Structural, magnetic, and electronic properties of VxCr2−xS3(0

A new family of vanadium-substituted chromium sulfides (VxCr2-xS3, 0 < x < 2) has been prepared and characterized by powder X-ray and neutron diffraction, SQUID magnetometry, electrical resistivity, and Seebeck coefficient measurements. Vanadium substitution leads to a single-phase region with a rhombohedral Cr2S3 structure over the composition range 0.0 < x e 0.75, while at higher vanadium contents (1.6 e x < 2.0) a second single-phase region, in which materials adopt a cation-deficient Cr3S4 structure, is observed. Materials with the Cr2S3 structure all exhibit semiconducting behavior. However, both transport and magnetic properties indicate an increasing degree of electron delocalization with increasing vanadium content in this compositional region. Materials that adopt a Cr3S4-type structure exhibit metallic behavior. Magnetic susceptibility data reveal that all materials undergo a magnetic ordering transition at temperatures in the range 90–118 K. Low-temperature magnetization data suggest that this involves a transition to a ferrimagnetic state.

Timing and localization of ionospheric signatures associated with substorm expansion phase onset

In this paper, we present case studies of the optical and magnetic signatures of the characteristics of the first minute of substorm expansion phase onset observed in the ionosphere. We find that for two isolated substorms, the onset of magnetic pulsations in the 24–96 s period wavelet band are colocated in time and space with the formation and development of small-scale optical undulations along the most equatorward preexisting auroral arc prior to auroral breakup. These undulations undergo an inverse spatial cascade into vortices prior to the release of the westward traveling surge. We also present a case study of a multiple activation substorm, whereby discrete onsets of ULF wave power above a predetermined quiet time threshold are shown to be associated with specific optical intensifications and brightenings. Moreover, in the multiple activation substorm event, we show that neither the formation of the small-scale undulations nor the formation of similar structures along a north–south aligned arc is sufficient to produce auroral breakup associated with expansion phase onset. It is only ∼10 min after these two disparate activation regions initiate that auroral breakup and the subsequent formation of a westward traveling surge occur. We discuss the implications of these results in terms of the triggering mechanisms likely to be occurring during these specific events.

Content validation for level of use of feature rich systems: a Delphi study of electronic medical records systems

Introduction. Feature usage is a pre-requisite to realising the benefits of investments in feature rich systems. We propose that conceptualising the dependent variable 'system use' as 'level of use' and specifying it as a formative construct has greater value for measuring the post-adoption use of feature rich systems. We then validate the content of the construct as a first step in developing a research instrument to measure it. The context of our study is the post-adoption use of electronic medical records (EMR) by primary care physicians. Method. Initially, a literature review of the empirical context defines the scope based on prior studies. Having identified core features from the literature, they are further refined with the help of experts in a consensus seeking process that follows the Delphi technique. Results.The methodology was successfully applied to EMRs, which were selected as an example of feature rich systems. A review of EMR usage and regulatory standards provided the feature input for the first round of the Delphi process. A panel of experts then reached consensus after four rounds, identifying ten task-based features that would be indicators of level of use. Conclusions. To study why some users deploy more advanced features than others, theories of post-adoption require a rich formative dependent variable that measures level of use. We have demonstrated that a context sensitive literature review followed by refinement through a consensus seeking process is a suitable methodology to validate the content of this dependent variable. This is the first step of instrument development prior to statistical confirmation with a larger sample.

Utilizing electronic effects in the modulation of BTPhen ligands with respect to the partitioning of minor actinides from lanthanides

Effects of bromine substitution at the 5 and 5,6-positions of the 1,10-phenanthroline nucleus of BTPhen ligand on their extraction properties for Ln(III) andAn(III) cations have been studied. Compared to C5-BTPhen, electronic modulation in BrC5-BTPhen and Br2C5-BTPhen enabled these ligands to be fine-tuned in order to enhance the separation selectivity of Am(III) from Eu(III)

Spectroscopic signatures of an Fmoc–tetrapeptide, Fmoc and fluorene

The hydrophobic Fmoc [N-(fluorenyl)-9-methoxycarbonyl] unit is often conjugated to peptides to confer amphiphilicity on the molecules, and to introduce the potential for aromatic stacking interactions. In this paper we report spectroscopic data for fluorene, Fmoc and Fmoc conjugated to a small peptide (GRDS in this case) to enable interpretation of spectroscopic data collected on complex structures that can be created with Fmoc–peptide molecules. We report absorbance data (ultra violet and infrared), circular dichroism, linear dichroism (both film and Couette flow orientation) and Raman spectra. Orientations of the Fmoc chromophores in the linear dichroism studies are deduced.

Electronic charge transfer between ceria surfaces and gold adatoms: a GGA+U investigation

We use density functional theory calculations with Hubbard corrections (DFT+U) to investigate electronic aspects of the interaction between ceria surfaces and gold atoms. Our results show that Au adatoms at the (111) surface of ceria can adopt Au0, Au+ or Au� electronic configurations depending on the adsorption site. The strongest adsorption sites are on top of the surface oxygen and in a bridge position between two surface oxygen atoms, and in both cases charge transfer from the gold atom to one of the Ce cations at the surface is involved. Adsorption at other sites, including the hollow sites of the surface, and an O–Ce bridging site, is weaker and does not involve charge transfer. Adsorption at an oxygen vacancy site is very strong and involves the formation of an Au� anion. We argue that the ability of gold atoms to stabilise oxygen vacancies at the ceria surface by moving into the vacancy site and attracting the excess electrons of the defect could be responsible for the enhanced reducibility of ceria surfaces in the presence of gold. Finally, we rationalise the differences in charge transfer behaviour from site to site in terms of the electrostatic potential at the surface and the coordination of the species.

Drivers of in-group and out-of-group electronic word-of-mouth (eWOM)

Purpose – The purpose of this study is to address a recent call for additional research on electronic word-of-mouth (eWOM). In response to this call, this study draws on the social network paradigm and the uses and gratification theory (UGT) to propose and empirically test a conceptual framework of key drivers of two types of eWOM, namely in-group and out-of-group. Design/methodology/approach – The proposed model, which examines the impact of usage motivations on eWOM in-group and eWOM out-of-group, is tested in a sample of 302 internet users in Portugal. Findings – Results from the survey show that the different drivers (i.e. mood-enhancement, escapism, experiential learning and social interaction) vary in terms of their impact on the two different types of eWOM. Surprisingly, while results show a positive relationship between experiential learning and eWOM out-of-group, no relationship is found between experiential learning and eWOM in-group. Research limitations/implications – This is the first study investigating the drivers of both eWOM in-group and eWOM out-of-group. Additional research in this area will contribute to the development of a general theory of eWOM. Practical implications – By understanding the drivers of different eWOM types, this study provides guidance to marketing managers on how to allocate resources more efficiently in order to achieve the company's strategic objectives. Originality/value – No published study has investigated the determinants of these two types of eWOM. This is the first study offering empirical considerations of how the various drivers differentially impact eWOM in-group and eWOM out-of-group.

Synthesis and Electronic Structure of Dissymmetrical, Naphthalene-Bridged Sandwich Complexes [Cp′Fe(μ‑C10H8)MCp*]x (x = 0, +1; M =Fe, Ru; Cp′ = η5‑C5H2‑1,2,4‑tBu3; Cp* = η5‑C5Me5)

The dissymmetrical naphthalene-bridged complexes [Cp′Fe(μ-C10H8)FeCp*] (3; Cp* = η5-C5Me5, Cp′ = η5-C5H2-1,2,4-tBu3) and [Cp′Fe(μ-C10H8)RuCp*] (4) were synthesized via a one-pot procedure from FeCl2(thf)1.5, Cp′K, KC10H8, and [Cp* FeCl(tmeda)] (tmeda = N,N,N′,N′- tetramethylethylenediamine) or [Cp*RuCl]4, respectively. The symmetrically substituted iron ruthenium complex [Cp*Fe(μ-C10H8)RuCp*] (5) bearing two Cp* ligands was prepared as a reference compound. Compounds 3−5 are diamagnetic and display similar molecular structures, where the metal atoms are coordinated to opposite sides of the bridging naphthalene molecule. Cyclic voltammetry and UV/vis spectroelectrochemistry studies revealed that neutral 3−5 can be oxidized to monocations 3+−5+ and dications 32+−52+. The chemical oxidation of 3 and 4 with [Cp2Fe]PF6 afforded the paramagnetic hexafluorophosphate salts [Cp′Fe(μ-C10H8)FeCp*]PF6 ([3]PF6) and [Cp′Fe(μ-C10H8)RuCp*]PF6 ([4]PF6), which were characterized by various spectroscopic techniques, including EPR and 57Fe Mössbauer spectroscopy. The molecular structure of [4]PF6 was determined by X-ray crystallography. DFT calculations support the structural and spectroscopic data and determine the compositions of frontier molecular orbitals in the investigated complexes. The effects of substituting Cp* with Cp′ and Fe with Ru on the electronic structures and the structural and spectroscopic properties are analyzed.

Syntheses, spectroelectrochemical studies, and molecular and electronic structures of ferrocenyl ene-diynes

The readily available complex 1,1-dibromo-2-ferrocenylethylene provides a convenient entry point for the preparation of a wide range of cross-conjugated 1,1-bis(alkynyl)-2-ferrocenylethenes through simple Pd(0)/Cu(I)-mediated cross-coupling reactions with 1-alkynes. The ferrocene moiety in compounds of the general form FcCHC(CCR)2 is essentially electronically isolated from the cross-conjugated π system, as evidenced by IR and UV−vis spectroelectrochemical experiments and quantum chemical calculations. In contrast to the other examples which give stable ferrocenium derivatives upon electrochemical oxidation, the aniline derivatives [FcCHC(CCC6H4NH2-4)2]+ and [FcCHC(CCC6H4NMe2-4)2]+ proved to be unstable on the time scale of the spectroelectrochemical experiments, leading to passivation of the electrode surface over time. There is no significant thermodynamic stabilization of the radical anion [FcCHC(CCC6H4NO2-4)2]− relative to the neutral and dianionic analogues, although the dianion [FcCHC(CCC6H4NO2- 4)2]2− could be studied as a relatively chemically stable species and is well described in terms of two linked nitrophenyl radicals. The capacity to introduce a relatively isolated point charge at the periphery of the cross-conjugated π system appears to make these complexes useful templates for the construction of electrochemically gated quantum interference transistors.

Comparison of a trained sensory panel and an electronic tongue in the assessment of bitter dairy protein hydrolsates

The bitter taste elicited by dairy protein hydrolysates (DPH) is a renowned issue for their acceptability by consumers and therefore incorporation into foods. The traditional method of assessment of taste in foods is by sensory analysis but this can be problematic due to the overall unpleasantness of the samples. Thus, there is a growing interest into the use of electronic tongues (e-tongues) as an alternative method to quantify the bitterness in such samples. In the present study the response of the e-tongue to the standard bitter agent caffeine and a range of both casein and whey based hydrolysates was compared to that of a trained sensory panel. Partial least square regression (PLS) was employed to compare the response of the e-tongue and the sensory panel. There was strong correlation shown between the two methods in the analysis of caffeine (R2 of 0.98) and DPH samples with R2 values ranging from 0.94-0.99. This study exhibits potential for the e-tongue to be used in bitterness screening in DPHs to reduce the reliance on expensive and time consuming sensory panels.

Spin-polarized electronic-structure of MnBiAl

The self-consistent spin-polarized band-structure calculation of ferromagnetic compound MnBiAl in its low-temperature phase has been performed. In this paper the calculation results are given. Comparison with the results of MnBi is performed in order to find the effect on electronic structure by doping with Al.

Drivers of in‐group and out‐of‐group electronic word‐of‐mouth (eWOM)

Purpose– The purpose of this study is to address a recent call for additional research on electronic word‐of‐mouth (eWOM). In response to this call, this study draws on the social network paradigm and the uses and gratification theory (UGT) to propose and empirically test a conceptual framework of key drivers of two types of eWOM, namely in‐group and out‐of‐group. Design/methodology/approach– The proposed model, which examines the impact of usage motivations on eWOM in‐group and eWOM out‐of‐group, is tested in a sample of 302 internet users in Portugal. Findings– Results from the survey show that the different drivers (i.e. mood‐enhancement, escapism, experiential learning and social interaction) vary in terms of their impact on the two different types of eWOM. Surprisingly, while results show a positive relationship between experiential learning and eWOM out‐of‐group, no relationship is found between experiential learning and eWOM in‐group. Research limitations/implications– This is the first study investigating the drivers of both eWOM in‐group and eWOM out‐of‐group. Additional research in this area will contribute to the development of a general theory of eWOM. Practical implications– By understanding the drivers of different eWOM types, this study provides guidance to marketing managers on how to allocate resources more efficiently in order to achieve the company's strategic objectives. Originality/value– No published study has investigated the determinants of these two types of eWOM. This is the first study offering empirical considerations of how the various drivers differentially impact eWOM in‐group and eWOM out‐of‐group.

Comparison of interplanetary signatures of streamers and pseudostreamers

If the source of the slow solar wind is a web comprising pseudostreamer belts connected to the streamer belt, then one expects the properties of interplanetary pseudostreamer flows to be similar to those of streamer flows. That expectation is tested with data from the slow wind preceding stream interfaces in stream interaction regions at 1 AU, where the interfaces separate what was originally slow and fast wind. Pseudostreamer cases were separated from streamer cases with the aid of the streamer identification tool developed by Owens et al. (2013), and superposed epoch analysis was performed to compare the patterns of a number of plasma and composition parameters. The results reveal that pseudostreamer flows have all of the slow-wind characteristics of streamer flows except that they are slightly less pronounced than streamer characteristics when compared to fast wind. The results are consistent with the concept that the solar wind displays a continuum of dynamic states rather than only slow and fast states.

Phase calibration of the EISCAT Svalbard Radar interferometer using optical satellite signatures

The link between natural ion-line enhancements in radar spectra and auroral activity has been the subject of recent studies but conclusions have been limited by the spatial and temporal resolution previously available. The next challenge is to use shorter sub-second integration times in combination with interferometric programmes to resolve spatial structure within the main radar beam, and so relate enhanced filaments to individual auroral rays. This paper presents initial studies of a technique, using optical and spectral satellite signatures, to calibrate the received phase of a signal with the position of the scattering source along the interferometric baseline of the EISCAT Svalbard Radar. It is shown that a consistent relationship can be found only if the satellite passage through the phase fringes is adjusted from the passage predicted by optical tracking. This required adjustment is interpreted as being due to the vector between the theoretical focusing points of the two antennae, i.e. the true radar baseline, differing from the baseline obtained by survey between the antenna foot points. A method to obtain a measurement of the true interferometric baseline using multiple satellite passes is outlined.