Residual stress analysis near a cold expanded hole in a textured alclad sheet using X-ray diffraction

In this paper we present the methods of determination and the stress obtained at the periphery of a cold expanded hole in a 2024-T3 Alclad aluminum alloy sheet. The measurements in the aluminum clad were performed by the sin²Ψ method, taking experimental precautions to deal with the texture effects. In the core aluminum a special method had to be implemented to determine the stress values in a direction not accessible to the X-ray diffraction. The strains were measured in sample orientations selected according to the texture characteristics and stress factorsF _ij were used to calculate the stress tensor. TheF _ij values were determined assuming a quasi-isotropic material behavior, after concluding that the stress results were not significantly affected by factors calculated for textured material. The residual stress profile, both in the clad and in the sheet, shows a nearly axisymmetric stress state. Compressive stresses were observed near the periphery of the hole, with values that are higher on the exit than on the entrance face. Residual stresses were also higher in the hoop direction than in the radial direction. They decreased with the radial distance to the hole and affected the previous stress state over a distance of 6 mm. The plastic deformation induced by the cold expansion is well evidenced by the FWHM values, which in the affected zone decrease with increasing distance from the hole edge.     

Formation of catalytic silver nanoparticles supported on branched polyethyleneimine derivatives

A new and straightforward method for screening highly catalytically active silver nanoparticle-polymer composites derived from branched polyethyleneimine (PEI) is reported. The one-step systematic derivatization of the PEI scaffold with alkyl (butyl or octyl) and ethanolic groups led to a structural diversity correlated to the stabilization of silver nanoparticles and catalysis. Analysis of PEI derivative libraries identified a silver nanoparticle-polymer composite that was able to efficiently catalyze the p-nitrophenol reduction by NaBH(4) in water with a rate constant normalized to the surface area of the nanoparticles per unit volume (k(1)) of 0.57 s(-1) m(-2) L. Carried out in the presence of excess NaBH(4), the catalytic reaction was observed to follow pseudo-first-order kinetics and the apparent rate constant was linearly dependent on the total surface area of the silver nanoparticles (Ag-NPs), indicating that catalysis takes place on the surface of the nanoparticles. All reaction kinetics presented induction periods, which were dependent on the concentration of substrates, the total surface of the nanoparticles, and the polymer composition. All data indicated that this induction time is related to the resistance to substrate diffusion through the polymer support. Hydrophobic effects are also assumed to play an important role in the catalysis, through an increase in the local substrate concentration.     

In Vivo Optical Properties of Melanocytic Skin Lesions: Common Nevi, Dysplastic Nevi and Malignant Melanoma

We present an in vivo study of the optical properties of common nevi, dysplastic nevi and malignant melanoma skin lesions in human subjects. Reflectance spectra were measured on 1379 skin lesions, in the visible and near-infrared spectral regions, using a spectral imaging system, in a clinical setting. Analysis of the data using a reflectance model revealed differences between the optical properties of melanin present in nevi and melanoma lesions. These differences, which are in agreement with our previous observations on average reflectance spectra, may be potentially useful for the noninvasive characterization of pigmented skin lesions and the early diagnosis of melanoma.     

The Role of Ion Pairs in the Second‐Order NLO Response of 4‐X‐1‐Methylpiridinium Salts

A series of 4‐X‐1‐methylpyridinium cationic nonlinear optical (NLO) chromophores (X=(E)‐CH?CHC₆H₅; (E)‐CH?CHC₆H₄‐4′‐C(CH₃)₃; (E)‐CH?CHC₆H₄‐4′‐N(CH₃)₂; (E)‐CH?CHC₆H₄‐4′‐N(C₄H₉)₂; (E,E)‐(CH?CH)₂C₆H₄‐4′‐N(CH₃)₂) with various organic (CF₃SO₃^?, p‐CH₃C₆H₄SO₃^?), inorganic (I^?, ClO₄^?, SCN^?, [Hg₂I₆]^2?) and organometallic (cis‐[Ir(CO)₂I₂]^?) counter anions are studied with the aim of investigating the role of ion pairing and of ionic dissociation or aggregation of ion pairs in controlling their second‐order NLO response in anhydrous chloroform solution. The combined use of electronic absorption spectra, conductimetric measurements and pulsed field gradient spin echo (PGSE) NMR experiments show that the second‐order NLO response, investigated by the electric‐field‐induced second harmonic generation (EFISH) technique, of the salts of the cationic NLO chromophores strongly depends upon the nature of the counter anion and concentration. The ion pairs are the major species at concentration around 10^?3 M , and their dipole moments were determined. Generally, below 5×10^?4 M , ion pairs start to dissociate into ions with parallel increase of the second‐order NLO response, due to the increased concentration of purely cationic NLO chromophores with improved NLO response. At concentration higher than 10^?3 M , some multipolar aggregates, probably of H type, are formed, with parallel slight decrease of the second‐order NLO response. Ion pairing is dependent upon the nature of the counter anion and on the electronic structure of the cationic NLO chromophore. It is very strong for the thiocyanate anion in particular and, albeit to a lesser extent, for the sulfonated anions. The latter show increased tendency to self‐aggregate.     

Sampling analytes from cheese products for fast detection using neutral desorption extractive electrospray ionization mass spectrometry

The development of analytical techniques suitable for sensitive, high-throughput, and nondestructive food analysis has been of increasing interest in recent years. In this study, mass-spectral fingerprints of various cheese products were rapidly recorded in the mass range of m/z 50–300 Da without any sample pretreatment, using neutral desorption extractive electrospray ionization mass spectrometry (ND-EESI-MS) in negative ion mode. The results demonstrate that both volatile and nonvolatile analytes on greasy cheese surfaces can be directly sampled by a neutral desorption gas beam. The influence of the neutral desorption gas flow on the analyte signal was systematically investigated. Under optimized experimental conditions, reproducible results were obtained using ND-EESI-MS. Principal component analysis was applied to differentiate a total of 49 individual cheese samples (four different types), which were purchased from three different supermarkets. All samples were successfully classified according to their types; but distributors and sensory properties were not distinguishable from the spectra data. The principal components 2, 3, and 4 scores showed an excellent capacity of distinguishing types of cheese. Molecular markers of interest can be identified using tandem mass spectrometry and matching the data with those from reference compounds. The experimental data show that ND-EESI-MS is able to sensitively and directly detect analytes on greasy surfaces without chemical contamination, providing a convenient method for high-throughput food analysis with a high degree of safety.     

Analytical techniques for single-cell metabolomics: state of the art and trends

Single-cell metabolomics is an emerging field that addresses fundamental biological questions and allows one to observe metabolic phenomena in heterogeneous populations of single cells. In this review, we assess the suitability of different detection techniques and present considerations on sample preparation for single-cell metabolomics. Although targeted analysis of single cells can readily be conducted using fluorescent probes and optical instruments (microscopes, fluorescence detectors), a comprehensive metabolomic approach requires a powerful label-free method, such as mass spectrometry (MS). Mass-spectrometric techniques applied to study small molecules in single cells include electrospray MS, matrix-assisted laser desorption/ionization MS, and secondary ion MS. Sample preparation is an important aspect to be taken into account during further development of methods for single-cell metabolomics.     

Simultaneous sampling of volatile and non-volatile analytes in beer for fast fingerprinting by extractive electrospray ionization mass spectrometry

By gently bubbling nitrogen gas through beer, an effervescent beverage, both volatile and non-volatile compounds can be simultaneously sampled in the form of aerosol. This allows for fast (within seconds) fingerprinting by extractive electrospray ionization mass spectrometry (EESI-MS) in both negative and positive ion mode, without the need for any sample pre-treatment such as degassing and dilution. Trace analytes such as volatile esters (e.g., ethyl acetate and isoamyl acetate), free fatty acids (e.g., caproic acid, caprylic acid, and capric acid), semi/non-volatile organic/inorganic acids (e.g., lactic acid), and various amino acids, commonly present in beer at the low parts per million or at sub-ppm levels, were detected and identified based on tandem MS data. Furthermore, the appearance of solvent cluster ions in the mass spectra gives insight into the sampling and ionization mechanisms: aerosol droplets containing semi/non-volatile substances are thought to be generated via bubble bursting at the surface of the liquid; these neutral aerosol droplets then collide with the charged primary electrospray ionization droplets, followed by analyte extraction, desolvation, ionization, and MS detection. With principal component analysis, several beer samples were successfully differentiated. Therefore, the present study successfully extends the applicability of EESI-MS to the direct analysis of complex liquid samples with high gas content.

Evolution of the solvent polarity in an electrospray plume

Solvent polarity plays an important role in electrospray ionization-mass spectrometry (ESI-MS), one of the most widely used analytical methods for biochemistry. To have a comprehensive understanding of how solvent polarity affects ESI-MS measurements, we systematically investigated the polarity change in the ESI plume formed from an ethanol solution using laser-induced fluorescence (LIF) spectroscopy. Two solvatochromic dyes (i.e., dyes whose fluorescence emission is sensitive to solvent polarity), Nile red and DCM (4-dicyanomethylene-2-methyl-6-p-dimethylaminostyryl-4H-pyran), were used as probes. The peak emission wavelengths of these two dyes exhibited significant red shifts (8–12 nm) when the measuring spot was moved away from the spray tip and in radial direction in the plume, indicating a dramatic polarity change during shrinking of the droplets. The emission intensities were also measured with a polarity-insensitive dye as a reference. The results are consistent with the peak wavelength measurements. Two key mechanisms responsible for the change of solvent polarity in the plume were considered, water entrainment from the surrounding air and solvent evaporation. Furthermore, quantitative analysis of the solvent polarity change was performed by using the Lippert-Mataga polarity parameter Δf. The value of Δf reached 0.305–0.307 at the periphery of the ESI plume, which means that the solvent polarity in the smaller droplet is close to that of a mixture of 30% water and 70% ethanol (Δf = 0.307), even though the bulk solvent was ethanol containing less than 1% water as an impurity.     

Microbial transformation of marine halogenated sesquiterpenes

The sesquiterpene pacifenol is one of the main constituents of the red alga Laurencia claviformis. Earlier work on the semisynthetic derivatives of pacifenol afforded a series of halogenated sesquiterpenes. The aim of the present work was to obtain new hydroxylated derivatives of halogenated sesquiterpenes by means of microbial transformation using Aspergillus niger, Gibberella fujikuroi and Mucor plumbeus. The best results were obtained with M. plumbeus. The microbiological transformation by M. plumbeus of pacifenol, and two semisynthetic derivatives, is described. The structures of the new compounds obtained were determined by spectroscopic means.