bluuebunny/crossref_metadata_2025 huggingface dataset:
Model Study on Potential Contributions of the Proposed Huangpu Gate to Flood Control in Taihu Lake Basin
Authors: Zhang Hanghui , Liu Shuguang , Ye Jianchun , Yeh Pat
Published: July 2016

Abstract. The Taihu Lake basin, one of the most developed and dynamic regions, is located in the hinterland of the Yangtze River Delta, Eastern China. The largest flood in history is the 1999 flood event with a return period of 1 in 200 years, which is above the current capacity of flooding defense in the basin with a return period of 1 in 50 years. Due to its flat saucer-like terrain, the capacity of the flood control system is dependent on the flood defense infrastructure and the peripheral tidal conditions. The Huangpu River, connecting the Taihu Lake and the Yangtze River, is one of the major drains, which is strongly influenced by high tide conditions in the coastal waters of the Yangtze River. Hence, constructing an estuary gate is considered one of the effective solutions to the flooding problem in the basin. This paper aims to quantitatively analyze the potential contributions of the proposed Huangpu gate to flood control capacity of the basin under various flooding scenarios. It is concluded that the Huangpu gate is an effective mean to evacuate the floodwaters, by reducing peak levels in the upper part of the tide-affected river. Its beneficiaries include the Taihu Lake, the related surrounding areas along the Taipu Canal and the Huangpu River basin.
Validation of Terrestrial Water Storage Variations as Simulated by Different Global Numerical Models with GRACE Satellite Observations
Authors: Zhang Liangjing , Dobslaw Henryk , Stacke Tobias , Güntner Andreas , Dill Robert , Thomas Maik
Published: July 2016

Abstract. Estimates of terrestrial water storage (TWS) variations from the satellite mission GRACE are used to assess the accuracy of four global numerical model realizations that simulate the continental branch of the global water cycle. Based on four different validation metrics, we demonstrate that for the 31 largest discharge basins worldwide all model runs agree with the observations to a very limited degree only, together with large spreads among the models themselves. Since we apply a common atmospheric forcing data-set to all hydrological models considered, we conclude that those discrepancies are not entirely related to uncertainties in meteorologic input, but instead to the model structure and parametrization, and in particular to the representation of individual storage compartments with different spatial characteristics in each of the models. TWS as monitored by the GRACE mission is therefore a valuable validation data-set for global numerical simulations of the terrestrial water storage since it is sensitive to very different model physics in individual basins, which offers helpful insight to modellers for the future improvement of large-scale numerical models of the global terrestrial water cycle.
Debris flow impact estimation on a rigid barrier
Authors: Vagnon Federico , Segalini Andrea
Published: July 2016

Abstract. The aim of this paper is to analyse debris flow impact against rigid and undrained barrier in order to propose a new formulation for the estimation of acting force after the flow impact to safe design protection structures. For this reason, this work concentrates on the flow impact, by performing a series of small scale tests in a specifically created flume. Flow characteristics (flow height and velocity) and applied loads (dynamic and static) on barrier were measured using four ultrasonic devices, four load cells and a contact surface pressure gauge. The results obtained were compared with main existing models and a new equation is proposed. Furthermore, a brief review of the small scale theory was provided to analyse the scale effects that can affect the results.
Porosity and permeability determination of organic-rich Posidonia shales based on 3-D analyses by FIB-SEM microscopy
Authors: Grathoff Georg H. , Peltz Markus , Enzmann Frieder , Kaufhold Stephan
Published: July 2016

Abstract. The goal of this study is to better understand the porosity and permeability in shales to improve modelling fluid and gas flow related to shale diagenesis. Two samples (WIC and HAD) were investigated, both mid-Jurassic organic-rich Posidonia shales from Hils area, central Germany of different maturity (WIC R0 0.53 % and HAD R0 1.45 %). The method for image collection was focused ion beam (FIB) microscopy coupled with scanning electron microscopy (SEM). For image and data analysis Avizo and GeoDict was used. Porosity was calculated from segmented 3-D FIB based images and permeability was simulated by a Navier Stokes–Brinkman solver in the segmented images. Results show that the quantity and distribution of pore clusters and pores (≥  40 nm) are similar. The largest pores are located within carbonates and clay minerals, whereas the smallest pores are within the matured organic matter. Orientation of the pores calculated as pore paths showed minor directional differences between the samples. Both samples have no continuous connectivity of pore clusters along the axes in the x, y, and z direction on the scale of 10 to 20 of micrometer, but do show connectivity on the micrometer scale. The volume of organic matter in the studied volume is representative of the total organic carbon (TOC) in the samples. Organic matter does show axis connectivity in the x, y, and z directions. With increasing maturity the porosity in organic matter increases from close to 0 to more than 5 %. These pores are small and in the large organic particles have little connection to the mineral matrix. Continuous pore size distributions are compared with mercury intrusion porosimetry (MIP) data. Differences between both methods are caused by resolution limits of the FIB-SEM and by the development of small pores during the maturation of the organic matter. Calculations show no permeability when only considering visible pores due to the lack of axis connectivity. Adding the organic matter with a background permeability of 1 × 10−21 m2 to the calculations, the total permeability increased by up to 1 order of magnitude for the low mature and decreases slightly for the overmature sample from the gas window. Anisotropy of permeability was observed. Permeability coefficients increase by 1 order of magnitude if simulations are performed parallel to the bedding. Our results compare well with experimental data from the literature suggesting that upscaling may be possible in the future as soon as maturity dependent organic matter permeability coefficients can be determined.
Velar palatalization in Slovenian: Local and long-distance interactions in a derived environment effect
Authors: Jurgec Peter
Published: July 2016

Slovenian velar palatalization has been described as a morphologically and lexically restricted, variable derived environment effect. This paper presents a corpus-based study that for the first time also considers synchronic phonological factors. Much of the variation turns out to be conditioned by local and long-distance consonant co-occurrence restrictions. In terms of local interactions, palatalization invariantly applies to remove an illicit consonant cluster while being blocked when it would result in an illicit consonant cluster. The more surprising finding is that other consonants within the stem also strongly affect palatalization. Palatalization of the stem-final velar is less likely if the stem contains another velar, and palatalization is categorically blocked if the stem contains a postalveolar obstruent, at any distance from the suffix. These data constitute a previously unreported type of local derived environment effects that are blocked at a distance. This interpretation of the Slovenian data sheds a new perspective on typologically similar patterns. The local and long-distance interactions found in Slovenian are modeled within the Maximum Entropy weighted constraint framework.
Internet Shopping Behaviors of Generation Y African-American Based on Apparel Production Involvement
Authors: Seo Jung-Im
Published: July 2016

This study investigates internet shopping behaviors of Generation Y African-Americans (GYAAs), based on their levels of apparel product involvement associated with internet shopping orientations, internet situational influences, internet behavioral intentions, and previous internet shopping experiences. Data were collected from African-American college students of several universities in southeastern United States. Of the total surveys collected, 240 completed surveys were analyzed using multivariate analysis of variance (MANOVA), univariate analysis of variance (ANOVA), one-way ANOVA, chi-square, and phi-coefficient. This study attempts to understand internet shopping behaviors of GYAA. This research demonstrates that GYAAs have unique internet shopping behaviors toward on-line apparel products, showing that two involvement groups differ significantly in many ways. Internet shopping is highly attractive to high-involvement GYAA consumers due to its entertainment during their web-surfing as well as many other reasons such as its fashion-consciousness and personality rather than the reasons of convenience, expense, and familiarity, which are more sensitive to low-involvement GYAA consumers.
De voordelen en nadelen klevend aan de afschaffing van de legitieme portie
Authors: Geerlof A.M.A.
Published: July 2016

De voordelen en nadelen klevend aan de afschaffing van de legitieme portie

Na 144 jaren een prominente rol in het Curaçaose erfrecht te hebben gespeeld, is de legitieme portie op 1 januari 2012 afgeschaft. In haar masterscriptie getiteld De voordelen en nadelen klevend aan de afschaffing van de legitieme portie onderzoekt de auteur de voor- en nadelen die deze wijziging teweegbrengen. Dit artikel is een bewerking van voornoemde masterscriptie.
The dealing of SIDS with recent challenges in taxation and tax systems – will domestic resource mobilization be the key to sustainable development?
Authors: Scoop E.M.L.
Published: July 2016

The dealing of SIDS with recent challenges in taxation and tax systems – will domestic resource mobilization be the key to sustainable development?

Tax revenues are used to invest in sustainable development and economic growth in order to strengthen the effective functioning of the state, combat poverty, deliver public services and achieve other goals. This also applies to developing countries. However, developing countries and, in particular, the so-called Small Islands Development States (SIDS), including Curaçao, face many challenges in achieving these goals. SIDS additionally face other challenges because of their specific social, economic and environmental vulnerabilities. SIDS should focus on strengthening domestic resource mobilization. Despite their progress in improving tax systems, international regulations such as CRS, FATCA, BEPS have brought new challenges.
Sentado en el andén
Authors: Martínez Sánchez Francisco
Published: July 2016

En este artículo se realiza una invitación a la reflexión crítica acerca de la evolución de la Tecnología Educativa y del contexto en el que se debería desarrollar su investigación. Una reflexión que se centra sobre todo en el ámbito de la educación superior, la Universidad, como lugar natural para investigar y difundir lo que supone la incorporación de estas tecnologías en la enseñanza y por extensión en la sociedad. Observar desde el andén, como las TIC han logrado situarse como una especialidad en sí mismas creando un distanciamiento de la Tecnología Educativa, dejando tras de sí un empobrecimiento conceptual y de justificación pedagógica de aquellas dentro de la acción didáctica.
Competencia digital y competencia digital docente: una panorámica sobre el estado de la cuestión
Authors: Gisbert Cervera Mercè , González Martínez Juan , Esteve Mon Francesc Marc
Published: July 2016

La investigación en Tecnología Educativa ha venido desarrollando en los últimos años los conceptos de competencia digital del estudiante y competencia digital docente. El primero tiene que ver con las capacidades necesarias para aprender en la Sociedad de la Información; el segundo, con la necesidad de ser competente en el uso de la tecnología educativa como docente. En relación con ambos conceptos, la investigación aplicada ha avanzado considerablemente en nuestro contexto. Detallamos los principales hitos hasta la fecha: conceptualizaciones, diseño de instrumentos de diagnóstico, desarrollo de rúbricas de evaluación y exploración de posibilidades 3D para el desarrollo de las competencias. Y, por último, se abordan las principales líneas de investigación que deben desarrollarse en el futuro de forma preferente.
GaInN-based tunnel junctions with graded layers
Authors: Takasuka Daiki , Akatsuka Yasuto , Ino Masataka , Koide Norikatsu , Takeuchi Tetsuya , Iwaya Motoaki , Kamiyama Satoshi , Akasaki Isamu
Published: July 2016

We demonstrated low-resistivity GaInN-based tunnel junctions using graded GaInN layers. A systematic investigation of the samples grown by metalorganic vapor phase epitaxy revealed that a tunnel junction consisting of a 4 nm both-sides graded GaInN layer (Mg: 1 × 1020 cm−3) and a 2 nm GaN layer (Si: 7 × 1020 cm−3) showed the lowest specific series resistance of 2.3 × 10−4 Ω cm2 at 3 kA/cm2 in our experiment. The InN mole fraction in the 4 nm both-sides graded GaInN layer was changed from 0 through 0.4 to 0. The obtained resistance is comparable to those of standard p-contacts with Ni/Au and MBE-grown tunnel junctions.
Comparison between power-law rheological parameters of living cells in frequency and time domains measured by atomic force microscopy
Authors: Takahashi Ryosuke , Okajima Takaharu
Published: July 2016

We investigated how stress relaxation mapping is quantified compared with the force modulation mapping of confluent epithelial cells using atomic force microscopy (AFM). Using a multi-frequency AFM technique, we estimated the power-law rheological behaviors of cells simultaneously in time and frequency domains. When the power-law exponent α was low (<0.1), the α values were almost the same in time and frequency domains. On the other hand, we found that at the high values (α > 0.1), α in the time domain was underestimated relative to that in the frequency domain, and the difference increased with α, whereas the cell modulus was overestimated in the time domain. These results indicate that power-law rheological parameters estimated by stress relaxation are sensitive to lag time during initial indentation, which is inevitable in time-domain AFM experiments.
Optical refractive index biosensor using evanescently coupled lateral Bragg gratings on silicon-on-insulator
Authors: Mendez-Astudillo Manuel , Takahisa Hiroki , Okayama Hideaki , Nakajima Hirochika
Published: July 2016

In this paper, we present a compact silicon-on-insulator optical biosensor based on lateral Bragg gratings evanescently coupled to a waveguide. The device is fabricated by electron-beam lithography and dry-etched in a single step with inductive coupled plasma reactive ion etching (ICP-RIE). Fully etched grating couplers are used to couple the light in and out of the chip, while lateral Bragg gratings are used as the sensing element of the device. A sensitivity of 22 nm/RIU is obtained by exposing the device to deionized water with different NaCl concentrations with a footprint area of 15 × 4 µm2 that allows for densely multiplexed solutions.
Oceanic teleconnection for carbon dioxide
Authors: Ito Takamitsu
Published: July 2016

Biogeochemical teleconnection links seemingly unrelated chemical/biological anomalies that are geographically separated by large distances. Bronselaer et al. propose a new mechanism for an interhemispheric teleconnection of air‐sea carbon dioxide fluxes in which the upwelling of the Southern Ocean triggers a series of perturbations leading to the alteration of the carbon uptake in the North Atlantic.
Imaging the plate boundary between Greenland and North America within the Kane Basin by means of geophysical data
Authors: Ehrhardt Axel , Schnabel Michael , Damm Volkmar , Piepjohn Karsten
Published: July 2016

The Nares Strait is a waterway separating NW Greenland and North America. The nature of the Nares Strait has been subject of discussion for decades, especially if it represents a transform fault that compensated the opening of the Baffin Bay in the Paleogene as Alfred Wegener supposed in 1912. The Kane Basin in the central part of Nares Strait provides an opportunity to cross the proposed fault. Geophysical data were acquired in 2001 and 2010, including among others multichannel and wide‐angle seismic data. The eastern part of the Kane Basin is characterized by a solid platform most likely representing a continuation of the Paleoproterozoic Inglefield‐Mobile‐Belt (Greenland). In the western part, a sedimentary basin with northwestward tilted and eroded layers of Cretaceous age can be resolved. The transition between those two units shows the plate boundary between Greenland and North America and can be considered as a relic of the Wegener Fault.
Reconciling observed and modeled temperature and precipitation trends over Europe by adjusting for circulation variability
Authors: Saffioti Claudio , Fischer Erich M. , Scherrer Simon C. , Knutti Reto
Published: July 2016

Europe experienced a pronounced winter cooling of about −0.37°C/decade in the period 1989–2012, in contrast to the strong warming simulated by the Coupled Model Intercomparison Project Phase 5 multimodel average during the same period. Even more pronounced discrepancies between observed and simulated short‐term trends are found at the local scale, e.g., a strong winter cooling over Switzerland and a pronounced reduction in precipitation along the coast of Norway. We show that monthly sea level pressure variability accounts for much of the short‐term variations of temperature over most of the domain and of precipitation in certain regions. Removing the effect of atmospheric circulation through a regression approach reconciles the observed temperature trends over Europe and Switzerland and the precipitation trend along the coast of Norway with the corresponding multimodel mean trends.
On the 630 nm red‐line pulsating aurora: Red‐line Emission Geospace Observatory observations and model simulations
Authors: Liang Jun , Donovan E. , Jackel B. , Spanswick E. , Gillies M.
Published: July 2016

In this study, we present observations of red‐line (630 nm) pulsating auroras using the camera system of Red‐line Emission Geospace Observatory (REGO), during a geomagnetic storm interval. We also develop a time‐dependent model to simulate the 630 nm auroral pulsations in response to modulated precipitation inputs and compare the model outputs with REGO observations. Key results are as follows. (1) Notwithstanding the long radiative timescale of the 630 nm emission, red‐line auroras can still be modulated by pulsating electron precipitations and feature noticeable oscillations, which constitute the red‐line pulsating auroral phenomena. (2) In a majority of cases, the oscillation magnitude of red‐line pulsating auroras is substantially smaller than that of the concurrent pulsating auroras seen on Thermal Emission Imaging System whitelight images (generally dominated by 557.7 nm green‐line emissions). Under certain circumstances, e.g., when the characteristic energy of the precipitation is very high, some of the pulsating auroras may not show discernible imprints on red line. (3) The altitude range contributing most to the red‐line pulsating aurora is systematically lower than that of the steady‐state red‐line aurora, since the slower O(1D) loss rate at higher altitudes tends to suppress the oscillation range of the 630 nm emission rate. (4) We find that some pulsating auroral patches are characterized by enhanced red‐to‐green color ratio during their on time, hinting that the percentage increase of the red‐line auroral component exceeds that of the green‐line auroral component for those patches. We suggest that those special patches might possibly be associated with lower energy (<1 keV) electron precipitations.
Glucosylsphingosine is a key biomarker of Gaucher disease
Authors: Murugesan Vagishwari , Chuang Wei‐Lien , Liu Jun , Lischuk Andrew , Kacena Katherine , Lin Haiqun , Pastores Gregory M. , Yang Ruhua , Keutzer Joan , Zhang Kate , Mistry Pramod K.
Published: July 2016

Gaucher disease (GD) involves the accumulation of glucosylceramide (GL1) and its deacylated lysolipid, glucosylsphingosine (lyso‐GL1) which is implicated in mediating immune dysregulation and skeletal disease. The aim of our study was to assess plasma Lyso‐GL1 as a biomarker of GD and its response to therapy.

Plasma lyso‐GL1 in 169 patients with GD type 1 (GD1) was measured by LC‐MS/MS. Significant predictors of plasma LGL1 were assessed by Pearson's correlation coefficient, Wilcoxon Mann Whitney test and multiple linear regression. Propensity scores were used to match patients on treatment mode: Enzyme Replacement Therapy (ERT) vs. Eliglustat Tartrate SRT (ELI‐SRT).

Plasma Lyso‐GL1 levels in healthy controls averaged 1.5 ng/ml (1.3–1.7; 95% CI). In untreated GD patients, the levels were massively elevated (180.9 ng/ml: 95% CI, 145.4–216.5) and imiglucerase ERT resulted in marked reduction (89 ng/ml: 95% CI, 69.2–129.4) (P < 0.001). Lyso‐GL1 correlated with chitotriosidase (r = 0.59 P < 0.001), CCL18 (r = 0.62 P <0.001), hepatomegaly (r = 0.28 P < 0.001), splenomegaly (r = 0.27 P = 0.003), splenectomy (P = 0.01) and treatment mode (P < 0.001). By multiple linear regression, the strongest predictors of lyso‐GL1 were age (P < 0.001), splenectomy (P = 0.02), Chitotriosidase (P < 0.001) and CCL18 levels (P = 0.001). After propensity score matching to obtain comparable groups of patients on ERT vs ELI‐SRT, lyso‐GL1 levels were lower among patients receiving ELI‐SRT by 113 ng/ml (95% CI: 136–90.3 ng/ml P < 0.001).

Plasma lyso‐GL1 is a key biomarker of GD. ERT reduced lyso‐GL1 levels. By propensity scoring, ELI‐SRT resulted in greater reduction of lyso‐GL1 than ERT. Am. J. Hematol. 91:1082–1089, 2016. © 2016 Wiley Periodicals, Inc.
Hocheffiziente Synthese von multiantennären “bisected” N‐Glycanen über Imidate
Authors: Mönnich Manuel , Eller Steffen , Karagiannis Theodoros , Perkams Lukas , Luber Thomas , Ott Dimitri , Niemietz Mathäus , Hoffman Joanna , Walcher Janika , Berger Lukas , Pischl Matthias , Weishaupt Markus , Wirkner Cathrin , Lichtenstein Rachel G. , Unverzagt Carlo
Published: July 2016

Die Gegenwart von N‐Glycanen mit einer bisecting GlcNAc‐Modifikation auf Glycoproteinen hat viele Auswirkungen in der Entwicklungs‐ und Immunbiologie. Allerdings ist es schwierig diese N‐Glycane aus der Natur oder durch Synthese zu erhalten. Für bisected N‐Glycane des komplexen Typs haben wir eine flexible und allgemeine Synthesemethode entwickelt, die auf modularen TFAc‐geschützten Donoren für alle Antennen basiert. Die TFAc‐geschützten N‐Glycane sind besonders geeignet für die späte Einführung eines bisecting GlcNAc‐Rests. Damit können erstmals gleichzeitig multiantennäre N‐Glycane und ihre bisected Derivate durch einen einzigen Syntheseweg erhalten werden. Dies gelingt sequentiell mit Imidatdonoren in beispiellosen Ausbeuten und sogar durch eine Eintopf‐Doppelglycosylierung. Mit der neuen Methode können die seltenen bisected N‐Glycane einfach erhalten werden und damit zur Aufklärung der biologischen Rollen von bisecting GlcNAc‐Modifikationen bereitgestellt werden.
An Epigenetics‐Inspired DNA‐Based Data Storage System
Authors: Mayer Clemens , McInroy Gordon R. , Murat Pierre , Van Delft Pieter , Balasubramanian Shankar
Published: July 2016

Biopolymers are an attractive alternative to store and circulate information. DNA, for example, combines remarkable longevity with high data storage densities and has been demonstrated as a means for preserving digital information. Inspired by the dynamic, biological regulation of (epi)genetic information, we herein present how binary data can undergo controlled changes when encoded in synthetic DNA strands. By exploiting differential kinetics of hydrolytic deamination reactions of cytosine and its naturally occurring derivatives, we demonstrate how multiple layers of information can be stored in a single DNA template. Moreover, we show that controlled redox reactions allow for interconversion of these DNA‐encoded layers of information. Overall, such interlacing of multiple messages on synthetic DNA libraries showcases the potential of chemical reactions to manipulate digital information on (bio)polymers.
Oxidation resistance and abrasive wear resistance of vitamin E stabilized radiation crosslinked ultra‐high molecular weight polyethylene
Authors: Bellare Anuj , D'angelo Fabio , Ngo Hung D , Thornhill Thomas S.
Published: July 2016

The effect of gamma radiation on the oxidation and wear resistance of ultra‐high molecular weight polyethylene (UHMWPE) has been extensively studied since these properties are critical for the longevity of UHMWPE components of total joint replacement prostheses. While gamma radiation increases wear resistance of UHMWPE, the free radical generated in the lamellar regions by radiation must be stabilized before oxidative degradation occurs as the polymer ages. Initially, post‐radiation melting conducted to quench free radicals but this treatment also decreases its mechanical properties. Recently, it has been replaced by incorporation of Vitamin E into UHMWPE to combat oxidative degradation. In this study, we assessed wear resistance of Vitamin E stabilized UHMWPE under abrasive wear conditions and oxidation resistance by shelf‐aging irradiated components for 2 years. Equilibrium swelling experiments showed that Vitamin E decreased crosslink density, which affected wear resistance, but oxidation resistance was better preserved with increasing concentration of Vitamin E. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44125.
Acoustical, thermal, and morphological properties of zein reinforced oil palm empty fruit bunch fiber bio‐composites
Authors: Jayamani Elammaran , Hamdan Sinin , Kok Heng Soon , Rahman Md Rezaur , Bin Bakri Muhammad Khusairy
Published: July 2016

In this research, biodegradable composites were prepared with zein as a polymer matrix and oil palm empty fruit bunch (OPEFB) as fiber reinforcement. The fibers were treated with sodium hydroxide (NaOH). The effects of sodium hydroxide treatment on sound absorption, thermal stability, and fiber‐polymer matrix interaction in composites were examined. The acoustical sound absorption coefficients of the composites were evaluated using two‐microphone transfer function impedance tube method. The spectral, thermal, and morphological studies of the composites were analyzed and characterized using scanning electron microscope (SEM), thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) spectroscopy. It was found that in all the biodegradable composites, the sound absorption coefficients increased as the frequency increased. Increases in fiber loading caused sound absorption coefficients of the composites to increase. The sodium hydroxide treatment showed a better interface adhesion on fiber and zein matrix. It was also found that this treatment increased the sound absorption coefficients. This was supported by qualitative analysis on the SEM micrographs and FTIR spectrum. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44164.
Fractional Order Modeling And Nonlinear Fractional Order Pi‐Type Control For PMLSM System
Authors: Song Bao , Zheng Shiqi , Tang Xiaoqi , Qiao Wenjun
Published: July 2016

In this paper, firstly a fractional order (FO) model is proposed for the speed control of a permanent magnet linear synchronous motor (PMLSM) servo system. To identify the parameters of the FO model, a practical modeling algorithm is presented. The algorithm is based on a pattern search method and its effectiveness is verified by real experimental results. Second, a new fractional order proportional integral type controller, that is, (PIμ)λ or FO[FOPI], is introduced. Then a tuning methodology is presented for the FO[FOPI] controller. In this tuning method, the controller is designed to satisfy four design specifications: stability requirement, specified gain crossover frequency, specified phase margin, flat phase constraint, and minimum integral absolute error. Both set point tracking and load disturbance rejection cases are considered. The advantages of the tuning method are that it fully considers the stability requirement and avoids solving a complex nonlinear optimization problem. Simulations are conducted to verify the effectiveness of the proposed FO[FOPI] controller over classical FOPI and FO[PI] controllers.
A Density Functional Theory Study of Side Chains Effects on the Intermolecular Interactions and Electronic Structures of Small Molecular Acceptors for Organic Photovoltaics
Authors: Ko Eunji , Kim Dongwook
Published: July 2016

Diketopyrolopyrole‐thiophene‐phenyl (DPPT‐Ph)‐based small acceptor molecules for organic photovoltaics application were investigated at density functional theory (DFT) level using ω
B97X‐D functional and 6‐31G(d) basis sets: Acceptor molecules include DPPT‐Ph and its cyanide analogs, o‐, m‐, and p‐DPPT‐PhCN molecules with either methyl or 2‐ethylhexyl groups attached on DPP unit. With methyl side chains, acceptor molecules form π‐stacked dimers, i.e., syn‐ and anti‐cofacial configurations. Strong π–π interactions between backbone of acceptor molecules in such dimers, however, turned out not to alter absorption spectra dramatically with respect to those of single molecule due to the negligible intensity of peaks pointing to the lowest‐lying excited states. On the other hand, the disruption of π–π interactions induced by the presence of side chains, albeit alleviates peak‐splitting, notably intensifies such peaks at the cost of intensity reduction of the most prominent neighboring peak. Our results place significant emphasis on the importance of the manipulation of side chain to improve the device performance of organic photovoltaics.
Artemisia arborescens Essential Oil Composition, Enantiomeric Distribution, and Antimicrobial Activity from Different Wild Populations from the Mediterranean Area
Authors: Said Mohammed El‐Amin , Militello Marcello , Saia Sergio , Settanni Luca , Aleo Aurora , Mammina Caterina , Bombarda Isabelle , Vanloot Pierre , Roussel Christian , Dupuy Nathalie
Published: July 2016

Aerial parts of Artemisia arborescens were collected from different sites of the Mediterranean area (southwestern Algeria and southern Italy) and the chemical composition of their essential oil (EO) extracted by hydrodistillation was studied by both gas chromatography (GC) equipped with an enantioselective capillary column and GC/mass spectrometry (GC/MS). The EOs obtained were tested against several Listeria monocytogenes strains. Using GC and GC/MS, 41 compounds were identified, accounting for 96.0 – 98.8% of the total EO. All EOs showed a similar terpene profile, which was rich in chamazulene, β‐thujone, and camphor. However, the concentration of such compounds varied among the EOs. A. arborescens EO inhibited up to 83.3% of the L. monocytogenes strains, but the inhibitory spectrum varied among the EOs, with those from Algeria showing a higher inhibition degree than the Italian EOs. Such effect likely depended on the ketone (β‐thujone + camphor) content of the EO. The differences in the EO composition support the hypothesis that A. arborescens has at least two different chemotypes: a β‐thujone and a chamazulene type. The EO inhibitory spectrum indicates the A. arborescens EO as a valuable option in the control of the food‐borne pathogens.
Further Thymol Derivatives from Ageratina cylindrica
Authors: Bustos‐Brito Celia , Esquivel Baldomero , Calzada Fernando , Yepez‐Mulia Lilian , Calderón José S. , Porras‐Ramirez Javier , Quijano Leovigildo
Published: July 2016

From the leaves of Ageratina cylindrica, in addition to the described [(2S)‐2‐{4‐formyl‐5‐hydroxy‐2‐[(2‐methylpropanoyl)oxy]phenyl}oxiran‐2‐yl]methyl benzoate (cylindrinol A, 8), seven new thymol derivatives were isolated and named cylindrinols B – H (1 – 7). The structures of these compounds were established as (2‐{4‐(hydroxymethyl)‐2‐[(2‐methylpropanoyl)oxy]phenyl}oxiran‐2‐yl)methyl benzoate (1), (2‐{4‐formyl‐2‐[(2‐methylpropanoyl)oxy]phenyl}oxiran‐2‐yl)methyl benzoate (2), (2‐{4‐[(acetyloxy)methyl]‐2‐[(2‐methylpropanoyl)oxy]phenyl}oxiran‐2‐yl)methyl benzoate (3), [2‐(2‐[(2‐methylpropanoyl)oxy]‐4‐{[(2‐methylpropanoyl)oxy]methyl}phenyl)oxiran‐2‐yl]methyl benzoate (4), [2‐(5‐hydroxy‐2‐[(2‐methylpropanoyl)oxy]‐4‐{[(2‐methylpropanoyl)oxy]methyl}phenyl)oxiran‐2‐yl]methyl benzoate (5), 2‐{4‐(hydroxymethyl)‐2‐[(2‐methylpropanoyl)oxy]phenyl}prop‐2‐en‐1‐yl benzoate (6), and 2‐hydroxy‐2‐[2‐hydroxy‐4‐(hydroxymethyl)‐phenyl]‐3‐[(2‐methylpropanoyl)oxy]propyl benzoate (7), by spectroscopic means. Compounds 1 showed moderate antiprotozoal activity on both protozoa. Compounds 4 and 5 showed selectivity on Giardia lamblia trophozoites. All isolated compounds were less active than two antiprotozoal drugs, metronidazole and emetine, used as positive controls. Compound 5 exhibited a high inhibitory effect on hyperpropulsive movement of the small intestine in rats; its effect was best than loperamide, antidiarrheal drug used as a positive control.
Chemometric Tools to Highlight the Variability of the Chemical Composition and Yield of Lebanese Origanum syriacum L. Essential Oil
Authors: Zgheib Raviella , Chaillou Sylvain , Ouaini Naim , Kassouf Amine , Rutledge Douglas , El Azzi Desiree , El Beyrouthy Marc
Published: July 2016

This study deals with the variation in the yield and composition of Lebanese Origanum syriacum L. essential oil (EO) according to harvesting time, drying methods used, and geographical location. Plant material was harvested twice a month all over 2013 and 2014 from Qartaba and Achkout located at high altitude and from Byblos at low altitude. EOs of the aerial parts were obtained by hydrodistillation. The highest yields were obtained at full flowering stage and slightly reduced after flowering. The GC/MS analysis revealed the presence of 50 components representing 90.49 – 99.82%, 88.79 – 100%, and 95.28 – 100% of the total oil extracted from plants harvested from Qartaba, Achkout, and Byblos, respectively. The major components in the oils were: carvacrol (2.1 – 79.8%), thymol (0.3 – 83.7%), p‐cymene (2.8 – 43.8%), thymoquinone (0.4 – 27.7%), γ‐terpinene (0.4 – 10.0%), octan‐3‐ol (0.3 – 4.9%), caryophyllene oxide (0.2 – 4.7%), oct‐1‐en‐3‐ol (0.3 – 3.7%), β‐caryophyllene (0.7 – 3.2%), cis‐sabinene hydrate (0.1 – 2.8%), terpinen‐4‐ol (0.1 – 2.8%), and α‐terpinene (0.2 – 2.2%). Independent components analysis (ICA) revealed that two groups were discriminated, reflecting compositional differences in the EOs profiles of the Lebanese oregano samples: O. syriacum grown in Qartaba and Achkout belongs to carvacrol chemotype, while O. syriacum grown in Byblos belongs to thymol chemotype. The flowering phase was the most productive period in terms of yield, bringing marked changes in the EO composition by increasing the amounts of carvacrol or thymol, and decreasing those of thymoquinone and p‐cymene.
Secondary Metabolites, Glandular Trichomes and Biological Activity of Sideritis montana L. subsp. montana from Central Italy
Authors: Venditti Alessandro , Bianco Armandodoriano , Frezza Claudio , Serafini Mauro , Giacomello Ginevra , Giuliani Claudia , Bramucci Massimo , Quassinti Luana , Lupidi Giulio , Lucarini Domenico , Papa Fabrizio , Maggi Filippo
Published: July 2016

Sideritis montana subsp. montana is a small annual herb occurring in countries bordering the Mediterranean and Balkan regions. The secondary metabolism of this plant has not been fully explored so far. The aim of the present study was to understand the complex mixture of secondary metabolites and the type of secretory structures. The polar constituents were isolated by column chromatography from the ethanolic extract, and their structure was elucidated by NMR and MS. The essential oil was isolated by hydrodistillation and analysed by GC/MS. The plant indumentum was studied by light and scanning electron microscopy. To complete the work, the essential oil antioxidant activity and cytotoxicity on tumor cells were evaluated by DPPH, ABTS, FRAP, and MTT methods. Four different classes of secondary metabolites were isolated, namely flavonoids, caffeoylquinic derivatives, glycosidic hydroquinones and iridoids. The essential oil was mainly characterized by sesquiterpenene hydrocarbons. Peltate and long‐capitate hairs were the main sites where terpenes and polar constituents are produced. The secondary metabolites found in S. montana subsp. montana are of chemotaxonomic interest, some of them being typical of the genus Sideritis. The trichomes types observed partially differ from those described in other members of the genus Sideritis. The essential oil showed noteworthy inhibition on tumor cells.
Chemical Variability and Biological Activities of Essential Oils of Micromeria inodora (Desf.) Benth. from Algeria
Authors: Benomari Fatima Zahra , Djabou Nassim , Medbouhi Ali , Khadir Abdelmounaim , Bendahou Mourad , Selles Chaouki , Desjobert Jean‐Marie , Costa Jean , Muselli Alain
Published: July 2016

The chemical composition of the essential oils isolated from the aerial parts of Micromeria inodora (Desf.) Benth. collected in 24 Algerian localities was investigated from the first time using GC‐FID, GC/MS and 13C‐NMR. Altogether, 83 components which accounted for 94.7% of the total oil composition were identified. The main compounds were trans‐sesquisabinene hydrate (1; 20.9%), α‐terpinyl acetate (2; 19.8%), globulol (3; 4.9%), caryophyllene oxide (4; 4.3%), β‐bisabolol (5; 2.9%) and trans‐7‐epi‐sesquisabinene hydrate (6; 2.6%). Comparison with the literature highlighted the originality of the Algerian M. inodora oil and indicated that 1 might be used as taxonomical marker. The study of the chemical variability allowed the discrimination of two main clusters confirming that there is a relation between the essential‐oil compositions and the soil nature of the harvest locations. Biological activity of M. inodora essential oil was assessed against fourteen species of microorganisms involved in nosocomial infections using paper disc diffusion and dilution agar assays. The in vitro study demonstrated a good activity against Gram‐positive strains such as Staphylococcus aureus, Bacillus cereus, Bacillus subtilis, and Enterococcus faecalis, and moderate activity against Candida albicans. These results might be useful for the future commercial valorization of M. inodora essential oil as a promising source of natural products with potential against various nosocomial community and toxinic infections.
Antifungal Monoterpene Derivatives from the Plant Endophytic Fungus Pestalotiopsis foedan
Authors: Xu Dan , Zhang Bing‐Yang , Yang Xiao‐Long
Published: July 2016

A new monoterpene lactone, (1R,4R,5R,8S)‐8‐hydroxy‐4,8‐dimethyl‐2‐oxabicyclo[3.3.1]nonan‐3‐one (1), along with one related known compound, (2R)‐2‐[(1R)‐4‐methylcyclohex‐3‐en‐1‐yl]propanoic acid (2), were isolated from the liquid culture of the plant endophytic fungus Pestalotiopsis foedan obtained from the branch of Bruguiera sexangula. The structure and absolute configuration of 1 were determined on the basis of extensive analysis of NMR spectra combined with computational methods via calculation of the optical rotation (OR) and 13C‐NMR. Both compounds exhibited strong antifungal activities against Botrytis cinerea and Phytophthora nicotianae with MIC values of 3.1 and 6.3 μg/ml, respectively, which are comparable to those of the known antifungal drug ketoconazole. Compound 2 also showed modest antifungal activity against Candida albicans with a MIC value of 50 μg/ml.
The Generation and Exploitation of Protein Mutability Landscapes for Enzyme Engineering
Authors: van der Meer Jan‐Ytzen , Biewenga Lieuwe , Poelarends Gerrit J.
Published: July 2016

The increasing number of enzyme applications in chemical synthesis calls for new engineering methods to develop the biocatalysts of the future. An interesting concept in enzyme engineering is the generation of large‐scale mutational data in order to chart protein mutability landscapes. These landscapes allow the important discrimination between beneficial mutations and those that are neutral or detrimental, thus providing detailed insight into sequence–function relationships. As such, mutability landscapes are a powerful tool with which to identify functional hotspots at any place in the amino acid sequence of an enzyme. These hotspots can be used as targets for combinatorial mutagenesis to yield superior enzymes with improved catalytic properties, stability, or even new enzymatic activities. The generation of mutability landscapes for multiple properties of one enzyme provides the exciting opportunity to select mutations that are beneficial either for one or for several of these properties. This review presents an overview of the recent advances in the construction of mutability landscapes and discusses their importance for enzyme engineering.
Reduced Graphene Oxide as a Metal‐Free Catalyst for the Light‐Assisted Fenton‐Like Reaction
Authors: Espinosa Juan C. , Navalón Sergio , Álvaro Mercedes , García Hermenegildo
Published: July 2016

Natural sunlight irradiation increases the catalytic activity of reduced graphene oxide (rGO) as metal‐free Fenton‐like catalyst for phenol degradation. Generation of hydroxyl radical intermediates was confirmed by EPR spectroscopy using a spin‐trapping agent.
Copper‐Catalyzed Skeletal Rearrangement of O‐Propargyl Oximes: A Mechanistic Manifold
Authors: González Comesaña Marta , Nieto Faza Olalla , Cid María Magdalena , Silva López Carlos
Published: July 2016

The Cu‐mediated skeletal rearrangement of O‐propargyl oximes features a mechanistic manifold that yields different compounds. Strategic modification of the substituent at the oxime moiety (R3) allows the selection of a preferred mechanistic route that leads to azete oxides/amidodienes (if R3 is an electron‐poor/‐rich aryl group) or to pyridine N‐oxides (if R3 is an olefin). In the present work, we explore the mechanism that leads to each product. All the computed mechanisms have in common an initial stepwise 2,3‐rearrangement that generates the key N‐allenylnitrone intermediate the further reactivity of which will depend on the nature of the R3 substituent. Our calculations reveal the subtle details that govern the different behavior of this reaction with each of the aforementioned substituents and disclose a complex and multistep pathway to different aminodienes.
Extraction of Anthocyanins Using a Laboratory Robot and Innovative Extraction Technologies
Authors: Bachtler Simone , Bart Hans‐Jörg
Published: July 2016

Solid‐liquid extraction using a laboratory robot, where anthocyanins are leached from dried red vine leaves, is evaluated with respect to precision and accuracy. The solid handling of the robot results in standard deviations between ± 0.6 and ± 1.8 depending on the particle size. For liquid handling the standard deviations are slightly higher depending on the volatility of the solvents. The validated, fully automated natural plant extraction robot achieves varying yields based on dry matter for methanol, water, and ethanol which are improved with increasing particle size. Manually performed extraction kinetics experiments are compared with the robot. With respect to process intensification, a comparison of yields obtained by microwave‐ and ultrasonic‐supported extraction compared to laboratory robot shaking and stirred single‐stage batch experiments was performed.
Iridium(I) Compounds as Prospective Anticancer Agents: Solution Chemistry, Antiproliferative Profiles and Protein Interactions for a Series of Iridium(I) N‐Heterocyclic Carbene Complexes
Authors: Gothe Yvonne , Marzo Tiziano , Messori Luigi , Metzler‐Nolte Nils
Published: July 2016

A series of structurally related mono‐ and bis‐NHC–iridium(I) (NHC: N‐heterocyclic carbene) complexes have been investigated for their suitability as potential anticancer drugs. Their spectral behaviour in aqueous buffers under physiological‐like conditions and their cytotoxicity against the cancer cell lines MCF‐7 and HT‐29 are reported. Notably, almost all complexes exhibit significant cytotoxic effects towards both cancer cell lines. In general, the cationic bis‐carbene complexes show higher stability and greater anticancer activity than their neutral mono‐carbene analogues with IC50 values in the high nanomolar range. Furthermore, to gain initial mechanistic insight, the interactions of these iridium(I)–NHC complexes with two model proteins, namely lysozyme and cytochrome c, were explored by HR‐ESI‐MS analyses. The different protein metalation patterns of the complexes can be roughly classified into two distinct groups. Those interactions give us a first idea about the possible mechanism of action of this class of compounds. Overall, our findings show that iridium(I)–NHC complexes represent very interesting candidates for further development as new metal‐based anticancer drugs.
ChemInform Abstract: Carbonate‐Bridged Lanthanoid Triangles: Single‐Molecule Magnet Behavior, Inelastic Neutron Scattering, and ab initio Studies.
Authors: Giansiracusa Marcus J. , Vonci Michele , Van den Heuvel Willem , Gable Robert W. , Moubaraki Boujemaa , Murray Keith S. , Yu Dehong , Mole Richard A. , Soncini Alessandro , Boskovic Colette
Published: July 2016

Compounds (IV) are characterized by single crystal XRD, magnetic measurements, inelastic neutron scattering, and CASSCF ab initio calculations.
ChemInform Abstract: Direct Electrophilic (Benzenesulfonyl)difluoromethylthiolation with a Shelf‐Stable Reagent.
Authors: Ismalaj Ermal , Le Bars Didier , Billard Thierry
Published: July 2016

The gram‐scale preparation of (benzenesulfonyl)difluoromethanesulfenamide is described and its electrophilic addition to terminal and internal alkenes, including cyclic ones, and alkynes as well as its electrophilic aromatic substitution of electron‐rich arenes and heteroarenes.
ChemInform Abstract: Synthesis of α‐Aminonitriles via a FeSO4‐Mediated Oxidative Cyanation of Tertiary Amines with Benzoyl Cyanide and Molecular Oxygen or TBHP.
Authors: Zhang Lianpeng , Gu Xin , Lu Ping , Wang Yanguang
Published: July 2016

Concerning the mechanism, a cascade way involving a Fe‐catalyzed oxidation of tertiary amine to iminium ions and trapping them by cyanide anion is suggested.
ChemInform Abstract: Trifluorination of Sulfides and Dithioketals Using IF5‐Pyridine‐HF.
Authors: Inoue Toshiya , Nakabo Sho , Hara Shoji
Published: July 2016

The stable fluorination reagent is used for the trifluorination of aryl alkyl sulfides with concomitant migration of the arylsulfanyl group.
ChemInform Abstract: Catalytic Enantioselective Synthesis of Amino Skipped Diynes.
Authors: Paioti Paulo H. S. , Abboud Khalil A. , Aponick Aaron
Published: July 2016

Nonracemic amino skipped diynes are prepared via an enantiodetermining C—C bond formation in excellent enantiomeric excess and with extremely broad substrate scope.
ChemInform Abstract: Phosphine‐Catalyzed Vicinal Acylcyanation of Alkynoates.
Authors: Murayama Hiroaki , Nagao Kazunori , Ohmiya Hirohisa , Sawamura Masaya
Published: July 2016

leading to acrylonitrile derivatives with a tetrasubstituted alkene moiety
ChemInform Abstract: Sequential Functionalization of the O—H and C(sp2)—O Bonds of Tropolones by Alkynes and N‐Sulfonyl Azides.
Authors: Seo Boram , Jeon Woo Hyung , Kim Chul‐Eui , Kim Sanghyuck , Kim Sung Hong , Lee Phil Ho
Published: July 2016

In addition to the title reaction various 2‐functionalizations of tropones with 4‐aryl or 4‐alkyl substituted N‐sulfonyl‐1,2,3‐triazoles are described.
ChemInform Abstract: A Magnetically Recyclable Iron Oxide‐Supported Copper Oxide Nanocatalyst (Fe3O4—CuO) for One‐Pot Synthesis of S‐Aryl Dithiocarbamates under Solvent‐Free Conditions.
Authors: Aryanasab F.
Published: July 2016

The title dithiocarbamates are conveniently and efficiently obtained by simple one‐pot three‐component Ullmann‐type condensation of amines, carbon disulfide, and aryl iodides.