Connections between concepts revealed by the electronic structure of carbon monoxide

Different models for the electronic structure of carbon monoxide are suggested in influential textbooks. Therefore, this electronic structure offers an interesting subject in teaching because it can be used as an example to relate seemingly conflicting concepts. Understanding the connections between ostensibly different methods and between different concepts, related or conflicting, is important in academic studies. The related reactivities of CO, O2, and N-2 and the notations of molecular orbitals are topics of interest and are discussed in detail.

HPMA copolymer-aminoglutethimide conjugates inhibit aromatase in MCF-7 cell lines

N-(2-Hydroxypropyl)methacrylamide (HPMA) copolymer–doxorubicin (Dox) has already shown clinical activity in breast cancer patients. Moreover, we have recently found that an HPMA conjugate containing a combination of both Dox and the aromatase inhibitor aminoglutethimide (AGM) shows significantly increased anti-tumour activity in vitro. To better understand the mechanism of action of HPMA copolymer–AGM conjugates several models were used here to investigate their effect on cell growth and aromatase inhibition. Cytotoxicity of HPMA copolymer conjugates containing AGM, Dox and also the combination AGM–Dox was determined by MTT assay in MCF-7 and MCF-7ca cells. Androstenedione (5 × 10− 8 M) stimulates the growth of MCF-7ca cells. Both free AGM and polymer-bound AGM (0.2–0.4 mg/ml) were shown to block this mitogenic activity. When MCF-7ca cells were incubated [3H]androstenedione both AGM and HPMA copolymer–GFLG–AGM (0.2 mg/ml AGM-equiv.) showed the ability to inhibit aromatase. Although, free AGM was able to inhibit isolated human placental microsomal aromatase in a concentration dependent manner, polymer-bound AGM was not, suggesting that drug release is essential for activity of the conjugate. HPMA copolymer conjugates containing aromatase inhibitors have potential for the treatment of hormone-dependant cancers, and it would be particularly interesting to explore further as potential therapies in post-menopausal women as components of combination therapy.

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.

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)

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.

Step edges in thin films of lamellar-forming diblock copolymer

Self-consistent field theory (SCFT) is used to study the step edges that occur in thin films of lamellar-forming diblock copolymer, when the surfaces each have an affinity for one of the polymer components. We examine film morphologies consisting of a stack of ν continuous monolayers and one semi-infinite bilayer, the edge of which creates the step. The line tension of each step morphology is evaluated and phase diagrams are constructed showing the conditions under which the various morphologies are stable. The predicted behavior is then compared to experiment. Interestingly, our atomic force microscopy (AFM) images of terraced films reveal a distinct change in the character of the steps with increasing ν, which is qualitatively consistent with our SCFT phase diagrams. Direct quantitative comparisons are not possible because the SCFT is not yet able to probe the large polymer/air surface tensions characteristic of experiment.

Morphology induced spinodal decomposition at the surface of symmetric diblock copolymer films

Atomic force microscopy is used to study the ordering dynamics of symmetric diblock copolymer films. The films order to form a lamellar structure which results in a frustration when the film thickness is incommensurate with the lamellae. By probing the morphology of incommensurate films in the early ordering stages, we discover an intermediate phase of lamellae arranged perpendicular to the film surface. This morphology is accompanied by a continuous growth in amplitude of the film surface topography with a characteristic wavelength, indicative of a spinodal process. Using selfconsistent field theory, we show that the observation of perpendicular lamellae suggests an intermediate state with parallel lamellae at the substrate and perpendicular lamellae at the free surface. The calculations confirm that the intermediate state is unstable to thickness fluctuations, thereby driving the spinodal growth of surface structures.

Monte Carlo field-theoretic simulations for melts of symmetric diblock copolymer

Monte Carlo field-theoretic simulations (MCFTS) are performed on melts of symmetric diblock copolymer for invariant polymerization indexes extending down to experimentally relevant values of N̅ ∼ 10^4. The simulations are performed with a fluctuating composition field, W_−(r), and a pressure field, W_+(r), that follows the saddle-point approximation. Our study focuses on the disordered-state structure function, S(k), and the order−disorder transition (ODT). Although shortwavelength fluctuations cause an ultraviolet (UV) divergence in three dimensions, this is readily compensated for with the use of an effective Flory−Huggins interaction parameter, χ_e. The resulting S(k) matches the predictions of renormalized one-loop (ROL) calculations over the full range of χ_eN and N̅ examined in our study, and agrees well with Fredrickson−Helfand (F−H) theory near the ODT. Consistent with the F−H theory, the ODT is discontinuous for finite N̅ and the shift in (χ_eN)_ODT follows the predicted N̅^−1/3 scaling over our range of N̅.

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.