bluuebunny/crossref_metadata_2025 huggingface dataset:
Tunable Band‐Selective UV‐Photodetectors by 3D Self‐Assembly of Heterogeneous Nanoparticle Networks
Authors: Nasiri Noushin , Bo Renheng , Hung Tak Fu , Roy Vellaisamy A. L. , Fu Lan , Tricoli Antonio
Published: September 2016

Accurate detection of ultraviolet radiation is critical to many technologies including wearable devices for skin cancer prevention, optical communication systems, and missile launch detection. Here, a nanoscale architecture is presented for band‐selective UV‐photodetectors, which features unique tunability and miniaturization potential. The device layout relies on the 3D integration of ultraporous layers of tailored nanoparticles. By tailoring the transmittance window between the indirect band gap of TiO2 nanoparticles and the sharp edge of the direct band gap of ZnO, a band‐selective photoresponse is achieved with tunable bandwidth to less than 30 nm and photo‐ to dark‐current ratios of several millions at a light intensity of 86 μW cm−2 and operation bias of 1 V. The potential of this integrated morphology is shown by fabrication of the first inherent UVA photodetector with selectivity against the edge of the UVB and visible light of nearly 60 times. This tunable architecture and nanofabrication approach are compatible with state‐of‐the micromachining technologies and provide a flexible solution for the engineering of wearable band‐selective photodetectors.
Efficient and Tunable Thermally Activated Delayed Fluorescence Emitters Having Orientation‐Adjustable CN‐Substituted Pyridine and Pyrimidine Acceptor Units
Authors: Pan Kuan‐Chung , Li Shu‐Wei , Ho Yu‐Yi , Shiu Yi‐Jiun , Tsai Wei‐Lung , Jiao Min , Lee Wei‐Kai , Wu Chung‐Chih , Chung Chin‐Lung , Chatterjee Tanmay , Li Yung‐Shin , Wong Ken‐Tsung , Hu Hung‐Chieh , Chen Chung‐Chia , Lee Meng‐Ting
Published: September 2016

A series of twisted D–π–A type emitters based on the acridine donor unit and CN‐substituted pyridine, pyrimidine, and benzene acceptor units are studied. They not only allow one to systematically probe the influence of different acceptor strengths, but also permit one to intriguingly probe the influence of tunable conformations (twist angles) within the acceptor moieties through controlling the orientation of asymmetric heteroaromatic ring relative to the donor component. Intramolecular charge‐transfer transitions are observed in all these compounds and emission wavelengths are widely tunable from deep blue to yellow not only by the general acceptor strength due to the characters of heteroarene and CN‐substitution pattern but also by the subtle control of in‐acceptor conformation (twist angles). Small triplet‐to‐singlet energy gaps (ΔEST) and significant thermally activated delayed fluorescence (TADF) characteristics are obtained in a series of D–π–A compounds with sufficient acceptor strengths and tunable in‐acceptor conformation, yielding a series of efficient blue‐green to yellow TADF emitters with promisingly high photoluminescence quantum yields of 90%–100%. Highly efficient blue‐green to yellow TADF organic light‐emitting diodes (OLEDs) having external quantum efficiencies of up to 23.1%–31.3% are achieved using these efficient TADF emitters, which are among the most efficient TADF OLEDs ever reported.
Origins of Bistability and Na Ion Mobility Difference in P2‐ and O3‐Na2/3Fe2/3Mn1/3O2Cathode Polymorphs
Authors: Katcho Nebil A. , Carrasco Javier , Saurel Damien , Gonzalo Elena , Han Man , Aguesse Frederic , Rojo Teofilo
Published: September 2016

Transition metal layered oxides are promising cathode materials for sodium‐ion batteries. Phase transitions involving different stacking sequences of the oxide layers often plague the electrochemistry of these materials during cycling, which strongly impacts in their electrochemical performance. However, the underlying mechanisms of these processes remain elusive. Interestingly, P2‐ and O3‐Na2/3Fe2/3Mn1/3O2phases are the first transition metal layered oxide polymorphs that have been synthesized with exactly the same composition. This offers unprecedented access to the study of bistability in these systems as well as isolates the effect of local structure on Na ion mobility. Here, first‐principles calculations and experiments are combined to unveil the physical origin of such bistability and identify important differences in Na ion diffusion between these two phases. It has been found that electrostatic interactions between oxide layers control the bistable nature of P2 and O3 phases. It is also put forward that the interlayer distance between oxide layers may be a useful descriptor to rationalize the relative stability of other P and O phases in general. Furthermore, this study tracks down to the molecular level the differences regarding Na ion mobility in P2‐ and O3‐Na2/3Fe2/3Mn1/3O2by computing activation energies and estimating diffusion coefficients.
Synthesis of 4‐Oxo‐but‐2‐enals through tBuONO and TEMPO‐Promoted Cascade Reactions of Homoallylic Alcohols
Authors: He Yan , Tian Miao‐Miao , Zhang Xin‐Ying , Fan Xue‐Sen
Published: September 2016

An efficient and stereoselective synthesis of (E)‐4‐oxo‐but‐2‐enals through tert‐butyl nitrite (tBuONO)‐ and 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO)‐promoted cascade reactions of homoallylic alcohols is presented. Mechanistically, the formation of the title compounds involves a cascade process including nitration of the carbon–carbon double bond, oxidation of the secondary alcohol unit, and Nef transformation of the in situ formed allylic nitro scaffold. In this process, tBuONO is an efficient nitration and oxidation reagent while TEMPO is believed to act as a mild oxidant and a novel reagent to promote the Nef reaction that is accomplished under mild and neutral conditions. As a further aspect, the (E)‐4‐oxo‐but‐2‐enals thus obtained were found to be suitable substrates to condense with hydrazine hydrate to give diversely substituted pyridazines with good efficiency.
A lethal case of mamushi (Gloydius blomhoffii) bite: severe bowel symptoms as a lethal sign
Authors: Okamoto Osamu , Nakashima Ryuta , Yamamoto Soichiro , Hashimoto Takuzo , Takasaki Tomomi , Tokuda Hayato , Sato Seiichi , Gamachi Ayako , Hashimoto Hiroyuki , Inagaki Nobuhiro
Published: September 2016

Case

We report a lethal case of a mamushi (Gloydius blomhoffii) bite. An 84‐year‐old woman was bitten by a mamushi snake on her right elbow. She was initially treated at another hospital, however, because the swelling expanded and her renal function worsened, she was transferred to our hospital. Compartment syndrome, thrombocytopenia, respiratory arrest, and elevated creatinine kinase and lactose dehydrogenase levels were seen; renal failure progressed, and ileus and peritonitis due to colon perforation occurred.

Outcome

The patient died 35 days after the bite. An autopsy revealed widespread necrosis of the ileum, colon, and liver.

Conclusion

This report supplies useful clinical information on the treatment of severe mamushi bite cases, and severe abdominal symptoms, such as ileus and melena, may be a lethal sign.
From Sponges to Nanotubes: A Change of Nanocrystal Morphology for Acute‐Angle Bent‐Core Molecules
Authors: Gorecka Ewa , Vaupotič Nataša , Zep Anna , Pociecha Damian
Published: September 2016

The crystalline (B4) phase made of acute‐angle bent‐core molecules (1,7‐naphthalene derivatives), which exhibits an unusual, highly porous sponge‐like morphology, is presented. However, if grown in the presence of low‐weight mesogenic molecules, the same crystal forms nanotubes with a very high aspect ratio. The nanotubes become unstable upon increasing the amount of dopant molecules, and the sponge‐like morphology reappears. The phase is optically active, and the optical activity is an order of magnitude smaller than in the B4 phase made of conventional bent‐core molecules. The optical activity is related to the spatial inhomogeneity of the layered structure and is reduced due to the low apex angle and low tilt of the molecules. The arrangement of molecules within the layers was deduced from the bathochromic absorption shift in the B4 phase.
A Copper‐Catalyzed Decarboxylative Amination/Hydroamination Sequence: Switchable Synthesis of Functionalized Indoles
Authors: Li Tian‐Ren , Cheng Bei‐Yi , Wang Ya‐Ni , Zhang Mao‐Mao , Lu Liang‐Qiu , Xiao Wen‐Jing
Published: September 2016

A copper‐catalyzed decarboxylative amination/hydroamination sequence of propargylic carbamates with various nucleophiles is described for the first time. It features an earth‐abundant metal catalyst, mild reaction conditions, and high efficiency. Further treatments of the resultant key intermediates using an acid or a base in one pot enable the controllable and divergent synthesis of two types of functionalized indoles. Moreover, experiments to demonstrate the synthetic potential of this methodology are performed.
Investigation of the binding of AuNPs–6‐mercaptopurine and the sensitive detection of 6‐mercaptopurine using resonance Rayleigh light scattering
Authors: Li Zhihong , Bi Shuyun , Wang Tianjiao , Wang Yu , Zhou Huifeng , Wu Jun
Published: September 2016

A highly sensitive method for the detection of 6‐mercaptopurine (MP) by resonance Rayleigh light scattering (RLS) method was developed. Gold nanoparticles (AuNPs) were synthesized by a modified seed method and characterized using transmission electron microscopy (TEM). AuNPs were bound to MP via covalent bonding to form the MP–AuNPs complex, which increased the RLS intensity of MP at 347 nm (increased by 65.7%). Under optimum conditions, the magnitude of the enhanced RLS intensity for MP–AuNPs was proportional to MP concentration in the range 0.0681–1.702 μg mL−1. The linear regression equation was represented as follows: ΔIRLS = 9.31 + 82.42c (r = 0.9948). The limit of detection (LOD, 3σ) was 3.32 ng mL−1. The system was applied successfully to detect MP in pharmaceuticals. MP recoveries were 99.9–101.7% with a relative standard deviation (RSD) (n = 5) of 0.59–0.77% for three synthetic samples, and 97.5–110.0% with an RSD of 0.98–2.10% (n = 5) for tablet samples.
Differential inhibition of human erythrocyte acetylcholinesterase by polyphenols epigallocatechin‐3‐gallate and resveratrol. Relevance of the membrane‐bound form
Authors: Salazar Paula B. , de Athayde Moncorvo Collado Alejandro , Canal‐Martínez Verónica , Minahk Carlos J.
Published: September 2016

The activity of acetylcholinesterase (AChE) from human erythrocytes was tested in the presence of the phenolic compounds resveratrol and epigallocatechin‐3‐gallate (EGCG). Even though the stilbene barely changed this enzymatic activity, EGCG did inhibit AChE. Importantly, it preferentially acted on the membrane‐bound enzyme rather than on its soluble form. Actually, it was shown that this flavonoid may bind to the red blood cell membrane surface, which may improve the interaction between EGCG and AChE. Therefore, caution should be taken when screening AChE inhibitors. In fact, testing compounds with the soluble form of the enzyme may underestimate the activity of some of these potential inhibitors, hence it would be advisable not to use them as a sole model system for screening. Moreover, erythrocyte AChE is proposed as a good model for these enzymatic assays. © 2016 BioFactors, 43(1):73–81, 2017
Tailor‐made biocatalysts enzymes for the fine chemical industry in China
Authors: Jiang Yu , Tao Rongsheng , Yang Sheng
Published: September 2016

The Center of Industrial Biotechnology (CIBT) was established in Huzhou for fine chemicals in 2006 and CIBT Shanghai was founded for bulk chemicals in 2008. CIBT is a non‐profit organization under auspices of the Shanghai Institutes for Biological Sciences, Shanghai Branch of the Chinese Academy of Sciences (CAS) and Huzhou Municipal Government. CIBT is affiliated with the CAS, which enables it to take advantage of the rich R&D resources and support from CAS; yet CIBT operates as an independent legal entity. The goal of CIBT is to incubate industrial biotechnologies and accelerate the commercialization of these technologies with corporate partners in China.
Position selectivity in face‐sensitive visual cortex to facial and nonfacial stimuli: an fMRI study
Authors: Nichols David F. , Betts Lisa R. , Wilson Hugh R.
Published: September 2016

Background

Evidence for position sensitivity in object‐selective visual areas has been building. On one hand, most of the relevant studies have utilized stimuli for which the areas are optimally selective and examine small sections of cortex. On the other hand, visual field maps established with nonspecific stimuli have been found in increasingly large areas of visual cortex, though generally not in areas primarily responsive to faces.

Methods

fMRI was used to study the position sensitivity of the occipital face area (OFA) and the fusiform face area (FFA) to both standard rotating wedge retinotopic mapping stimuli and quadrant presentations of synthetic facial stimuli. Analysis methods utilized were both typical, that is, mean univariate BOLD signals and multivoxel pattern analysis (MVPA), and novel, that is, distribution of voxels to pattern classifiers and use of responses to nonfacial retinotopic mapping stimuli to classify responses to facial stimuli.

Results

Polar angle sensitivity was exhibited to standard retinotopic mapping stimuli with a stronger contralateral bias in OFA than in FFA, a stronger bias toward the vertical meridian in FFA than in OFA, and a bias across both areas toward the inferior visual field. Contralateral hemispheric lateralization of both areas was again shown using synthetic face stimuli based on univariate BOLD signals, MVPA, and the biased contribution of voxels toward multivariate classifiers discriminating the contralateral visual field. Classifiers based on polar angle responsivity were used to classify the patterns of activation above chance levels to face stimuli in the OFA but not in the FFA.

Conclusions

Both the OFA and FFA exhibit quadrant sensitivity to face stimuli, though the OFA exhibits greater position responsivity across stimuli than the FFA and includes overlap in the response pattern to the disparate stimulus types. Such biases are consistent with varying position sensitivity along different surfaces of occipito‐temporal cortex.
Publication fate of abstracts presented at British association of clinical anatomists annual meetings
Authors: Furness Hugh N. , Miller George W. , Lewis Thomas L.
Published: September 2016

Dissemination of research is an integral part of the scientific process. Failure to disseminate research limits the scope for critical appraisal and potentially wastes valuable resources. The gold standard for dissemination of research is peer‐reviewed publication following presentation at a national meeting. The primary objective of this study was quantitative assessment of the abstracts presented at British Association of Clinical Anatomists (BACA) summer and winter meetings with regards to the rates of subsequent publication and comparison to other medical specialties. Published abstracts from the summer and winter meetings of BACA between the years of 2000 and 2014 were analyzed. MEDLINE was searched to identify peer‐reviewed publications arising from each presented abstract. In total, 1,807 abstracts were presented between the years of 2000 and 2014. The mean number of abstracts presented each year was 60.2, (range 26–157). In total, 20.4% of abstracts were subsequently published in MEDLINE‐indexed journals with a median publication time of 19 months. The mean number of cadaveric prosections was 45.2 ± 78.8, (range 1–960). Analysis of abstracts focusing on radiographic imaging found the mean number of scans was 224.4 ± 807.1, (range 1–6,439). Biannual meetings of BACA are a forum for the presentation of high‐quality anatomical research. BACA meeting abstracts have generally reduced publication rates compared to some surgical specialty meetings; however, there is no analysis available for an equivalent anatomical meeting. Further work should try to identify reasons that may hinder or limit subsequent publication of the anatomy abstracts presented at BACA. Clin. Anat. 30:133–139, 2017. © 2016 Wiley Periodicals, Inc.
Two Opposing d‐Amino Acids Give Zigzag Hairpin Epitopes an Additional Kink to Create Antibody‐Selective Peptide Antigens
Authors: Schrimpf Andreas , Geyer Armin
Published: September 2016

We have developed peptides that are able to distinguish between subgroups of polyclonal antibodies. These β‐hairpin peptides act as conformational epitopes with specific shape and flexibility; they have been analyzed by NMR and CD spectroscopy, and have been shown to identify known disease markers. As a standalone mini β‐sheet, a hairpin is stabilized by alternating pairs of hydrogen‐bonded and non‐bonded amino acids on its two opposing peptide strands. A single d mutation disrupts this secondary structure, the correlated double‐d mutation of two opposing amino acids compensates for this destabilizing effect. The designed kink was introduced into both hydrogen‐bonded and ‐non‐bonded positions of an all‐l hairpin that is a known conformational epitope in molecular recognition. Our peptides enabled the discrimination of different human rheumatoid arthritis autoantibodies in an ELISA assay.
Exploring the Reactivity of α‐Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]‐Wittig Rearrangement and the Mechanistic Proposal Revisited
Authors: Velasco Rocío , Silva López Carlos , Nieto Faza Olalla , Sanz Roberto
Published: September 2016

By carefully controlling the reaction temperature, treatment of aryl benzyl ethers with tBuLi selectively leads to α‐lithiation, generating stable organolithiums that can be directly trapped with a variety of selected electrophiles, before they can undergo the expected [1,2]‐Wittig rearrangement. This rearrangement has been deeply studied, both experimentally and computationally, with aryl α‐lithiated benzyl ethers bearing different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron‐poor aryl groups that favor the anionic pathway.
Enantioselective Organocatalytic Cascade Approach to Different Classes of Benzofused Acetals
Authors: Paz Bruno Matos , Klier Lydia , Næsborg Line , Lauridsen Vibeke Henriette , Jensen Frank , Jørgensen Karl Anker
Published: September 2016

A novel enantioselective organocatalytic strategy is presented for the synthesis of tetrahydrofurobenzofuran and methanobenzodioxepine natural product core structures. The strategy is based on a pair of divergent reaction pathways in which hydroxyarenes react with γ‐keto‐α,β‐unsaturated aldehydes, catalyzed by a chiral secondary amine. One reaction pathway, which leads to chiral 5,5‐fused acetals with two stereocenters—the tetrahydrofurobenzofuran scaffolds—proceeds in moderate yields and up to 96 % ee. The other reaction pathway provides 5,6‐bridged methanobenzodioxepine scaffolds with three stereocenters in moderate to good yields and up to 95 % ee. The reaction is remarkable as it can proceed with catalyst loadings as low as 0.25 mol %, providing one of the highest known turnover numbers in iminium ion catalysis. Furthermore, the hemiacetal tetrahydrofurobenzofuran can undergo functionalizations including reduction, oxidation, and allylation. Finally, the effects involved in the substrate control for the divergent pathways, based on both experimental and computational studies, have been investigated. A model involving steric, electronic and stereoelectronic interactions is discussed to rationalize the observed selectivities.
Highly Axial Magnetic Anisotropy in a N3O5 Dysprosium(III) Coordination Environment Generated by a Merocyanine Ligand
Authors: Selvanathan Pramila , Huang Gang , Guizouarn Thierry , Roisnel Thierry , Fernandez‐Garcia Guglielmo , Totti Federico , Le Guennic Boris , Calvez Guillaume , Bernot Kévin , Norel Lucie , Rigaut Stéphane
Published: September 2016

A spiropyran‐based switchable ligand isomerizes upon reaction with lanthanide(III) precursors to generate complexes with an unusual N3O5 coordination sphere. The air‐stable dysprosium(III) complex shows a hysteresis loop at 2 K and a very strong axial magnetic anisotropy generated by the merocyanine phenolate donor.
Mono‐ and Bimetallic Alkynyl Metallocenes and Half‐Sandwich Complexes: A Simple and Versatile Synthetic Approach
Authors: Valderas Carolina , Marzo Leyre , de la Torre María C. , García Ruano José Luis , Alemán José , Casarrubios Luis , Sierra Miguel A.
Published: September 2016

A general process for the synthesis of alkynyl mono and dimetallic metallocenes and half‐sandwich complexes has been developed. This approach uses the addition of lithium derivatives of sandwich or half‐sandwich complexes to arylsulfonylacetylenes. The reaction occurs in two steps (lithiation and anti‐Michael addition to alkynylsulfone followed by elimination of the ArSO2 moiety) to form the corresponding mono‐ or bimetallic alkynes in clearly higher yields, simpler experimental procedures, and more environmentally benign conditions than those of the so far reported for the synthesis of this type of products. The electrochemical properties of the newly obtained complexes have also been studied.
Dynamische Methode zur Berechnung thermodynamischer Gleichgewichte in reaktiven Mehrphasensystemen
Authors: Zinser Alexander , Sundmacher Kai
Published: September 2016

Ein allgemeiner Ansatz zur Berechnung thermodynamischer Gleichgewichte für nichtreaktive und reaktive Mehrphasensysteme wird vorgestellt. Dieser basiert auf der Simulation der dynamischen Evolution eines Gemisches aus einem beliebigen Nichtgleichgewichtszustand in das thermodynamische Gleichgewicht hinein. Der Vorteil dieses Ansatzes ist, dass er komplexe Mehrkomponentensysteme behandeln kann, ohne numerische Schwierigkeiten zu bereiten. Die Anwendung der vorgestellten Methode wird anhand verschiedener Gleichgewichtssituationen des Stoffsystems der Butylacetat‐Synthese erläutert.
3D physiological model of the aortic valve incorporating small coronary arteries
Authors: Mohammadi Hossein , Cartier Raymond , Mongrain Rosaire
Published: September 2016

The diseases of the coronary arteries and the aortic root are still the leading causes of mortality and morbidity worldwide. In this study, a 3D global fluid‐structure interaction of the aortic root with inclusion of anatomically inspired small coronary arteries using the finite element method is presented. This innovative model allows to study the impact and interaction of root biomechanics on coronary hemodynamics and brings a new understanding to small coronary vessels hemodynamics. For the first time, the velocity profiles and shear stresses are reported in distal coronary arteries as a result of the aortic flow conditions in a global fluid‐structure interaction model.
Dioxidomolybdenum(VI) Complexes of Tripodal Tetradentate Ligands for Catalytic Oxygen Atom Transfer between Benzoin and Dimethyl Sulfoxide and for Oxidation of Pyrogallol
Authors: Maurya Mannar R. , Uprety Bhawna , Avecilla Fernando
Published: September 2016

The reactions of the tripodal tetradentate ONNO donor ligands 6,6′‐{[(2‐morpholinoethyl)azanediyl]bis(methylene)}bis(2,4‐di‐tert‐butylphenol) (H2L1), 6,6′‐{[(2‐morpholinoethyl)azanediyl]bis(methylene)}bis(2,4‐dimethylphenol) (H2L2) and 6,6′‐{[(2‐morpholinoethyl)azanediyl]bis(methylene)}bis[2‐(tert‐butyl)‐4‐methylphenol] (H2L3) with [MoVIO2(acac)2] (acac = acetylacetonato) in a 1:1 molar ratio in MeOH gave the corresponding cis‐dioxidomolybdenum(VI) complexes [MoO2(L1)], [MoO2(L2)] and [MoO2(L3)], respectively, in excellent yields. These complexes were characterized by various spectroscopic (IR, UV/Vis, 1H and 13C NMR), electrochemical, thermogravimetric, single‐crystal XRD, and powder XRD (PXRD) studies. In these complexes, the geometry around the cis‐[MoO2]2+ core is distorted octahedral, and the ligands are tetradentate and coordinate through two Ophenolate, one Ntripodal, and one Nmorpholine atoms. One of the oxido groups and the morpholine nitrogen atom occupy the axial sites. These complexes were used for catalytic oxygen atom transfer between benzoin and dimethyl sulfoxide (DMSO) in acetonitrile at 80 °C, and the formation of benzil was followed by HPLC. Detailed kinetic studies revealed a first‐order rate in benzoin and catalyst, and the rate constant for the second‐order oxygen atom transfer reaction was 0.0162 m–1 h–1. The formation of the dinuclear intermediates [LMoV–µ‐O‐MoVL] was established by MALDI‐TOF MS and UV/Vis spectroscopy. Its reversible nature was further supplemented by UV/Vis spectroscopy. These complexes also catalyze the oxidation of pyrogallol in a fashion similar to that of transhydroxylases. Under aerobic conditions, the initially formed oxidation product phloroglucinol undergoes further oxidative coupling in the presence of H2O2 to give purpurogallin as the final product. This process follows Michaelis–Menten‐type kinetics with respect to pyrogallol; the kcat values obtained were 394, 300 and 247 h–1 for [MoVIO2(L1)], [MoVIO2(L2)] and [MoVIO2(L3)], respectively.
Energetic Materials Trends in 5‐ and 6‐Membered Cyclic Peroxides Containing Hydroperoxy and Hydroxy Substituents
Authors: Gamage Nipuni‐Dhanesha H. , Stiasny Benedikt , Kratz Eric G. , Stierstorfer Jörg , Martin Philip D. , Cisneros G. Andrés , Klapötke Thomas M. , Winter Charles H.
Published: September 2016

Ten peroxide compounds based upon the 3,6‐di(hydroperoxy)‐1,2‐dioxane, 2‐hydroxy‐6‐hydroperoxy‐1,2‐dioxane, 3,5‐di(hydroperoxy)‐1,2‐dioxolane, and 3‐hydroxy‐5‐hydroperoxy‐1,2‐dioxolane skeletons have been synthesized, structurally characterized, and fully evaluated for their energetic materials properties. The solid‐state structures of these compounds are dominated by hydrogen bonding interactions involving the hydroperoxy and hydroxy groups. Energetic materials testing shows that most of the compounds are highly sensitive toward impact and friction, with similar properties to highly sensitive peroxides such as triacetone triperoxide. 3,5‐Diethyl‐5‐hydroperoxy‐1,2‐dioxolan‐3‐ol (3b) and 3,5‐dimethyl‐5‐hydroperoxy‐1,2‐dioxolan‐3‐ol (5b) have lower impact and friction sensitivities than the other compounds, with values that are appropriate for use as primary explosives.
Natural compounds and vegetable powders improve the stability and antioxidant properties of Brassica napus L. var. oleifera (rapeseed) oil
Authors: Tundis Rosa , Tenuta Maria Concetta , Loizzo Monica R. , Bonesi Marco , Menichini Francesco , Duthie Garry
Published: September 2016

This work evaluated the strategies to increase the oxidative stability and the potential health benefits of Brassica napus L. var. oleifera (rapeseed) oil enriched with natural compounds. The effect of storage, light, and heating on the oxidative stability of rapeseed oil was compared with olive oil. Oxidative stability was assessed by using Rancimat and thiobarbituric acid reactive‐substances assay (TBARS) production. Different concentrations of individual phenol compounds, extracts, and vegetable powders were added to the cold‐pressed rapeseed oil. The most positive effects were observed with addition of freeze dried powders. The rapeseed oil chemical profile was analyzed by gas chromatography (GC) and gas chromatography‐mass spectrometry (GC‐MS) and the antioxidant effects of rapeseed oil fortified with vegetable powders were investigated with different in vitro assays. Results suggested that beetroot, carrot, tomato, and swede can offer effective alternatives or adjuncts to synthetic antioxidants during frying and storage of rapeseed oil.

Practical applications: Brassica napus L. var. oleifera (rapeseed) oil is one of the most consumed oil. In this study, we evaluated the possible approaches to increase rapeseed oil oxidative stability and potential health benefits by using different natural products (beetroot, broccoli, carrot, celery, green pea, onion, red pepper, spinach, swede, tomato, and yellow pea). Results clearly showed that natural products may increase the stability of rapeseed oil, particularly when within a matrix rather than as an extract or pure compound. These evidences are significant for both consumers and oil industry.

Rapeseed oil oxidative stability is investigated. Rapeseed oil composition is determined by GC‐MS. Increased antioxidant activity of rapeseed oil with powders supplementation is evidenced. Vegetable powders can offer effective alternative to synthetic antioxidants during frying and storage of rapeseed oil. Rapeseed oil oxidative stability is investigated. Rapeseed oil composition is determined by GC‐MS. Increased antioxidant activity of rapeseed oil with powders supplementation is evidenced. Vegetable powders can offer effective alternative to synthetic antioxidants during frying and storage of rapeseed oil.
Effect of Fe (III) on Pseudokirchneriella subcapitata at circumneutral pH in standard laboratory tests is explained by nutrient sequestration
Authors: Arbildua Jose J. , Villavicencio German , Urrestarazu Paola , Opazo Margaret , Brix Kevin V. , Adams William J. , Rodriguez Patricio H.
Published: September 2016

The complex chemistry of iron (Fe) at circumneutral pH in oxygenated waters and the poor correlation between ecotoxicity results in laboratory and natural waters have led to regulatory approaches for iron based on field studies (US Environmental Protection Agency Water Quality Criteria and European Union Water Framework Directive proposal for Fe). The results of the present study account for the observed differences between laboratory and field observations for Fe toxicity to algae (Pseudokirchneriella subcapitata). Results from standard 72-h assays with Fe at pH 6.3 and pH 8 resulted in similar toxicity values measured as algal biomass, with 50% effect concentrations (EC50) of 3.28 mg/L and 4.95 mg/L total Fe(III), respectively. At the end of the 72-h exposure, however, dissolved Fe concentrations were lower than 30 μg/L for all test concentrations, making a direct toxic effect of dissolved iron on algae unlikely. Analysis of nutrient concentrations in the artificial test media detected phosphorus depletion in a dose-dependent manner that correlated well with algal toxicity. Subsequent experiments adding excess phosphorus after Fe precipitation eliminated the toxicity. These results strongly suggest that observed Fe(III) toxicity on algae in laboratory conditions is a secondary effect of phosphorous depletion. Environ Toxicol Chem 2017;36:952–958. © 2016 SETAC
Assessment Capacity Building at a Research University
Authors: Stitt‐Bergh Monica
Published: September 2016

Higher education institutions use program‐level learning outcomes assessment to improve programs, enhance student learning, and meet external requirements. An assessment office at a research university used a variety of evaluation capacity‐building (ECB) activities to increase faculty and administrators’ engagement in assessment and use of findings for program improvement. To investigate six desired ECB outcomes, the author analyzed survey responses and program assessment reports (2008–2014). The findings showed success in four ECB outcomes: positive attitudes toward assessment, motivation to engage, knowledge and skills, and department climate. However, two outcomes fell below expectations: department resources and use of findings. A correlation study revealed several significant, positive relationships between outcomes and faculty engagement with the strongest relationship being between level of faculty assessment experience and knowledge and skills. Because use of findings for program improvement and better student learning are primary assessment purposes, these results are valuable for campus planning of future capacity‐building activities. New ECB efforts that focus on faculty capacity to discuss assessment with colleagues, department resources, and most important, ways to use assessment findings are planned.
Synthesis, odour characteristics and antibacterial activities of the stereoisomeric forms of whisky lactone and its thiono analogues
Authors: Shimotori Yasutaka , Hoshi Masayuki , Okabe Hayato , Miyakoshi Tetsuo , Kanamoto Taisei , Nakashima Hideki
Published: September 2016

Four stereoisomers of whisky lactone were selectively synthesized in over 99% enantiomeric excess using an amino acid derivative as a resolving agent. Cbz‐L‐proline was the most effective resolving agent, and both trans‐ and cis‐stereoisomers were comparatively easily separated. Odour characteristics of whisky thionolactone were different among four stereomeric isomers, and only (3S,4R)‐whisky thionolactone had mushroom and cis‐jasmone like note. Among all isomers, only (3R,4S)‐whisky lactone showed antibacterial activities against Staphylococcus aureus. Whisky thionolactone had higher activities than whisky lactone, and (3R,4S)‐whisky thionolactone showed the strongest activities of all tested samples. Copyright © 2016 John Wiley & Sons, Ltd.
Compression between microcontinents in the Cathaysian Block during the early Yanshanian: petrogenesis of the Tangquan pluton in Southwest Fujian Province, Southeast China
Authors: Zhao Xilin , Yu Shengyao , Mao Jianren , Liu Kai , Yu Minggang , Jiang Yang , Chen Zhihong , Hou Kejun , Peng Yinbiao
Published: September 2016

Southeast China is characterized by widespread Mesozoic igneous rocks, which have drawn a great deal of attention in recent decades because of their tectonic significance and related large‐scale mineralization. Among these igneous rocks, The Tangquan pluton in Southwest Fujian Province is the only adakitic pluton that has been discovered within the Cathaysian Block. It is mainly composed of a central unit of granodiorite with peripheral granodioritic porphyries. Two medium‐grained granodiorite samples have zircon U‐Pb ages of 162.2 ± 2.0 Ma and 163.0 ± 1.4 Ma, indicating intrusion in Middle Jurassic times. Adakite‐like geochemical features of the pluton include high Sr/Y (46.7) and (La/Yb)N(25.5) values, and low Y (12.2 ppm) and Yb (1.04 ppm) abundances. All samples have low εNd(t) values (average −9.49) and high initial87Sr/86Sr ratios (average 0.708242). These results suggest that the adakitic rocks were generated by partial melting in thickened crust. The Tangquan pluton probably formed during the extrusion collision of microcontinents within the Cathaysian Block related to subduction of the Pacific Plate, which caused crustal thickening and partial melting of Neoproterozoic crust with arc‐like magmatic characteristics. Because the extrusion collision occurred between microcontinents in an intraplate (Cathaysian Block) setting, the effects of the extrusion collision were not as strongly felt as those involved in the Jiangshan‐Shaoxing Fault along which numerous adakitic rocks were emplaced with related porphyry‐type copper deposits. Copyright © 2016 John Wiley & Sons, Ltd.
Where are the limits of model predictive capabilities?
Authors: Refsgaard J.C. , Højberg A.L. , He X. , Hansen A.L. , Rasmussen S.H. , Stisen S.
Published: September 2016

Distributed hydrological models can make predictions with much finer spatial resolution than the supporting field data. They will, however, usually not have a predictive capability at model grid scale due to limitations of data availability and uncertainty of model conceptualizations. In previous publications, we have introduced the Representative Elementary Scale (RES) concept as the theoretically minimum scale at which a model with a given conceptualization has a potential for obtaining a predictive accuracy corresponding to a given acceptable accuracy. The new RES concept has similarities to the 25‐year‐old Representative Elementary Area concept, but it differs in the sense that while Representative Elementary Area addresses similarity between subcatchments by sampling within the catchment, RES focuses on effects of data or conceptualization uncertainty by Monte Carlo simulations followed by a scale analysis. In the present paper, we extend and generalize the RES concept to a framework for assessing the minimum scale of potential predictability of a distributed model applicable also for analyses of different model structures and data availabilities. We present three examples with RES analyses and discuss our findings in relation to Beven's alternative blueprint and environmental modeling philosophy from 2002. While Beven here addresses model structural and parameter uncertainties, he does not provide a thorough methodology for assessing to which extent model predictions for variables that are not measured possess opportunities to have meaningful predictive accuracies, or whether this is impossible due to limitations in data and models. This shortcoming is addressed by the RES framework through its analysis of the relationship between aggregation scale of model results and prediction uncertainties and for considering how alternative model structures and alternative data availability affects the results. We suggest that RES analysis should be applied in all modeling studies that aim to use simulation results at spatial scales smaller than the support scale of the calibration data.
Promotion of cells to close gaps and encourage cell coverage, by radio frequency glow discharge treatment
Authors: Ali Hanan , Baier Robert E. , Dziak Rosemary , Andreana Sebastiano
Published: September 2016

Exposure of dental abutments to cleaning and sterilizing Radio Frequency Glow Discharge Treatment (RFGDT) triggered greater degrees of human gingival fibroblast (HGF) attachment and spreading over their surfaces. Enhanced cell growth and metabolic activity of such HGFs were found which might lead to improved cellular margins in the smile‐revealing "esthetic zone". This investigation, approved by the Institutional Review Board, employed in vitro studies of HGFs to support in vivo clinical applications of differentially treated titanium healing abutments to demonstrate the possible improvements for tissue growth around dental implants. Harvested commercially pure titanium (cpTi) abutments from three clinical cases per group revealed that separation of the abutments from the human gingival tissues occurred mainly intercellularly rather than directly from the tissue, suggesting that placement of an RFGDT permanent abutment would trigger tissue‐integration more completely than noted with usual alcohol‐cleaned abutments. This work confirmed and extended observations of prior studies that RFGDT materials have mitogenic effects that might be captured for stimulating desired tissue growth around implanted biomaterial appliances. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 169–177, 2017.
Relational‐Cultural Theory and Supervision: Evaluating Developmental Relational Counseling
Authors: Duffey Thelma , Haberstroh Shane , Ciepcielinski Emily , Gonzales Clarissa
Published: September 2016

This article overviews relational‐cultural theory and developmental relational counseling (DRC) and reports the results of a randomized study evaluating supervisory relational health as defined by DRC theoretical constructs. As measured by an adaptation of the Relational Health Index (Liang et al., ), counseling students enrolled in clinical courses identified clear preferences for supervisory relationships that promoted accurate relational awareness, compassion, clarity, feedback receptivity, and responsible use of power.
Everything Has Changed: An Interview With Judy Jordan
Authors: Trepal Heather , Duffey Thelma
Published: September 2016

Judy Jordan is one of the founding scholars of relational‐cultural theory (RCT). In this interview, Judy (a) gives historical and personal insight into the development of RCT, (b) describes how the theory has been received both in the United States and internationally, and (c) discusses possible future directions for RCT scholarship.
The Impact of Wellness‐Focused Supervision on Mental Health Counseling Practicum Students
Authors: Meany‐Walen Kristin K. , Davis‐Gage Darcie , Lindo Natalya A.
Published: September 2016

Professional counseling organizations tout the importance of wellness for counselors and counselors‐in‐training. The authors used a wellness‐focused supervision model with mental health practicum students to assess the model's degree of treatment effect at improving students' wellness over the course of the semester. Participants' demographics included three women, one man, three European Americans, and one Latino/a. Single‐case design results revealed that ongoing wellness‐focused interventions are helpful in improving participants' level of wellness; implications for practice are provided.
­NOD Mice Having a Lyn Tyrosine Kinase Mutation Exhibit Abnormal Neutrophil Chemotaxis
Authors: Wu Yue , Hannigan Michael , Zhan Lijun , Madri Joseph A. , Huang Chi‐Kuang
Published: September 2016

Neutrophils from NOD (Non‐Obese Diabetic) mice exhibited reduced migration speed, decreased frequency of directional changes, and loss of directionality during chemotaxis (compared to wild‐type [WT] C57BL/6 mice). Additionally, F‐actin of chemotaxing NOD neutrophils failed to orient toward the chemoattractant gradient and NOD neutrophil adhesion was impaired. A point mutation near the autophosphorylation site of Lyn in NOD mice was identified. Point mutations of G to A (G1412 in LynA and G1199 in LynB) cause a change of amino acid E393 (glutamic acid) to K (lysine) in LynA (E393→K) (E372 of LynB), affecting fMLP‐induced tyrosine phosphorylation. These data indicate that the Lyn mutation in NOD neutrophils is likely responsible for dysregulation of neutrophil adhesion and directed migration, implying the role of Lyn in modulating diabetic patient's susceptibility to bacterial and fungal infections. J. Cell. Physiol. 232: 1689–1695, 2017. © 2016 Wiley Periodicals, Inc.
How does a CC double bond cleave in the gas phase? Fragmentation of protonated ketotifen in mass spectrometry
Authors: Chai Yunfeng , Wang Lu , Wang Lin
Published: September 2016

In the literature, it is reported that the protonated ketotifen mainly undergoes CC double bond cleavage in electrospray ionization tandem mass spectrometry (ESI‐MS/MS); however, there is no explanation on the mechanism of this fragmentation reaction. Therefore, we carried out a combined experimental and theoretical study on this interesting fragmentation reaction. The fragmentation of protonated ketotifen (m/z 310) always generated a dominant fragment ion at m/z 96 in different electrospray ionization mass spectrometers (ion trap, triple quadrupole and linear trap quadrupole (LTQ)‐orbitrap). The mechanism of the generation of this product ion (m/z 96) through the CC double bond cleavage was proposed to be a sequential hydrogen migration process (including proton transfer, continuous two‐step 1,2‐hydride transfer and ion‐neutral complex‐mediated hydride transfer). This mechanism was supported by density functional theory (DFT) calculations and a deuterium labeling experiment. DFT calculations also showed that the formation of the product ion m/z 96 was most favorable in terms of energy. This study provides a reasonable explanation for the fragmentation of protonated ketotifen in ESI‐MS/MS, and the fragmentation mechanism is suitable to explain other CC double bond cleavage reactions in mass spectrometry. Copyright © 2016 John Wiley & Sons, Ltd.
The multiple conformational charge states of zinc(II) coordination by 2His‐2Cys oligopeptide investigated by ion mobility‐mass spectrometry, density functional theory and theoretical collision cross sections
Authors: Wagoner Stephanie M. , Deeconda Manogna , Cumpian Kayleah L. , Ortiz Rafael , Chinthala Swetha , Angel Laurence A.
Published: September 2016

Whether traveling wave ion mobility‐mass spectrometry (IM‐MS), B3LYP/LanL2DZ density functional theory, and ion size scaled Lennard‐Jones (LJ) collision cross sections (CCS) from the B3LYP optimized structures could be used to determine the type of Zn(II) coordination by the oligopeptide acetyl‐His1‐Cys2‐Gly3‐Pro4‐Tyr5‐His6‐Cys7 (amb5) was investigated. The IM‐MS analyses of a pH titration of molar equivalents of Zn(II):amb5 showed that both negatively and positively charged complexes formed and coordination of Zn(II) increased as the His and Cys deprotonated near their pKa values. The B3LYP method was used to generate a series of alternative coordination structures to compare with the experimental results. The method predicted that the single negatively charged complex coordinated Zn(II) in a distorted tetrahedral geometry via the 2His‐2Cys substituent groups, whereas, the double negatively charged and positively charged complexes coordinated Zn(II) via His, carbonyl oxygens and the C‐terminus. The CCS of the B3LYP complexes were calculated using the LJ method and compared with those measured by IM‐MS for the various charge state complexes. The LJ method provided CCS that agreed with five of the alternative distorted tetrahedral and trigonal bipyramidal coordinations for the doubly charged complexes, but provided CCS that were 15 to 31 Å2 larger than those measured by IM‐MS for the singly charged complexes. Collision‐induced dissociation of the Zn(II) complexes and a further pH titration study of amb5B, which included amidation of the C‐terminus, suggested that the 2His‐2Cys coordination was more significant than coordinations that included the C‐terminus. Copyright © 2016 John Wiley & Sons, Ltd.
Profiling of hydroxycinnamoylquinic acids in plant extracts using in‐source CID fragmentation
Authors: Nagy Ádám , Abrankó László
Published: September 2016

Hydroxycinnamoylquinic acids (HCQAs) are a major class of phenolic plant secondary metabolites, belonging to the chlorogenic acid family. Various health‐beneficial properties of HCQAs have been shown, which has drawn interest for HCQA profiling in plants of human consumption. However, this task remains challenging, because several isomeric HCQAs can be present in the sample with identical molecular formulae and the limited availability of reference standards poses additional challenges to their identification. In the present work, a high performance liquid chromatography–electrospray ionization–quadrupole time‐of‐flight–mass spectrometry (HPLC‐ESI‐Q/TOF‐MS) method accompanied with an effective data filtering protocol is presented, which is shown to be suitable for the identification of HCQAs in plant materials in a non‐targeted manner. Both collision‐induced dissociation (CID) fragmentation performed in a collision cell and in‐source (CID) fragmentation were used to produce accurate mass fragments. It was shown that fragmentation characteristics required for identification of regio‐isomers of HCQAs can be achieved with in‐source CID fragmentation, enabling the use of a single‐stage MS system with in‐source fragmentation for convincing identification of HCQAs. Based on a thorough validation of identified HCQA compounds using coffee bean extracts as reference samples, comprehensive profiling of HCQAs in two apricot (Prunus armeniaca L.) genotypes (‘Preventa’ and ‘Gönci magyarkajszi’) was carried out for the first time and the following 10 HCQAs were shown to be present in apricot fruit: 3‐caffeoylquinic acid (CQA), cis‐3‐CQA, 4‐CQA, 5‐CQA, cis‐5‐CQA, 3,5‐diCQA, 3‐p‐coumaroylquinic acid (pCoQA), 4‐pCoQA, 3‐feruloylquinic acid (FQA) and cis‐3‐FQA. Copyright © 2016 John Wiley & Sons, Ltd.

Highlights

An HPLC‐ESI‐Q/TOF‐MS method suitable for the identification of hydroxycinnamoyilquinic acids (HCQAs) in plant material in a non‐targeted manner was developed.

Single‐stage, high‐resolution MS system with in‐source fragmentation was shown to be suitable for convincing identification of HCQAs.

Comprehensive profiling of HCQAs in two apricot (Prunus armeniaca L.) genotypes was carried out for the first time.

Copyright © 2016 John Wiley & Sons, Ltd.