Demographic Influences on Consumer Ethnocentrism: A Two-Study Analysis Demonstrating How Industry-Specific Personal Characteristics Impact the Occupation, Education, Marital Status, Sex and Race Dynamic

Two national surveys were conducted in the United States to test the influence of seven demographic variables on consumer ethnocentrism. Study 1 suggests a social class influence (education and occupation) on consumer ethnocentrism towards automobile brands in the United States, plus a significant relationship between marital status and consumer ethnocentrism. Study 2 tests the impact of U.S. automobile industry-specific knowledge, beliefs, and job-related behavior on ethnocentrism using similar demographic variables. Without considering industry-specific measures, occupation again significantly impacts consumer ethnocentricity among participants. However, when industry-specific measures are included, the underlying influence of gender and race on consumer ethnocentrism is revealed

Outer-Sphere Contributions to the Electronic Structure of Type Zero Copper Proteins

Bioinorganic canon states that active-site thiolate coordination promotes rapid electron transfer (ET) to and from type 1 copper proteins. In recent work, we have found that copper ET sites in proteins also can be constructed without thiolate ligation (called “type zero” sites). Here we report multifrequency electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), and nuclear magnetic resonance (NMR) spectroscopic data together with density functional theory (DFT) and spectroscopy-oriented configuration interaction (SORCI) calculations for type zero Pseudomonas aeruginosa azurin variants. Wild-type (type 1) and type zero copper centers experience virtually identical ligand fields. Moreover, O-donor covalency is enhanced in type zero centers relative that in the C112D (type 2) protein. At the same time, N-donor covalency is reduced in a similar fashion to type 1 centers. QM/MM and SORCI calculations show that the electronic structures of type zero and type 2 are intimately linked to the orientation and coordination mode of the carboxylate ligand, which in turn is influenced by outer-sphere hydrogen bonding

Magnetic Properties of Monomer and Dimer Tetrahedral VOx Entities Dispersed on Amorphous Silica-based Materials: Prediction of EPR Parameters from Relativistic DFT Calculations and Broken Symmetry Approach to Exchange Couplings

Molecular structures of the isolated tetrahedral oxovanadium(IV) and bridged μ-oxo-divanadium(IV) complexes hosted by the clusters mimicking surfaces of amorphous silica-based materials were investigated using density functional theory (DFT) calculations. Principal values of the g and A tensors for the monomer vanadyl species were obtained using the coupled-perturbed DFT level of theory and the spin–orbit mean-field approximation (SOMF). Magnetic exchange interaction for the μ-oxo bridged vanadium(IV) dimer was investigated within the broken symmetry approach. An antiferromagnetic coupling of the individual magnetic moments of the vanadium(IV) centers in the [VO–O–VO]2+ bridges was revealed and discussed in detail. The coupling explains pronounced decrease of the electron paramagnetic resonance signal (EPR) intensity, observed for the reduced VOx/SiO2 samples with the increasing coverage of vanadia, in terms of transformation of the paramagnetic monomer species into the dimers with S = 0 ground state

Image-guided liver surgery: intraoperative projection of computed tomography images utilizing tracked ultrasound

AbstractBackgroundUltrasound (US) is the most commonly used form of image guidance during liver surgery. However, the use of navigation systems that incorporate instrument tracking and three-dimensional visualization of preoperative tomography is increasing. This report describes an initial experience using an image-guidance system with navigated US.MethodsAn image-guidance system was used in a total of 50 open liver procedures to aid in localization and targeting of liver lesions. An optical tracking system was employed to localize surgical instruments. Customized hardware and calibration of the US transducer were required. The results of three procedures are highlighted in order to illustrate specific navigation techniques that proved useful in the broader patient cohort.ResultsOver a 7-month span, the navigation system assisted in completing 21 (42%) of the procedures, and tracked US alone provided additional information required to perform resection or ablation in six procedures (12%). Average registration time during the three illustrative procedures was <1min. Average set-up time was approximately 5min per procedure.ConclusionsThe Explorer™ Liver guidance system represents novel technology that continues to evolve. This initial experience indicates that image guidance is valuable in certain procedures, specifically in cases in which difficult anatomy or tumour location or echogenicity limit the usefulness of traditional guidance methods

A revised asteroid polarization-albedo relationship using WISE/NEOWISE data

We present a reanalysis of the relationship between asteroid albedo and polarization properties using the albedos derived from the Wide-field Infrared Survey Explorer. We find that the function that best describes this relation is a three-dimensional linear fit in the space of log(albedo)-log(polarization slope)-log(minimum polarization). When projected to two dimensions the parameters of the fit are consistent with those found in previous work. We also define p* as the quantity of maximal polarization variation when compared with albedo and present the best fitting albedo-p* relation. Some asteroid taxonomic types stand out in this three-dimensional space, notably the E, B, and M Tholen types, while others cluster in clumps coincident with the S- and C-complex bodies. We note that both low albedo and small (D<30 km) asteroids are under-represented in the polarimetric sample, and we encourage future polarimetric surveys to focus on these bodies.Comment: 16 pages, Accepted to Ap

NEOWISE Studies of Spectrophotometrically Classified Asteroids: Preliminary Results

The NEOWISE dataset offers the opportunity to study the variations in albedo for asteroid classification schemes based on visible and near-infrared observations for a large sample of minor planets. We have determined the albedos for nearly 1900 asteroids classified by the Tholen, Bus and Bus-DeMeo taxonomic classification schemes. We find that the S-complex spans a broad range of bright albedos, partially overlapping the low albedo C-complex at small sizes. As expected, the X-complex covers a wide range of albedos. The multi-wavelength infrared coverage provided by NEOWISE allows determination of the reflectivity at 3.4 and 4.6 $\mu$m relative to the visible albedo. The direct computation of the reflectivity at 3.4 and 4.6 $\mu$m enables a new means of comparing the various taxonomic classes. Although C, B, D and T asteroids all have similarly low visible albedos, the D and T types can be distinguished from the C and B types by examining their relative reflectance at 3.4 and 4.6 $\mu$m. All of the albedo distributions are strongly affected by selection biases against small, low albedo objects, as all objects selected for taxonomic classification were chosen according to their visible light brightness. Due to these strong selection biases, we are unable to determine whether or not there are correlations between size, albedo and space weathering. We argue that the current set of classified asteroids makes any such correlations difficult to verify. A sample of taxonomically classified asteroids drawn without significant albedo bias is needed in order to perform such an analysis.Comment: Accepted to Ap

On the feasibility of N2 fixation via a single-site FeI/FeIV cycle: Spectroscopic studies of FeI(N2)FeI, FeIV=N, and related species

The electronic properties of an unusually redox-rich iron system, [PhBPR 3]FeNx (where [PhBPR 3] is [PhB(CH2PR2)3]−), are explored by Mössbauer, EPR, magnetization, and density-functional methods to gain a detailed picture regarding their oxidation states and electronic structures. The complexes of primary interest in this article are the two terminal iron(IV) nitride species, [PhBPiPr 3]FeN (3a) and [PhBPCH2Cy 3]FeN (3b), and the formally diiron(I) bridged-Fe(μ-N2)Fe species, {[PhBPiPr 3]Fe}2(μ-N2) (4). Complex 4 is chemically related to 3a via a spontaneous nitride coupling reaction. The diamagnetic iron(IV) nitrides 3a and 3b exhibit unique electronic environments that are reflected in their unusual Mössbauer parameters, including quadrupole-splitting values of 6.01(1) mm/s and isomer shift values of −0.34(1) mm/s. The data for 4 suggest that this complex can be described by a weak ferromagnetic interaction (J/D < 1) between two iron(I) centers. For comparison, four other relevant complexes also are characterized: a diamagnetic iron(IV) trihydride [PhBPiPr 3]Fe(H)3(PMe3) (5), an S = 3/2 iron(I) phosphine adduct [PhBPiPr 3]FePMe3 (6), and the S = 2 iron(II) precursors to 3a, [PhBPiPr 3]FeCl and [PhBPiPr 3]Fe-2,3:5,6-dibenzo-7-aza bicyclo[2.2.1]hepta-2,5-diene (dbabh). The electronic properties of these respective complexes also have been explored by density-functional methods to help corroborate our spectral assignments and to probe their electronic structures further

Density functional theory

Density functional theory (DFT) finds increasing use in applications related to biological systems. Advancements in methodology and implementations have reached a point where predicted properties of reasonable to high quality can be obtained. Thus, DFT studies can complement experimental investigations, or even venture with some confidence into experimentally unexplored territory. In the present contribution, we provide an overview of the properties that can be calculated with DFT, such as geometries, energies, reaction mechanisms, and spectroscopic properties. A wide range of spectroscopic parameters is nowadays accessible with DFT, including quantities related to infrared and optical spectra, X-ray absorption and Mössbauer, as well as all of the magnetic properties connected with electron paramagnetic resonance spectroscopy except relaxation times. We highlight each of these fields of application with selected examples from the recent literature and comment on the capabilities and limitations of current methods

Todellista asiakasarvoa luomassa – myynnistä arvomyyntiin : case Mediamaisteri Oy

Tämän opinnäytetyön tavoite oli case-yritys Mediamaisteri Oy:n B2B-myyntiprosessin kehittäminen. Tarkoitus oli hyödyntää palvelumuotoilua lisäämään asiakasymmärrystä ja tukemaan asiakkaiden kokeman arvon muodostumista sekä positiivisten asiakaskokemusten syntymistä myyntiprosessin alkuvaiheen asiakaskohtaamisissa. Lisäksi tarkoitus oli kiteyttää empiirisen aineiston pohjalta saatu tieto asiakasprofiileiksi, joita voidaan hyödyntää asiakaslähtöisten ratkaisujen suunnittelussa heti asiakkuuden alusta ja ensimmäisestä myyntitapaamisesta lähtien. Opinnäytetyön tutkimuksellisen osuuden toteuttamisen pohjana on kvalitatiivinen tutkimusote ja palvelumuotoilun prosessi. Tutkimuskohde tarkennettiin kuvaamalla Mediamaisteri Oy:n asiakkuuden alkuvaiheen palvelupolku, josta rajattiin tutkimuksen kohteeksi ensimmäinen asiakastapaaminen ja sitä edeltävä aika, jolloin asiakas kiinnostuu yrityksen palveluista ja ensikontakti yritykseen tapahtuu. Tutkimusaineisto muodostuu kuudesta Mediamaisteri Oy:n yritysasiakkaan haastattelusta, jotka toteutettiin virtuaalisesti teemahaastattelun muodossa. Aineiston analysoinnissa hyödynnettiin induktiivista sisällönanalyysiä. Opinnäytetyön teoreettinen viitekehys rakentuu B2B-myynnin, asiakasarvon muodostumisen ja positiivisen asiakaskokemuksen teorioista. Opinnäytetyön empiirisessä osassa kuvataan yksityiskohtaisesti työn toteuttaminen ja toteutuksen vaiheittainen eteneminen. Opinnäytetyön tuloksien mukaan Mediamaisteri Oy:n yritysasiakkaan positiivinen asiakaskokemus palvelujen hankintavaiheessa ja ensimmäisen asiakastapaamisen aikana koostuu myyjäyrityksen koetusta osaamisesta ja ammattitaidosta, palveluasenteesta, asiakaslähtöisyydestä, vuorovaikutustaidoista, yhteistyötaidoista, avoimuuden ja luottamuksen tunteen herättämisestä ja projektinhallinnasta. Opinnäytetyön tutkimusaineiston pohjalta kerätty asiakastieto kiteytettiin Mediamaisteri Oy:n yritysasiakkaan asiakasprofiileiksi, joita voidaan tulevaisuudessa hyödyntää yrityksen asiakaslähtöisen myyntiprosessin kehittämisessä suuntaamaan toimintaa kohti todellista asiakasarvoa asiakkuuden alkuvaiheesta alkaen. Voidaan todeta, että opinnäytetyön tuloksilla on yhteyttä opinnäytetyön viitekehyksessä esitettyyn aikaisempaan teoreettiseen tietoon B2B-myynnistä, asiakasarvon muodostumisesta ja positiivisesta asiakaskokemuksesta. Opinnäytetyön tuloksissa ilmeni, että asiakasymmärryksen tavoittelu jää palvelujen hankintavaiheessa ja ensimmäisessä asiakastapaamisessa usein pinnalliselle tasolle. Jatkotutkimus etenkin vuorovaikutustaitojen merkityksestä B2B-myyntiprosessin alussa ja ensimmäisessä B2B-myyntitapaamisessa arvonluonnin ja arvomyynnin edellyttämän asiakasymmärryksen saavuttamiseksi on suositeltavaa.The aim of this thesis was to develop the B2B sales process of the case company Mediamaisteri Oy. The purpose was to utilize service design to promote the customer insight and to support the formation of the customer value and positive customer experiences in customer touchpoints during the early stages of the sales process. In addition, the purpose was to crystallize the information obtained from the empirical data into customer profiles that can be used to design customer-oriented solutions right from the beginning of a customer relationship and the initial B2B sales meeting. The basis for carrying out the empirical part of the thesis was the qualitative research and the process of service design. The research subject was defined by describing the business client’s customer journey in the beginning of the customer relationship with Mediamaisteri Oy, and by focusing to the initial B2B sales meeting and the time when the client became interested in the company's services and made the first contact. The research material consisted of six interviews of Mediamaisteri Oy's business clients, made as online theme interviews. The material was analyzed by utilizing inductive content analysis. The theoretical framework of the thesis was based on the theories of B2B sales, customer value creation and positive customer experience. In the empirical part of the thesis, the implementation of the work and the steps of the process are described in detail. The findings of the thesis indicate that the positive customer experience of a Mediamaisteri business client during the procurement phase and the initial B2B sales meeting consists of proven expertise and professionalism, service attitude, customer orientation, interaction skills, co-operation skills, openness and trust, and the project management. The research data collected was crystallized into the business client profiles of Mediamaisteri Oy, which can be used in the future to develop the customer-oriented sales process of the company in order to direct the business towards the real customer value starting right from the beginning of the customer relationship. It can be concluded that the results of the thesis are related to the previous theoretical knowledge of B2B sales, customer value creation and a positive customer experience presented in the theoretical framework of the thesis. The results of the thesis showed that the pursuit of customer understanding during the procurement phase and the initial B2B sales meeting often remains superficial. Further research on the significance of interaction skills in the beginning of the sales process and at the initial B2B sales meeting is desirable to achieve value creation and value-based customer insight

Photochemistry of Furyl- and Thienyldiazomethanes: Spectroscopic Characterization of Triplet 3-Thienylcarbene

Photolysis (λ \u3e 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N2 at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm–1, |E/hc| = 0.0554 cm–1; |D/hc| = 0.579 cm–1, |E/hc| = 0.0315 cm–1). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon—an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λmax = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C5H4S or C5H4O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively)