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Rois Benassi Adriano Benedetti Ferdinando Taddei Roberto Cappelletti Dante Nardi Alberto Tajana 《Magnetic resonance in chemistry : MRC》1982,20(1):26-30
Aryl- and 2-furylaldehyde ethylaminoacetylhydrazones were examined in different solvents and over a wide temperature range with 1H NMR in order to study their conformational properties. Nearly equal amounts of the E/Z isomers, relative to the C?N bond, are present, even when the solvents and the substituents on the aldimino carbon produce small changes in the isomeric mixture. The activation parameters of the thermal isomerization process were measured, and the results are in the line with a lateral-shift type mechanism, also supported by theoretical calculations on a model compound. No other internal process was noted from the low-temperature spectral behaviour, and this was interpreted in terms of a highly biased equilibrium concerning the rotation around the C(O)? N bond. Chemical shifts obtained in different solvents also enable the most stable arrangement of the whole molecule of these compounds to be postulated. 相似文献
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We consider an insurance risk process with the possibility to invest the capital reserve into a portfolio consisting of a risky asset and a riskless asset. The stock price is modelled by an exponential Lévy process and the riskless interest rate is assumed to be constant. We aim at the risk assessment of the integrated risk process in terms of a high quantile or the far out distribution tail. We indicate an application to an optimal investment strategy of an insurer. 相似文献
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O. Kostadinova A. Chrissanthopoulos T. Petkova S.N. Yannopoulos 《Journal of solid state chemistry》2011,184(2):447-454
We report an investigation of the structure and vibrational modes of (AgI)x (AsSe)100−x, bulk glasses using Raman spectroscopy and first principles calculations. The short- and medium-range structural order of the glasses was elucidated by analyzing the reduced Raman spectra, recorded at off-resonance conditions. Three distinct local environments were revealed for the AsSe glass including stoichiometric-like and As-rich network sub-structures, and cage-like molecules (As4Sen, n=3, 4) decoupled from the network. To facilitate the interpretation of the Raman spectra ab initio calculations are employed to study the geometric and vibrational properties of As4Sen molecular units that are parts of the glass structure. The incorporation of AgI causes appreciable structural changes into the glass structure. AgI is responsible for the population reduction of molecular units and for the degradation of the As-rich network-like sub-structure via the introduction of As-I terminal bonds. Ab initio calculations of mixed chalcohalide pyramids AsSemI3−m provided useful information augmenting the interpretation of the Raman spectra. 相似文献
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Dependence of surface potential (electrostatic potential at the inner Helmholtz plane, Ψ(0)) at the silver bromide aqueous electrolyte interface was measured as a function of the activities of Br(-) and Ag(+) by using a single crystal silver bromide electrode (SCr-AgBr). Absolute values of surface potentials were obtained from electrode potentials of SCr-AgBr and isoelectric points. Measurements were performed at different temperatures in the range from 10 to 50°C. Corresponding equilibrium constants of interfacial reactions were obtained using the surface complexation model and interpreted via the van't Hoff equation. As a result of the interpretation for the binding of bromide ions leading to a negative surface charge, the thermodynamic parameters obtained were Δ(n)H(°)=-33kJmol(-1) and Δ(n)S(°)=-31Jmol(-1)K(-1); and for the binding of silver ions leading to a positive surface charge, Δ(p)H(°)=-72kJmol(-1) and Δ(p)S(°)=-196Jmol(-1)K(-1). Association of counterions (CI) with oppositely charged surface sites partially compensates the surface charge. Assuming approximately the same affinities for anions (NO(3)(-)) and cations (K(+)) thermodynamic parameters for their binding were obtained as Δ(CI)H(°)≈7kJmol(-1) and Δ(CI)S(°)≈105Jmol(-1)K(-1). 相似文献
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The article describes a general treatment of the catalytic reaction mechanism at an electrode expanding in accord with any power law, the stationary electrode and the dropping mercury electrode being special cases. Reversible, irreversible and quasi-reversible electrode reactions are embraced by the treatment. A general expression for the current-voltage characteristic was derived, which was applied to different electrolysis regimes. The cases when the regeneration reaction will influence the catalytic wave characteristics are also discussed. 相似文献
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Tajana Kostadinova Nikolaos Politakos Ana Trajcheva Jadranka Blazevska-Gilev Radmila Tomovska 《Molecules (Basel, Switzerland)》2021,26(16)
Graphene/noble metal substrates for surface enhanced RAMAN scattering (SERS) possess synergistically improved performance, due to the strong chemical enhancement mechanism accounted to graphene and the electromagnetic mechanism raised from the metal nanoparticles. However, only the effect of noble metal nanoparticles characteristics on the SERS performance was studied so far. In attempts to bring a light to the effect of quality of graphene, in this work, two different graphene oxides were selected, slightly oxidized GOS (20%) with low aspect ratio (1000) and highly oxidized (50%) GOG with high aspect ratio (14,000). GO and precursors for noble metal nanoparticles (NP) simultaneous were reduced, resulting in rGO decorated with AgNPs and AuNPs. The graphene characteristics affected the size, shape, and packing of nanoparticles. The oxygen functionalities actuated as nucleation sites for AgNPs, thus GOG was decorated with higher number and smaller size AgNPs than GOS. Oppositely, AuNPs preferred bare graphene surface, thus GOS was covered with smaller size, densely packed nanoparticles, resulting in the best SERS performance. Fluorescein in concentration of 10−7 M was detected with enhancement factor of 82 × 104. This work demonstrates that selection of graphene is additional tool toward powerful SERS substrates. 相似文献
8.
T. Petkova B. Monchev O. Kostadinova P. Petkov S.N. Yannopoulos 《Journal of Non》2009,355(37-42):2063-2067
We report a structural investigation of bulk Ge-rich Ge–S–AgI chalcohalide glasses. A vibrational spectroscopic study of the quaternary system (AgI)x (GeS1.5)100−x (0 xAgI 20) has been undertaken using infrared spectroscopy and Fourier transform Raman scattering. It was found that the GeS1.5 Raman spectrum is compatible with a glass structure composed of corner- and edge-sharing mixed GeSnGe4−n (n = 0–4) tetrahedra where units with n = 2–4 dominate, whilst the fraction of corner-sharing units are significantly lower than the corresponding fraction in the stoichiometric GeS2 glass. The addition of AgI has revealed a subtle but systematic effect in the structure of the Ge-rich glass matrix, manifested by mild decrease of the ES units and the concomitant increase of complex GeSnI4−n or GeSnGemI4-n−m tetrahedra whose vibrational modes form a continuum at low frequencies. Although, AgI seems to cause subtle structural changes due to the formation of Ge–I bonds, it is also evident that AgI does not act as a real modifier that would depolymerize appreciably the Ge–S network structure. 相似文献
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Elena Kostadinova Pavlina Dolashka Stefka Kaloyanova Ludmyla Velkova Todor Deligeorgiev Wolfgang Voelter Ivan Petkov 《Journal of fluorescence》2012,22(6):1609-1615
In this study, an improved, rapid, high yield synthesis of N,N’-4,4’-bis(benzyl-2-boronic acid)-bipyridinium dibromide (o-BBV) is described. The obtained o-BVV is applied in a two-component saccharide sensing system (complex) where it serves as a fluorescence quencher and a saccharide receptor. This system was applied to different natural oligosaccharides isolated from molluscan Rapana venosa (RvH1-a) and arthropodan Carcinus aestuarii (CaeH) hemocyanins (Hcs) and cyclodextrins (CDs). The carbohydrate contents of both Hcs were calculated in our previous work to be 1,6 % and 7 % for CaeH and RvH1-a, respectively. We propose that the difference in fluorescence increase of the native CaeH and RvH1-a when titrating them with the complex is due to the fact that the carbohydrate content of CaeH is lower and the carbohydrate chains are buried in between the structural subunits of the native molecule, while the glycans of the functional unit RvH1-a are exposed on the surface of the molecule leading to a 4-fold fluorescence’s intensity change. 相似文献