pinecone/core-2020-05-10-deduplication huggingface dataset:
Value Co-creation with Stakeholders Using Action Research as a Meta-methodology in a Funded Research Project

A large applied research study is a challenging exercise in project management and is often unpredictable because of its complexity. In the beginning, funding bodies, ethics committees, and participating organizations expect a plan of what is intended. As the research evolves, researchers must meet the expectations of stakeholders while being responsive to the emergent reality that the research faces and partly uncovers. This article describes action research used as an umbrella process that enabled us to manage the research project. We used action research as a meta-methodology—that is, a process that can subsume multiple subprocesses and under which these contradicting demands can be satisfied. In particular, two characteristics enable action research to do this. One is its cyclic process, iteratively tracing out a rhythm of planning, acting, and observing the results. The other is the nesting of its cycles, applied at scales ranging from the overall study to the moment-by-moment facilitation. We illustrate this use of action research with examples from a long-term applied study of leadership in faith-based, not-for-profit organizations
Mixed Methods Use in Project Management Research

Despite positivist traditions mixed methods (MM) research is increasingly being used in management disciplines. The aim of the study is to examine the use and quality of MM in project management research. A content analysis of articles from three project management journals was undertaken. The MM articles identified were analysed in terms of sequencing, dominance and integration. Our findings suggest the need for capacity building in relation to the good reporting of MM studies. We conclude that the study of complex phenomena can benefit from MM in a field needing to b r e a k f r e e from a level of methodological inertia
A Contingency Approach on the Impact of Front-End Success on Project Portfolio Success

This is the article as published by PMIThe pre-project or ideation phase is often
disregarded in project portfolio management.
Senior managers put more emphasis
on later project stages, and researchers predominantly
investigate the front end from a
single project perspective. This study investigates
how and under which circumstances
the performance of the front end affects
project portfolio success. Using a sample
of 175 firms, we confirm a strong positive
relationship between front-end success and
project portfolio success. Results show that
this effect becomes stronger for larger project
portfolios, for portfolios with more interdependency
between projects and, finally,
for firms that have a strategic orientation
toward riskiness.1,Tillatels
Ru(III)​, Os(VIII)​, Pd(II)​, and Pt(IV) catalyzed oxidation of glycyl-​glycine by sodium N-​chloro-​p-​toluenesulfonamide: comparative mechanistic aspects and kinetic modeling

The Ru(III)​/Os(VIII)​/Pd(II)​/Pt(IV)​-​catalyzed kinetics of oxidn. of glycylglycine (Gly-​Gly) by sodium N-​chloro-​p-​toluenesulfonamide (chloramine-​T; CAT) in NaOH medium has been investigated at 308 K.  The stoichiometry and oxidn. products in each case were found to be the same but their kinetic patterns obsd. are different.  Under comparable exptl. conditions, the oxidn.-​kinetics and mechanistic behavior of Gly-​Gly with CAT in NaOH medium is different for each catalyst and obeys the underlying rate laws.  Rate = k [CAT]​t [Gly-​Gly]​o [Ru(III)​]​[OH-​]​x.  Rate = k [CAT]​t[Gly-​Gly]​x [Os(VIII)​]​y[OH-​]​z.  Rate = k [CAT]​t[Gly-​Gly]​x [Pd(II)​]​[OH-​]​y.  Rate = k [CAT]​t[Gly-​Gly]​o [Pt(IV)​]​x[OH-​]​y.  For all cases, x, y, z < 1.  The anion of CAT, CH3C6H4SO2NCl-​, has been postulated as the common reactive oxidizing species in all the cases.  Under comparable exptl. conditions, the relative ability of these catalysts towards oxidn. of Gly-​Gly by CAT are in the order: Os(VIII) > Ru(III) > Pt(IV) > Pd(II)​.  This trend may be attributed to the different d-​electronic configuration of the catalysts.  Further, the rates of oxidn. of all the four catalyzed reactions have been compared with uncatalyzed reactions, under identical exptl. conditions.  It was found that the catalyzed reaction rates are 7- to 24-​fold faster.  Based on the obsd. exptl. results, detailed mechanistic interpretation and the related kinetic modeling have been worked out for each catalyst
The enthalpies of dissociation of the N-O bonds in two quinoxaline derivatives

The present work reports the first experimental thermochemical study of mono-N-oxides derived from quinoxaline, namely, 3-methoxycarbonyl-2-methyl-quinoxaline N-oxide and 3-ethoxycarbonyl-2-methyl-quinoxaline N-oxide. The values of the enthalpies of formation, in the condensed state, and of the enthalpies of sublimation, derived from static bomb calorimetry and Calvet microcalorimetry measurements, respectively, are combined to derive the standard molar enthalpies of formation in the gaseous phase for these two compounds. From the latter values, the first and second N-O bond dissociation enthalpies for the corresponding di-N-oxides have been obtained. The gas-phase experimental results are also compared with calculated data obtained with a density functional theory approach. Copyright (c) 2008 John Wiley & Sons, Ltd
Synthesis and evaluation of new thienyl and bithienyl-bis-indolylmethanes as colorimetric sensors for anions

The synthesis and full characterization of new bis-indolylmethanes containing thienyl and bithienyl moieties are reported. The sensor ability of the compounds in the presence of halide ions (F-, Cl-, Br- and I-), NO3-, ClO4-, SO42-, CN- and OH- ions was investigated in acetonitrile. The experimental results indicate that they could act as selective chromogenic-sensing molecules for the most basic anions F-, CN- and OH-, as a well-defined color change from yellow to pink was observed. The interaction constants between compounds 1 and 2 in the presence of F-, CN- and OH- were calculated and increased in the order OH- > F- > CN-.Fundação para a Ciência e a Tecnologia  (FCT
Quantum catalysis? A comment on tunnelling contributions for catalysed and uncatalysed reactions

Appreciation for the contribution of nuclear quantum effects (NQEs) to chemical reactivity predates transition-state theory (TST). Quantum corrections to rate constants for the reactions catalysed by lactate dehydrogenase (LDH) and formate dehydrogenase (FDH) and the same reactions in water are estimated by Bell's one-dimensional approximate method and give tunnelling contributions to catalysis of 1.6 and 0.95, respectively. Published results for NQEs, including both tunnelling and zero-point energies, estimated by the quantum classical path method for LDH, carbonic anhydrase, glyoxylase I and lipoxygenase, together with the corresponding reactions in water, are reviewed: the respective contributions to catalysis are 0.66, 5, 1 and 1. In the absence of better evidence that an enzymic rate enhancement is due to a significantly larger quantum correction for the enzyme-catalysed reaction than for an appropriate uncatalysed reference reaction, it is suggested that the term 'quantum catalysis' should be used with caution and restraint
QM/MM kinetic isotope effects for chloromethane hydrolysis in water

Computational simulations for chloromethane hydrolysis have been performed using hybrid quantum-mechanical/molecular-mechanical methods with explicit solvation by large numbers of water molecules. In the first part of the paper, we present results for 2° 2H3, 1° 14C, and 1° 37Cl kinetic isotope effects (KIEs) at 298 K with both the AM1/TIP3P and B3LYP/6-31G* QM methods for the nucleophile H2O and electrophile CH3Cl surrounded by 496 solvating TIP3P water molecules. An initial Hessian computed for a subset of this system including up to 104 MM water molecules was reduced in size by successive deletion of rows and columns, and KIEs were evaluated for each. We suggest that accurate calculations of KIEs in solvated systems should involve a subset Hessian including the substrate together with any solvent atoms making specific interactions with any isotopically substituted atom. In the second part of the paper, the ensemble-averaged 2° α-2H3 KIE calculated with the B3LYP/6-31+G(d,p)/TIP3P method is shown to be in good agreement with experiment. This comparison is meaningful because it includes consideration of uncertainties owing to sampling of a range of representative thermally accessible solvent configurations. We also present ensemble-averaged 14C and 37Cl KIEs which have not as yet been determined experimentally
Substituent effects on the dehydration of arene hydrates in aqueous solution.

Rate constants have been determined by UV spectrophotometry at 25 °C for the acid-catalyzed dehydration of different types of monocyclic arene hydrates including those substituted at the 1-, 2- or 3-positions. General acid catalysis was not observed, and linear plots of pseudo-first-order rate constants for dehydration against hydronium concentration were obtained. A Hammett plot of the second-order rate constants for acid-catalyzed dehydration, kH (M−1s−1), of unsubstituted- (8a), 3-substituted (8b, 8c, 8d, 8e) and 1-substituted-benzene hydrates (14f and 14h) shows an excellent correlation with σ+ values and yields a large negative ρ-value of –6.5. The results are consistent with rate-determining formation of a benzenium ion in which direct mesomeric interaction with the substituent occurs, presumably permitted by the coplanar arrangement of the diene and carbocation centre in the intermediate. Data points for 2-substituted arene hydrates (13f, 13g, 13h, 13i) deviate negatively from the Hammett plot as direct mesomeric interaction with the substituent is not possible in the corresponding benzenium intermediates
Proton transfer reactions of hydrazine-boranes

International audienceHydrazine-borane and hydrazine-diborane contain respectively 15.4 and 16.9 wt% of hydrogen and are potential materials for hydrogen storage. In this work we present the gas-phase complexation energies, acidities and basicities of hydrazine-borane and hydrazine-bisborane calculated at MP2/6-311+G(d,p) level. We also report the release of dihydrogen from both protonated complexes (Ghydrazine-borane = –20.9 kcal/mol and Ghydrazine-bisborane = –27.2 kcal/mol) which is much more exergonic than from analogues amine-boranes. The addition of the first BH3 to the hydrazine releases 17.1 kcal/mol and the second addition releases 15.8 kcal/mol. The attachment of BH3 also increases the N-H acidity of hydrazine by 46.3 kcal/mol. It was found that the B-H deprotonation leads to intramolecular rearrangement. The basicity values for hydrazine-borane and –bisborane are 180 and 172.8 kcal/mol respectively. For both complexes the protonation centres are located at the boron moiety. The protonated structure of hydrazine-bisborane is cyclic and can be described as H2 captured between a negatively charged B-H hydrogen and positive boron (B-H••H2••B). Atoms in Molecules analysis is used to investigate bond paths in concerning structures
On the reactivity of naphthalene and biphenyl dianions: tying up loose ends concerning an SN2-ET dichotomy in alkylation reactions

Naphthalene and biphenyl dianions are interesting compounds that can be obtained by double reduction of the corresponding arenes in solution with certain alkali metals. These dianions are highly reactive and rather elusive species with very high laying and highly delocalized electrons. They share many aspects of the reactivity of the alkali metal they originated from and consequently behave primarily as strong electron transfer (ET) reagents. We report here kinetic evidence for a different type of reactivity in their alkylation reactions with alkyl fluorides. By using cyclopropylmethyl fluoride (c-C3H5CH2F) as a very fast radical probe, we were able to settle that this alkylation does not involve the classical electron transfer reaction followed by radical coupling between diffusing radicals, but supports the alternative SN2 concerted mechanism, discerning thus this mechanistic SN2-ET dichotomy.This work was generously supported by the Spanish Ministerio de Educación y Ciencia (CTQ2011-24165) and the Universidad de Alicante. IB thanks the Instituto de Síntesis Orgánica for financial support
Quantification of the nucleophilic reactivity of nicotine

Rate and equilibrium constants of the reactions of nicotine and structurally related compounds with benzhydrylium ions have been determined UV-Vis spectroscopically using stopped-flow and laser-flash techniques. The pyridine nitrogen of nicotine was identified as the site of thermodynamically and kinetically controlled attack. Quantum chemical calculations showed that the introduction of a pyrid-3-yl moiety into the 2-position of N-methylpyrrolidine (to give nicotine) reduces the Lewis basicity of the pyrrolidine ring by 24kJmol(-1), whereas the analogous introduction of a phenyl ring decreases this quantity by only 11kJmol(-1)
Density functional theoretical studies on photoswitching and charge migration dynamics of thio and selenoureidopeptides

Density functional theoretical calculations have been performed to investigate the changes in electronic structure at ground and excited states of ureidopeptides on substitution with higher chalcogens like sulphur and selenium for oxygen. This replacement results in a reduced preference towards the intramolecular hydrogen bonding interaction, thus linear conformers are found to be stable at both states. Nevertheless, conformational switching observed during this process is mainly due to n to Ï�* transition that leads to the dihedral angle Ï� change from trans to cis with a rotational barrier of 10 to 17 kcal mol-1. The computed barrier is lesser than that reported for oxopeptides (20Â kcal mol-1). And, the hole migration dynamics after immediate ionization illustrates that the hole originated at ureido end evolves in time (2â��4Â fs) while the hole generated at the carboxylate end will not evolve as reported for ureidopeptides. The usage of these candidates as photoswitches has also been explored. Copyright Â© 2017 John Wiley & Sons, Ltd
A Theoretical Study of Cr/oxide Catalysts for Dehydrogenation of Short Alkanes

Natural gas reserves are being produced at increasing rates world wide, thus providing an
abundance of short-alkane feedstock for the petrochemical industry. Effective routes to
selective activation of short alkanes may represent a bottleneck of this development. In
this respect, processes of catalytic dehydrogenation have significant economic potential.
Several catalysts have been investigated and some are implemented industrially. At the
core of one such catalyst are species of chromium oxide supported on the surface of amorphous
alumina. Since the original report by Frey and Huppke in 1933, this system has
been under study, the literature expanding with the development of experimental methods.
However, due to the heterogeneity of the Cr/alumina surfaces a structure-activity
relationship has not been determined to date. Opinions are converging regarding the oxidation
state of active chromium, but little is known about the nano-range surroundings
of the active site. The involvement of oxygen ligands is a popular issue related to the
mechanism of catalysis. Other remaining questions concern the chromium nuclearity of
the active surface site and the role of the oxide support.
With the development of quantum chemical tools and powerful hardware, computational
modelling emerges as a manageable complement to experiment. The combination
may lead to novel insight into the structure-activity relationship on Cr/oxide surfaces.
Ultimately this may contribute to more effective catalysts by rational design.
For this thesis, model catalysts have been investigated computationally with respect
to (i) mechanisms of catalytic dehydrogenation, and (ii) surface reactions of chromium
precursor species leading to the active catalyst. The work includes simulated annealing to
generate realistic surface models, and reactivity studies based on cluster and embeddedcluster
approaches. Based on these computations, two mechanisms of catalytic dehydrogenation
appear viable depending on the nano range surrounding the active site. One
mechanism is found to involve cleavage and reformation of a Cr–O bond. However, the
activation energy of this mechanism is found prohibitively high unless the Cr–O bond is
weakened by structural strain. Alternatively, a pre-catalytic step of C–H activation in
alkane involving irreversible cleavage of a Cr–O bond is found leading to formation of a
hydridochromium moiety, which appears highly active according to a second mechanism
of catalytic dehydrogenation. Regarding the role of the support, this is proposed one of
providing precursor species and sustaining the reactive sites. Moreover, it appears that
polynuclear sites of the active chromium species are formed in the typical steps of catalyst
preparation. These results form the basis for a hypothesis on which novel experiments
are suggested
Kinetic solvent effects on 1,3-dipolar cycloadditions of benzonitrile oxide

The kinetics of 1,3-dipolar cycloadditions of benzonitrile oxide with a series of N-substituted maleimides and with cyclopentene are reported for water, a wide range of organic solvents and binary solvent mixtures. The results indicate the importance of both solvent polarity and specific hydrogen-bond interactions in governing the rates of the reactions. The aforementioned reactions are examples for which these factors often counteract, leading to a complex dependence of rate constants on the nature of the solvent. For the reactions of N-ethylmaleimide and N-n-butylmaleimide with benzonitrile oxide, isobaric activation parameters have been determined in several organic solvents, water, and water–1-propanol mixtures. Interestingly, the activation parameters reveal significant differences in solvation in different solvents that are not clearly reflected in the rate constants. In highly aqueous mixtures, enforced hydrophobic interactions lead to an increase in rate constant, relative to organic solvents. However, the overall rate enhancement in water is modest, if present at all, because the solvent polarity diminishes the rate constant. This pattern contrasts with common Diels–Alder reactions, where polarity, hydrogen-bond donor capacity and enforced hydrophobic interactions work together, which can result in impressive rate accelerations in water.
The use of Nile Red to monitor the aggregation behavior in ternary surfactant–water–organic solvent systems

Ternary systems of surfactants, water and organic solvents were studied by monitoring the steady-state fluorescence of the versatile solvatochromic probe Nile Red. We found not only that Nile Red can be used throughout the whole isotropic regions in the phase diagram, but also that subtle changes in the aggregation state of the surfactant can be monitored. The formation of inverted micelles in n-hexane could be followed upon the addition of small amounts of water, in addition to the formation of normal micelles in water and water–organic solvent mixtures. In aqueous C12EO4 solutions the temperature-dependent micelle-to-vesicle-to-inverted micelle transition was visualized by Nile Red fluorescence. Finally, the incorporation of solvent into the micellar interior could also be monitored using Nile Red as the probe.
Cycloadditions in mixed aqueous solvents: the role of the water concentration

We examined the kinetics of a series of cycloaddition reactions in mixtures of water with methanol, acetonitrile and poly(ethylene glycol) (MW 1000). The reactions include the Diels–Alder (DA) reaction between cyclopentadiene and N-n-butylmaleimide or acridizinium bromide, the retro-Diels-Alder (RDA) reaction of 1,4,4a,9a-tetrahydro-4a-methyl-(1α,4α,4aα,9aα)-1,4-methaneanthracene-9,10-dione and the 1,3-dipolar cycloaddition of benzonitrile oxide with N-n-butylmaleimide. Plots of logk vs the molar concentration or volume fraction of water are approximately linear, but with a characteristic break around 40 M water. This break, absent for the RDA reaction, is ascribed to hydrophobic effects. Comparison with aqueous mixtures of the more hydrophobic 1-propanol shows that these mixtures induce qualitatively similar effects on the rate, but that preferential solvation effects cause the mixtures of 1-propanol to exhibit a more complex behavior of logk on composition. The results are analyzed using the Abraham–Kamlett–Taft model. The solvent effects in aqueous mixtures are not satisfactorily described by this model. For some cycloadditions, small maxima in rate are observed in highly aqueous mixtures of alcohols. The origin of these maxima and the aforementioned breaks is most likely the same.
Research on voting advice applications : state of the art and future directions (editorial)

Version of Record online: 24 OCT 2016Voting Advice Applications (VAAs) have experienced a great deal of success over the past decade, and are now used in many countries around the world. This editorial introduces a Special Issue resulting from a section of the 2015 European Consortium for Political Research (ECPR) conference in Montreal, organized by the ECPR's official VAA Research Network. It discusses the global spread and the popularity of these tools, addresses the history and different branches of VAA research, the current state of the art, and the remaining puzzles in the field. It also focuses attention on the wealth of research that is examining the effects of VAAs on political parties, candidates, and voters, as well as how VAA design choices affect the advice given to voters and their subsequent voting behavior. We hope this Special Issue will also highlight the potential of VAA-generated data for studying party positioning over time and across countries, allowing for comparative analyses of the characteristics and development of parties and party systems
Ideological and Temporal Components of Network Polarization in Online
  Political Participatory Media

Political polarization is traditionally analyzed through the ideological
stances of groups and parties, but it also has a behavioral component that
manifests in the interactions between individuals. We present an empirical
analysis of the digital traces of politicians in politnetz.ch, a Swiss online
platform focused on political activity, in which politicians interact by
creating support links, comments, and likes. We analyze network polarization as
the level of intra- party cohesion with respect to inter-party connectivity,
finding that supports show a very strongly polarized structure with respect to
party alignment. The analysis of this multiplex network shows that each layer
of interaction contains relevant information, where comment groups follow
topics related to Swiss politics. Our analysis reveals that polarization in the
layer of likes evolves in time, increasing close to the federal elections of
2011. Furthermore, we analyze the internal social network of each party through
metrics related to hierarchical structures, information efficiency, and social
resilience. Our results suggest that the online social structure of a party is
related to its ideology, and reveal that the degree of connectivity across two
parties increases when they are close in the ideological space of a multi-party
system.Comment: 35 pages, 11 figures, Internet, Policy & Politics Conference,
  University of Oxford, Oxford, UK, 25-26 September 201