bluuebunny/crossref_metadata_2025 huggingface dataset:
Adapting the CATIMO grass model to meadow bromegrass grown in western Canada
Authors: Bonesmo H. , Baron V. S. , Young D. , Bélanger G. , Jing Q.
Published: October 2013

Bonesmo, H., Baron, V. S., Young, D., Bélanger, G. and Jing, Q. 2014. Adapting the CATIMO grass model to meadow bromegrass grown in western Canada. Can. J. Plant Sci. 94: 61–71. The Canadian Timothy Model (CATIMO) simulates the growth and nutritive value of timothy grown in eastern and western Canada, Norway, and Finland, but has not been parameterized for meadow bromegrass (Bromus riparius Rehm.) grown under Canadian prairie conditions. We parameterized and evaluated the CATIMO model to simulate the dry matter (DM) yield and N concentration of meadow bromegrass grown in western Canada with data from sequential sampling in primary growth and regrowth from two field experiments for a total of 5 yr of observation. Primary growth DM yield was simulated well [R2=0.95; normalized root mean square error (NRMSE) =16%; model simulation efficiency (EF)=0.93]. Simulations of the regrowth DM yield (R2=0.49, NRMSE=39%, EF=0.47) were not as successful as that of the primary growth, but they were within expected ranges for regrowth DM yields in western Canada. Forage N concentration was poorly simulated in primary growth (R2=0.32, NRMSE=38%, EF=−0.95) and regrowth (R2=0.27, NRMSE=30%, EF=−2.43). Plant-available soil moisture down to 30 cm was simulated well (R2=0.74, NRMSE=19%, EF=0.50). The parameterized model for meadow bromegrass expands the use of the CATIMO model to drier geographical areas where timothy may not be common, and it represents a first attempt to provide DM yield assessment of meadow bromegrass under Canadian Prairie conditions for whole-farm modeling.
AAC Meadowview alfalfa
Authors: Acharya S. N.
Published: October 2013

Acharya, S. N. 2014. AAC Meadowview alfalfa. Can J. Plant Sci. 94: 187–189. AAC Meadowview alfalfa (Medicago sativa) was developed by the Agriculture and Agri-Food Canada Research Centre, Lethbridge, Alberta. This cultivar, tested as AT05 in Western Forage Trials, is derived from parental clones selected for high forage yield under low pH conditions and resistance to both bacterial wilt (BW) (caused by Corynebacterium insidiosum) or Verticillium Wilt (VW) (caused by Verticillium albo-atrum Reinke & Berthold). When grown under irrigated and rainfed conditions of western Canada AT05 out yielded Beaver (check) by 5%. AAC Meadowview is well suited to forage and seed production in western Canada where VW and acidic soil conditions may be of concern. AAC Meadowview received Canadian Food Inspection Agency's registration number 7402 on 2013 Jun. 06. Breeder seed for the cultivar will be produced by AAFC and the multiplication and distribution rights were awarded to Northstar Seeds through a competitive process.
A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms
Authors: Sarwar G. , Godowitch J. , Henderson B. H. , Fahey K. , Pouliot G. , Hutzell W. T. , Mathur R. , Kang D. , Goliff W. S. , Stockwell W. R.
Published: October 2013

Abstract. We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 enhances ozone compared to CB05TU at all ambient levels. Although it exhibited greater overestimates at lower observed concentrations, it displayed an improved performance at higher observed concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. Any air pollution control strategies developed using the two mechanisms do not differ appreciably.
The coupling between the solar wind and proton fluxes at GEO
Authors: Boynton R. J. , Billings S. A. , Amariutei O. A. , Moiseenko I.
Published: October 2013

Abstract. The relationship between the solar wind and the proton flux at geosynchronous Earth orbit (GEO) is investigated using the error reduction ratio (ERR) analysis. The ERR analysis is able to search for the most appropriate inputs that control the evolution of the system. This approach is a black box method and is able to derive a mathematical model of a system from input-output data. This method is used to analyse eight energy ranges of the proton flux at GEO from 80 keV to 14.5 MeV. The inputs to the algorithm were solar wind velocity, density and pressure; the Dst index; the solar energetic proton (SEP) flux; and a function of the interplanetary magnetic field (IMF) tangential magnitude and clock angle. The results show that for lowest five energy channels (80 to 800 keV) the GEO proton fluxes are controlled by the solar wind velocity with a lag of two to three days. However, above 350 keV, the SEP fluxes, accounts for a significant portion of the GEO proton flux variance. For the highest three energy channels (0.74 to 14.5 MeV), the SEPs account for the majority of the ERR. The results also show an anisotropy of protons with gyrocenters inside GEO and outside GEO, where the protons inside GEO are controlled partly by the Dst index and also an IMF-clock angle function.
Estimating carbonate parameters from hydrographic data for the intermediate and deep waters of the Southern Hemisphere oceans
Authors: Bostock H. C. , Mikaloff Fletcher S. E. , Williams M. J. M.
Published: October 2013

Abstract. Using ocean carbon data from global datasets, we have developed several multiple linear regression (MLR) algorithms to estimate alkalinity and dissolved inorganic carbon (DIC) in the intermediate and deep waters of the Southern Hemisphere (south of 25° S) from only hydrographic data (temperature, salinity and dissolved oxygen). A Monte Carlo experiment was used to identify a potential density (σθ) of 27.5 as an optimal break point between the two regimes with different MLR algorithms. The algorithms provide a good estimate of DIC (R2=0.98) and alkalinity (R2=0.91), and excellent agreement for aragonite and calcite saturation states (R2=0.99). Combining the algorithms with the CSIRO Atlas of Regional Seas (CARS), we have mapped the calcite saturation horizon (CSH) and aragonite saturation horizon (ASH) for the Southern Ocean at a spatial resolution of 0.5°. These maps are more detailed and more consistent with the oceanography than the previously gridded GLODAP data. The high-resolution ASH map reveals a dramatic circumpolar shoaling at the polar front. North of 40° S the CSH is deepest in the Atlantic (~ 4000 m) and shallower in the Pacific Ocean (~ 2750 m), while the CSH sits between 3200 and 3400 m in the Indian Ocean. The uptake of anthropogenic carbon by the ocean will alter the relationships between DIC and hydrographic data in the intermediate and deep waters over time. Thus continued sampling will be required, and the MLR algorithms will need to be adjusted in the future to account for these changes.
Simulating microbial degradation of organic matter in a simple porous system using the 3-D diffusion based model MOSAIC
Authors: Monga O. , Garnier P. , Pot V. , Coucheney E. , Nunan N. , Otten W. , Chenu C.
Published: October 2013

Abstract. This paper deals with the simulation of microbial degradation in soil within pore space at microscopic scale. Pore space was described using sphere network coming from a geometrical modeling algorithm. The biological model was improved regarding previous work in order to include transformation of dissolved organic compounds and diffusion processes. Our model was tested using experimental results of a simple substrate decomposition (Fructose) within a simple media (the sand). Diverse microbial communities were inoculated. Separated incubations in microcosms were carried out using 5 different bacterial communities at 2 different water potentials of −10 cm and −100 cm of water. We calibrated the biological parameters by means of experimental data obtained at high water content and we tested the model without any parameters change at low water content. Same as for experimental data, our simulation results showed the decrease in water content involved the decrease of mineralisation. The model was able to simulate the decrease of connectivity between substrate and microorganism due the decrease of water content.
Global and regional sea surface temperature trends during Marine Isotope Stage 11
Authors: Milker Y. , Rachmayani R. , Weinkauf M. F. G. , Prange M. , Raitzsch M. , Schulz M. , Kučera M.
Published: October 2013

Abstract. The Marine Isotope Stage (MIS) 11 (424–374 ka) was characterized by a protracted deglaciation and an unusually long climatic optimum. It remains unclear to what degree the climate development during this interglacial reflects the unusually weak orbital forcing or greenhouse gas trends. Previously, arguments about the duration and timing of the MIS11 climatic optimum and about the pace of the deglacial warming were based on a small number of key records, which appear to show regional differences. In order to obtain a global signal of climate evolution during MIS11, we compiled a database of 78 sea surface temperature (SST) records from 57 sites spanning MIS11, aligned these individually on the basis of benthic (N = 28) or planktonic (N = 31) stable oxygen isotope curves to a common time frame and subjected 48 of them to an empirical orthogonal function (EOF) analysis. The analysis revealed a high commonality among all records, with the principal SST trend explaining almost 49% of the variability. This trend indicates that on the global scale, the surface ocean underwent rapid deglacial warming during Termination V, in pace with carbon dioxide rise, followed by a broad SST optimum centered at ~410 kyr. The second EOF, which explained ~18% of the variability, revealed the existence of a different SST trend, characterized by a delayed onset of the temperature optimum during MIS11 at ~398 kyr, followed by a prolonged warm period lasting beyond 380 kyr. This trend is most consistently manifested in the mid-latitude North Atlantic and Mediterranean Sea and is here attributed to the strength of the Atlantic meridional overturning circulation. A sensitivity analysis indicates that these results are robust to record selection and to age-model uncertainties of up to 3–6 kyr, but more sensitive to SST seasonal attribution and SST uncertainties >1 °C. In order to validate the CCSM3 (Community Climate System Model, version 3) predictive potential, the annual and seasonal SST anomalies recorded in a total of 74 proxy records were compared with runs for three time slices representing orbital configuration extremes during the peak interglacial of MIS11. The modeled SST anomalies are characterized by a significantly lower variance compared to the reconstructions. Nevertheless, significant correlations between proxy and model data are found in comparisons on the seasonal basis, indicating that the model captures part of the long-term variability induced by astronomical forcing, which appears to have left a detectable signature in SST trends.
Global glacier changes: a revised assessment of committed mass losses and sampling uncertainties
Authors: Mernild S. H. , Lipscomb W. H. , Bahr D. B. , Radić V. , Zemp M.
Published: October 2013

Abstract. Most glaciers and ice caps (GIC) are out of balance with the current climate. To return to equilibrium, GIC must thin and retreat, losing additional mass and raising sea level. Because glacier observations are sparse and geographically biased, there is an undersampling problem common to all global assessments. Here, we further develop an assessment approach based on accumulation-area ratios (AAR) to estimate committed mass losses and analyze the undersampling problem. We compiled all available AAR observations for 144 GIC from 1971 to 2010, and found that most glaciers and ice caps are farther from balance than previously believed. Accounting for regional and global undersampling errors, our model suggests that GIC are committed to additional losses of 32 ± 12% of their area and 38 ± 16% of their volume if the future climate resembles the climate of the past decade. These losses imply global mean sea-level rise of 163 ± 69 mm, assuming total glacier volume of 430 mm sea-level equivalent. To reduce the large uncertainties in these projections, more long-term glacier measurements are needed in poorly sampled regions.
THERMOGRAVIMETRIC ANALYSIS OF THE KINETICS OF BOUND-RUBBER FORMATION ON SURFACE-MODIFIED SILICA
Authors: Law Yuk Yu , Feke Donald L. , Manas-Zloczower Ica
Published: October 2013

Thermogravimetric analysis (TGA) has been used to study the kinetics of bound-rubber formation on the surface of silica modified with a bi-functional alkoxysilane coupling agent (CA) over the temperature range of 110 to 150 °C. The bound-rubber formation is attributed to the direct binding of a polymer chain with a number of nonpolar interactive sites provided by the CA molecules on the silica surface. A kinetic model developed for the reaction process suggests that the bound-rubber morphology is altered at temperatures above 110 °C.
EFFECTS OF SURFACE TREATMENTS AND SILICA SIZE ON MECHANICAL PROPERTIES OF SILICA-REINFORCED ELASTOMERIC COMPOSITES
Authors: Ryu Sang-Ryeoul , Lee Jun-Man , Lee Dong-Joo
Published: October 2013

The effect of surface treatments with atmospheric pressure flame plasma (APFP) and epoxy silane (ES) was studied experimentally to improve the mechanical properties of silica- (volume 40% and mean diameters of 2.2, 12.4, 26.6, and 110 μm) reinforced elastomeric composites. The tensile strength (TS) of the composites increased significantly with decreasing mean diameter. When the diameter was 2.2 μm, the TS of the composite was approximately 1.4 times higher than that of the matrix (2.52 MPa). In addition, the TS of the silica-reinforced composites treated with APFP and ES was increased by 8.8 to 13.3% and 9.9 to 12.5%, respectively, compared with that of the matrix. A larger particle size generally resulted in better surface treatment effects. When the diameter was 26.6 μm, the tensile modulus (TM) of the composite was increased approximately twofold compared with the matrix (0.88 MPa), and the TM of the silica-reinforced composites treated with APFP and ES was increased by 15.6 to 22.8% and 21.1 to 25.8%, respectively, compared with the matrix. Therefore, the importance of surface treatments increases with increasing filler particle size. A conventional silane-coupling agent treatment has few disadvantages, such as the use of organic solvents. Nevertheless, the APFP treatment is a fast, economic, and eco-friendly method for improving the mechanical properties.
Substitution of Conventional High-temperature Syntheses of Inorganic Compounds by Near-room-temperature Syntheses in Ionic Liquids
Authors: Groh Matthias F. , Müller Ulrike , Ahmed Ejaz , Rothenberger Alexander , Ruck Michael
Published: October 2013

The high-temperature syntheses of the low-valent halogenides P2I4, Te2Br, a-Te4I4, Te4(Al2Cl7)2, Te4(Bi6Cl20), Te8(Bi4Cl14), Bi8(AlCl4)2, Bi6Cl7, and Bi6Br7, as well as of WSCl4 and WOCl4 have been replaced by resource-efficient low-temperature syntheses in room temperature ionic liquids (RTILs). The simple one-pot syntheses generally do not require elaborate equipment such as two zone furnaces or evacuated silica ampoules. Compared to the published conventional approaches, reduction of reaction time (up to 80%) and temperature (up to 500 K) and, simultaneously, an increase in yield were achieved. In the majority of cases, the solid products were phase-pure. X-Ray diffraction on single crystals (redetermination of 11 crystal structures) has demonstrated that the quality of the crystals from RTILs is comparable to that of products obtained by chemical transport reactions.
[HMIM][Br9]: a Room-temperature Ionic Liquid Based on a Polybromide Anion
Authors: Haller Heike , Hog Michael , Scholz Franziska , Scherer Harald , Krossing Ingo , Riedel Sebastian
Published: October 2013

[HMIM][Br9] ([HMIM]=1-hexyl-3-methylimidazolium) has been investigated by Raman spectroscopy, single-crystal X-ray diffraction and NMR spectroscopy. Conductivity measurements show a high electrical conductivity like other polybromides.
The Differential Capacitance of Ionic Liquid / Metal Electrode Interfaces – A Critical Comparison of Experimental Results with Theoretical Predictions
Authors: Wallauer Jens , Drüschler Marcel , Huber Benedikt , Roling Bernhard
Published: October 2013

Results of potential-dependent differential capacitance measurements on the interface between six different ionic liquids and the (111) surface of single-crystalline gold are presented. The measurements were done by means of broadband impedance spectroscopy in a frequency range from 10 mHz to 1 MHz. We discuss the influence of the IL cation, the IL anion and the cations’ alkyl chain length on the interfacial capacitance. Our results suggest that (i) there is no simple relationship between the cation size and the value of the differential capacitance, (ii) the general shape of the potentialdependent differential capacitance curve is more strongly influenced by the IL anion, and (iii) experimental differential capacitance curves do not exhibit a simple “camel-” or “bell-shaped” curvature as predicted by mean-field theories. Furthermore, the broadband measurements show that two capacitive processes can be distinguished, which take place on millisecond and second time scales, respectively. While a millisecond time scale is expected for double-layer charging governed by the bulk conductivity of the IL, the existence of a slow process points to additional barriers for charge transport at the interface. The capacitance contribution of the slow process is most pronounced for ILs based on the N-butyl-N-methyl-pyrrolidinium ([Pyr1,4]) cation. A comparison of capacitance data with insitu STM data from previous studies suggests that the slow process is connected to herringbone-type structures at the interface. While the herringbone superstructure of the Au(111) surface is well known in aqueous electrochemistry, a herringbone-type structure of adsorbed ions was described in a recent MD simulation paper by Federov and coworkers (K. Kirchner, T. Kirchner, V. Ivaništĕv, M. V. Fedorov, Electrochim. Acta 2013, in press: doi: 10.1016/j.electacta.2013.05.049).
Surface-active Ionic Liquids for Micellar Extraction of Piperine from Black Pepper
Authors: Ressmann Anna K. , Zirbs Ronald , Pressler Martin , Gaertner Peter , Bica Katharina
Published: October 2013

We present the application of ionic liquid-aqueous micellar solutions as isolation media for the pharmaceutically active ingredient piperine from black pepper. Several surface-active ionic liquids including a biodegradable betaine derivative were used for the extraction of piperine, and a strong correlation between extraction yield and the critical micelle concentration of the respective ionic liquid was found. A scaled strategy for the isolation of piperine was developed that allowed recovery and recycling of the aqueous ionic liquid micellar solution for five runs without any loss in extraction efficiency.
How to Explain Electoral Turnout at the Individual Level
Authors: Linek Lukáš
Published: October 2013

In the last two decades, turnout research has disintegrated into a plethora of studies which focus on partial aspects of turnout. The overall idea of why people vote has been lost. Despite extensive research on turnout, we know relatively little about why people vote. The aim of this text is to present and critically discuss basic theories that explain voter turnout at the individual level. Overall, six theories are presented: the theory of socio-economic status and resources, the theory of civic orientations, the theory of mobilization and involvement in society, the theory of rational choice, the theory of valence politics, and the theory of habitual voting. These theories are discussed mainly from three aspects: (1) the causal mechanisms explaining why people vote; (2) the extent to which each theory links the decision to participate in an election with the decision about which party or candidate to vote for, as well as the sequence of these decisions; and (3) the timing of voters’ decisions to participate in an election. The author argues that because of the heterogeneity of voters and the nature of the decision whether or not to vote, it is necessary to understand individual theories not as competitive, but rather as complementary.
Comparison of the West European Regional Second Chambers and Alternatives of Regionalization of the Senate of the Parliament of the Czech Republic
Authors: Murár Filip
Published: October 2013

The aim of the presented paper is to frame specific alternatives for the regional reform of the second chamber of the Czech legislature on the basis of a comparative analysis of regional second chambers in Western Europe. The similarities and differences between second chambers of parliament in Italy, Spain, the Netherlands and France are identified (with respect to their historical origin, the method of election, size, political composition, constitutional powers, relation to the first chamber and relation to the executive branch of power). Also the strength of the second chambers is analyzed and the chambers are put on Lijphart’s typological scale according to the criteria of congruence and symmetry. The analysis is then the source for two main alternatives for the possible regional reform of the Czech Senate – representative regional reform and functional regional reform.
Le leadership transformationnel comme source d’engagement syndical
Authors: Fortin-Bergeron Chloé , Doucet Olivier , Hennebert Marc-Antonin
Published: October 2013

Si certains travaux sur le renouveau syndical reconnaissent l’importance de s’intéresser au fait représentatif et plus particulièrement à la relation représentant-représenté, les effets du leadership des représentants syndicaux sur leurs membres demeurent très peu étudiés. Pour pallier ce déficit analytique, cette étude analyse l’effet direct du leadership transformationnel du représentant syndical sur l’engagement syndical ainsi que l’effet modérateur de la justice distributive et procédurale du syndicat local sur cette relation.

Des analyses de régressions linéaires multiples, menées auprès d’un échantillon de 834 travailleurs syndiqués d’une entreprise québécoise, soutiennent l’existence d’un lien positif entre le leadership transformationnel du représentant syndical et l’engagement envers le syndicat, et ce, après avoir contrôlé certaines caractéristiques des répondants dont l’âge, le sexe, l’ancienneté et le niveau de scolarité. En outre, nos résultats démontrent que la justice syndicale de type procédural modère cette relation. En ce sens, un syndicat local reconnu comme offrant des procédures justes et équitables viendrait rehausser les efforts de leadership de ses représentants.

Sur le plan théorique, cette étude supporte la théorie des échanges sociaux ainsi que le modèle d’engagement au groupe, en démontrant notamment que la justice et le leadership transformationnel jouent sur des mécanismes affectifs similaires. Sur le plan pratique, les résultats soulignent l’importance, pour les syndicats locaux, de se pencher sur les pratiques et sur les modes de fonctionnement au niveau local qui sont susceptibles de favoriser la perception de justice procédurale. Ces constats ouvrent ainsi de nouvelles avenues de recherche relatives aux efforts de revitalisation des syndicats locaux et, plus spécifiquement, aux effets du leadership syndical et à la dynamique sous-jacente à la relation représentant-représenté.
Le retour au travail lors d’un deuil périnatal
Authors: Gagnon Mélanie , Beaudry Catherine
Published: October 2013

Cette recherche empirique qualitative de type exploratoire a pour objectif principal de lever le voile sur l’expérience de retour au travail d’employés vivant un deuil périnatal. Plusieurs recherches s’attachent à décrire et à étudier les conséquences d’un deuil périnatal chez les parents. Il est alors établi que le deuil périnatal se distingue des autres types de deuil, bien que l’intensité de la douleur vécue soit aussi importante.

Pour l’heure, la littérature en ressources humaines se fait plutôt discrète sur la problématique du deuil périnatal spécifiquement en contexte de retour au travail. De fait, il devient nécessaire de référer à des études s’intéressant au retour au travail à la suite d’autres types de difficultés personnelles. À ce sujet, les écrits soulèvent trois catégories de facteurs influençant le retour au travail : les facteurs sociaux, organisationnels et individuels.

L’importance de la perte que le deuil périnatal représente pour les parents endeuillés est souvent sous-estimée au sein des organisations. Lorsque les parents reviennent au travail après la perte de l’enfant à naître ou de leur nourrisson, ils sont fréquemment encore bien ancrés dans leur « processus de deuil » et d’adaptation à celui-ci. Or, le retour au travail dans le cadre d’un tel type de deuil est généralement peu encadré par les organisations. Cette étude fait donc état du vécu des employés en deuil au moment de leur réinvestissement en emploi. Afin d’explorer leur expérience, trois groupes de discussion ont été menés au Québec, avec des femmes ayant vécu la perte de leur enfant à naître ou de leur nourrisson.

L’analyse de contenu a permis de conclure que la prise d’un congé à la suite du décès de l’enfant à naître ou du nourrisson, bien qu’importante, est insuffisante à elle seule, puisque lors de la reprise du travail, l’adaptation au deuil n’est pas terminée. Le facteur qui semble le plus déterminant au regard d’une réinsertion réussie s’avère le soutien que procurent les organisations par le biais de diverses pratiques, les plus importantes étant l’accès à un programme d’aide aux employés et l’aménagement du travail.
Dis-identification in Organizations and Its Role in the Workplace
Authors: Chang Kirk , Kuo Chien-Chih , Su Man , Taylor Julie
Published: October 2013

Considerable theory and research has revealed that organizational identification (OID) benefits individuals and groups and that OID facilitates the development of long-term commitment and support towards an organization. Prior studies have highlighted the importance of an identification mechanism in the workplace, i.e., how employees define their self-concepts vis-à-vis their connections with their organizations. In contrast to previous research, we explore the process by which employees divorce their identity from that of their organization, i.e., defining who they are by what they are not. Interestingly, how individuals dis-identify themselves from the organization still remains unclear, and the concept of dis-identification in organization (DiO) has not drawn much academic attention. The paucity of research in this area leaves theories under-developed; thus, our research seeks to shed new light on the concept of DiO and understand its importance at work.

An anonymous questionnaire survey was conducted, recruiting 304 employees across eight organizations in Taiwan. Different from prior studies, this research stated that OID and DiO were neither heterogeneous nor independent constructs. Statistical evidence affirmed this statement further and explained that OID and DiO were inter-related constructs. Moreover, two DiO antecedents were discovered, including: person-organization fit and abusive supervision. Unlike in previous studies, DiO was not correlated with poor employee performance; rather, it was correlated with workplace deviance, an intention of quitting the job, and voice-extra-role-behaviour.

Organizations are complex entities by their very nature. Whether an organization can continue, function and succeed may depend upon a series of organizational characteristics. An organization is like a social arrangement that pursues collective goals, controls its own performance, and has a boundary separating it from its environment. One such organizational characteristic is identification. With a better understanding of OID/DiO, managers and HR practitioners can better observe the influence of OID/DiO and develop policies to increase employees’ identification and decrease dis-identification. Ultimately, employers, employees and society will enjoy the benefits of better organizations, e.g., higher working morale, more performance output, stronger membership/cohesion, and lower turnover.
Des conflits de rôle au stress perçu
Authors: Codo Sylvie , Soparnot Richard
Published: October 2013

De nombreuses recherches présentent le soutien social perçu comme un levier efficace de gestion du stress au travail. Notre recherche propose de vérifier cette hypothèse en interrogeant le rôle modérateur attribué au soutien social perçu provenant des supérieurs et des subordonnés dans les relations entre les conflits de rôle et le stress chez des managers intermédiaires (MI) et des managers de proximité (MP) du secteur public. Le modèle exigences-ressources professionnelles (Bakker et Demerouti, 2007) nous a servi de cadre théorique. D’après ce modèle, le soutien social perçu constitue une ressource professionnelle permettant d’atténuer les effets délétères des exigences professionnelles sur la santé mentale. Les données collectées auprès de 310 managers dans des administrations publiques locales confirment partiellement cette hypothèse. En effet, notre recherche ne permet pas d’appuyer dans un premier temps l’influence modératrice du soutien social perçu provenant des supérieurs et du soutien social perçu provenant des subordonnés dans la relation entre les conflits de rôle et le stress perçu chez les MI. Des résultats similaires sont observés dans certains cas chez des MP. Conséquemment, l’hypothèse de la non-mobilisation du soutien social comme une ressource professionnelle par les managers dans certaines conditions est avancée pour discuter ces résultats. Ces derniers révèlent dans un second temps que l’efficacité du soutien social perçu dépend de plusieurs facteurs : la nature et la source du soutien social perçu, le type de conflit de rôle en présence et le niveau hiérarchique des managers bénéficiaires (MI et MP). Ainsi, plus que MI, les MP semblent plus réceptifs au soutien social d’estime perçu provenant de leurs supérieurs lorsqu’ils sont confrontés aux conflits de rôle. Par conséquent, leur niveau de stress diminue. Afin de gérer le stress des MP occasionné par les conflits de rôle, nos implications managériales sont orientées vers une reconnaissance de leurs compétences professionnelles.
Solid‐phase Organic Synthesis of Drugs and Natural Products
Authors: Scott Peter J. H.
Published: October 2013

Solid‐phase organic synthesis (SPOS), in which molecules are constructed on insoluble polymer resin beads, has had an enormous impact on organic synthesis since its introduction in 1963. The ability to purify reactions by simple filtration and subsequent washing of the beads facilitates driving reactions to completion through the use of reagent excesses unsuitable for traditional solution‐phase reactions and purification techniques. These advantages are particularly amenable to the synthesis of drugs and natural products, where driving reactions to completion and having a straightforward means of purifying and recovering small amounts of valuable products are of paramount importance. Reflecting this, SPOS has been widely applied to the art and science of total synthesis, and the solid‐phase synthesis of numerous ambitious targets has been realized. This chapter reviews the many elegant solid‐phase syntheses of drugs and natural products reported to date, highlighting strategies permitting asymmetric synthesis and reporting on experimental procedures for key solid‐phase manipulations.
Asymmetric Phase‐Transfer Catalysis
Authors: Ohmatsu Kohsuke , Uraguchi Daisuke , Ooi Takashi
Published: October 2013

Asymmetric phase‐transfer catalysis based on the use of chiral onium salts has become a topic of great scientific interest, and enormous efforts have resulted in significant advances, making it feasible to perform various bond‐forming reactions under mild biphasic conditions. This chapter describes fruitful applications of phase‐transfer reactions for the asymmetric total syntheses of biologically relevant organic compounds. Asymmetric phase‐transfer alkylation of a glycine‐derived Schiff base provides the straightforward route to a wide variety of natural and unnatural α‐amino acids, and therefore it has emerged as a powerful tool for the efficient asymmetric synthesis of α‐amino‐acid–derived natural products and pharmaceuticals. Other stereoselective phase‐transfer reactions, such as the Mannich‐type reaction, Henry reaction, Michael addition, protonation, epoxidation, and α‐hydroxylation, have also been used in the practical total synthesis of various complex molecules.
Stereoselective Nozaki‐Hiyama‐Kishi Reaction
Authors: Hargaden Gráinne C. , Guiry Patrick J.
Published: October 2013

This chapter reviews the literature on the development of the Nozaki‐Hiyama‐Kishi (NHK) reaction into an important chromium‐mediated, stereoselective, carbon–carbon, bond‐forming process. The initial research employed stoichiometric quantities of chromium, and this was exploited in the key steps of a range of total syntheses. Thereafter, the NHK reaction was further developed with the discovery of the catalytic variant. The focus of recent investigations has been on the application of this reaction in asymmetric synthesis. The asymmetric NHK typically employed a range of salen‐ and oxazoline‐derived chiral ligands and tethered bis(8‐quinolinato)‐chromium complexes. To date, good‐to‐high enantioselectivities have been obtained in a variety of NHK‐type processes, including allylation, crotylation, methallylation, allenylation, propargylation, homoallenylation, and vinylation of a range of aldehydes, with limited examples employing ketones as substrates. Selected examples of the asymmetric NHK in total synthesis will be described, in addition to selected experimental procedures.
Stereoselective Formation of 2‐Deoxyglycosidic Bonds in Biologically Active Natural Products
Authors: Takahashi Daisuke , Toshima Kazunobu
Published: October 2013

This chapter deals with selected and recent stereocontrolled glycosylation methods including direct and indirect glycosylations, as well as withde novosynthetic approaches to 2‐deoxyglycosides. In addition, representative and significant applications of these methods to biologically active natural products possessing 2‐deoxyglycosides are introduced.
Solid‐StateNMRSpectroscopy in Drug Design and Discovery
Authors: Middleton David A. , Patching Simon G.
Published: October 2013

This chapter gives an overview and describes the current status and future potential for solid‐state nuclear magnetic resonance (NMR) spectroscopy in drug design and discovery. Using illustrated examples, it deals first with the unique roles that the technique can provide in the pharmaceutical development process, including characterization and analysis of drug compound polymorphism, chiral purity and quantitation, and the use of “NMR crystallography” for solving the structures of small organic molecules, polymers, and biomacromolecules. It then deals with applications of the technique in the drug discovery process, including investigation of drug–membrane interactions, for screening ligand–receptor interactions, and for elucidating the structures of ligand‐binding sites. The importance of isotope labeling is also considered and demonstrated with the stereoselective synthesis of a site‐specific labeled ligand.
Determination of Absolute Configuration Using Chiroptical Methods
Authors: Batista JoÃo Marcos
Published: October 2013

Among different methods capable of determining the absolute configuration (AC) of chiral organic compounds, including pharmaceutical drugs and natural products, the use of chiroptical spectroscopic methods has recently faced a renaissance. These methods involve optical rotation (OR), optical rotatory dispersion (ORD), electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA). The widespread use of such spectroscopic tools derives mainly from the availability of commercial instrumentation and the recent advances in quantum chemical calculations to predict theoretical spectra. This chapter is aimed at covering the current state‐of‐the‐art of chiroptical spectroscopy in combination with quantum chemical calculations to determine the AC of chiral molecules. While providing some background and examples on OR and ORD, as well as in more recent techniques, such as ROA, this chapter will be focused on the use of both electronic and vibrational forms of circular dichroism to solve stereochemical problems. A practical stepwise approach will be adopted to guide the reader through the advantages and limitations of each technique pointing out how to measure and calculate chiroptical properties. Finally, recent examples of the application of the above‐mentioned chiroptical methods, either alone or in combination, for the analysis of pharmaceutical drugs and natural products will be provided.
Chiral Chromatographic Methods in the Analysis and Purification of Enantiomers
Authors: Novell Arnau , Minguillón Cristina
Published: October 2013

The increasing significance of chirality in the different fields involving products aimed to interact with biological systems has led to the need to control and produce enantiomerically pure compounds. Chromatography using chiral stationary phases (CSPs) plays an outstanding role in this context.

Diverse chromatographic modalities are used in the separation of enantiomers. Among them, enantioselective liquid chromatography is considered at present to be one of the most general methods for the analytical control of the enantiomeric content in samples. Additionally, liquid chromatography is increasingly applied in the purification and isolation of enantiomers from their mixtures. The diversity of CSPs, their characteristics, and their chromatographic conditions of use will be discussed.
X
‐ray Crystallography and
1
H
NMR
Anisotropy Methods for Determination of Absolute Configurations
Authors: Harada Nobuyuki
Published: October 2013

In the stereoselective synthesis of drugs and natural products, it is critical to determine the absolute configurations (ACs) of reaction products. To determine the ACs of chiral compounds, many spectroscopic and diffraction methods have been developed. Among them, X‐ray crystallographic Bijvoet and circular dichroism (CD) exciton chirality methods enable one to determine ACs in a nonempirical manner. On the other hand, X‐ray crystallography using a chiral internal reference and
1
H nuclear magnetic resonance (NMR) spectroscopy using a chiral anisotropy reagent are relative and/or empirical methods, but they are more practical for organic synthetic studies because the methods have the advantage of preparing enantiopure compounds by high‐performance liquid chromatography (HPLC) separation and of establishing unambiguously the ACs. As chiral reagents useful for both the preparation of enantiopure compounds by HPLC separation and the simultaneous determination of their ACs, we have developed camphorsultam‐dichlorophthalic acid (CSDP acid) for X‐ray crystallography and 2‐methoxy‐2‐(1‐naphthyl)propionic acid (MαNP acid) for
1
H NMR spectroscopy and X‐ray crystallography. In this chapter, the outline and applications of these X‐ray and NMR methods are explained using various interesting data.
Discovery of a New Class of Immunosuppressants from Trichothecium roseum Co‐inspired by Cross‐Kingdom Similarity in Innate Immunity and Pharmacophore Motif
Authors: Zhang Ai Hua , Wang Xing Qi , Han Wen Bo , Sun Yang , Guo Ye , Wu Qi , Ge Hui Ming , Song Yong Chun , Ng Seik Weng , Xu Qiang , Tan Ren Xiang
Published: October 2013

The limited selection of immunosuppressants in the clinic hampers the efficient management of immune disorders such as rejections after organ transplantations. However, the search for new immunosuppressive compounds remains random and creates inevitably financial and laborious wastes. Herein, we present an immunity‐inspired discovery strategy that rationally allows an efficient identification of immunosuppressive compounds from the endophyte culture, as exemplified by the new peptide trichomide A. This compound exerts its immunosuppressive action more selectively than cyclosporin A. It was found that trichomide A decreases the expression of Bcl‐2, increases the expression of Bax, and has a small or negligible effect on the expressions of p‐Akt, CD25, and CD69. Our study strengthens the idea that the cross‐kingdom similarity in immunity among living things could provide a shorter route towards the identification of natural products valuable for the development of new immunosuppressants.
Reaction‐Based Ratiometric Chemosensor for Instant Detection of Cyanide in Water with High Selectivity and Sensitivity
Authors: Lin Qi , Liu Xin , Wei Tai‐Bao , Zhang You‐Ming
Published: October 2013

A highly selective chemosensor 1 based on an acylhydrazone group as binding site and naphthalene group as the fluorescence signal group were described, which could instantly detect CN− in water with specific selectivity and high sensitivity. The detection of cyanide was performed via the nucleophilic attack of cyanide anion on the carbonyl group, which could be confirmed by 1H NMR, 13C NMR, ESI‐MS and DFT calculations. The addition of CN− to sensor 1 induced a remarkable color change from colorless to yellow and generated a blue fluorescence, these sense procedure could not interfered by other coexistent competitive anions (F−, Cl−, Br−, I−, AcO−, H2PO4−, HSO4−, ClO4−, SCN−, S2−, NO3− and SO42−). The detection limits were 5.0×10−7 M and 2.0×10−9 M of CN− using the visual fluorescent color changes and fluorescence spectra changes respectively, which is far lower than the WHO guideline of 1.9×10−6 M. Test strips based on sensor 1 were fabricated, which could act as a convenient and efficient CN− test kit to detect CN− in pure water for “in‐the‐field” measurement.
Water‐ and Organo‐Dispersible Gold Nanoparticles Supported by Using Ammonium Salts of Hyperbranched Polystyrene: Preparation and Catalysis
Authors: Gao Lei , Nishikata Takashi , Kojima Keisuke , Chikama Katsumi , Nagashima Hideo
Published: October 2013

Gold nanoparticles (1 nm in size) stabilized by ammonium salts of hyperbranched polystyrene are prepared. Selection of the R groups provides access to both water‐ and organo‐dispersible gold nanoparticles. The resulting gold nanoparticles are subjected to studies on catalysis in solution, which include reduction of 4‐nitrophenol with sodium borohydride, aerobic oxidation of alcohols, and homocoupling of phenylboronic acid. In the reduction of 4‐nitrophenol, the catalytic activity is clearly dependent on the size of the gold nanoparticles. For the aerobic oxidation of alcohols, two types of biphasic oxidation are achieved: one is the catalyst dispersing in the aqueous phase, whereas the other is in the organic phase. The catalysts are reusable more than four times without loss of the catalytic activity. Selective synthesis of biphenyl is achieved by the homocoupling of phenylboronic acid catalyzed by organo‐dispersible gold nanoparticles.
Selective Transportation of Microdroplets Assisted by a Superhydrophobic Surface with pH‐Responsive Adhesion
Authors: Cheng Zhongjun , Du Ming , Lai Hua , Du Ying , Zhang Naiqing , Sun Kening
Published: October 2013

We report a new strategy to realize the selective transportation of microdroplets assisted by a superhydrophobic surface with pH‐responsive adhesion. On the surface, only basic microdroplets can be pinned and acidic or neutral microdroplets can easily roll off. Therefore, by using the surface as a “mechanical hand”, microdroplets can be transported selectively according to one’s requirements by simply controlling the pH of the solution. The special ability of the surface to achieve selective transportation is ascribed to the following two reasons: 1) superhydrophobicity, which can avoid the wetting problem, and 2) pH‐responsive adhesion, which results from the combined effect of chemical variation of the carboxylic acid group and microstructures on the surface. Furthermore, we also demonstrated a process of selective transportation of microdroplets for applications in droplet‐based microreactors through our surface. The results reported herein advance a new method to realize the selective transportation of microdroplets and we believe that this method could potentially be used in a wide range of applications, such as biomolecular detection and transportation in biochips.
Heterogeneous versus Homogeneous Copper(II) Catalysis in Enantioselective Conjugate‐Addition Reactions of Boron in Water
Authors: Kitanosono Taku , Xu Pengyu , Kobayashi Shū
Published: October 2013

We have developed CuII‐catalyzed enantioselective conjugate‐addition reactions of boron to α,β‐unsaturated carbonyl compounds and α,β,γ,δ‐unsaturated carbonyl compounds in water. In contrast to the previously reported CuI catalysis that required organic solvents, chiral CuII catalysis was found to proceed efficiently in water. Three catalyst systems have been exploited: cat. 1: Cu(OH)2 with chiral ligand L1; cat. 2: Cu(OH)2 and acetic acid with ligand L1; and cat. 3: Cu(OAc)2 with ligand L1. Whereas cat. 1 is a heterogeneous system, cat. 2 and cat. 3 are homogeneous systems. We tested 27 α,β‐unsaturated carbonyl compounds and an α,β‐unsaturated nitrile compound, including acyclic and cyclic α,β‐unsaturated ketones, acyclic and cyclic β,β‐disubstituted enones, acyclic and cyclic α,β‐unsaturated esters (including their β,β‐disubstituted forms), and acyclic α,β‐unsaturated amides (including their β,β‐disubstituted forms). We found that cat. 2 and cat. 3 showed high yields and enantioselectivities for almost all substrates. Notably, no catalysts that can tolerate all of these substrates with high yields and high enantioselectivities have been reported for the conjugate addition of boron. Heterogeneous cat. 1 also gave high yields and enantioselectivities with some substrates and also gave the highest TOF (43 200 h−1) for an asymmetric conjugate‐addition reaction of boron. In addition, the catalyst systems were also applicable to the conjugate addition of boron to α,β,γ,δ‐unsaturated carbonyl compounds, although such reactions have previously been very limited in the literature, even in organic solvents. 1,4‐Addition products were obtained in high yields and enantioselectivities in the reactions of acyclic α,β,γ,δ‐unsaturated carbonyl compounds with diboron 2 by using cat. 1, cat. 2, or cat. 3. On the other hand, in the reactions of cyclic α,β,γ,δ‐unsaturated carbonyl compounds with compound 2, whereas 1,4‐addition products were exclusively obtained by using cat. 2 or cat. 3, 1,6‐addition products were exclusively produced by using cat. 1. Similar unique reactivities and selectivities were also shown in the reactions of cyclic trienones. Finally, the reaction mechanisms of these unique conjugate‐addition reactions in water were investigated and we propose stereochemical models that are supported by X‐ray crystallography and MS (ESI) analysis. Although the role of water has not been completely revealed, water is expected to be effective in the activation of a borylcopper(II) intermediate and a protonation event subsequent to the nucleophilic addition step, thereby leading to overwhelmingly high catalytic turnover.