bluuebunny/crossref_metadata_2025 huggingface dataset:
Statistical analysis of ULF seismomagnetic phenomena at Kakioka, Japan, during 2001–2010
Authors: Han Peng , Hattori Katsumi , Hirokawa Maiko , Zhuang Jiancang , Chen Chieh‐Hung , Febriani Febty , Yamaguchi Hiroki , Yoshino Chie , Liu Jann‐Yenq , Yoshida Shuji
Published: May 2014

To clarify and verify the ultralow frequency (ULF) seismomagnetic phenomena, we have performed statistical studies on the geomagnetic data observed at the Kakioka (KAK) station, Japan, during 2001–2010. We investigated the energy of ULF geomagnetic signals of the frequency around 0.01 Hz using wavelet transform analysis. To minimize the influences of artificial noises and global geomagnetic perturbations, we used only the geomagnetic data observed at nighttime (LT 2:30 A.M. to 4:00 A.M.) and utilized observations from a remote station, Kanoya, as a reference. Statistical results of superposed epoch analysis have indicated that ULF magnetic anomalies are more likely to appear before sizable earthquake events (Es > 108) rather than after them, especially 6–15 days before the events. Further statistical investigations show clearly that the ULF geomagnetic anomalies at KAK station are more sensitive to larger and closer events. Finally, we have evaluated the precursory information of ULF geomagnetic signals for local sizable earthquakes using Molchan's error diagram. The probability gain is around 1.6 against a Poisson model. The above results have indicated that the ULF seismomagnetic phenomena at KAK clearly contain precursory information and have a possibility of improving the forecasting of large earthquakes.
Internal variability of North Atlantic tropical cyclones
Authors: Done James M. , Bruyère Cindy L. , Ge Ming , Jaye Abigail
Published: May 2014

Using a regional model initial condition ensemble, this study quantifies the magnitude of internal variability of North Atlantic tropical cyclone frequency for a case study year and identifies potential physical sources. For tropical cyclone formations from easterly waves, the simulated internal variability of tropical cyclone frequency for 1998 is approximately two fifths of the total (externally forced and internal) variability of observed tropical cyclone frequency. The simulated internal variability of tropical cyclone frequency is found to arise in approximately equal measure from variability of easterly wave occurrence and development and variability of the transition from incipient warm cores to tropical cyclones. Variable interaction between developing tropical cyclones and vertical wind shear associated with upper level cyclones is identified as a potentially important contributing factor to tropical cyclone internal variability.
Operating Principles
Authors: Bargende Michael , Schmidt Dietmar , Berner Hans‐Jürgen , Grill Michael
Published: May 2014

All types of internal combustion engines (ICEs) have a working chamber limited by rigid walls, with one movable wall to enable volume changes; this is usually accomplished by a piston. Power is produced by the volume change, which in turn is generated by the variable gas pressure of the working volume in the cylinder. Different strategies can be applied to manage the processes as efficiently as possible for different applications.

This chapter classifies the different working principles used in existing ICEs and also briefly describes about possible future concepts. The classification includes an overview of spark‐ and compression‐ignition combustion principles and alternative concepts such as homogeneous charge compression ignition (HCCI) combustion.

ICEs are most conveniently described and classified by way of certain characteristic design properties and performance measures, which allow for quantitative comparisons. This chapter defines the most common characteristic properties of ICEs, such as the compression ratio, the air/fuel ratio, and various efficiencies. In particular, the section on ICE efficiency provides a general formulation of efficiency that expresses all relevant efficiencies in one equation.

The chapter ends with the description of some widely used metrics specific to ICEs, including mean effective pressures, specific fuel consumption, and mean piston speed. Finally, some examples of typical engine maps and tables are given.
Photocatalytic Conversion of CO2 into Renewable Hydrocarbon Fuels: State‐of‐the‐Art Accomplishment, Challenges, and Prospects
Authors: Tu Wenguang , Zhou Yong , Zou Zhigang
Published: May 2014

Photocatalytic reduction of CO2 into hydrocarbon fuels, an artificial photosynthesis, is based on the simulation of natural photosynthesis in green plants, whereby O2 and carbohydrates are produced from H2O and CO2 using sunlight as an energy source. It couples the reductive half‐reaction of CO2 fixation with a matched oxidative half‐reaction such as water oxidation, to achieve a carbon neutral cycle, which is like killing two birds with one stone in terms of saving the environment and supplying future energy. The present review provides an overview and highlights recent state‐of‐the‐art accomplishments of overcoming the drawback of low photoconversion efficiency and selectivity through the design of highly active photocatalysts from the point of adsorption of reactants, charge separation and transport, light harvesting, and CO2 activation. It specifically includes: i) band‐structure engineering, ii) nanostructuralization, iii) surface oxygen vacancy engineering, iv) macro‐/meso‐/microporous structuralization, v) exposed facet engineering, vi) co‐catalysts, vii) the development of a Z‐scheme system. The challenges and prospects for future development of this field are also present.
Straightforward Synthesis of the Brønsted Acid hfipOSO3H and its Application for the Synthesis of Protic Ionic Liquids
Authors: Beichel Witali , Panzer Johann M. U. , Hätty Julian , Ye Xiaowei , Himmel Daniel , Krossing Ingo
Published: May 2014

The easily accessible hexafluoroisopropoxysulfuric acid (1, hfipOSO3H; hfip=C(H)(CF3)2) was synthesized by the reaction of hexafluoroisopropanol and chlorosulfonic acid on the kilogram scale and isolated in 98 % yield. The calculated gas‐phase acidity (GA) value of 1 is 58 kJ mol−1 lower in ΔG° than that of sulfuric acid (GA value determined by a CCSD(T)‐MP2 compound method). Considering the gas‐phase dissociation constant as a measure for the intrinsic molecular acid strength, a hfipOSO3H molecule is more than ten orders of magnitude more acidic than a H2SO4 molecule. The acid is a liquid at room temperature, distillable at reduced pressure, stable for more than one year in a closed vessel, reactive towards common solvents, and decomposes above 180 °C. It is a versatile compound for further applications, such as the synthesis of ammonium‐ and imidazolium‐based air‐ and moisture‐stable protic ionic liquids (pILs). Among the six synthesized ionic compounds, five are pILs with melting points below 100 °C and three of them are liquids at nearly room temperature. The conductivities and viscosities of two representative ILs were investigated in terms of Walden plots, and the pILs were found to be little associated ILs, comparable to conventional aprotic ILs.
In‐vitro‐Rekonstitution eines zellulären Phasenübergangs unter Beteiligung der mRNA‐Decapping‐Maschinerie
Authors: Fromm Simon A. , Kamenz Julia , Nöldeke Erik R. , Neu Ancilla , Zocher Georg , Sprangers Remco
Published: May 2014

In eukaryotischen Zellen können die Komponenten des 5′‐3′‐Abbaumechanismus der Boten‐RNA (mRNA) einen schnellen Phasenübergang durchlaufen. Die resultierenden zytoplasmatischen Zentren werden Processing Bodys (P‐bodys) genannt. Allerdings sind die zugrundeliegenden molekularen Details dieser Selbstaggregation weitgehend unbestimmt. Wir wenden hier eine Bottom‐up‐Methode an, um zu testen, ob mRNA‐Abbaufaktoren Phasenübergänge in vitro durchlaufen können. Dieser Ansatz umfasst NMR‐Spektroskopie, isotherme Titrationskalometrie, Röntgenkristallographie und Fluoreszenzmikroskopie. Wir zeigen, dass das Dcp2‐Decapping‐Enzym der Spalthefe Schizosaccharomyces pombe, sein Hauptaktivator Dcp1 sowie die Gerüstproteine Edc3 und Pdc1 ausreichen, um einen Phasenübergangsprozess einzuleiten. Zwischenmolekulare Wechselwirkungen zwischen der Edc3‐LSm‐Domäne und mindestens zehn helikalen, leucinreichen Motiven in Dcp2 und Pdc1 bilden den Kern des Wechselwirkungsnetzwerks. Wir zeigen, dass die Blockade dieser Wechselwirkungen das Clusteringverhalten in vitro und in vivo behindert.
Visible‐Light‐Induced Electron Transport from Small to Large Nanoparticles in Bimodal Gold Nanoparticle‐Loaded Titanium(IV) Oxide
Authors: Naya Shin‐ichi , Niwa Tadahiro , Kume Takahiro , Tada Hiroaki
Published: May 2014

A key to realizing the sustainable society is to develop highly active photocatalysts for selective organic synthesis effectively using sunlight as the energy source. Recently, metal‐oxide‐supported gold nanoparticles (NPs) have emerged as a new type of visible‐light photocatalysts driven by the excitation of localized surface plasmon resonance of Au NPs. Here we show that visible‐light irradiation (λ>430 nm) of TiO2‐supported Au NPs with a bimodal size distribution (BM‐Au/TiO2) gives rise to the long‐range (>40 nm) electron transport from about 14 small (ca. 2 nm) Au NPs to one large (ca. 9 nm) Au NP through the conduction band of TiO2. As a result of the enhancement of charge separation, BM‐Au/TiO2 exhibits a high level of visible‐light activity for the one‐step synthesis of azobenzenes from nitrobenzenes at 25 °C with a yield greater than 95 % and a selectivity greater than 99 %, whereas unimodal Au/TiO2 (UM‐Au/TiO2) is photocatalytically inactive.
Combining Photoredox‐Catalyzed Trifluoromethylation and Oxidation with DMSO: Facile Synthesis of α‐Trifluoromethylated Ketones from Aromatic Alkenes
Authors: Tomita Ren , Yasu Yusuke , Koike Takashi , Akita Munetaka
Published: May 2014

Trifluoromethylated ketones are useful building blocks for organic compounds with a trifluoromethyl group. A new and facile synthesis of ketones with a trifluoromethyl substituent in the α‐position proceeds through a one‐pot photoredox‐catalyzed trifluoromethylation–oxidation sequence of aromatic alkenes. Dimethyl sulfoxide (DMSO) serves as a key and mild oxidant under these photocatalytic conditions. Furthermore, an iridium photocatalyst, fac[Ir(ppy)3] (ppy=2‐phenylpyridine), turned out to be crucial for the present photoredox process.
Construction and DNA Condensation of Cyclodextrin‐Coated Gold Nanoparticles with Anthryl Grafts
Authors: Zhao Di , Chen Yong , Liu Yu
Published: May 2014

The condensation of DNA in a controlled manner is one of the key steps in gene delivery and gene therapy. For this purpose, a water‐soluble supramolecular nanostructure is constructed by coating 14 β‐cyclodextrins onto the surface of a gold nanoparticle, followed by the noncovalent association of different amounts of anthryl‐modified adamantanes with coated β‐cyclodextrins. The strong binding of β‐cyclodextrins with anthryl adamantanes (KS=8.61×104 M−1) efficiently stabilizes the supramolecular nanostructure. Spectrophotometric fluorescence spectra and microscopic studies demonstrated that, with many anthryl grafts that can intercalate in the outer space of the DNA double helix, this supramolecular nanostructure showed good condensation abilities to calf thymus DNA. Significantly, the condensation efficiency of supramolecular nanostructure towards DNA could be conveniently controlled by adjusting the ratio between gold nanoparticles and anthryl adamantane grafts, leading to the formation of DNA condensates of a size that are suitable for the endocytosis of hepatoma cells, which will make it potentially applicable in many fields of medicinal science and biotechnology.
Wurster’s Blue‐type Cation Radicals Framed in a 5,10‐Dihydrobenzo[a]indolo[2,3‐c]carbazole (BIC) Skeleton: Dual Electrochromism with Drastic Changes in UV/Vis/NIR and Fluorescence
Authors: Suzuki Takanori , Sakano Yuto , Tokimizu Yusuke , Miura Youhei , Katoono Ryo , Fujiwara Kenshu , Yoshioka Naoki , Fujii Nobutaka , Ohno Hiroaki
Published: May 2014

Electron‐donating dihydrobenzindolocarbazoles (BICs) 1 a–c, which adopt planar disk‐shaped geometries, were prepared by gold(I)‐catalyzed cyclization as a key step. Due to the presence of a 1,4‐phenylenediamine (PD) moiety in the framework, they undergo reversible one‐electron oxidation to the corresponding Wurster’s Blue (WB)‐type species that exhibits NIR absorptions up to λ=1200 nm. In the case of the N,N′‐dimethyl derivative, cation radical 1 c+. is stable enough to be isolated as a salt and X‐ray analysis indicated paraquinoid‐type bond alternation in the WB core unit, whereas the bond lengths in the peripheral benzene rings are identical to those in the neutral donor. Upon electrochemical interconversion, the redox pairs of 1 a–c and 1 a–c+. exhibited an electrochromic response in the UV/Vis/NIR region, which was accompanied by a drastic change in the fluorescence spectrum because only neutral donors 1 a–c are highly emissive (ΦF: 0.7–0.8).
DISCRIMINATION LEARNING IN ADULTS WITH NEUROCOGNITIVE DISORDERS
Authors: Steingrimsdottir Hanna Steinunn , Arntzen Erik
Published: May 2014

Alzheimer's disease is the most commonly known neurocognitive disorder characterized by deterioration in areas such as memory, attention, and activities of daily living. From a behavioral perspective, memory and attentional deficits may be described as deterioration of stimulus control. This paper provides a case study of discrimination behavior in a patient with neurocognitive disorder. The purpose of the current study was twofold: (i) to study the effect of using presumed familiar pictures in arbitrary matching‐to‐sample tasks and (ii) to study variables that affect stimulus control in a patient diagnosed with vascular dementia. There were 12 conditional discrimination experimental conditions with various types of stimuli, from familiar pictures to identity matching. The results showed that the participant's responses were not in accord with experimenter‐defined stimulus classes when using familiar pictures. However, intact stimulus control by sample stimulus was established following systematic procedural changes in the conditional discrimination tasks. Copyright © 2014 John Wiley & Sons, Ltd.
Analysis of 10 systemic pesticide residues in various baby foods using liquid chromatography–tandem mass spectrometry
Authors: Yang Angel , Abd El‐Aty A. M. , Park Jong‐Hyouk , Goudah Ayman , Rahman Md. Musfiqur , Do Jung‐Ah , Choi Ok‐Ja , Shim Jae‐Han
Published: May 2014

Ten systemic pesticides, comprising methomyl, thiamethoxam, acetamiprid, carbofuran, fosthiazate, metalaxyl, azoxystrobin, diethofencarb, propiconazole, and difenoconazole, were detected in 13 baby foods (cereals, boiled potatoes, fruit and milk) using QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) for sample preparation and liquid chromatography tandem mass spectrometry for analysis. The matrix‐matched calibration curves showed good linearity with determination coefficients (R2) > 0.992. The limits of detection and quantitation were 0.0015–0.003 and 0.005–0.01 mg/kg, respectively. The mean recoveries of three different concentrations ranged from 69.2 to 127.1% with relative standard deviations <20%. The method was successfully applied to 13 actual samples collected from a local market, and none of the samples were found to contain pesticide residues. This method is suitable for the identification and quantification of systemic pesticides with matrix‐matched standards in various baby foods. Copyright © 2013 John Wiley & Sons, Ltd.
Determination of anxiolytic veterinary drugs from biological fertilizer blood meal using liquid chromatography high‐resolution mass spectrometry
Authors: Choi Jeong‐Heui , Lamshöft Marc , Zühlke Sebastian , Park Jong‐Hyouk , Rahman Md. Musfiqur , El‐Aty A. M. Abd , Spiteller Michael , Shim Jae‐Han
Published: May 2014

A liquid environment‐friendly agricultural material originating from animal blood, blood meal, was employed to detect anxiolytic veterinary drugs using a combination of liquid–liquid extraction (LLE) and positive electrospray ionization Orbitrap mass spectrometry. Every positive ion of the analytes was consistent with [M + H]+, and the accurate mass analysis and mass spectral filtration with a 2‐ppm mass tolerance window were applied to identify and quantitate the analytes and metabolites. The developed LLE method was validated with the lowest calibrated level, linearity (r2), recovery, repeatability and the within‐laboratory reproducibility, which were in the ranges of 0.3–1 µg/L, 0.9963–0.9995, 48.3–117.5%, 1.1–12.6% and 2.3–15.7%, respectively. The LLE method was compared with a solid‐phase extraction (SPE) method; however, its recoveries were <70% for most of the analytes despite good repeatability of 1.2–7.4%. The analytes and the ascertained acepromazine, azaperone and xylazine metabolites were monitored in four actual liquid blood meal samples, and none of the targeted compounds were observed. Copyright © 2013 John Wiley & Sons, Ltd.
Quantitation of sulfur‐containing amino acids, homocysteine, methionine and cysteine in dried blood spot from newborn baby by HPLC‐fluorescence detection
Authors: Wada Mitsuhiro , Kuroki Mana , Minami Yuu , Ikeda Rie , Sekitani Yui , Takamura Noboru , Kawakami Shigeru , Kuroda Naotaka , Nakashima Kenichiro
Published: May 2014

Sulfur‐containing amino acids (SAAs), homocysteine (Hcy), methionine (Met) and cysteine (Cys) in blood are related to homocystinuria, an inborn error of metabolism. In this study, an assay method with HPLC‐fluorescence detection to quantify the SAAs in a dried blood spot was established and applied to samples from newborn babies (n = 200). Sample pretreatment involving reduction, derivatization with 4‐(N,N‐dimethylaminosulfonyl)‐7‐fluoro‐2,1,3‐benzoxadiazole, and liquid–liquid extraction with ethyl acetate gave the separation of the derivatives with retention times within 12 min. The method was enough sensitive to determine the SAAs in a dried blood spot with 0.04–0.14 µm as the limit of detection at a signal‐to‐noise ratio of 3. However, the absolute recoveries were very low (5.7% for Hcy, 4.6% for Cys) except for Met (105.4%) owing to inefficient recovery of Hcy and Cys from the blood matrix. Other validation parameters such as accuracy (93.5–106.2%) and intra‐ (≤9.0%) and inter‐day precisions (≤8.7%) were acceptable. The reliability of a dried blood spot as an analytical sample was estimated. Furthermore, the proposed method was successfully applied to dried blood spots prepared from newborn babies. Copyright © 2014 John Wiley & Sons, Ltd.
Recent advances in proteomics: towards the human proteome
Authors: Wang Kui , Huang Canhua , Nice Edouard
Published: May 2014

After the successful completion of the Human Genome project in 2003, the next major challenge was to understand when and where the encoded proteins were expressed, and to generate a map of the complex, interconnected pathways, networks and molecular systems (the human proteome) that, taken together, control the workings of all cells, tissues, organs and organisms. Proteomics will be fundamental for such studies. This review summarizes the key discoveries that laid down the foundations for proteomics as we now know it, and describes key recent technological advances that will undoubtedly contribute to achieving the initial goal of the Human Proteome Organization of identifying and characterizing at least one protein product and representative post‐translational modifications, single amino acid polymorphisms and splice variant isoforms from the 20,300 human protein‐coding genes within the next 10 years. Successful unraveling of the human proteome will undoubtedly improve our understanding of human biology at the cellular level and lay the foundations for improved diagnostic, prognostic, therapeutic and preventive medical outcomes as we enter the era of personalized medicine. Copyright © 2014 John Wiley & Sons, Ltd.
A dispersive liquid–liquid microextraction method based on the solidification of a floating organic drop combined with HPLC for the determination of lovastatin and simvastatin in rat urine
Authors: Zhao Longshan , Zhao Pan , Wang Linli , Ma Xiaowei , Hou Xiaohong , Li Famei
Published: May 2014

A dispersive liquid–liquid microextraction method based on solidification of floating organic drop combined with HPLC was developed for the determination of lovastatin and simvastatin in rat urine for the first time. 1‐Dodecanol and methanol were used as the extraction and disperser solvents, respectively. Several important parameters influencing the micro‐extraction efficiency were studied and systematically optimized, including the type and volume of extraction solvent and disperser solvent, extraction time, pH and salt concentration. The analytes were separated on a Kromasil C18 column at 30°C with a mobile phase of methanol and 0.2% acetic acid in water (83:17, v/v) and detected at 238 nm. Under the optimal conditions, the maximum number of enrichment factors for both analytes was 27. The linear ranges were 20.08–1004 and 20.00–1000 µg/L with the correlation coefficients ranging from 0.9990 to 0.9994 for lovastatin and simvastatin, respectively. The volume of organic solvent consumed in extraction was <0.3 mL, and the extraction time was 10 min. The newly developed environment‐friendly sample pretreatment method will be a good alternative to conventional techniques, such as solid‐phase extraction, liquid–liquid extraction and protein precipitation, for the HPLC determination of lovastatin and simvastatin in biological samples. Copyright © 2014 John Wiley & Sons, Ltd.
Determination of protein‐unbound rhynchiphylline brain distribution by microdialysis and ultra‐performance liquid chromatography with tandem mass spectrometry
Authors: Lee Chia‐Jung , Hsueh Thomas Y. , Lin Lie‐Chwen , Tsai Tung‐Hu
Published: May 2014

The stem with hook of Uncaria rhynchophylla (Chinese herbal name Gou‐Teng) is a traditional Chinese medicine that has been ethnopharmacologically used to extinguish wind and clean interior heat. Rhynchophylline (RHY), a tetracyclic oxindole alkaloid isolated from U. rhynchophylla, displays significant antineuroinflammatory effects. However, there is no evidence to indicate that rhynchophylline can cross the blood–brain barrier and be detected in the brain. In this study, an in vivo microdialysis sampling method coupled with UPLC/MS/MS was employed for the continuous simultaneous monitoring of unbound RHY in rat blood and brain. The precursor ion → product ion transition at m/z 385.2 → 160.0 for rhynchophylline was monitored. A calibration curve gave good linearity (r > 0.996) over the concentration range from 0.5 to 1000 ng/mL. The results demonstrated that rhynchophylline could be detected in the brain and plasma from 15 min to 6 h after its administration (1 or 10 mg/kg, i.v.). All the pharmacokinetic parameters of rhynchophylline in the brain and plasma were obtained. These results show that rhynchophylline can cross the blood–brain barrier and they provide useful clinical information. Copyright © 2014 John Wiley & Sons, Ltd.
Anatomical mapping of the nasal muscles and application to cosmetic surgery
Authors: Konschake Marko , Fritsch Helga
Published: May 2014

We present an anatomical mapping of the most important muscles influencing the nose, incorporating constant anatomical structures, and their spatial correlations. At our disposal were the midfaces of 18 bodies of both sexes, obtained by informed consent from body donors aged between 60 and 80 years. Macroscopically, we dissected the nasal regions of eight corpses, six midfaces were prepared according to plastination histology, four by creating plastinated slices. On their way from their periosteal origin to the edge of the skin, the muscles of the nose cross the subcutaneous adipose tissue, dividing it into superficial and deep layers. The individual muscle fibers insert into the skin directly at the reticular corium. Sometimes, they reach the border of the epidermis which represents a special arrangement of corial muscle attachments. The course of the anatomical fibers of individual nasal muscles presented macroscopically and microscopically in this study offers surgeons a detailed overview of the anatomically important muscular landmarks of the midface. Clin. Anat. 27:1178–1184, 2014. © 2014 Wiley Periodicals, Inc.
Tailoring Photoluminescence Properties in Ionic Nanoparticle Networks
Authors: Kronstein Martin , Akbarzadeh Johanna , Drechsel Christina , Peterlik Herwig , Neouze Marie‐Alexandra
Published: May 2014

To investigate the original and promising luminescence properties of ionic nanoparticle networks (INN), various material compositions were investigated. In this work, the linker used to network the silica nanoparticles was varied; numerous substituted or non‐substituted imidazolium, pyrazolium and pyridinium linkers are presented. Photoluminescence experiments on the INN hybrid materials revealed strong emission bands over a broad range in the visible region of the light spectrum. Varying the aromatic linker between the imidazolium units induced clear shifts of the emission maxima up to 100 nm, as a consequence of π–π stacking interactions. Steric hindrance and inductive effects of the substituents, introduced on the aromatic units, also strongly influenced the luminescence properties of the materials by modifying the π–π stacking between the imidazolium rings. Small and wide‐angle X‐ray scattering (SAXS, WAXS) experiments revealed a clear trend between the obtained structural parameters (short‐range order parameter and distance of the aromatic units within the hybrid material) and the luminescence quantum yields of the INN materials.
Direct Metal‐Catalyzed Regioselective Functionalization of Enamides
Authors: Gigant Nicolas , Chausset‐Boissarie Laëtitia , Gillaizeau Isabelle
Published: May 2014

Enamides are stable enamine surrogates and provide key intermediates for the synthesis of small but complex nitrogen‐containing compounds. Metal‐catalyzed regioselective functionalization of enamides provides a rapid method to synthesize useful nitrogen containing heterocycles. This review discloses the recent progress made in the development of the CH functionalization of enamides involving efficient and atom‐economical routes. Syntheses of different heterocycles are classified based on the site reactivity of enamides and key mechanistic insights are given for each transformation.
Transition‐Metal‐Ion‐Mediated Polymerization of Dopamine: Mussel‐Inspired Approach for the Facile Synthesis of Robust Transition‐Metal Nanoparticle–Graphene Hybrids
Authors: Yang Liping , Kong Junhua , Zhou Dan , Ang Jia Ming , Phua Si Lei , Yee Wu Aik , Liu Hai , Huang Yizhong , Lu Xuehong
Published: May 2014

Inspired by the high transition‐metal‐ion content in mussel glues, and the cross‐linking and mechanical reinforcement effects of some transition‐metal ions in mussel threads, high concentrations of nickel(II), cobalt(II), and manganese(II) ions have been purposely introduced into the reaction system for dopamine polymerization. Kinetics studies were conducted for the Ni2+–dopamine system to investigate the polymerization mechanism. The results show that the Ni2+ions could accelerate the assembly of dopamine oligomers in the polymerization process. Spectroscopic and electron microscopic studies reveal that the Ni2+ions are chelated with polydopamine (PDA) units, forming homogeneous Ni2+–PDA complexes. This facile one‐pot approach is utilized to construct transition‐metal‐ion–PDA complex thin coatings on graphene oxide, which can be carbonized to produce robust hybrid nanosheets with well‐dispersed metallic nickel/metallic cobalt/manganese(II) oxide nanoparticles embedded in PDA‐derived thin graphitic carbon layers. The nickel–graphene hybrid prepared by using this approach shows good catalytic properties and recyclability for the reduction ofp‐nitrophenol.
Study of the implementation of a robust MPC in a propylene/propane splitter using rigorous dynamic simulation
Authors: Hinojosa Aldo Ignacio , Odloak Darci
Published: May 2014

This work addresses the application of the Robust Infinite Horizon Model Predictive Control (RIHMPC) to a heat integrated propylene distillation system at a Petrobras refinery. The approach proposed here is tested on the rigorous dynamic simulation software (Dynsim®) that reproduces the system as a virtual plant and is able to communicate with the MPC algorithms developed in Matlab, through an Open Platform Communication (OPC) interface. The controller is based on a minimal order state‐space model that is equivalent to the system step response and considers the zone control of the outputs and optimizing targets for the inputs. The optimizing targets are obtained through the steady‐state economic optimization using the real‐time optimization package (ROMeo®1). The proposed integration approach provides convergence and stability to the closed‐loop system. The propylene distillation system is simulated with the proposed control and optimization strategies and the results show that, from the economic performance and robustness viewpoint, for this particular system, the proposed robust MPC is significantly better than the nominal IHMPC based on a single linear model obtained at the most probable operating point.
Direct In Situ Nitridation of Nanostructured Metal Oxide Deposited Semiconductor Interfaces: Tuning the Response of Reversibly Interacting Sensor Sites
Authors: Laminack William I. , Gole James L.
Published: May 2014

Metal‐oxide nanostructure‐decorated extrinsic semiconductor interfaces modified through in situ nitridation greatly expand the range of sensor interface response. Select metal‐oxide sites, deposited to an n‐type nanopore‐coated microporous interface, direct a dominant electron‐transduction process for reversible chemical sensing, which minimizes chemical‐bond formation. The oxides are modified to decrease their Lewis acidity through a weak interaction to form metal oxynitride sites. Conductometric and X‐ray photoelectron spectroscopy measurements demonstrate that in situ treatment changes the reversible interaction with the analytes NH3 and NO. The sensor range is extended, which creates a distinct new family of responses determined by the Lewis acidity/basicity of a given analyte relative to that of the nanostructures chosen to decorate the interface. The analyte response, broadened in a substantial and predictable way by nitridation, is explained by the recently developing inverse hard/soft acid/base model (IHSAB) of reversible electron transduction.
Two‐Dimensional NMR Spectroscopy with Temperature‐Sweep
Authors: Bermel Wolfgang , Dass Rupashree , Neidig Klaus‐Peter , Kazimierczuk Krzysztof
Published: May 2014

Two‐dimensional nuclear magnetic resonance (NMR) spectroscopy is useful for studying temperature‐dependent effects on molecular structure. However, experimental time is usually long, because sampling is repeated at several temperatures. A novel solution to the problem is proposed, in which signal sampling is performed in parallel to the linear temperature‐sweep.
A Discrete Cobalt Complex Obtained from a 1 D Coordination Polymer for Highly Selective Sensing of the Mercury(II) Ion
Authors: Mishra Anurag , Jo Jae‐Ho , Kim Hyunuk , Woo Sangkook , Chi Ki‐Whan
Published: May 2014

A unique structural transformation in a 1 D chain coordination network 2 is converted to a discrete compound 3 accompanied by a change in the ion‐exchange system. Remarkably, 3 produced a turn‐on fluorescence and selective sensing for Hg2+, whereas other ions, such as K+, Mg2+, Ca2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, and Cd2+, did not show any notable effects. Thus, the Hg2+‐selective fluorescent chemosensor was free from interference by competing metal ions.
Reol: R interface to the Encyclopedia of Life
Authors: Banbury Barbara L. , O'Meara Brian C.
Published: May 2014

The Encyclopedia of Life is a website that hosts information about life on Earth. Its mission is to increase awareness and understanding of living nature through a freely accessible digital source. Information is publicly available through graphical webpages (browser interface) or through an application programming interface (API). We developed Reol, an open‐source package for the R environment, which downloads data from the EOL API, searches for and extracts specific information, and builds tables with quantitative data and/or hierarchical classifications. We provide a detailed description how Reol can be used as a bridge between the R environment and the EOL API to extract quantitative or hierarchical content. It will be particularly useful for researchers who want information about taxonomic groups of interest (for example: how much information is known about flatworm species? What are the taxonomic synonyms for bird species?) or construct a taxonomic tree. Reol is a tool for researchers who wish to download and gather data from EOL or its provider pages. We provide numerous functions within R for downloading, gathering data in different forms, creating taxonomic trees, and plotting data, which work with functions already available through various packages. It joins a growing body of R packages that interact with web‐based APIs to streamline data acquisition, thereby easing the analysis of large publicly available datasets.
Assessing the rock glacier kinematics on three different timescales: a case study from the southern Swiss Alps
Authors: Scapozza Cristian , Lambiel Christophe , Bozzini Claudio , Mari Stefano , Conedera Marco
Published: May 2014

Surface temperature increases since the 1990s have often been associated with an increase in the speed of rock glaciers. Evidence of similar links on the centennial to millennial scale are, however, still lacking due to less focus to date on the medium‐ and long‐term kinematics of these landforms. In order to assess (palaeo)climatic variations in rock glacier kinematics, we analysed the movements of the Stabbio di Largario rock glacier in the southern Swiss Alps using three different timescales. The Schmidt hammer exposure‐age dating (SHD) was applied to study long‐term kinematics in order to extrapolate the minimal age of the formation of the rock glacier, which may have started its development after the Mid‐Holocene climate optimum, and to detect possible accelerations of the horizontal surface velocity during the Medieval Warm Period. Georeferentiation and orthorectification of six historical photographs of the rock glacier taken between ad 1910 and today were analysed using monoplotting to detect the rock glacier displacement on the decennial scale from the end of the Little Ice Age. Finally, differential global positioning system (dGPS) monitoring data available since ad 2009 were used to assess annual and seasonal creep rates of the rock glacier at present. Our results show a link between the periods of increase in mean air temperature on different timescales and variations in rock glacier kinematics and provide important new insights into rock glacier development and evolution on the long‐term scale. Copyright © 2014 John Wiley & Sons, Ltd.
Combined effects of bisphenol A and cadmium on growth and nitrate assimilation of soybean seedling roots
Authors: Sun Zhaoguo , Wang Lihong , Wang Qingqing , Zhou Qing , Huang Xiaohua
Published: May 2014

Bisphenol A (BPA) and cadmium (Cd) pollution exist simultaneously in many regions. However, little information is available regarding the combined effects of BPA and Cd pollution on plants. Plant roots are in direct contact with the soil, which is an important compartment of BPA and Cd. In the present study, the effects of combined BPA and Cd pollution on soybean seedling roots were evaluated in pot experiments. Combined treatment with BPA and Cd at low concentrations (1.5 mg/kg BPA and 0.2 mg/kg Cd) improved soybean seedling root growth. However, other combined BPA and Cd treatments, including combined treatment with BPA (Cd) at the low concentration and Cd (BPA) at the high concentration as well as combined treatment with BPA and Cd at the high concentration, inhibited soybean seedling root growth. The improvement or inhibition of soybean seedling root growth was greater in the combined BPA and Cd treatments than in single treatments. The effects of the combined BPA and Cd treatments on root growth resulted from changes in nitrate assimilation. In addition, the combined effects of BPA and Cd on the nitrate and ammonium contents in roots are discussed. The present research provides a basic understanding of the combined effects of BPA and Cd pollution on plant roots. Environ Toxicol Chem 2014; 33:2013–2019. © 2014 SETAC
Nanoparticulate zinc oxide as a coating material for orthopedic and dental implants
Authors: Memarzadeh Kaveh , Sharili Amir S. , Huang Jie , Rawlinson Simon C. F. , Allaker Robert P.
Published: May 2014

Orthopedic and dental implants are prone to infection. In this study, we describe a novel system using zinc oxide nanoparticles (nZnO) as a coating material to inhibit bacterial adhesion and promote osteoblast growth. Electrohydrodynamic atomisation (EHDA) was employed to deposit mixtures of nZnO and nanohydroxyapatite (nHA) onto the surface of glass substrates. Nano‐coated substrates were exposed to Staphylococcus aureus suspended in buffered saline or bovine serum to determine antimicrobial activity. Our results indicate that 100% nZnO and 75% nZnO/25% nHA composite‐coated substrates have significant antimicrobial activity. Furthermore, osteoblast function was explored by exposing cells to nZnO. UMR‐106 cells exposed to nZnO supernatants showed minimal toxicity. Similarly, MG‐63 cells cultured on nZnO substrates did not show release of TNF‐α and IL‐6 cytokines. These results were reinforced by both proliferation and differentiation studies which revealed that a substrate coated with exclusively nZnO is more efficient than composite surface coatings. Finally, electron and light microscopy, together with immunofluorescence staining, revealed that all cell types tested, including human mesenchymal cell (hMSC), were able to maintain normal cell morphology when adhered onto the surface of the nano‐coated substrates. Collectively, these findings indicate that nZnO can, on its own, provide an optimal coating for future bone implants that are both antimicrobial and biocompatible. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 103A: 981–989, 2015.
Efficient One‐Pot Solvent‐Free Synthesis of 1H‐Pyrazolo[1,2‐b]phthalazine‐5,10‐diones Catalyzed by Sulfonic Acid Functionalized Nanoporous Silica (SBA‐Pr‐SO3H)
Authors: Ziarani Ghodsi Mohammadi , Mohtasham Nina Hosseini , Badiei Alireza , Lashgari Negar
Published: May 2014

A green protocol has been developed for the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐diones by one‐pot cyclocondensation reaction of phthalhydrazide, aromatic aldehydes, and malononitrile or ethyl cyanoacetate using sulfonic acid functionalized SBA‐15 (SBA‐Pr‐SO3H) as a heterogeneous solid acid catalyst under solvent‐free conditions.
Mode Specificity, Bond Selectivity, and Product Energy Disposal in X + CH4/CHD3 (X=H, F, O(3P), Cl, and OH) Hydrogen Abstraction Reactions: Perspective from Sudden Vector Projection Model
Authors: Jiang Bin , Guo Hua
Published: May 2014

Reactions between methane and various radicals have become the workhorse in our understanding of mode specificity and bond selectivity in bimolecular reactions. In this work, the recently proposed Sudden Vector Projection (SVP) model is used to gain insight into the existing experimental and theoretical data on these reactions. The SVP model attributes mode specificity and bond selectivity to the coupling of reactant modes/bonds with the reaction coordinate at the transition state. In the sudden limit, the strength of the coupling can be simply computed by projecting the corresponding reactant normal mode vector onto that of the imaginary frequency mode at the saddle point. In addition, the SVP model can be used to predict energy disposal in the products, thanks to microscopic reversibility. It is shown that most of the mode‐specific and bond‐selective chemistry in X + CH4/CHD3 (X=H, F, O(3P), Cl, and OH) reactions can be reasonably understood with this simple model.
Doxorubicin‐Loaded Nanogel Assemblies with pH/Thermo‐triggered Payload Release for Intracellular Drug Delivery
Authors: Chiang Wen‐Hsuan , Huang Wen‐Chia , Chang Yu‐Jen , Shen Ming‐Yin , Chen Hsin‐Hung , Chern Chorng‐Shyan , Chiu Hsin‐Cheng
Published: May 2014

For improving intracellular doxorubicin (DOX) delivery, DOX‐encapsulated nanogel assemblies with pH/thermo‐responsive drug release are developed. DOX and a graft copolymer comprising acrylic acid (AAc) and 2‐methacryloyloxyethyl acrylate (MEA) units as the backbone and with poly(N‐isopropylacrylamide) (PNIPAAm) and monomethoxy poly(ethylene glycol) as the grafts at pH 7.4 and 4 °C undergo electrostatically induced co‐association into copolymer/DOX nanocomplexes. After being crosslinked by polymerization of the MEA moieties, the complex nanoconstructs exhibit a unique nanogel‐like architecture. Taking advantage of the extensive electrostatic attraction of the DOX molecules with ionized AAc residues and π–π stacking among copolymer‐bound DOX molecules, the DOX‐loaded nanogels show a relatively high payload content. With the milieu pH being reduced from 7.4 to 4.7, the drug release is appreciably promoted due to the massive disruption of ionic AAc/DOX pairings. The thermo‐evolved phase transition of the PNIPAAm grafts further accelerates drug elution, particularly at pH 4.7. In vitro characterization indicates that the DOX‐embedded nanogels endocytosed by HeLa cells can progressively release DOX within acidic organelles. As a result, the viability of cancer cells treated with DOX‐loaded nanoparticles can be further reduced by prolonging incubation time. This work demonstrates the great potential of the DOX‐loaded nanogel assemblies for effective intracellular drug delivery.

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Supramolecular Assembly of C3 Peptidic Molecules into Helical Polymers
Authors: Dai Yutang , Zhao Xin , Su Xinyan , Li Guangyu , Zhang Afang
Published: May 2014

Self‐assembly of C3 discotic molecules bearing dipeptide pendants into helical supramolecular polymers is investigated. The dipeptides are constituted from glycine and alanine with altered sequence, aiming at modulating the steric hindrance and examining the steric effects on the assembly. This steric hindrance effect is further illustrated with a dipeptide formed from glycine and valine, which carries a much larger isopropyl side unit. Their supramolecular polymerization is examined in various organic solvents and at different temperatures. The assembly morphology is directly visualized with atomic force microscopy. It is found that small changes in the dipeptide motifs in combination with solvent structure and the solution concentrations lead to different expression of the supramolecular assembly.

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Radical‐driven peptide backbone dissociation tandem mass spectrometry
Authors: Oh Han Bin , Moon Bongjin
Published: May 2014

In recent years, a number of novel tandem mass spectrometry approaches utilizing radical‐driven peptide gas‐phase fragmentation chemistry have been developed. These approaches show a peptide fragmentation pattern quite different from that of collision‐induced dissociation (CID). The peptide fragmentation features of these approaches share some in common with electron capture dissociation (ECD) or electron transfer dissociation (ETD) without the use of sophisticated equipment such as a Fourier‐transform mass spectrometer. For example, Siu and coworkers showed that CID of transition metal (ligand)‐peptide ternary complexes led to the formation of peptide radical ions through dissociative electron transfer (Chu et al., 2000. J Phys Chem B 104:3393–3397). The subsequent collisional activation of the generated radical ions resulted in a number of characteristic product ions, including a, c, x, z‐type fragments and notable side‐chain losses. Another example is the free radical initiated peptide sequencing (FRIPS) approach, in which Porter et al. and Beauchamp et al. independently introduced a free radical initiator to the primary amine group of the lysine side chain or N‐terminus of peptides (Masterson et al., 2004. J Am Chem Soc 126:720–721; Hodyss et al., 2005 J Am Chem Soc 127: 12436–12437). Photodetachment of gaseous multiply charged peptide anions (Joly et al., 2008. J Am Chem Soc 130:13832–13833) and UV photodissociation of photolabile radical precursors including a C–I bond (Ly & Julian, 2008. J Am Chem Soc 130:351–358; Ly & Julian, 2009. J Am Soc Mass Spectrom 20:1148–1158) also provide another route to generate radical ions. In this review, we provide a brief summary of recent results obtained through the radical‐driven peptide backbone dissociation tandem mass spectrometry approach. © 2014 Wiley Periodicals, Inc. Mass Spec Rev 34: 116–132, 2015.
Psychogenic Movement Disorders: Gait Is a Give‐Away!
Authors: Balint Bettina , van Winsen Lisa M.L. , Bhatia Kailash P. , Bloem Bas R.
Published: May 2014

The aim of this article is to point out that an incongruity of gait disorder (either in relation to the presenting movement disorder or incongruity with any type of organic gait disorder) is a useful clue in diagnosing psychogenic movement disorders. To illustrate this, we present a case series of patients with various types of psychogenic movement disorders (rest tremor, myoclonus, dystonia, and chorea). Incongruity of the walking pattern with the presenting movement disorder was a revealing diagnostic clue in all cases. “Incongruity” is currently a main plank in the diagnosis of psychogenic conditions. Our series emphasizes that incongruity of the gait pattern may be the most important sign in a patient where it is otherwise difficult to establish whether the movement disorder is congruous or incongruous with an organic disorder.
Val66Met polymorphism in the BDNF gene in children with bronchial asthma
Authors: Jesenak Milos , Babusikova Eva , Evinova Andrea , Banovcin Peter , Dobrota Dusan
Published: May 2014

Objectives

Bronchial asthma is a chronic respiratory disease characterized by airway inflammation. There is increasing evidence that neurotrophins play an important role in the development and maintenance of neurogenic airway inflammation in chronic allergic diseases.

Working Hypothesis

Brain‐derived neurotrophic factor (BDNF) is a member of the neurotrophin family and has several important functions in the airways. There are only a few reports on the association between genetic variations in the BDNF gene and various allergic diseases, and the results are generally conflicting. Therefore, we aimed to study the functional polymorphism Val66Met (also called rs6265 or G196A) in the BDNF gene in a group of asthmatic children and healthy controls.

Study Design, Patient‐Selection, and Methodology

We studied 248 asthmatic patients (aged 12.28 ± 0.24 years) and 249 healthy children (aged 13.14 ± 0.48 years). Analysis of the Val66Met polymorphism of the BDNF gene was performed by polymerase chain reaction (PCR) and PCR products were digested by PmlI.

Results

The prevalence of the Val66Met polymorphisms (Val/Val, Val/Met, and Met/Met) was 61.7%, 33.5%, and 4.8% in asthmatics, respectively, and 47.0%, 51.8%, and 1.2% in healthy subjects, respectively. We observed a significant association of the Met/Met variant genotype with asthmatics (OR = 4.17, 95% CI = 1.16–14.96, P = 0.018). The Val/Met genotype was protective against bronchial asthma (OR = 0.69, 95% CI = 0.48–0.99, P = 0.045), especially in girls (OR = 0.34, 95% CI = 0.20–0.59, P = 0.001).

Conclusion

Specific BDNF gene polymorphism may contribute to bronchial asthma susceptibility. Our study suggested the positive association between selected functional BDNF polymorphism (rs6265) and asthma in children. Pediatr Pulmonol. 2015; 50:631–637. © 2014 Wiley Periodicals, Inc.