Rapid fingerprinting of red wines by MALDI mass spectrometry

Here we report a simple and fast method for wine fingerprinting based on direct matrix-assisted laser desorption/ionization (MALDI) mass spectrometry analysis of different red wine samples, useful for batch-to-batch analysis and for the detection of key compounds even in trace amounts which may vary from vintage to vintage, and from one treatment to another one. A series of 20 samples from different wines were subjected to MALDI mass spectrometry. We found that 2,5-dihydroxybenzoic acid is far superior with respect to all the matrices tested To the best of our knowledge this is the first application of an effective wine profiling not limited to detection of anthocyanins. More than 80 molecular species were detected. Moreover, qualitative and quantitative differences were observed, owing to the nature and relative abundance of different chemical compounds among the wines.     

A speciality theorem for curves in P<Superscript>5</Superscript>

Let be an integral projective curve. One defines the speciality index e(C) of C as the maximal integer t such that , where ω _C denotes the dualizing sheaf of . Extending a classical result of Halphen concerning the speciality of a space curve, in the present paper we prove that if is an integral degree d curve not contained in any surface of degree  < s, in any threefold of degree  < t, and in any fourfold of degree  < u, and if , then Moreover equality holds if and only if C is a complete intersection of hypersurfaces of degrees u, , and . We give also some partial results in the general case , .      

Tip-enhanced Raman scattering: Influence of the tip-surface geometry on optical resonance and enhancement

The tip-sample distance (z) dependence of tip-enhanced Raman scattering (TERS) has been investigated. The intensities of both, the Raman lines and the broad TERS background, exhibit strong decays with increasing z, which are nearly complete within 10 nm withdrawal of the STM tip in z direction. Interestingly, the maximum of the broad Lorentzian-shaped TER background is substantially blue shifted in energy with z. This effect is ascribed to a corresponding blue shift of the energies of localized plasmon modes upon tip retraction. Both experimental results fit very well data of a simple theoretical near-field model.     

Double pulse laser induced breakdown spectroscopy applied to natural and artificial materials from cultural heritages: A comparison with micro-X-ray fluorescence analysis

The laser-induced breakdown spectroscopy (LIBS) is an applied physical technique that has shown in recent years its great potential for rapid qualitative analysis of materials. Thanks to the possibility to implement a portable instrument that perform LIBS analysis, this technique is revealed to be particularly useful for in situ analysis in the field of cultural heritages. The purpose of this work is to evaluate the potentiality of LIBS technique in the field of cultural heritages, with respect to the chemical characterization of complex matrix as calcareous and refractory materials for further quantitative analyses on cultural heritages. X-Ray Fluorescence (XRF) analyses were used as reference. Calibration curves of certified materials used as standards were obtained by XRF analyses. The LIBS measurements were performed with a new mobile instrument called Modì (Mobile Double pulse Instrument for LIBS Analysis). The XRF analyses were performed with a portable instrument ArtTAX. LIBS and XRF measurement were performed on both reference materials and samples (bricks and mortars) sampled in the ancient Greek–Roman Theatre of Taormina. Although LIBS measurements performed on reference materials have shown non linear response to concentrations, and so we were not able to obtain quantitative results, an integrated study of XRF and LIBS signals permitted us to distinguish among chemical features and degradation state of measured building materials.     

Proteomic strategies for the identification of proteinaceous binders in paintings

The identification of proteinaceous components in paintings remains a challenging task for several reasons. In addition to the minute amount of sample available, complex and variable chemical composition of the paints themselves, possible simultaneous presence of several binders and contaminants, and degradation of the original materials due to aging and pollution are complicating factors. We proposed proteomic strategies for the identification of proteins in binders of paintings that can be adapted to overcome the requirements and difficulties presented by specific samples. In particular, we worked on (1) the development of a minimally invasive method based on the direct tryptic cleavage of the sample without protein extraction; (2) the use of microwave to enhance the enzymatic digestion yield, followed by the analysis of the peptide mixtures by nanoLC-MS/MS with electrospray ionization (ESI). Moreover, as an additional tool to tackle the problem of contaminating proteins, we exploited the possibility of generating an exclusion list of the mass signals that in a first run had been fragmented and that the mass spectrometer had to ignore for fragmentation in a subsequent run. The methods, tested on model samples, allowed the identification of milk proteins in a sample from paintings attributed to Cimabue and Giotto, thirteenth-century Italian masters, decorating the vaults of the upper church in the Basilica of St. Francis in Assisi, Italy.     

A distributed combustion solver for engine simulations on grids

Multi-dimensional models for predictive simulations of modern engines are an example of multi-physics and multi-scale mathematical models, since lots of thermofluiddynamic processes in complex geometrical configurations have to be considered. Typical models involve different submodels, including turbulence, spray and combustion models, with different characteristic time scales. The predictive capability of the complete models depends on the accuracy of the submodels as well as on the reliability of the numerical solution algorithms. In this work we propose a multi-solver approach for reliable and efficient solution of the stiff Ordinary Differential Equation (ODE) systems arising from detailed chemical reaction mechanisms for combustion modeling. Main aim was to obtain high-performance parallel solution of combustion submodels in the overall procedure for simulation of engines on distributed heterogeneous computing platforms. To this aim we interfaced our solver with the CHEMKIN-II package and the KIVA3V-II code and carried out multi-computer simulations of realistic engines. Numerical experiments devoted to test reliability of the simulation results and efficiency of the distributed combustion solver are presented and discussed.     

Non-local boundary value problems of arbitrary order

We give a new unified method of establishing the existence ofmultiple positive solutions for a large number of non-lineardifferential equations of arbitrary order with any allowed numberof non-local boundary conditions (BCs). In particular, we areable to determine the Green's function for these problems withvery little explicit calculation, which shows that studyinga more general version of a problem with appropriate notationcan lead to a simplification in approach. We obtain existenceand non-existence results, some of which are sharp, and givenew results for both non-local and local BCs. We illustratethe theory with a detailed account of a fourth-order problemthat models an elastic beam and also determine optimal valuesof constants that appear in the theory.     

Temperature maps measurements on 3D surfaces with infrared thermography

The use of the infrared camera as a temperature transducer in wind tunnel applications is convenient and widespread. Nevertheless, the infrared data are available in the form of 2D images while the observed surfaces are often not planar and the reconstruction of temperature maps over them is a critical task. In this work, after recalling the principles of IR thermography, a methodology to rebuild temperature maps on the surfaces of 3D object is proposed. In particular, an optical calibration is applied to the IR camera by means of a novel target plate with control points. The proposed procedure takes also into account the directional emissivity by estimating the viewing angle. All the needed steps are described and analyzed. The advantages given by the proposed method are shown with an experiment in a hypersonic wind tunnel.     

Synthesis and applications of copillar[5]arene dithiols

Abstract

A novel copillar[4+1]arene incorporating alkylthiol substituents was synthesised in three steps and structurally characterised as the first example of a pillar[n]arene to incorporate two terminal thiols on the same aromatic ring. The macrocycle was attached to gold electrodes through a standard dipping technique. Cyclic voltammetry demonstrated selectivity for Li⁺ over other alkali metal cations. The copillar[4+1]arene was also used as a capping agent in the preparation of 3 nm gold nanoparticles.     

In situ assembly of octahedral Fe(II) complexes for the enantiomeric excess determination of chiral amines using circular dichroism spectroscopy

A method for discriminating between α-chiral primary amine enantiomers is reported. The method utilizes circular dichroism (CD) spectroscopy and a sensing ensemble composed of 2-formyl-3-hydroxypyridine (4) and Fe(II)(TfO)(2). Aldehyde 4 reacts rapidly with chiral amines to form chiral imines, which complex Fe(II) to form a series of diastereomeric octahedral complexes that are CD-active in both the UV and visible regions of the spectrum. NMR studies showed that for enantiomerically pure imine complexes, the Δ-fac isomer is preferred. A statistical analysis of the distribution of stereoisomers accurately modeled the calibration curves for enantiomeric excess (ee). CD signals appearing in the UV region were bisignate, and the nulls of the CD signals were coincident with maxima in the UV spectrum, consistent with exciton coupling. Time-dependent density functional theory and semiempirical calculations confirmed that the CD signals in the UV region arise from coupling of the π-π* transitions in the imine chromophores and that they can be used to describe the signs and magnitudes of the curves accurately. The CD signals in the visible region arise from metal-to-ligand charge-transfer bands, and these signals can be used to determine the ee values of chiral amines with an average absolute error of ±5%. Overall, the strategy presented herein represents a facile in situ assembly process that uses commercially available simple reagents to create large optical signals indicative of ee values.