bluuebunny/crossref_metadata_2025 huggingface dataset:
Separating the effects of changes in land cover and climate: a hydro-meteorological analysis of the past 60 yr in Saxony, Germany
Authors: Renner M. , Brust K. , Schwärzel K. , Volk M. , Bernhofer C.
Published: January 2014

Abstract. Understanding and quantifying the impact of changes in climate and land use/land cover on water availability is a prerequisite to adapt water management; yet, it can be difficult to separate the effects of these different impacts. In this paper we illustrate a separation and attribution method based on a Budyko framework. We assume that evapotranspiration (ET) is limited by the climatic forcing of precipitation (P) and evaporative demand (E0), but modified by land-surface properties. Impacts of changes in climate (i.e., E0/P) or land-surface changes on ET alter the two dimensionless measures describing relative water (ET/P) and energy partitioning (ET/E0), which allows us to separate and quantify these impacts. We use the separation method to quantify the role of environmental factors on ET using 68 small to medium range river basins covering the greatest part of the German Federal State of Saxony within the period of 1950–2009. The region can be considered as a typical central European landscape with considerable anthropogenic impacts. In the long term, most basins are found to follow the Budyko curve which we interpret as a result of the strong interactions of climate, soils and vegetation. However, two groups of basins deviate. Agriculturally dominated basins at lower altitudes exceed the Budyko curve while a set of high altitude, forested basins fall well below. When visualizing the decadal dynamics on the relative partitioning of water and energy the impacts of climatic and land-surface changes become apparent. After 1960 higher forested basins experienced large land-surface changes which show that the air pollution driven tree damages have led to a decline of annual ET on the order of 38%. In contrast, lower, agricultural dominated areas show no significant changes during that time. However, since the 1990s effective mitigation measures on industrial pollution have been established and the apparent brightening and regrowth has resulted in a significant increase of ET across most basins. In conclusion, data on both, the water and the energy balance is necessary to understand how long-term climate and land cover control evapotranspiration and thus water availability. Further, the detected land-surface change impacts are consistent in space and time with independent forest damage data and thus confirm the validity of the separation approach.
Estudio del equilibrio y cinética de adsorción de Cd(II), Ni(II) y Cr(VI) usando Quitosano y Quitosano modificado con cobre
Authors: Castro S. , Cerda R. , Betanco N. , Canelo F. , López X. , García A. , Benavente M.
Published: January 2014

En este trabajo, se estudió el equilibrio y la cinética de adsorción de Cd(II), Ni(II) en quitosano y Cr(VI) en quitosano modificado con cobre. Para ello, soluciones de iones metálicos a diferentes concentraciones, fueron puestas en contacto con el adsorbente y se agitaron por un período de 3 – 4 h. Al final del proceso, las muestras fueron analizadas en un espectrómetro de absorción atómica. Los datos experimentales del equilibrio de adsorción de los iones metálicos fueron evaluados aplicando las isotermas de Langmuir y Freundlich; mientras los datos cinéticos fueron evaluados utilizando los modelos cinéticos de pseudo-primer orden y pseudo-segundo orden. Los resultados del  proceso demostraron que los iones fueron eficazmente adsorbidos por el quitosano (Cd y Ni) y por el Cu-quitosano (Cr). Además, se comprobó que los datos experimentales del equilibrio de adsorción de Cr(VI) y Ni(II) se ajustan al modelo de Langmuir; mientras que los datos experimentales del Cd(II) fueron mejor ajustados por el modelo de Freundlich. Mediante el uso de la isoterma de Langmuir se determinó la capacidad máxima de adsorción de cromo (29.7 mg/g Cu-quitosano), cadmio (102.0 mg/g quitosano) y níquel (83.31 mg/g quitosano). Los resultados de la cinética de adsorción de los iones metálicos mostraron que los datos experimentales fueron mejor ajustados por el modelo de pseudo-segundo orden; es decir, el paso limitante en la velocidad es la reacción de adsorción y no la transferencia de masa. DOI: http://dx.doi.org/10.5377/nexo.v26i2.1285 Nexo Revista Científica Vol. 26, No. 02, pp. 56-68/Diciembre 2013
Of Horsemen and Hermits: Mongolia, North Korea, and the New Security Architecture in Northeast Asia
Authors: Noerper Stephen E
Published: January 2014

No abstract available. DOI: http://dx.doi.org/10.5564/mjia.v0i10.116 The Mongolian Journal of International Affairs; Number 10, 2003, Pages 29-36
Mongolian economy at the threshold of globalization era
Authors: Baatar Tsend
Published: January 2014

No abstract available. DOI: http://dx.doi.org/10.5564/mjia.v0i10.117 The Mongolian Journal of International Affairs; Number 10, 2003, Pages 37-45
The Dynamic of Repression: The Global Impact of the Stalinist Model, 1944-1953
Authors: Balazs Szalontai
Published: January 2014

No abstract available. DOI: http://dx.doi.org/10.5564/mjia.v0i10.123 The Mongolian Journal of International Affairs; Number 10, 2003, Pages 120-155
Empirical Analysis of a Self-Service Check-In Implementation in Singapore Changi Airport
Authors: Lee CKM , Ng Yuankei , Lv Yaoqiong , Taezoon Park
Published: January 2014

The purpose of this paper is to provide an empirical analysis an airport passenger operation and to improve its efficiency. An investigation was conducted to evaluate the quantitative and qualitative efficiency of the self-service check-in booth in Singapore Changi Airport. Through Arena simulation software, this investigation gives an estimation of how much processing time and queuing time the self-service check-in booths have been reduced, providing a quantitative analysis of the self-service check-in booth. A modified technology acceptance model featuring a prediction of how well passengers accept this new concept has also been used in this investigation. The results show that the self-service check-in booth's operation is generally efficient based on quantitative and qualitative analysis, providing a recommendable service to customers.
Design of a Wildlife Avoidance Planning System for Autonomous Harvesting Operations
Authors: Bochtis Dionysis D. , Sørensen Claus G. , Green Ole , Hameed Ibrahim A. , Berruto Remigio
Published: January 2014

Harvesting and mowing operations are among the main potential stressors affecting wildlife within agricultural landscapes, leading to large animal losses. A number of studies have been conducted on harvesting practices to address the problem of wildlife mortality, providing a number of management actions or field area coverage strategies. Nevertheless, these are general rules limited to simple-shaped fields, and which are not applicable to more complex operational situations. The objectives of the present study were to design a system capable of deriving a wildlife avoidance driving pattern for any field shape complexity and field boundary conditions (in terms of escape and non-escape areas) and applicable to different animal behaviours. The assumed animal escape reactions are the result of the parameterization of a series of developed behavioural functions. This parameterization will be able to adapt any knowledge that is or might become available as a result of dedicated future experiments on animal behaviour for different species or different animal ages.
An Adaptive Neural Network Learning-based Solution for the Inverse Kinematics of Humanoid Fingers
Authors: Kim Byoung-Ho
Published: January 2014

This paper presents an adaptive neural network learning-based solution for the inverse kinematics of humanoid fingers. For the purpose, we specify an effective finger model by considering the interphalangeal joint coordination inherent in human fingers. In order to find a proper joint combination for any fingertip trajectory, we propose an adaptive learning scheme by using a multi-layered neural network. It is interesting to use an adaptive learning rate algorithm that leads the neural network to get the inverse kinematic solution quickly. The usefulness of the proposed approach is verified by exemplary simulations for the general motion of humanoid fingers.
Global Labor Justice and the Limits of Economic Analysis
Authors: Preiss Joshua
Published: January 2014

This article considers the economic case for so-called sweatshop wages and working conditions. My goal is not to defend or reject the economic case for sweatshops. Instead, proceeding from a broadly pluralist understanding of value, I make and defend a number of claims concerning the ethical relevance of economic analysis for values that different agents utilize to evaluate sweatshops. My arguments give special attention to a series of recent articles by Benjamin Powell and Matt Zwolinski, which represent the latest and best defense of the economic case for sweatshops. In the process, I challenge Zwolinski’s “non-worseness claim” (NWC), and the idea that opposition to sweatshop wages and working conditions fails to respect that the autonomy of would-be sweatshop workers. Ultimately, I conclude that even if the economic case for sweatshops rests on a solid empirical foundation, agents possess good reason to advocate for better wages and working conditions for sweatshop workers, and to prefer less exploitative or coercive relationships. Sweatshop labor undermines a compelling vision of free markets, according to both Kantian and republican conceptions of freedom, and the relationships formed by those who participate in such markets.
Lipoidic Cells Ovary Cancer, Clinic Case and Literature Review
Authors: Arturo Novoa Vargas  , Karla Sánchez Bautista  , Ismael Coudillo Luna
Published: January 2014

Objective:Analyzed a case of woman with virilizan ovary tumor, where clinics manifestations made easy diagnosis of a anexial tumor producing masculine hormones with neoplastic thorax effusion and ascites. Specific tumoral serum marks for diagnosis, and posoperatory evolution. We made a medical prospective literature review.
Methods:We studied a female case 35 years old, with an androgenic malignity ovary tumor, Analysis was worked ina Regional General Hospital of a State of Mexico, Mexico last year. Prospective studying a tumor of the ovary, produces masculine hormones.
Discussion:Rare tumor, represents, almost 0.5% all ovarian tumors. Its secrets masculine hormones; with broaden voice, acne, facial and corporal hair increased, large clitoris, androgenic calvicie patter. Those tumors grow in all ages women groups, but usually in young women, almost is unilateral (95%). We show a clinical case of woman, 35 years old with androgenic dates, She carried out surgery for ovarian tumor. Histopathology report confirmed a malign ovary cordons sexual cells, with high malign grade compound, approximated 30 cm mayor diameter with integral capsule. Stage IC. Were used 6 cycles intravenous systemic chemotherapy. At present, her tumoral marks are negative and gradually have been disappeared androgenic clinical manifestations.
Conclusions:Rare malign ovary tumor, produces androgenic clinical manifestation. Grove up tumor marks like serum testosterone; cytorreductive surgery is cornerstone treatment. Prognosis disease is up to grade of cell differentiation and stage in surgical-pathological events. Five years survive in stage I, is approximate in 70 to 90% of cases.
Quantifying Maternal and Paternal Disease History Using Log-Rank Score with an Application to a National Cohort Study
Authors: Feng Rui , Patel Hersh , Howard George
Published: January 2014

Both maternal and paternal disease history can be important predictors of the risk of common conditions such as heart disease or cancer because of shared environmental and genetic risk factors. Sometimes maternal and paternal history can have remarkably different effects on offspring’s status. The results are often affected by how the maternal and paternal disease histories are quantified. We proposed using the log-rank score (LRS) to investigate the separate effect of maternal and paternal history on diseases, which takes parental disease status and the age of their disease onset into account. Through simulation studies, we compared the performance of the maternal and paternal LRS with simple binary indicators under two different mechanisms of unbalanced parental effects. We applied the LRS to a national cohort study to further segregate family risks for heart diseases. We demonstrated using the LRS rather than binary indicators can improve the prediction of disease risks and better discriminate the paternal and maternal histories. In the real study, we found that the risk for stroke is closely related with maternal history but not with paternal history and that maternal and paternal disease history have similar impact on the onset of myocardial infarction.
Modelos de negocio emergentes en la industria del videojuego
Authors: Trenta Milena
Published: January 2014

La industria del videojuego está viviendo un proceso de transformación en su manera de crear valor, debido al éxito de los juegos casuales y a la consolidación de nuevas plataformas de juego, cuales las redes sociales, los teléfonos inteligentes, las tabletas y los sitios de juego on line. A consecuencia de estos fenómenos, surgen nuevos modelos de negocio. Posteriormente al estudio del volumen de ingresos generados por los videojuegos distribuidos por canales digitales y de los hábitos de consumo de los usuarios, este trabajo aporta una descripción de los modelos de negocio emergentes en la industria del videojuego. Finalmente, se observa que, frente a la actual situación, las principales compañías del sector diversifican su negocio y las pequeñas empresas aprovechan la multiplicación de los canales de distribución. Mientras que, los usuarios se inclinan por los videojuegos comercializados mediante modelos de negocio que permiten personalizar el consumo y establecer relaciones sociales.
Diseño, imagen y comunicación de productos de lujo. Estudio arquetípico de los atributos esenciales para su identificación
Authors: López María Aurora López , Martín Isabel Rodrigo , Martín Luis Rodrigo
Published: January 2014

Palabras clave: diseño, imagen, comunicación, lujo, atributos arquetípicos.Resumen: El estudio de un fenómeno multidisciplinar como lo es el concepto de “lujo” en la actualidad, dada su dimensión económica,  social  y cultural, nos ofrece un interesante enfoque desde el que abordar con gran pragmatismo la realidad. De este modo, la presente investigación indaga en los entresijos de toda su industria, mediante una profundización en el conocimiento de los atributos identificativos que permiten averiguar el índice de pertenencia de los diferentes bienes y servicios del mercado con respecto a dicho universo categórico, construyendo una matriz arquetípica que con determinación establece las pautas necesarias para ello, y cuya extrapolación a otros ámbitos de índole diferente es tan factible que, de transferírseles dichos atributos, podrían no sólo enriquecerse, sino mejorarse en la línea acertada que exige nuestra nueva era de consumo tecnológico y producción digital.Keywords: design, image, communication, luxury, archetypal attributes.Abstract: The study of a multidisciplinary phenomenon as is the concept of "luxury" at present, given its economic, social and cultural, offers an interesting approach from which deal with great pragmatism our reality. Thus, this research explores the intricacies of all its industry, through a deeper knowledge of identifying attributes that find out the membership rate of different market goods and services with respect to such categorical universe, developing an archetypal head mould that establishes guidelines determination necessary for this, and whose extrapolation to other areas of a different nature is as likely that, these attributes transferred to them, could not only rich, but improved in the correct line that demands our new era of technological consumption and digital production.
Colonialismo digital, atención y lectura en tiempos de cambio
Authors: Reinón Pedro Medina , Ramos Javier Maseda
Published: January 2014

A partir del libro Contro il colonialismo digitale de Roberto Casati, se analizan las nuevas formas de lectura de textos digitales para establecer sus especificidades, principalmente en lo que concierne a posibles cambios cognitivos, con el objetivo de estudiar cuál puede ser el medio idóneo destinado a la enseñanza. Este análisis tendrá una primera aproximación ontológica al texto digital para reflexionar posteriormente sobre las prácticas que se están implantando en nuestra sociedad.Palabras clave: texto digital, libro, lectura, percepción, atención, enseñanza
Antes del Diseño
Authors: González Solas Javier
Published: January 2014

La práctica profesional del diseño está sometida a una dispersión que dificulta la reflexión sobre ella misma. Y la enseñanza universitaria se ha convertido en gran parte en una práctica más. De este modo la ausencia de una reflexión radical, anterior en el tiempo (revisión de la historia) y anterior en el método (pensar antes de hacer), puede convertirse en un colaboracionismo amoral con todo tipo de catástrofe intelectual y sociopolítica. La perspectiva aquí adoptada proviene de una toma de posición, también previa, a lo que a veces se toma como científico. Frente a un estado de cosas difícil de cambiar, cabe asumirlo tal cual y reducirse a un papel instrumental (antipolítico), o reflexionar. Y ese sería el papel político de la Universidad.
Low-Cost Spectrograph Based on a WebCam: A Student Project
Authors: Trindade A. , Falcão B. , Carramate L. F. N. D. , Marques M. I. S. F. , Ferreira R. A. S. , André P. S.
Published: January 2014

This work describes the implementation of a low-cost spectrometer produced with common objects and proposed as a pedagogical students' project. This task aims to introduce the theme of image detection and to stimulate the students to develop skills in the field of optics and photonics. The performance of the developed spectrometer was tested in the characterisation of several sources such as light emitting diodes (LEDs) operating in the visible spectral range and the results were compared with those obtained with a commercial spectrometer. Foreseeing a possible application, the spectrometer was used to calculate the emission ( x,y) colour coordinates following the Commission Internationale d'Eclairage (CIE) definition of the LEDs. The calculated ( x,y) colour coordinates using the built spectrometer compare well with those calculated using the emission data measured using a commercial spectrometer, pointing out that the proposed methodology provides good resolution and precision in the calculation of the CIE colour coordinates. This project was offered with success in 2010 to students from the Optoelectronics unit of the Physics Engineering Masters degree at Aveiro University, Portugal.
Quantifying hiss‐driven energetic electron precipitation: A detailed conjunction event analysis
Authors: Li W. , Ni B. , Thorne R. M. , Bortnik J. , Nishimura Y. , Green J. C. , Kletzing C. A. , Kurth W. S. , Hospodarsky G. B. , Spence H. E. , Reeves G. D. , Blake J. B. , Fennell J. F. , Claudepierre S. G. , Gu X.
Published: January 2014

We analyze a conjunction event between the Van Allen Probes and the low‐altitude Polar Orbiting Environmental Satellite (POES) to quantify hiss‐driven energetic electron precipitation. A physics‐based technique based on quasi‐linear diffusion theory is used to estimate the ratio of precipitated and trapped electron fluxes (R), which could be measured by the two‐directional POES particle detectors, using wave and plasma parameters observed by the Van Allen Probes. The remarkable agreement between modeling and observations suggests that this technique is applicable for quantifying hiss‐driven electron scattering near the bounce loss cone. More importantly, R in the 100–300 keV energy channel measured by multiple POES satellites over a broad L magnetic local time region can potentially provide the spatiotemporal evolution of global hiss wave intensity, which is essential in evaluating radiation belt electron dynamics, but cannot be obtained by in situ equatorial satellites alone.
Measuring miscible fluid displacement in porous media with magnetic resonance imaging
Authors: Muir Colleen E. , Petrov Oleg V. , Romanenko Konstantin V. , Balcom Bruce J.
Published: January 2014

The development of new quantitative magnetic resonance imaging (MRI) technologies open new opportunities for measurements of mass transport in porous media. The current work examines a simple miscible displacement process of H2O and D2O in porous media samples. Laboratory measurements of dispersion in porous media traditionally monitor the effluent intensity of an injected tracer. We employ MRI to obtain quantitative water saturation profiles, and to measure dispersion in rock core plugs. The saturation profiles are modeled with PHREEQC, a fluid transport modeling program. We demonstrate how independent magnetic resonance measurements can be employed to estimate three important input parameters for PHREEQC, mobile porosity, immobile porosity, and dispersivity. Bulk Carr Purcell Meiboom Gill (CPMG) T2 distribution measurements were undertaken to estimate mobile and immobile porosity. Bulk alternating‐pulsed‐gradient‐stimulated‐echo (APGSTE) measurements were undertaken to measure dispersivity. The imaging method employed, T2 mapping Spin Echo Single Point Imaging (SE‐SPI), also provides information about the pore size distributions in the rock cores, and how the fluid occupancy of the pores changes during the displacement process.
Criminology and Public Policy
Authors: Fagan Abigail A.
Published: January 2014

There has historically been a large gap between criminology and public policies intended to reduce crime and incarceration. Many criminal justice practices have not been based on scientific information about what causes crime or how to reduce it. In turn, many practices routinely used to control crime have not been effective in reducing individuals' likelihood of offending. While the need to create evidence‐based policies and practices is being increasingly recognized, and there are signs that the gap between research and practice is shrinking, additional efforts need to be made in order to significantly impact on rates of crime and incarceration. This entry provides examples of (largely ineffective) practices that are not based on scientific information as well as evidence‐based policies with more potential to affect crime rates, and outlines steps for ensuring increased collaboration and communication between academics, policy makers, and practitioners.
Felson, Marcus
Authors: Medina José E.
Published: January 2014

Marcus Felson is one of the most cited authors of the late twentieth and early twenty‐first centuries. His greatest impact has been in the area of criminology in general and crime science in particular because of his formulation and later development of routine activities theory. Initially established in the area of predatory crime and later extended to other categories of crime such as sex crimes or cybercrime, it is considered the foundation of what would come to be known as opportunity theories.
Thrombosis and survival in essential thrombocythemia: A regional study of 1,144 patients
Authors: Montanaro Marco , Latagliata Roberto , Cedrone Michele , Spadea Antonio , Rago Angela , Di Giandomenico Jonny , Spirito Francesca , Porrini Raffaele , De Muro Marianna , Leonetti Sabrina Crescenzi , Villivà Nicoletta , De Gregoris Cinzia , Breccia Massimo , Montefusco Enrico , Santoro Cristina , Cimino Giuseppe , Majolino Ignazio , Mazzucconi Maria Gabriella , Alimena Giuliana , Andriani Alesssandro
Published: January 2014

To identify prognostic factors affecting thrombosis‐free survival (TFS) and overall survival (OS), we report the experience of a Regional cooperative group in a real‐life cohort of 1,144 patients with essential thrombocythemia (ET) diagnosed from January 1979 to December 2010. There were 107 thrombotic events (9.4%) during follow‐up [60 (5.3%) arterial and 47 (4.1%) venous thromboses]. At univariate analysis, risk factors for a shorter TFS were: age >60 years (P < 0.0054, 95% CI 1.18–2.6), previous thrombosis (P < 0.0001, 95% CI 1.58–4.52) and the presence of at least one cardiovascular risk factor (P = 0.036, 95% CI 1.15–3.13). Patients with a previous thrombosis occurred ≥24 months before ET diagnosis had a shorter TFS compared to patients with a previous thrombosis occurred <24 months (P = 0.0029, 95% CI 1.5–6.1); furthermore, patients with previous thrombosis occurred <24 months did not show a shorter TFS compared with patients without previous thrombosis (P = 0.303, 95% CI 0.64–3.21). At multivariate analysis for TFS, only the occurrence of a previous thrombosis maintained its prognostic impact (P = 0.0004, 95% CI 1.48–3.79, RR 2.36). The 10‐year OS was 89.9% (95% CI 87.3–92.5): at multivariate analysis for OS, age >60 years (P < 0.0001), anemia (P < 0.0001), male gender (P = 0.0019), previous thromboses (P = 0.0344), and white blood cell >15 × 109/l (P = 0.0370) were independent risk factors. Previous thrombotic events in ET patients are crucial for TFS but their importance seems related not to the occurrence per se but mainly to the interval between the event and the diagnosis. Am. J. Hematol. 89:542–546, 2014. © 2014 Wiley Periodicals, Inc.
Direkte Modulation von Rab‐GTPase‐Effektor‐Wechselwirkungen
Authors: Spiegel Jochen , Cromm Philipp M. , Itzen Aymelt , Goody Roger S. , Grossmann Tom N. , Waldmann Herbert
Published: January 2014

Kleine GTPasen fungieren als molekulare Schalter bei der Kontrolle zahlreicher essenzieller zellulärer Prozesse. Während eine fehlerhafte Funktion oder Regulierung von GTPasen in einer Vielzahl von humanen Erkrankungen eine wichtige Rolle spielt, hat es sich als schwierig erwiesen, diese Proteinklasse direkt zu adressieren, da ihre Regulierung und biologische Wirkung über ausgedehnte und gering profilierte Proteinoberflächen vermittelt werden. Hier beschreiben wir die Entwicklung von Inhibitoren für Protein‐Protein‐Wechselwirkungen von Rab‐GTPasen, die eine Schlüsselrolle bei der Regulation vesikulärer Transportprozesse spielen. Auf der Basis von Kristallstrukturen von Rab‐Proteinen gebunden an ihre Wechselwirkungspartner wurden so genannte “stapled peptides” entwickelt. Diese Peptide zeichnen sich durch signifikant gesteigerte Affinitäten aus. Eines der modifizierten Peptide, StRIP3, bindet selektiv an aktives Rab8a und inhibiert eine Rab8a‐Effektor‐Wechselwirkung in vitro.
Organozinc Pivalate Reagents: Segregation, Solubility, Stabilization, and Structural Insights
Authors: Hernán‐Gómez Alberto , Herd Emma , Hevia Eva , Kennedy Alan R. , Knochel Paul , Koszinowski Konrad , Manolikakes Sophia M. , Mulvey Robert E. , Schnegelsberg Christoph
Published: January 2014

The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D8]THF solution these reagents exist as separated Me(p‐C6H4)ZnCl and Mg(OPiv)2 species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)2 enhances the air stability of aryl zinc species by sequestering H2O contaminants. Coupling reactions of Me(p‐C6H4)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)2. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)2Li2(Cl)2(OPiv)2Zn].
Aufspaltung des Wellenpakets und Doppelpfad‐Desaktivierung im photoangeregten Sehpigment Isorhodopsin
Authors: Polli Dario , Weingart Oliver , Brida Daniele , Poli Emiliano , Maiuri Margherita , Spillane Katelyn M. , Bottoni Andrea , Kukura Philipp , Mathies Richard A. , Cerullo Giulio , Garavelli Marco
Published: January 2014

Isorhodopsin ist ein dem Rhodopsin analoges Sehprotein. Es hat die gleiche Opsin‐Umgebung, bindet aber statt 11‐cis‐Retinal die 9‐cis‐Form. Dessen Photoisomerisierung ist etwa dreimal langsamer und viel weniger effizient. Das dafür zugrundeliegende mechanistische Prinzip wird hier mit einer Kombination aus quantenmechanischen/molekülmechanischen Simulationen und ultraschneller optischer Spektroskopie mit Sub‐20‐fs‐Auflösung und einem Spektralbereich bis ins nahe Infrarot aufgedeckt. Während sich das photoangeregte Wellenpaket im Rhodopsin zielgerichtet durch eine einzelne konische Durchschneidung zwischen dem angeregten und dem Grundzustand bewegt, spaltet es im Isorhodopsin auf und beschreitet zwei konkurrierende Desaktivierungspfade mit unterschiedlichen Reaktionstrichtern. Einer wird schnell erreicht, ist aber im Wesentlichen unproduktiv. Der andere Pfad ist aufgrund erhöhter sterischer Wechselwirkungen mit der Umgebung verlangsamt, führt aber entlang eine “Vorwärts”‐Pedalbewegung zum Photoprodukt.
Spectroscopic and Computational Study of a Nonheme Iron Nitrosyl Center in a Biosynthetic Model of Nitric Oxide Reductase
Authors: Chakraborty Saumen , Reed Julian , Ross Matthew , Nilges Mark J. , Petrik Igor D. , Ghosh Soumya , Hammes‐Schiffer Sharon , Sage J. Timothy , Zhang Yong , Schulz Charles E. , Lu Yi
Published: January 2014

A major barrier to understanding the mechanism of nitric oxide reductases (NORs) is the lack of a selective probe of NO binding to the nonheme FeB center. By replacing the heme in a biosynthetic model of NORs, which structurally and functionally mimics NORs, with isostructural ZnPP, the electronic structure and functional properties of the FeB nitrosyl complex was probed. This approach allowed observation of the first S=3/2 nonheme {FeNO}7 complex in a protein‐based model system of NOR. Detailed spectroscopic and computational studies show that the electronic state of the {FeNO}7 complex is best described as a high spin ferrous iron (S=2) antiferromagnetically coupled to an NO radical (S= 1/2) [Fe2+‐NO.]. The radical nature of the FeB‐bound NO would facilitate NN bond formation by radical coupling with the heme‐bound NO. This finding, therefore, supports the proposed trans mechanism of NO reduction by NORs.
Solid‐Phase Incorporation of an ATRP Initiator for Polymer–DNA Biohybrids
Authors: Averick Saadyah E. , Dey Sourav K. , Grahacharya Debasish , Matyjaszewski Krzysztof , Das Subha R.
Published: January 2014

The combination of polymers with nucleic acids leads to materials with significantly advanced properties. To obviate the necessity and complexity of conjugating two macromolecules, a polymer initiator is described that can be directly covalently linked to DNA during solid‐phase synthesis. Polymer can then be grown from the DNA bound initiator, both in solution after the DNA‐initiator is released from the solid support as well as directly on the solid support, simplifying purification. The resulting polymer‐DNA hybrids were examined by chromatography and fluorescence methods that attested to the integrity of hybrids and the DNA. The ability to use DNA‐based supports expands the range of readily available molecules that can be used with the initiator, as exemplified by direct synthesis of a biotin polymer hybrid on solid‐support. This method expands the accessibility and range of advanced polymer biohybrid materials.
Total Synthesis of the Monoterpenoid Indole Alkaloid (±)‐Aspidophylline A
Authors: Teng Mingxing , Zi Weiwei , Ma Dawei
Published: January 2014

Aspidophylline A belongs to the akuammiline alkaloid family, the members of which possess intriguing cagelike structures and diverse biological activities. Herein we report a 15‐step synthesis of this alkaloid from conveniently available starting materials. The key elements of the synthesis include an intramolecular oxidative coupling to create the tetracyclic furoindoline motif of the natural product and a [Ni(cod)2]‐mediated cyclization to install its piperidine ring.
Chemical phosphorylation improves the moisture resistance of soy flour‐based wood adhesive
Authors: Zhu Dan , Damodaran Srinivasan
Published: January 2014

A green‐chemistry approach to improve the moisture resistance of soy flour (SF)‐based wood adhesive is described. Chemical phosphorylation of SF (PSF), using POCl3 as the phosphorylating agent, dramatically increased its wet bond strength. The optimum POCl3:SF ratio that produced maximum wet bond strength was about 0.15 (g g−1). The increase in wet bond strength of PSF (PSF0.15) was mostly due to the phosphate groups incorporated into the proteins and carbohydrates, and to a lesser degree to phosphorylation‐induced protein denaturation. The attached phosphate groups acted as cross‐linking agents, either via covalent esterification with hydroxyl groups on wood chips or via ionic and hydrogen‐bonding interactions with functional groups in wood chips. At hot‐press temperatures above 160°C the wet bond strength of PSF0.15 was >2.6 MPa, a level that might be acceptable for interior‐used hardwood plywood and particleboard. POCl3 is a low cost, general‐purpose reagent and therefore PSF‐based adhesive is expected to be environmentally friendly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40451.
Inhibition of Mycobacterium tuberculosis Transaminase BioA by Aryl Hydrazines and Hydrazides
Authors: Dai Ran , Wilson Daniel J. , Geders Todd W. , Aldrich Courtney C. , Finzel Barry C.
Published: January 2014

7,8‐Diaminopelargonic acid synthase (BioA) of Mycobacterium tuberculosis is a recently validated target for therapeutic intervention in the treatment of tuberculosis (TB). Using biophysical fragment screening and structural characterization of compounds, we have identified a potent aryl hydrazine inhibitor of BioA that reversibly modifies the pyridoxal‐5′‐phosphate (PLP) cofactor, forming a stable quinonoid. Analogous hydrazides also form covalent adducts that can be observed crystallographically but are incapable of inactivating the enzyme. In the X‐ray crystal structures, small molecules induce unexpected conformational remodeling in the substrate binding site. We compared these conformational changes to those induced upon binding of the substrate (7‐keto‐8‐aminopelargonic acid), and characterized the inhibition kinetics and the X‐ray crystal structures of BioA with the hydrazine compound and analogues to unveil the mechanism of this reversible covalent modification.
Prevalence of aspirin resistance in Asian‐Indian patients with stable coronary artery disease
Authors: Chadha D.S. , Sumana Budha , Karthikeyan Ganesan , Jayaprasad V. , Arun Shet S.
Published: January 2014

Objective

To evaluate the prevalence of pharmacological resistance to aspirin therapy by measuring platelet functions using the technique of light transmission aggregometry.

Background

Aspirin is the cornerstone of antiplatelet therapy in patients with coronary artery disease (CAD). However, a substantial proportion of patients manifest breakthrough thrombotic events despite regular intake of aspirin suggesting therapeutic resistance to aspirin.

Methods

We prospectively studied 126 patients with stable coronary artery disease at a tertiary center, who were recruited after ensuring compliance with a single formulation of aspirin (enteric coated aspirin 150 mg). Platelet aggregation was measured using light transmission aggregometry with ADP (10 µM) and Arachidonic acid (0.5 mg/mL). Pharmacological aspirin resistance was defined as the combined demonstration of mean platelet aggregation of ≥70% with 10 µM ADP and a mean aggregation of ≥20% with 0.5 mg/mL A.A. Patients satisfying either one of the above criteria were defined as semi‐responders. Patients satisfying neither criterion were defined as “aspirin responders”.

Results

Out of 126 patients with stable CAD, 64 % were responders, 36% were non responders (semi‐responders = 34% and resistant = 2%). Of the laboratory parameters, only the total leukocyte count was significantly associated with the presence of aspirin resistance (P < 0.03).

Conclusion

Pharmacological resistance to aspirin is noted in 36% (semi‐responders = 34% and resistant = 2%) of Asian Indian patients with stable CAD. Long‐term follow up of these patients will assist in determining the clinical importance of this phenomenon. © 2014 Wiley Periodicals, Inc.
ChemInform Abstract: LiMn2O4 Nanoparticles Anchored on Graphene Nanosheets as High‐Performance Cathode Material for Lithium‐Ion Batteries.
Authors: Lin Binghui , Yin Qing , Hu Hengrun , Lu Fujia , Xia Hui
Published: January 2014

Nanocrystalline LiMn2O4/graphene nanosheet (GNS) composite is hydrothermally prepared by dispersing GNS in H2O followed by addition of KMnO4 and LiOH (autoclave, 180 °C, 5 h).
ChemInform Abstract: High‐Pressure Synthesis and Characterization of Li2Ca3[N2]3 — An Uncommon Metallic Diazenide with [N2]2‐ Ions.
Authors: Schnick Wolfgang , et al. et al.
Published: January 2014

Li2Ca3[N2]3 is synthesized from a stoichiometric mixture of LiN3 and Ca(N3)2 in a multianvil device (9 GPa, 1023 K, 20 min).
ChemInform Abstract: Synthesis and Characterization of Novel Polyoxometalates with an Inverted‐Keggin Structure as a New Class of Building Unit.
Authors: Ueda Tadaharu , Machida Kazuki , Shiro Motoo , Kaneno Daisuke
Published: January 2014

(NPr4)4 (Pr‐PO3)4Mo12O36 (I), (NPr4)4(HOOC‐ (CH2)2‐PO3) 4Mo12O36 (II), and (NBu4)4 (H2C=CH‐PO3)4Mo12O36 (III) are precipitated at room temperature from H2O/MeCN molybdate solutions, the corresponding tetraalkylammonium bromide, and propylphosphonic acid, 2‐carboxyethylphosphonic acid, and vinylphosphonic acid, respectively.
ChemInform Abstract: Pd17In4Se4, a Metal‐Rich Palladium—Indium Selenide with an Open‐Framework Structure.
Authors: Zakharova Elena Yu. , Churakov Andrei V. , Doert Thomas , Kuznetsov Alexey N.
Published: January 2014

Needle‐like crystals of the new title compound are synthesized from a mixture of the elements in a ratio of Pd:In:Se = 7:2:1 (silica ampule, 750 °C, 7—10 d).
ChemInform Abstract: Alkoxybromination of Olefins Using Ammonium Bromide and Oxone.
Authors: Kumar Macharla Arun , Naresh Mameda , Rohitha Chozhiyath Nappunni , Narender Nama
Published: January 2014

A mild, efficient, highly regio‐ and stereoselective method for the alkoxybromination of various olefins is given.
ChemInform Abstract: Electrophilic α‐Oxygenation Reaction of β‐Ketoesters Using N‐Hydroxycarbamates: Control of the Ambident Reactivity of Nitrosoformate Intermediates.
Authors: Frazier Charles P. , Sandoval David , Palmer Leoni I. , de Alaniz Javier Read
Published: January 2014

A high O‐selectivity is observed in this nitrosocarbonyl aldol reaction.
ChemInform Abstract: Environmetally Benign Michael and Claisen Schmidt Reaction of Aromatic Carbonyl Compounds by Alkaline Polyionic Resin.
Authors: Jaitak Vikas , Kaul V. K. , Das Pralay
Published: January 2014

An alkaline, polystyrene‐supported ammonium salt is successfully applied as catalyst in regioselective Michael and Claisen—Schmidt reactions.
ChemInform Abstract: Highly Atom‐Efficient and Chemoselective Reduction of Ketones in the Presence of Aldehydes Using Heterogeneous Catalysts.
Authors: Takahashi Yusuke , Mitsudome Takato , Mizugaki Tomoo , Jitsukawa Koichiro , Kaneda Kiyotomi
Published: January 2014

The presented approach is also applicable to a column reactor, leading to a gram‐scale synthesis.
ChemInform Abstract: Synthesis of 2‐Bromo‐1‐aryl‐1H‐indenes via a Ag(I) Promoted Domino 2π‐Electrocyclic Ring‐Opening/4π‐Electrocyclization Reaction of 1,2‐Diaryl Substituted gem‐Dibromocyclopropanes.
Authors: Rosocha Gregory , Batey Robert A.
Published: January 2014

A domino reaction sequence yields indenes both from symmetric gem‐dibromocyclopropanes (I) and (IV), and unsymmetrical gem‐dibromocyclopropanes (VII), via a silver(I)‐promoted ionization and 2π‐disrotatory electrocyclic ring‐opening, followed by a 4π‐conrotatory electrocyclic ring‐closing reaction of the allylic carbocation intermediate.
ChemInform Abstract: Palladium‐Catalyzed Intramolecular Fluorooxylation of Styrenes.
Authors: Yuan Zheliang , Peng Haihui , Liu Guosheng
Published: January 2014

Pd‐Catalyzed reaction of (Z)‐configured hydroxyethyl styrenes (I) with NFSI results in the formation of 1‐aryl‐2‐fluorotetrahydrofurans with low trans selectivity.
ChemInform Abstract: Syntheses and Crystal Structures of 2,7‐Di(trimethylsilyl)thieno[3,2‐e]benzothiophene, 1,2,5,6(5)‐Tetra(trimethylsilyl)‐1,2,5,6 (2,3)‐tetrathiophenacyclooctaphan‐3(z),7(z)‐diene, and 2,7‐Di(trimethylsilyl)thieno[3,2‐e]benzothiophene‐4‐ol.
Authors: Wang Zhihua , Shi Jianwu , Tian Xinyong , Xu Li , Li Chunli , Wang Hua
Published: January 2014

McMurry reaction of dicarbaldehyde (III) efficiently affords the thienobenzothiophene (IV) along with two unexpected compounds (V) and (VI).
ChemInform Abstract: 1,2,3‐Triazoles as Versatile Directing Group for Selective sp2 and sp3 C—H Activation: Cyclization vs. Substitution.
Authors: Ye Xiaohan , He Zhengrong , Ahmed Tonia , Weise Keith , Akhmedov Novruz G. , Petersen Jeffrey L. , Shi Xiaodong
Published: January 2014

The choice of the substitution pattern of the triazole‐containing directing group determines whether a substitution or cyclization takes place.
ChemInform Abstract: Synthesis of 3‐(Diarylmethylene)oxindoles via a Palladium‐Catalyzed One‐Pot Reaction: Sonogashira—Heck—Suzuki—Miyaura Combined Reaction.
Authors: Dong Guang Ri , Park Sunhwa , Lee Dahye , Shin Kye Jung , Seo Jae Hong
Published: January 2014

A Pd‐catalyzed cascade reaction consisting of an intramolecular Heck‐type cyclization and subsequent Suzuki—Miyaura coupling is achieved under typical Sonogashira reaction conditions to yield diarylmethylene indolones (IV).
ChemInform Abstract: Coumarins: Facile and Expeditious Synthesis via Keggin‐Type Heteropolycompounds under Solvent‐Free Condition.
Authors: Rafiee Ezzat , Fakhri Akram , Joshaghani Mohammad
Published: January 2014

Rapid procedures for the synthesis of structurally diverse coumarin derivatives via Pechmann reactions of acetoacetates with mono‐ or polyphenols are described using supported heteropoly‐compounds as catalyst.
ChemInform Abstract: Highly Stereoselective Transformation of (1S,3S)‐cis‐1,3‐Disubstituted Tetrahydro‐β‐carbolines into (1S,3R)‐trans‐1,3‐Disubstituted Tetrahydro‐β‐carbolines: An Improved Asymmetric Synthesis of Tadalafil from L‐Tryptophan.
Authors: Dong Jing , Meng Tian‐Zhuo , Shi Xiao‐Xin , Zou Wen‐Hui , Lu Xia
Published: January 2014

By applying this method the synthesis of compound (VI) is realized which can be used as precursor for the synthesis of tadalafil.
ChemInform Abstract: Post Ugi Gold(I)‐ and Platinum(II)‐Catalyzed Alkyne Activation: Synthesis of Diversely Substituted Fused Azepinones and Pyridones.
Authors: Kumar Amit , Vachhani Dipak D. , Modha Sachin G. , Sharma Sunil K. , Parmar Virinder S. , Van der Eycken Erik V.
Published: January 2014

The Ugi four‐component reaction of 2‐pyrrole aldehydes and analogous indole and benzothiophene aldehydes with primary amines, isonitriles, and alkynoic acids offers the expected adducts (V), (XI), and (XIV) which can be readily used for the synthesis of various fused pyridones and azepinones.
ChemInform Abstract: Total Synthesis and Structural Revision of Incargutines A and B.
Authors: Kinbara Atsushi , Yamagishi Takehiro , Ouchi Hiroki , Miyaoka Hiroaki
Published: January 2014

The total synthesis of the proposed structures (Ia) and (IIa) of Incargutines A and B reveals significant differences in their spectral properties compared to the natural products.
ChemInform Abstract: Propagative Exfoliation of High Quality Graphene.
Authors: Feng Lan , Liu Yue‐Wen , Tang Xing‐Yan , Piao Yanmei , Chen Shu‐Fen , Deng Shun‐Liu , Xie Su‐Yuan , Wang YuHuang , Zheng Lan‐Sun
Published: January 2014

High quality graphene sheets are prepared via exfoliation of graphite by repeated (8 cycles) reductive, propagative alkylation in Li and naphthalene containing THF to which 1‐bromododecane (6‐bromohexanoic acid, 11‐bromoundecanoic acid, or methyl‐6‐bromohexanoate) is slowly added (reaction time of 12 h).
ChemInform Abstract: Recent Advances in Phthalocyanine‐Based Sensitizers for Dye‐Sensitized Solar Cells.
Authors: Ragoussi Maria‐Eleni , Ince Mine , Torres Tomas
Published: January 2014

Review: 104 refs.
ChemInform Abstract: Spin Hyperpolarization in NMR to Address Enzymatic Processes in vivo
Authors: Koptyug Igor V.
Published: January 2014

Review: 186 refs.
ChemInform Abstract: Fragment‐Based Drug Discovery: The Shape of Things to Come
Authors: Drysdale Martin J.
Published: January 2014

Review: 51 refs.
ChemInform Abstract: Elucidating Silk Structure Using Solid‐State NMR
Authors: Asakura Tetsuo , Suzuki Yu , Nakazawa Yasumoto , Holland Gregory P. , Yarger Jeffery L.
Published: January 2014

Review: 104 refs.
A comparison of three methods to regenerate activated carbon saturated by diesel fuels
Authors: Han Xue , Wishart Erin , Zheng Ying
Published: January 2014

The three regeneration methods (thermal treatment, ultrasonication, and solvent extraction) were studied to regenerate the adsorptive capacity of the activated carbons (ACs) that were saturated by the nitrogen and sulphur containing compounds of diesel fuels. This is one of the few reports that give attention to the regeneration of heteroaromatic compounds contaminated ACs. Both model diesel and light cycled oil (LCO) were served as feedstocks. High regeneration rates can be obtained for all three approaches when model diesel was used as the feed. As model diesel was replaced by LCO, a significant drop in capacity restoration can be observed for the first few cycles and then the decrease rate slowed down. Solvent extraction outperformed the other two methods. The causes to lower regeneration performance were also analysed. It is shown that the regenerated carbons had a lower porosity and surface area and fewer surface oxygen functional groups than fresh carbon regardless of the regeneration methods employed. Significant micropore blockage was observed in the carbon regenerated by the thermal approach due to the coke deposit under thermal conditions. Mesopores formed during the regeneration by ultrasonication are considered to promote the carbon adsorption capacity.
Dependence of the Efficiency Improvement of Black‐Dye‐Based Dye‐Sensitized Solar Cells on Alkyl Chain Length of Quaternary Ammonium Cations in Electrolyte Solutions
Authors: Ozawa Hironobu , Okuyama Yu , Arakawa Hironori
Published: January 2014

Dependence of the suppression of the backward electron transfer reaction from the TiO2 photoelectrode to I3− in the electrolyte on the alkyl chain length of the quaternary ammonium cation has been investigated for further efficiency improvement of high‐performance cosensitized dye‐sensitized solar cells (DSCs). The tetraheptylammonium cation was found to be more effective than the tetraethylammonium and tetrabutylammonium cations for the suppression of the backward electron transfer reaction without changing the conduction band energy of TiO2. 12.0 % conversion efficiency, which is the second highest efficiency for DSCs based on ruthenium sensitizers, was achieved in the cosensitized DSC with Black dye and D131 by using an electrolyte solution containing a moderate concentration of tetraheptylammonium iodide.