interactions. The results suggest that heterogeneous systems like ionic liquids in the presence of external stimuli can be designed for reaction systems associated with not only O2 but also for CO2, CS2, etc. and many other similar solvent molecules for many promising applications.
Wacker Oxidation of Terminal Alkenes Over ZrO2‐Supported Pd Nanoparticles Under Acid‐ and Cocatalyst‐Free Conditions
Authors: Zhang Zhenzhong , Kumamoto Yuhya , Hashiguchi Taishin , Mamba Tetsuya , Murayama Haruno , Yamamoto Eiji , Ishida Tamao , Honma Tetsuo , Tokunaga Makoto
Published: August 2017

Highly efficient Wacker oxidation of aromatic or aliphatic terminal alkenes into methyl ketones and benzofurans is developed by using reusable Pd0 nanoparticles (NPs) supported on ZrO2 under acid‐ and cocatalyst‐free conditions. Molecular oxygen or air can be utilized as the terminal oxidant, which results in the formation of H2O as the only theoretical byproduct. The activation of the Pd NPs by O2 plays an important role in promoting this reaction. Interestingly, PdO supported on ZrO2 showed no activity. Additionally, the Pd particle size significantly affects the catalytic activity, with an apparent optimal diameter of 4–12 nm. In addition to the heterogeneous catalyst forms, the Pd NPs can be generated from a Pd0 complex during the reaction, and these particles are even recyclable.
Angelica Lactones: From Biomass‐Derived Platform Chemicals to Value‐Added Products
Authors: Lima Carolina G. S. , Monteiro Julia L. , de Melo Lima Thiago , Weber Paixão Marcio , Corrêa Arlene G.
Published: August 2017

The upgrading of biomass‐derived compounds has arisen in recent years as a very promising research field in both academia and industry. In this sense, a lot of new processes and products have been developed, often involving levulinic acid as a starting material or intermediate. In the last few years, though, other scaffolds have been receiving growing attention, especially, angelica lactones. Considering these facts and the emergent applications of said molecules, in this review we will discuss their preparation and applications; the use of these frameworks as starting materials in organic synthesis to produce potential bioactive compounds will be covered, as will their use as a foundation to highly regarded compounds such as liquid alkanes with prospective use as fuels and polymers.
“What” and “where” was when? Memory for the temporal order of episodic events in children
Authors: Scarf Damian , Boden Hannah , Labuschagne Lisa G. , Gross Julien , Hayne Harlene
Published: August 2017

In the past, researchers have shown that the individual components of episodic memory (i.e “what,” “where,” and “when”) may emerge at different points in development. Specifically, while children as young as three can accurately report the “what” and “where” of an event, they struggle to accurately report when the event occurred. One explanation for children's difficulty in reporting when an event took place is a rudimentary understanding, and ability to use, temporal terms. In the current experiment, we employed a physical timeline to aid children's reporting of the order in which a series of episodic events occurred. Overall, while 4‐, 5‐, and 6‐year olds performed above chance, 3‐year olds did not. Our findings suggest that 3‐year olds’ limited ability to produce temporal terms may not be the rate‐limiting step preventing them from identifying when events occurred in their recent past.
Simultaneous monitoring of maternal and fetal heart rate variability during labor in relation with fetal gender
Authors: Gonçalves Hernâni , Fernandes Diana , Pinto Paula , Ayres‐de‐Campos Diogo , Bernardes João
Published: August 2017

Male gender is considered a risk factor for several adverse perinatal outcomes. Fetal gender effect on fetal heart rate (FHR) has been subject of several studies with contradictory results. The importance of maternal heart rate (MHR) monitoring during labor has also been investigated, but less is known about the effect of fetal gender on MHR. The aim of this study is to simultaneously assess maternal and FHR variability during labor in relation with fetal gender. Simultaneous MHR and FHR recordings were obtained from 44 singleton term pregnancies during the last 2 hr of labor (H1,H2). Heart rate tracings were analyzed using linear (time‐ and frequency‐domain) and nonlinear indices. Both linear and nonlinear components were considered in assessing FHR and MHR interaction, including cross‐sample entropy (cross‐SampEn). Mothers carrying male fetuses (n = 22) had significantly higher values for linear indices related with MHR average and variability and sympatho‐vagal balance, while the opposite occurred in the high‐frequency component and most nonlinear indices. Significant differences in FHR were only observed in H1 with higher entropy values in female fetuses. Assessing the differences between FHR and MHR, statistically significant differences were obtained in most nonlinear indices between genders. A significantly higher cross‐SampEn was observed in mothers carrying female fetuses (n = 22), denoting lower synchrony or similarity between MHR and FHR. The variability of MHR and the synchrony/similarity between MHR and FHR vary with respect to fetal gender during labor. These findings suggest that fetal gender needs to be taken into account when simultaneously monitoring MHR and FHR.
Mammal diversity and metacommunity dynamics in urban green spaces: implications for urban wildlife conservation
Authors: Gallo Travis , Fidino Mason , Lehrer Elizabeth W. , Magle Seth B.
Published: August 2017

As urban growth expands and natural environments fragment, it is essential to understand the ecological roles fulfilled by urban green spaces. To evaluate how urban green spaces function as wildlife habitat, we estimated mammal diversity and metacommunity dynamics in city parks, cemeteries, golf courses, and natural areas throughout the greater Chicago, Illinois, USA region. We found similar α‐diversity (with the exception of city parks), but remarkably dissimilar communities in different urban green spaces. Additionally, the type of urban green space greatly influenced species colonization and persistence rates. For example, coyotes (Canis latrans) had the highest, but white‐tailed deer (Odocoileus virginianus) the lowest probability of persistence in golf courses compared to other green space types. Further, most species had a difficult time colonizing city parks even when sites were seemingly available. Our results indicate that urban green spaces contribute different, but collectively important, habitats for maintaining and conserving biodiversity in cities.
Halogenated closo‐Dodecaborate Anions Stabilize Weakly Bound [(Me3NH)3X]2+ (X = Cl, Br) Dications in the Solid State
Authors: Bolli Christoph , Derendorf Janis , Jenne Carsten , Keßler Mathias
Published: August 2017

Cocrystallization of [Me3NH]2[B12Y12] (Y = Cl, Br, I) with 1 equiv. of [Me3NH]X (X = Cl, Br) from acetonitrile/diethyl ether solution produced large colorless single crystals of [(Me3NH)3X][B12Y12]. Four different compounds of this type were prepared and structurally characterized. The compounds consist of weakly coordinating perhalogenated closo‐dodecaborate [B12Y12]2– dianions and unprecedented weakly bound discrete [(Me3NH)3X]2+ dications. The [(Me3NH)3X]2+ dications are built up from a central halide anion and three [Me3NH]+ cations bound by N–H···X hydrogen bonds. The cations have a pyramidal structure, as determined by X‐ray diffraction, which is in contrast to quantum‐chemical calculations, which predict a trigonal‐planar structure. While the [(Me3NH)3Cl]2+ and [(Me3NH)3Br]2+ cations were easily prepared, attempts to synthesize the corresponding [(Me3NH)3F]2+ and [(Me3NH)3I]2+ cations failed. Three further crystal structures containing the angulated [(Me3NH)2X]+ cation stabilized by [B12Cl12]2–, [B12Br12]2–, or [Me3NB12Cl11]– are reported as well.
Catalytic Cooperativity, Nuclearity, and O2/H2O2 Specificity of Multi‐Copper(II) Complexes of Cyclen‐Tethered Cyclotriphosphazene Ligands in Aqueous Media
Authors: Wang Le , Ye Yong , Lykourinou Vasiliki , Yang Junliang , Angerhofer Alexander , Zhao Yufen , Ming Li‐June
Published: August 2017

Three ligands L1, L2, and L3 with 2, 4, and 6 1,4,7,10‐tetraazacyclododecane (cyclen) moieties attached to a cyclotriphosphazene core, respectively, were synthesized, and oxidation activities of their CuII complexes were investigated. Aerobic oxidation of catechol by these complexes follows an intramolecular dinuclear pathway with significant cooperativity (i.e., θ ≈ 1.5 out of a maximum of 2 for two potential substrate binding sites) and kinetic constants (i.e., kcat = 17.5 × 10–3 s–1, Km = 2.8 mm, and quite remarkable catalytic specificity kcat/Km 12.5 m–1 s–1 per di‐Cu center), while that by untethered CuII–cyclen follows a bimolecular dinuclear pathway without noticeable cooperativity (θ = 0.96) and fourfold lower kcat, despite their similar dinuclear mechanisms. The proximity of CuII centers is suggested by EPR spectra and relaxations, showing a broad spectral component particularly in Cu6L3. Thermodynamic parameters also indicate the significance of multi‐CuII sites in the oxidative catalysis. Air is a more specific oxidation agent for the representative complex Cu2L1, showing 3.2‐fold higher catalytic specificity kcat/Km than H2O2 toward a catechol substrate. The research provides further molecular basis for future design of O2/H2O2‐specific oxidation of multi‐domain Cu complexes.
Exploiting the Continuous in situ Generation of Mesyl Azide for Use in a Telescoped Process
Authors: O'Mahony Rosella M. , Lynch Denis , Hayes Hannah L. D. , Ní Thuama Eilís , Donnellan Philip , Jones Roderick C. , Glennon Brian , Collins Stuart G. , Maguire Anita R.
Published: August 2017

The hazardous diazo transfer reagent mesyl azide has been safely generated and used in situ for continuous diazo transfer as part of an integrated synthetic process with an embedded safety quench. Diazo transfer to β‐keto esters and a β‐ketosulfone was successful. In‐line phase separation, by means of a continuous liquid–liquid separator, enabled direct telescoping with a thermal Wolff rearrangement.
Unveiling the 6,8‐Rearrangement in 8‐Phenyl‐5,7‐dihydroxyflavylium and 8‐Methyl‐5,7‐dihydroxyflavylium through Host–Guest Complexation
Authors: Basílio Nuno , Lima João Carlos , Cruz Luís , de Freitas Victor , Pina Fernando , Ando Hiroki , Kimura Yuki , Oyama Kin‐Ichi , Yoshida Kumi
Published: August 2017

8‐Phenyl‐5,7‐dihydroxyflavylium and 8‐methyl‐5,7‐dihydroxyflavylium were synthesized to observe the 6,8‐rearrangement. 8‐Phenyl and 8‐methyl residues were introduced by Suzuki–Miyaura reaction of 8‐iodochrysin, then reduced by LiAlH4 to give the corresponding 3‐deoxyanthocyanidins. At pH 1.0 the stable form is the 8‐substituted flavylium cation in both compounds. At higher pH values the quinoidal bases are the stable species and some evidence for the 6,8‐rearrangement was obtained, but the respective spectral variations are very small. This was overcome by using a modified cyclodextrin (captisol), which favors the formation of the trans‐chalcone at the expense of the quinoidal bases. The trans‐chalcone was isolated and dissolved in CD3OD/DCl (pD < 1) to give a mixture of the two flavylium isomers. This was confirmed by ESI‐MS analysis (recorded in positive ion mode) of the two isomers after separation by HPLC, which gave the same peak ([M]+ m/z 253). The 6‐isomer slowly reverts to the most stable 8‐isomer. The 6,8‐rearrangement was also observed after irradiation of the trans‐chalcone (in the presence of captisol) at pH 5. Acidification of this photostationary state gave a mixture of both flavylium cations. The UV/Vis absorption of the flavylium cation (6‐isomer) was blueshifted in comparison to the 8‐isomer.
Safety and tolerability of lacosamide monotherapy in the elderly: A subgroup analysis from lacosamide trials in diabetic neuropathic pain
Authors: Bainbridge Jacquelyn , De Backer Marc , Eckhardt Klaus , Tennigkeit Frank , Bongardt Sabine , Sen David , Werhahn Konrad J. , Shaibani Aziz , Faught Edward
Published: August 2017

Objective

To assess the safety profile of lacosamide monotherapy in elderly (≥65 years) subjects with diabetic neuropathic pain (DNP).

Methods

Of 1,863 DNP subjects in double‐blind, randomized, placebo‐controlled trials of lacosamide monotherapy (NCT00861445, NCT00235469, NCT00238524, NCT00135109, NCT00350103), 502 were elderly. Safety data from elderly subjects were compared with that of younger subjects (<65 years) within these DNP trials. It should be noted that lacosamide is approved for the treatment of focal (partial‐onset) seizures; it is not approved/recommended for the treatment of DNP.

Results

Overall, cardiovascular diseases were prevalent in the DNP population, as was the use of cardiac, blood pressure, diabetes, and cholesterol‐lowering medications among both young and elderly subjects. The most frequently reported adverse events (AEs) for lacosamide monotherapy (200, 400, and 600 mg/day combined) in elderly versus younger subjects were dizziness (16.2% vs. 13.2%), nausea (10.0% vs. 9.4%), and headache (8.0% vs. 8.7%). Incidences of cardiac disorder AEs were higher in elderly versus younger subjects receiving placebo (6.2% vs. 3.9%), lacosamide 200 (4.8% vs. 3.3%), lacosamide 400 (7.0% vs. 4.1%), and lacosamide 600 mg/day (7.7% vs. 4.0%). Discontinuation rates because of any AE in the elderly versus younger subjects were similar for placebo (8.8% vs. 7.0%) and lacosamide 200 mg/day (9.6% vs. 11.9%) and higher for lacosamide 400 (25.1% vs. 10.8%) and lacosamide 600 mg/day (52.7% vs. 28.3%).

Significance

Lacosamide monotherapy was well tolerated in elderly subjects with DNP, with an overall AE profile consistent with that reported in epilepsy trials.
Offshore aeolian sediment transport across a human‐modified foredune
Authors: Nordstrom Karl F. , Jackson Nancy L.
Published: August 2017

Concepts derived from previous studies of offshore winds on natural dunes are evaluated on a dune maintained for shore protection during three offshore wind events. The potential for offshore winds to form a lee‐side eddy on the backshore or transfer sediment from the dune and berm crest to the water are evaluated, as are differences in wind speed and sediment transport on the dune crest, berm crest and a pedestrian access gap.

The dune is 18–20 m wide near the base and has a crest 4.5 m above backshore elevation. Two sand‐trapping fences facilitate accretion. Data were obtained from wind vanes on the crest and lee of the dune and anemometers and sand traps placed across the dune, on the beach berm crest and in the access gap. Mean wind direction above the dune crest varied from 11 to 3 deg from shore normal. No persistent recirculation eddy occurred on the 12 deg seaward slope. Wind speed on the berm crest was 85–89% of speed at the dune crest, but rates of sediment transport were 2.27 times greater during the strongest winds, indicating that a wide beach overcomes the transport limitation of a dune barrier. Limited transport on the seaward dune ramp indicates that losses to the water are mostly from the backshore, not the dune. The seaward slope gains sand from the landward slope and dune crest. Sand fences causing accretion on the dune ramp during onshore winds lower the seaward slope and reduce the likelihood of detached flows during offshore winds. Transport rates are higher in access gaps than on the dune crest despite lower wind speeds because of flatter slopes and absence of vegetation. Transport rates across dunes and through gaps can be reduced using vegetation and raised walkover structures. Copyright © 2017 John Wiley & Sons, Ltd.
Accuracy of 50‐g glucose challenge test to detect International Association of Diabetes and Pregnancy Study Groups criteria‐defined hyperglycemia
Authors: Olagbuji Biodun N. , Aderoba Adeniyi K. , Kayode Oluwatosin O. , Awe Christianah O. , Akintan Adesina L. , Olagbuji Yetunde W. ,   the Gestational Diabetes Study Group‐Nigeria
Published: August 2017

Objectives

To determine the accuracy of the 50‐g glucose challenge test (GCT) in detecting hyperglycemia in pregnancy (HIP) across a range of glucose thresholds relative to the International Association of Diabetes and Pregnancy Study Groups diagnostic criteria, and to determine the accuracy of the 50‐g GCT among patients with different risk status.

Methods

The present prospective cohort study included women aged 18–45 years at 24–31+6 weeks of pregnancy who presented at the Mother and Child Hospital, Akure, Nigeria, between September 1, 2015, and February 29, 2016. Patients underwent the 50‐g GCT followed by the 75‐g oral glucose tolerance test (OGTT). The accuracy of different 50‐g GCT thresholds in diagnosing HIP was assessed based on International Association of Diabetes and Pregnancy Study Groups diagnostic criteria, with the 75‐g OGTT used as a clinical reference standard.

Results

Of 280 patients enrolled, 46 (16.4%) had HIP. The sensitivity of the 50‐g GCT to detect HIP decreased from 47.8% (95% confidence interval [CI], 32.9–63.1) at a 7.2‐mmol/L threshold to 32.6% (95% CI, 19.5–48.0) at a 8.0‐mmol/L threshold; the specificity improved from 84.2% (95% CI, 78.9–88.6) to 95.3% (95% CI, 91.7–97.6), respectively.

Conclusion

The 50‐g GCT performed poorly compared with the 75‐g OGTT for detecting HIP. It appears to be an unsuitable replacement for the 75‐g OGTT.
MATERNAL TRAUMA AFFECTS PRENATAL MENTAL HEALTH AND INFANT STRESS REGULATION AMONG PALESTINIAN DYADS
Authors: Isosävi Sanna , Diab Safwat Y. , Kangaslampi Samuli , Qouta Samir , Kankaanpää Saija , Puura Kaija , Punamäki Raija‐Leena
Published: August 2017

We examined how diverse and cumulated traumatic experiences predicted maternal prenatal mental health and infant stress regulation in war conditions and whether maternal mental health mediated the association between trauma and infant stress regulation. Participants were 511 Palestinian mothers from the Gaza Strip who reported exposure to current war trauma (WT), past childhood emotional (CEA) and physical abuse, socioeconomic status (SES), prenatal mental health problems (posttraumatic stress disorder and depression symptoms), and perceived stress during their secondtrimester of pregnancy as well as infant stress regulation at 4 months. While all trauma types were associated with high levels of prenatal symptoms, CEA had the most wide‐ranging effects and was uniquely associated with depression symptoms. Concerning infant stress regulation, mothers’ CEA predicted negative affectivity, but only among mothers with low WT. Against hypothesis, the effects of maternal trauma on infant stress regulation were not mediated by mental health symptoms. Mothers’ higher SES was associated with better infant stress regulation whereas infant prematurity and male sex predisposed for difficulties. Our findings suggest that maternal childhood abuse, especially CEA, should be a central treatment target among war‐exposed families. Cumulated psychosocial stressors might increase the risk for transgenerational problems.
The effects of receptive and expressive instructional sequences on varied conditional discriminations
Authors: Bao Shimin , Sweatt Kristin T. , Lechago Sarah A. , Antal Sarah
Published: August 2017

Many Early Intensive Behavioral Intervention (EIBI) curricula recommend teaching receptive responding before targeting expressive responding (Leaf & McEachin, 1999; Lovaas, 2003). However, a small literature base suggests that teaching expressive responses first may be more efficient when teaching children with ASD and other developmental disabilities (Petursdottir & Carr, 2011). The present study employed an alternating treatments design to compare the effects of three instructional sequences to teach feature, function, and class to three children diagnosed with ASD: (a) receptive–expressive, (b) expressive–receptive, and (c) mixed. The results suggested that expressive–receptive was the most efficient training sequence for all three participants. Additionally, greater emergent responding was observed with the expressive–receptive training sequence.
Necrotic cell death occur via JNK pathway with the activity of transcription factor c‐Jun by 4‐MC in INS‐1 cell line
Authors: Karatug Kacar Ayse , Bolkent Sehnaz
Published: August 2017

In this study, it was aimed to determine the doses of 4‐methylcatechol causing cell death in rat insulinoma β‐cells (INS‐1), to find out the type of cellular death at these doses, and to investigate the molecular mechanism of cellular death occurring. More necrotic cells were observed than apoptosis with the administration of 350, 400, and 450 μM 4‐methylcatechol. Lactate dehydrogenase levels, reactive oxygen species, mitochondrial potential loss, ATP, and GTP losses increased at these doses. The JNK and ERK cellular pathway were screened. We observed an increase in p‐RAF1 activity, the active JNK amount, the total c‐Jun amount, while a decrease in p‐RAF1 expression, the total JNK amount, JNK expression, ATF2 expression, active ERK, and its expression and Elk1 expression. It was concluded that cells perform necrotic death by the following options: i) phosphorylated RAF1 activates the JNK pathway with the activity of transcription factor c‐Jun; ii) Hsp 70 and Hsp 90 do not show a change inside the cell, rendering the JNK pathway active.
Patellofemoral and tibiofemoral alignment in a fully weight‐bearing upright MR: Implementation and repeatability
Authors: Macri Erin M. , Crossley Kay M. , d'Entremont Agnes G. , Hart Harvi F. , Forster Bruce B. , Wilson David R. , Ratzlaff Charles R. , Walsh Anne M. , Khan Karim M.
Published: August 2017

Purpose

To develop methods for evaluating 3D patellofemoral and tibiofemoral alignment in vertical open‐bore magnetic resonance (MR) scanners, with participants upright and fully weight‐bearing; and to evaluate the repeatability of these methods in individuals with patellofemoral osteoarthritis (OA) and in asymptomatic knees.

Materials and Methods

Our methods extend previously validated, reliable methods for evaluating alignment into an upright MR environment. In 10 participants with early patellofemoral OA and 10 with asymptomatic knees, we acquired sagittal T1‐weighted turbo spin echo images in a 3T scanner to create accurate participant‐specific 3D anatomical surface models. In a vertical open‐bore 0.5T MR scanner, we obtained lower‐resolution sagittal gradient echo images to capture bony position and orientation data. Participants were scanned in a position of squatting with the knees flexed 30°, three separate times to evaluate repeatability. Bone segmentation was performed manually, surface models were registered to data from the 0.5T scanner, and 3D patellofemoral and tibiofemoral alignment was calculated in all six degrees of freedom (three rotations and three translations).

Results

Intraclass correlation coefficients (ICCs) were ≥0.94, with the exception of patellar spin (0.79). Standard errors of measure (SEM) were <2° rotation and <0.9 mm translation. Repeatability remained adequate when stratified by group, with the exception of patellar spin (ICC 0.57 for asymptomatic knees vs. 0.91 for OA knees).

Conclusion

We demonstrate methods for evaluating 3D alignment in upright fully weight‐bearing participant positions in a vertical open‐bore MR scanner. With the exception of patellar spin, repeatability was good to excellent.

Level of Evidence: 3

Technical Efficacy: Stage 1

J. Magn. Reson. Imaging 2018;47:841–847.
Improved prediction of direction‐dependent, acute axonal injury in piglets
Authors: Atlan Lorre S. , Smith Colin , Margulies Susan S.
Published: August 2017

To guide development of safety equipment that reduces sports‐related head injuries, we sought to enhance predictive relationships between head movement and acute axonal injury severity. The severity of traumatic brain injury (TBI) is influenced by the magnitude and direction of head kinematics. Previous studies have demonstrated correlation between rotational head kinematics and symptom severity in the adult. More recent studies have demonstrated brain injury age‐ and direction‐dependence, relating head kinematics to white matter tract‐oriented strains. We have recently developed and assessed novel rotational head kinematic parameters as predictors of white matter damage in the female immature piglet. We show that many previously published rotational kinematic injury predictor metrics poorly predict acute axonal pathology induced by rapid, non‐impact head rotations and that inclusion of cerebral moments of inertia (MOI) in rotational head injury metrics refines prediction of diffuse axonal injury following rapid head rotations for two immature age groups. Rotational Work (RotWork) was the best significant predictor of traumatic axonal injury in both newborn and pre‐adolescent piglets following head rotations in the axial, coronal, and sagittal planes. An improvement over current metrics, we find that RotWork, which incorporates head rotation rate, direction, and brain shape, significantly enhanced acute traumatic axonal injury prediction. For similar injury extent, the RotWork threshold is lower for the newborn piglet than the pre‐adolescent.
Characterization of steryl glycosides in marine microalgae by gas chromatography–triple quadrupole mass spectrometry (GC–QQQ‐MS)
Authors: Yu Shanshan , Zhang Yufan , Ran Yun , Lai Wenyi , Ran Zhaoshou , Xu Jilin , Zhou Chengxu , Yan Xiaojun
Published: August 2017

BACKGROUND

Steryl glycosides (SGs) are sterol conjugates found in various plants, especially in those making up human diets. It has been demonstrated that SGs have potential health benefits, and they could be used as food supplements in a variety of food matrixes. Marine microalgae are a potential resource for human food and ingredients. In this study, gas chromatography–triple quadrupole mass spectrometry (GC–QQQ‐MS) was used to characterize unknown SGs in eight microalgae belonging to different classes (Isochrysis galbana 3011, Pavlova viridis, Platymonas helgolandica, Conticribra weissflogii, Thalassiosira pseudonana, Nitzschia closterium, Gymnodinium sp., and Karlodinum veneficum).

RESULTS

The SGs were first extracted from lyophilized algae with chloroform–methanol, purified by solid‐phase extraction and analyzed as trimethylsilyl derivatives. Nine SGs have been identified. In particular, new SGs like occelasteryl glycoside and stellasteryl glycoside were found in Gymnodinium sp., 24‐methylene cholesteryl glycoside was detected in P. helgolandica, and 4,24‐dimethylcholestan‐3‐yl glycoside was identified as the main constituent of microalga K. veneficum. The results also showed that the compositions of SGs in different microalgae varied, with a range of 5.234 to 0.036 g kg−1, and microalga P. viridis contained the most abundant SGs.

CONCLUSION

GC–QQQ‐MS is a powerful tool to detect SGs with different structures from a variety of microalgae. The compositions of SGs in different microalgae varied greatly. Microalgae are a good source of highly valued SGs. © 2017 Society of Chemical Industry
Plant growth‐promoting bacteria elevate the nutritional and functional properties of black cumin and flaxseed fixed oil
Authors: Dimitrijević Snežana , Pavlović Marija , Maksimović Svetolik , Ristić Mihajlo , Filipović Vladimir , Antonović Dušan , Dimitrijević‐Branković Suzana
Published: August 2017

BACKGROUND

In order to study the influence of plant growth‐promoting bacteria (PGPB) belonging to Streptomyces sp., Paenibacillus sp., and Hymenobacter sp. on fixed oil content of flaxseed and black cumin, 2‐year field experiments were conducted. PGPB was applied during seedtime of plants. The extraction of oil from seeds was performed using supercritical CO2.

RESULTS

The addition of PGPB significantly increases the content of C18:1 (from 16.06 ± 0.03% to 16.97 ± 0.03%) and C18:3 (from 42.97 ± 0.2% to 45.42 ± 0.5%) in flaxseed oil and C18:2 (from 52.68 ± 0.50% to 57.11 ± 0.40%) and C20:2 (from 4.34 ± 0.02% to 4.54 ± 0.03%) in black cumin seed oil. The contents of total polyphenols, flavonoids, and carotenoids, as well as antioxidant activity measured by ferric‐reducing ability of plasma assay, were found to be greater in the oil from the seeds of plants treated with the PGPB, compared with the respective non‐treated samples.

CONCLUSION

The use of PGPB enhances plant nutritive properties; these represent a great source for obtaining valuable functional food ingredients. © 2017 Society of Chemical Industry