Characterization of a sucrose/starch matrix through positron annihilation lifetime spectroscopy: unravelling the decomposition and glass transition processes

The triplet state of positronium, o-Ps, is used as a probe to characterize a starch-20% w/w sucrose matrix as a function of temperature (T). A two-step decomposition (of sucrose, and then starch) starts at 440 K as shown by a decrease in the o-Ps intensity (I(3)) and lifetime (τ(3)), the latter also disclosing the occurrence of a glass transition. Upon sucrose decomposition, the matrix acquires properties (reduced size and density of nanoholes) that are different from those of pure starch. A model is successfully established, describing the variations of both I(3) and τ(3) with T and yields a glass transition temperature, T(g) = (446 ± 2) K, in spite of the concomitant sucrose decomposition. Unexpectedly, the starch volume fraction (as probed through thermal gravimetry) decreases with T at a higher rate than the free volume fraction (as probed through PALS).     

A note on “Methods for constructing distance matrices and the inverse eigenvalue problem”

In this paper, a symmetric nonnegative matrix with zero diagonal and given spectrum, where exactly one of the eigenvalues is positive, is constructed. This solves the symmetric nonnegative eigenvalue problem (SNIEP) for such a spectrum. The construction is based on the idea from the paper Hayden, Reams, Wells, “Methods for constructing distance matrices and the inverse eigenvalue problem”. Some results of this paper are enhanced. The construction is applied for the solution of the inverse eigenvalue problem for Euclidean distance matrices, under some assumptions on the eigenvalues.     

Calculating all elements of minimal index in the infinite parametric family of simplest quartic fields

It is a classical problem in algebraic number theory to decide if a number field is monogeneous, that is if it admits power integral bases. It is especially interesting to consider this question in an infinite parametric familiy of number fields. In this paper we consider the infinite parametric family of simplest quartic fields K generated by a root ξ of the polynomial P _t (x) = x ⁴ ? tx ³ ? 6x ² +tx+1, assuming that t > 0, t ≠ 3 and t ² +16 has no odd square factors. In addition to generators of power integral bases we also calculate the minimal index and all elements of minimal index in all fields in this family.     

On the vanishing of some non-semisimple orbital integrals

We prove the vanishing of the (possibly twisted) orbital integrals of certain functions on real Lie groups at non-semisimple elliptic elements. This applies to Euler–Poincaré functions and makes some results of [7] (Chenevier and Clozel, 2009) unconditional.     

Synthesis of branched oxime-linked peptide mimetics of the MUC1 containing a universal T-helper epitope

Our goal was to develop mimics of MUC1, highly immunogenic to induce an efficient immune response against the tumor-associated form of MUC1, and sufficiently different from the natural antigen to bypass the tolerance barrier in humans. With the aim of obtaining a well-defined peptide construct as a means of evoking the precise immune responses required in immunotherapy, we synthesized artificial mimics of the MUC1 protein composed of two MUC1 repeat units of inverse orientation and a universal T-helper epitope. To synthesize these heteromeric peptide constructs, we followed a convergent approach using chemoselective ligation based on oxime chemistry. A stem peptide was first synthesized bearing two orthogonally masked aldehydes. After successive deprotection, two oxime bonds can be specifically generated. The proposed strategy proved to be concise and robust, and allowed the synthesis of the tri-branched protein in a very satisfactory yield. The different constructs were tested for their ability to generate antibodies able to recognize the MUC1 protein.     

Elemental Analysis of Stone Fruits by Inductively Coupled Plasma Mass Spectrometry and Direct Mercury Analysis

This study reports the concentrations of eight trace essential (Zn, Mn, Cu, Ni, Cr, Co, V, and Se) and four toxic elements (Pb, As, Cd, and Hg) in commonly consumed stone fruits from South Korea. The samples were digested by microwave-induced combustion and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The concentrations of mercury were analyzed by direct mercury analysis (DMA). The analytical techniques were validated by linearity, limits of detection and quantification, precision, recovery, and for accuracy by analyzing a spinach leave-certified reference material; satisfactory results were obtained in all cases. The concentrations of essential trace elements varied considerably among the stone fruits. Generally stone fruits contained comparatively high concentrations of Zn (0.946 to 7.86?µg/g) and Mn (below the limit of detection to 1.66?µg/g), while lower contents of Cu (0.214 to 1.24?µg/g), Cr (0.032 to 0.114?µg/g), Ni (0.006 to 0.091?µg/g), Co (0.004 to 0.016?µg/g), V (below the limit of detection to 0.023?µg/g), and Se (0.0002 to 0.005?µg/g) were obtained. The concentrations (µg/g) of toxic metals were 0.007 (peach) to 0.016 (cherry) for Pb, 0.001 (plum) to 0.007 (cherry) for As, 0.002 (apricot and cherry) to 0.003 (peach) for Cd, and 0.0003 (peach) to 0.0016 (jujube) for Hg. The values for the estimated dietary intakes, target hazard quotients, and hazard indices were lower than the recommended safety limits by World Health Organization. Therefore, the analyzed stone fruits were deemed to be safe for human consumption.     

Optical properties of semiconducting iron disilicide thin films

The iron silicides samples were prepared by annealing of iron films evaporated onto silicon wafers and capped with amorphous silicon thin overlayers. Semiconducting FeSi₂ phase is formed by annealing at the temperatures from 550°C to 850°C. The optical properties of the FeSi₂ layers have been deduced from reflectance and transmittance measurements carried out in the temperature range of (77–380) K. The spectral dependence of the absorption coefficient favours direct allowed transitions with forbidden energy gap of 0.87eV at the room temperature. The application of a simple three-parameter semiempirical formula to the temperature dependence of the direct energy gaps leads to the following best fit parameters: the band gap at zero temperature E _g (0) = (0.895 ± 0.004)eV, the dimensionless coupling parameter S = 2.0 ± 0.3, and the average phonon energy <hw> = (46 ± 8)meV. By examining all the reported triplets of parameters for -FeSi₂ fabricated by different techniques and thermal processes, an obvious discrepancy can be found for the lattice coupling parameter and average phonon energy, although the bandgaps at 0 K are very similar. Unlike the theoretical prediction and the earlier reported result, our results do not show any evidence of a particularly strong electron-phonon interaction, which would give the lower carrier mobilities. -FeSi₂ seems to be an intriguing material where states with energies near the band edges permit ambiguous interpretation of the character of transitions. From optical model for the thin film-substrate system we found the index of refraction to be (5–5.9) in the photon energy interval from 0.65 to 1.15eV. There is also indication of an additional higher-energy absorption edge at l.05eV.     

High sensitive matrix-free mass spectrometry analysis of peptides using silicon nanowires-based digital microfluidic device

We present for the first time an electrowetting on dielectric (EWOD) microfluidic system coupled to a surface-assisted laser desorption-ionization (SALDI) silicon nanowire-based interface for mass spectrometry (MS) analysis of small biomolecules. Here, the transfer of analytes has been achieved on specific locations on the SALDI interface followed by their subsequent mass spectrometry analysis without the use of an organic matrix. To achieve this purpose, a device comprising a digital microfluidic system and a patterned superhydrophobic/superhydrophilic silicon nanowire interface was developed. The digital microfluidic system serves for the displacement of the droplets containing analytes, via an electrowetting actuation, inside the superhydrophilic patterns. The nanostructured silicon interface acts as an inorganic target for matrix-free laser desorption-ionization mass spectrometry analysis of the dried analytes. The proposed device can be easily used to realize several basic operations of a Lab-on-Chip such as analyte displacement and rinsing prior to MS analysis. We have demonstrated that the analysis of low molecular weight compounds (700 m/z) can be achieved with a very high sensitivity (down to 10 fmol μL(-1)).     

Identification and separation of saxitoxins using hydrophilic interaction liquid chromatography coupled to traveling wave ion mobility‐mass spectrometry

The aim of this work was to develop a reliable and efficient analytical method to characterise and differentiate saxitoxin analogues (STX), including sulphated (gonyautoxins, GTX) and non‐sulphated analogues. For this purpose, hydrophilic interaction liquid chromatography (HILIC) was used to separate sulphated analogues. We also resorted to ion mobility spectrometry to differentiate the STX analogues because this technique adds a new dimension of separation based on ion gas phase conformation. Positive and negative ionisation modes were used for gonyautoxins while positive ionisation mode was used for non‐sulphated analogues. Subsequently, the coupling of these three complementary techniques, HILIC‐IM‐MS, permitted the separation and identification of STX analogues; isomer differentiation was achieved in HILIC dimension while non‐sulphated analogues were separated in the IM‐MS dimension. Additional structural characteristics concerning the conformation of STXs could be obtained using IM‐MS measurements. Thus, the collision cross sections (CCS) of STXs are reported for the first time in the positive ionisation mode. These experimental CCSs correlated well with the calculated CCS values using the trajectory method. Copyright © 2015 John Wiley & Sons, Ltd.     

Magnetic Bistability of Individual Single‐Molecule Magnets Grafted on Single‐Wall Carbon Nanotubes

A POM to remember : Hexanuclear Fe^III polyoxometalate (POM) single‐molecule magnets (see structure) can be noncovalently assembled on the surface of single‐wall carbon nanotubes. Complementary characterization techniques (see TEM image and magnetic hysteresis loops) demonstrate the integrity and bistability of the individual molecules, which could be used to construct single‐molecule memory devices.