Direct sample fraction deposition using electrospray in narrow-bore size-exclusion chromatography/matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for polymer characterization

A direct sample fraction deposition method was developed for off-line size-exclusion chromatography (SEC)/matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry. By using electrospray, the SEC eluent, together with a suitable matrix solution added coaxially, was directly deposited on the MALDI plate. Owing to the formation of very small droplets in electrospray, solvent evaporation is much faster. The fractionation volume in narrow-bore SEC, which can directly be collected in one MALDI spot, can easily be optimized in the range of a few microlitres. In addition, fairly homogeneous sample spots were obtained. The possible influence of composition variation of the SEC effluent on the analytical results using direct fraction deposition was investigated; no substantial effects were observed. The applicability of the method was demonstrated by characterizing a broad poly(methyl methacrylate) sample. Copyright 2000 John Wiley & Sons, Ltd.     

Nucleophilic aromatic substitutions on 4,5-dicyanopyridazine. Pyrrole and indole systems as carbon nucleophiles

4,5-Dicyanopyridazine was found to react with pyrrole and indole counterparts not only as heterocyclic azadiene in inverse electron-demand Hetero Diels–Alder reactions, as previously evidenced, but even as a very reactive heterocyclic electrophile at C-4 carbon, in formal S_NAr2 processes where a CN group acts as leaving group. In particular, operating in acetic acid as solvent, nucleophilic addition–elimination sequences allowed a facile access to pyrrolyl- and indolylpyridazines, through the corresponding 1,4-dihydropyridazine adducts.     

Comparison results for oscillation of nonlinear differential equations

((without abstract.))     

An equivalence theorem on properties A, B for third order differential equations

Differential equations are often classified according to oscillatory/nonoscillatory properties of their solutions as equations having property A or property B. The aim of the paper is to state an equivalence theorem between property A and property B for third order differential equations. Some applications, to linear as well as to nonlinear equations, are given too. Particularly, we give integral criteria ensuring property A or B for nonlinear equations. Our only assumption on nonlinearity is its superlinearity in neighbourhood of infinity, hence our results apply also to Emden-Fowler type equations.The second author wishes to thank C.N.R. of Italy and Grant Agency of Czech Republic (grant 201/96/0410) which made this research possible.     

Optical monitoring of volcanic sulphur dioxide emissions—comparison between four different remote-sensing spectroscopic techniques

The emissions of sulphur dioxide from the Italian volcanoes Mt. Etna and Stromboli were studied in ship-borne underpasses of their plumes. Four different optical spectroscopy techniques were used and inter-compared. All techniques utilise the absorption signature of the gas in the wavelength region of around 300 nm. A differential absorption lidar was employed in active gas concentration assessment. In parallel, a differential optical absorption spectroscopy system (DOAS) provided spectrally resolved absorption spectra. In one configuration the DOAS used a vertically looking telescope and the absorption of the sky-light was studied, while a different DOAS implementation utilised the sun disc as the light source in slant-angle, long-path absorption measurements. Parallel measurements with the customary correlation spectroscopy method were also performed. Path length Monte Carlo simulations of the down-welling radiation through the volcanic plume at different sun altitude and azimuth angles have been performed taking into account also the effects of other geometric parameters as the plume height and extension. The results are discussed with special emphasis on systematic effects due to scattering.     

A homogenized viscoelastic model for masonry structures

A linear viscous model for evaluating the stresses and strains produced in masonry structures over time is presented. The model is based on rigorous homogenization procedures and the following two assumptions: that the structure is composed of either rigid or elastic blocks, and that the mortar is viscoelastic. The hypothesis of rigid block is particularly suitable for historical masonry, in which stone blocks may be assumed as rigid bodies, while the hypothesis of elastic blocks may be assumed for newly constructed brickwork structures. The hypothesis of viscoelastic mortar is based on the observation that non-linear phenomena may be concentrated in mortar joints. Under these assumptions, constitutive homogenized viscous functions are obtained in an analytical form.Some meaningful cases are discussed: masonry columns subject to minor and major eccentricity, and a masonry panel subject to both horizontal and vertical loads. The major eccentricity case is analysed taking into account both the effect of viscosity and the no-tension hypothesis, whereas the bi-dimensional loading case is analysed to verify the sensitivity of masonry behaviour to viscous function. In the masonry wall considered, the principal stresses are both of compression, and the no-tension assumption may therefore be discounted.     

A homogenized Love–Kirchhoff model for out-of-plane loaded random 2D lattices: Application to “quasi-periodic” brickwork panels

A homogenization procedure for finding the bending stiffness of a 2D regular lattice with random local interactions is proposed. The kinematic and static methods are used to provide explicit upper and lower bounds for the homogenized moduli. The proposed homogenization procedure is applied to a masonry obtained by a random perturbation of the periodic running bond masonry [Cecchi, A., Sab, K., 2009. Discrete and continuous models for in plane loaded random elastic brickwork. Eur. J. Mech. A 28, 610–625].A numerical evaluation of the scatter between the discrete models and the 2D Love–Kirchhoff model is performed on a test case, for various values of the random perturbation parameter and of the parameter that characterizes the heterogeneity of the wall. As expected, when the number of heterogeneities in the structure is large enough, the average response of the random discrete model converges to an asymptotic response. It is shown that this asymptotic response is very close to that of the periodic discrete model which is in turn very close to the response of the deterministic homogenized model. Similarly to the conclusion of Cecchi and Sab [Cecchi A., Sab K., 2009. Discrete and continuous models for in plane loaded random elastic brickwork. Eur. J. Mech. A. 28, 610–625.] dedicated to in-plane loading, the present results concerning out-of-plane loading show (both by means of a discrete model and a homogenized model) that the running bond pattern may be used successfully to analyze historical masonries with blocks having irregular widths in the horizontal direction.     

Diels-alder reactions with 2-(Arylsulfinyl)-1,4-benzoquinones: effect of aryl substitution on reactivity, chemoselectivity, and pi-facial diastereoselectivity

Diels-Alder reactions of (SS)-2-(2'-methoxynaphthylsulfinyl)-1, 4-benzoquinone (1b), 2-(p-methoxyphenylsulfinyl)-1,4-benzoquinone (1c), and 2-(p-nitrophenylsulfinyl)-1,4-benzoquinone (1d) with cyclopentadiene are reported. These cycloadditions allowed the highly chemo- and stereoselective formation of both diastereoisomeric endo-adducts resulting from reaction on the unsubstituted double bond C(5)-C(6) of quinones working under thermal and Eu(fod)(3)- or BF(3).OEt(2)-catalyzed conditions. The synthesis of endo-adduct [4aS,5S,8R,8aR,SS]-9d resulting from cycloaddition on the substituted C(2)-C(3) double bond was achieved in a chemo- and diastereoselective way from quinone 1d in the presence of ZnBr(2). The reactivity and selectivity of the process proved to be dependent on the electron density of the arylsulfinyl group.     

Relative influence of noncovalent interactions on the melting points of a homologous series of 1,2‐dibromo‐4,5‐dialkoxybenzenes

Crystal structures are presented for two members of the homologous series of 1,2‐dibromo‐4,5‐dialkoxybenzenes, viz. those with decyloxy and hexadecyloxy substituents, namely 1,2‐dibromo‐4,5‐bis(decyloxy)benzene, C₂₆H₄₄Br₂O₂, (II), and 1,2‐dibromo‐4,5‐bis(hexadecyloxy)benzene, C₃₈H₆₈Br₂O₂, (III). The relative influences which halogen bonding, π–π stacking and van der Waals interactions have on these structures are analysed and the results compared with those already found for the lightest homologue, 1,2‐dibromo‐4,5‐dimethoxybenzene, (I) [Cukiernik, Zelcer, Garland & Baggio (2008). Acta Cryst. C 64 , o604–o608]. The results confirm that the prevalent interactions stabilizing the structures of (II) and (III) are van der Waals contacts between the aliphatic chains. In the case of (II), weak halogen C—Br...(Br—C)′ interactions are also present and contribute to the stability of the structure. In the case of (III), van der Waals interactions between the aliphatic chains are almost exclusive, weaker C—Br...π interactions being the only additional interactions detected. The results are in line with commonly accepted models concerning trends in crystal stability along a homologous series (as measured by their melting points), but the earlier report for n = 1, and the present report for n = 10 and 16, are among the few providing single‐crystal information validating the hypothesis.     

Comparative study of oxaprozin complexation with natural and chemically-modified cyclodextrins in solution and in the solid state

The complexing, solubilizing and amorphizing abilities toward oxaprozin (a poorly water-soluble anti-inflammatory agent) of some β-cyclodextrin derivatives (hydroxypropyl-βCd, heptakis-2,6-di-O-methyl-βCd (DIMEB) amorphous randomly substituted methyl-βCd (RAMEB) and semi-crystalline methyl-βCd (CRYSMEΒ)) were investigated and compared with those of natural (α-, β-, γ-) cyclodextrins. The role of both the cavity size, the amorphous or crystalline state and the presence and type of substituent on the ability of cyclodextrins in establishing effective interactions with the drug has been evaluated. Equimolar drug-cyclodextrin solid systems were prepared by blending, kneading, co-grinding, sealed-heating, coevaporation, and colyophilization. Drug-carrier interactions were studied in both the liquid and solid state by phase-solubility analysis, differential scanning calorimetry, X-ray powder diffractometry, FT-IR spectroscopy and scanning electron microscopy. βCd showed the best performance among the natural Cds, indicating that its cavity was the most suitable for accommodating the drug molecule. The presence of substituents on the rim of the βCd cavity significantly improved its complexing and solubilizing effectiveness towards the drug, and methylated derivatives were better than the hydroxy-propylated ones The amorphous nature of the partner was also important: among the examined methyl-derivatives, RAMEB proved to be the most effective in performing solid state interactions and in improving drug wettability and dissolution properties.