Dihydrogen to dihydride isomerization mechanism in [(C5Me5)FeH2(Ph2PCH2CH2PPh2)]+ through the experimental and theoretical analysis of kinetic isotope effects

The isomerization of complex [Cp*Fe(dppe)(eta2-H2)]+, generated in situ by low-temperature protonation of Cp*Fe(dppe)H with either HBF4 or CF3COOH, to the dihydride tautomer trans-[Cp*Fe(dppe)(H)2]+ is irreversible and follows first-order kinetics in the -10 to +15 degrees C range with Delta H double dagger = 21.6 +/- 0.8 kcal mol(-1) and DeltaS double dagger = 5 +/- 3 eu. The isomerization rate constant is essentially independent of the nature and quantity of a strong acid. Density functional theory (DFT) calculations on various models, including the complete system at both the quantum mechanics/molecular mechanics (QM/MM) and full QM levels, probe the relative importance of steric and electronic effects for the relative stability of the nonclassical and classical isomers and identify two likely isomerization mechanisms: a "direct" pathway involving simultaneous H-H bond breaking and cis-trans isomerization and a "via Cp" pathway involving agostic C5Me5H intermediates. Both pathways are characterized by activation energies in close correspondence with the experimental value (21.3 and 22.2 kcal mol(-1), respectively). Further kinetic studies were carried out for the Cp*Fe(dppe)H + CF3COOD and Cp*Fe(dppe)D + CF3COOD systems at 273 K. The [Cp*Fe(dppe)(eta2-HD)]+ complex establishes a very rapid isotope redistribution equilibrium with the eta2-H2 and eta2-D2 analogues. The equilibrium constant value (K = 3.3 +/- 0.3) indicates a significant equilibrium isotope effect. Simulation of the rate data provides access to the individual isomerization rate constants kHH, kHD, and kDD for the three isotopomers, yielding kinetic isotope effects: kHH/kHD = 1.24 +/- 0.01 and kHD/kDD = 1.58 +/- 0.01 (and, consequently, kHH/kDD = 1.96 +/- 0.02). The analysis of the DFT-calculated frequencies, using the [Cp*Fe(dhpe)H2]+ model system, for the [Cp*Fe(dhpe)(eta2-XY)]+ isotopomers as well as transition states for the "direct" (TSdir) and "via Cp" (TSrot) pathways (X = H, D) allowed the computation of the expected isotope effects. A comparison with the experiment strongly suggests that the mechanism occurs via the "direct" pathway for the present system, although the small difference in the calculated energy barriers suggests that the "via Cp" pathway may be preferred in other cases.     

Nonaqueous capillary electrophoresis method for the enantiomeric purity determination of S-timolol using heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin: validation using the accuracy profile strategy and estimation of uncertainty

Nonaqueous capillary electrophoresis (NACE) was successfully applied to the enantiomeric purity determination of S-timolol maleate using heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin (HDMS-beta-CD) as chiral selector. With a background electrolyte made up of a methanolic solution of 0.75 M formic acid, 30 mM potassium camphorsulfonate and containing 30 mM HDMS-beta-CD, the determination of 0.1% of R-timolol in S-timolol could be performed with an enantiomeric resolution of 8.5. Pyridoxine was selected as internal standard. The NACE method was then fully validated by applying a novel strategy using accuracy profiles. It is based on beta-expectation tolerance intervals for the total measurement error which includes trueness and intermediate precision. The uncertainty of measurements derived from beta-expectation tolerance intervals was estimated at each concentration level of the validation standards. To confirm the suitability of the developed and validated method, several real samples of S-timolol maleate containing R-timolol maleate at different concentrations were analysed and the results were compared to those obtained by liquid chromatography.     

Characterization of Pd-Cu alloy nanoparticles on gamma-Al2O3-supported catalysts

Cu-Pd/Al2O3 bimetallic catalysts have been characterized by XRD, TEM, and EDX techniques. The surface structure has been investigated by FT-IR spectroscopy of low-temperature adsorbed CO in the reduced and in the oxidized state. Evidence has been provided of the formation of Cu-Pd alloy nanoparticles, both of the alpha-phase (disordered fcc) and of the beta-phase (ordered CsCl-type). IR spectra suggest that Cu likely decorates the edges while Pd mostly stays at the main faces. Part of copper disperses as Cu+ on the support even after reduction. The presence of copper seems to modify strongly the sate of oxidized Pd centers in oxidized high-Pd content materials. The redox chemistry of the system, where Pd is reduced more easily than Cu, appears to be very complex.     

LC method for the determination of R-timolol in S-timolol maleate: Validation of its ability to quantify and uncertainty assessment

This article presents the validation results of a chiral liquid chromatographic (LC) method previously developed for the quantitative determination of R-timolol in S-timolol maleate samples. A novel validation strategy based on the accuracy profiles was used to select the most appropriate regression model, to assess the method accuracy within well defined acceptance limits and to determine the limits of quantitation as well as the concentration range.The validation phase was completed by the investigation of the risk profiles of various acceptable regression models in order to ensure the risk of obtaining the future measurements outside the acceptance limits fixed a priori.On the other hand, the present paper also shows how data used in this validation approach can be used to estimate the measurement uncertainty. The uncertainty derived from β-expectation tolerance interval (), which is equal to the uncertainty of measurements as well as the expanded uncertainty (U_x) using a coverage factor k = 2 was estimated. The uncertainty estimates obtained from validation data were finally compared with those obtained from interlaboratory and robustness studies.     

Synthesis of the novel conjugated ω,ω′-diaryl/heteroaryl hexatriene system with the central double bond in a heteroaromatic ring: photochemical transformations of 2,3-divinylfuran derivatives

New β,β′-aryl/heteroaryl 2,3-divinylfuran derivatives (9a-d) in which a hexatriene system is a part of heteroaromatic ring have been synthesized and their photochemical properties were investigated. The primary process observed was the isomerization to trans,trans-isomers 9a-d followed by photochemical rearrangement of the furan ring giving the phototransposition products (I-IV). Stilbenes (20, 21) and phenanthrenes (22, 25, and 26), formed as secondary products from the competitive intermolecular cycloadditions, were also observed.     

Precision study on capillary electrophoresis methods for metacycline

A CE method for metacycline (MTC) determination was investigated in an inter-laboratory experiment. Many problems were encountered in this study, most of which were related to the transfer of the method to different CE equipment. The reported problems could be classified into different categories: problems related to the precision, to the parameters in the protocol, and to the MTC peak shape. As the peak shape problem was partially responsible for the poor precision, a new CE method was developed in order to obtain a good MTC peak shape on all equipment. The precision of this new method for MTC determination was examined in an intermediate precision study, where the influence of the factors "time" and "equipment" was investigated. Although the new method could be transferred to different instruments, the precision remained poor mainly due to the contributions of the between-replicate and the between-injection variances.     

Development of a model for the analysis of wheel wear in railway vehicles

In railway applications, the estimation of the wear at the wheel-rail contact is an important field of study, mainly correlated to the planning of maintenance interventions, vehicle stability and the possibility to carry out specific strategies for the wheel profile optimization. In this work Authors present a model conceived for the evaluation of the wheel profile evolution due to wear, which is organized in two parts, mutually interactive: a vehicle model for the dynamic analysis and a model for the wear estimation. The wheel wear evolution is reproduced by dividing the overall chosen mileage to be simulated in discrete spatial steps: at each step the dynamic simulations are performed by means of the vehicle model keeping the wheel profile constant, while the wheel geometry is updated through the wear model only at the end of the discrete step. Thus, the two parts of the whole model work alternately until the completion of the whole established mileage. Clearly, the choice of an appropriate step length is one of the most important aspect of the procedure and it affects directly the result accuracy and the required computational time to complete the analysis. The entire model has been validated in collaboration with Trenitalia S.p.A and RFI, which has provided the technical documentation and the experimental results relating to some tests performed on a scenery that exhibits serious problems in terms of wear represented by the vehicle ALn 501 “Minuetto” on the Aosta-Pre Saint Didier line.     

On network form and function

Moving from the observation that drainage network configurations minimizing total energy dissipation are stationary solutions of the general equation describing landscape evolution, we review theoretical and observational evidence on river patterns and their scale-invariant structure. Exact results complemented by numerical annealing of the basic equation in the presence of additive noise suggest that configurations at (or very close to) the global minimum of energy dissipation differ from dynamically accessible states, which have rather different scaling properties and conform much better to natural forms. Thus we argue that, at least in the fluvial landscape, Nature works through imperfect searches for dynamically accessible optimal configurations. We also show that optimal networks are spanning loopless configurations only under precise physical requirements. This is stated in a form applicable to generic networks, suggesting that other branching structures occurring in Nature (e.g. scale-free and looping) may possibly arise through optimality to selective pressures. Indeed, we show that this is the case.     

Characterization of lapis lazuli and corresponding purified pigments for a provenance study of ultramarine pigments used in works of art

In this paper, we propose an analytical methodology for attributing provenance to natural lapis lazuli pigments employed in works of art, and for distinguishing whether they are of natural or synthetic origin. A multitechnique characterization of lazurite and accessory phases in lapis lazuli stones from Afghan, Siberian and Chilean quarries, on the pigments obtained by their purification, and on synthetic ultramarine pigments was performed. According to the results obtained, infrared spectroscopy is not a suitable technique for distinguishing the provenance of lapis lazuli, but a particular absorbance band makes it relatively easy to determine whether it is of natural or synthetic origin. On the other hand, EDS elemental composition and XRD patterns show the presence of specific mineral phases associated with specific lapis lazuli sources, and can be used to distinguish the provenance of the stones as well as—albeit to a lesser extent—the corresponding purified blue pigments. In contrast, FEG-SEM observations clearly show different stone textures depending on their provenance, although these distinctive features do not persist in the corresponding pigments. PCA analyses of EDS data allow Afghan lapis lazuli stone to be distinguished from Chilean and Siberian ones, and can distinguish between the pigments resulting from their purification as well as synthetic blue ones. Although this methodology was developed using a limited number of samples, it was tested on lapis lazuli pigments collected from three paintings (from the fourteenth to sixteenth centuries) in order to perform a preliminary validation of the technique, and based on the results, the provenance of the blue pigments employed in those artworks is proposed. Finally, upon analytically monitoring the process of purifying lapis lazuli to obtain the corresponding pigments, it was found that ion-exchange reactions occur between the alkali modifiers of silicate/aluminosilicate phases and free carboxylic acids present in the doughy mixture of natural terpenes and ground stone, namely pastello. These reactions favor (i) the retention of silicate phases in the organic mixture and (ii) the selective extraction of lazurite due to the formation of Br?nsted acidic sites [Al(OH)Si], which are responsible for its high hydrophilicity in comparison to the one of the other species present in the lapis lazuli stone.     

On the stable set of associated prime ideals of a monomial ideal

It is shown that any set of nonzero monomial prime ideals can be realized as the stable set of associated prime ideals of a monomial ideal. Moreover, an algorithm is given to compute the stable set of associated prime ideals of a monomial ideal.