Optimization of an Untargeted DART-HRMS Method Envisaging Identification of Potential Markers for Saffron Authenticity Assessment.

Saffron is one of the most expensive agricultural products in the world and as such, the most commonly adulterated spice, with undeclared plant-based surrogates or synthetic components simulating color and morphology. Currently, saffron quality is certificated in the international trade market according to specific ISO guidelines, which test aroma, flavor, and color strength. However, it has been demonstrated that specific adulterants such as safflower, marigold, or turmeric up to 20% (w/w) cannot be detected under the prescribed approach; therefore, there is still a need for advanced and sensitive screening methods to cope with this open issue. The current investigation aims to develop a rapid and sensitive untargeted method based on an ambient mass spectrometry ionization source (DART) and an Orbitrap™high-resolution mass analyzer to discriminate pure and adulterated saffron samples with either safflower or turmeric. The metabolic profiles of pure and adulterated model samples prepared at different inclusion levels were acquired. Unsupervised multivariate analysis was carried out based on hierarchical cluster analysis and principal component analysis as first confirmation of the discriminating potential of the metabolic profile acquired under optimized DART-HRMS conditions. In addition, a preliminary selection of potential markers for saffron authenticity was accomplished, identifying compounds able to discriminate the type of adulteration down to a concentration level of 5%.

BENCHMARKING THE DOSE MAP SOFTWARE FOR CLINICAL IMPLEMENTATION AND ESTABLISHMENT OF A LOCAL FOLLOW-UP PROTOCOL FOR THE MANAGEMENT OF SKIN INJURES FOLLOWING COMPLEX INTERVENTIONAL CARDIOLOGY PROCEDURES.

This paper aims to validate the accuracy of the peak skin dose (Dskin,max) computed by the Dose Map software (DMS)-general electric and establish a local follow-up protocol for the management of patient skin injuries following complex interventional cardiology procedures (ICPs). Dskin,max was computed by the DMS and was simultaneously measured by a dense mesh of 72 thermoluminescent dosemeters for 20 ICP. Measured and computed Dskin,max were compared using Lin's concordance coefficient (${\rho}_c$). The implementation of a local follow-up strategy was based on a computed Dskin,max of 2 Gy. After eliminating 2 outliers, the average deviation between the two methods was 6% (range: -36 to +40%). Concordance between the two methods was moderate with ${\rho}_c$ (confidence interval) of 0.9128 (0.8541-0.9486). DMS computes Dskin,max with an acceptable accuracy and can be used to setup an individual follow-up process for patients with high skin exposure and risks.

Topography Measurements Using High Mass Resolution Time-of-Flight Secondary Ion Mass Spectrometry: Application to Banknotes.

An unconventional approach using the time-of-flight secondary ion mass spectrometry (TOF-SIMS) technique to determine the height topography at the microscale is detailed in this work with an application to cotton paper banknotes. The study was conducted by determining the effect of all related factors and parameters on the height measurement by taking the simplest model made from two Post-it sheets. For each sample, the difference in the TOF of the same secondary ion coming from two different heights was successfully attributed to the step height of the studied areas' topography, which was measured using classic methods. The measurement was independent of the orientation of the topography with regard to the primary ion beam and the electron beam azimuth. Moreover, the adjustment of the extraction gap with different layers has no effect on such measurements. However, a range of the analyzer acceptance energy values could be considered to achieve the expected outcomes only if the different analyzers' component energies are also changing accordingly. Heights between 20 and 180 µm were successfully measured using this new method. An added benefit to this method over other height measurement methods is the ability to discern areas with different chemical compositions, which eventually may help aid understanding of the sample in question.

Hydrophobization of chitosan films by surface grafting with fluorinated polymer brushes.

Chitosan with its surface-properties and biodegradability is a promising biomaterial for green packaging applications. Till now, this application is still limited due to chitosan high sensitivity to water. Some existing studies deal with the incorporation of hydrophobic additives to enhance water-proof performances of chitosan films. As these additives may impair the film properties, our study focuses on chitosan efficient hydrophobization by means of simple and successful surface grafting reactions. Chitosan films prepared by solvent casting were modified by means of surface-initiated activators regenerated by electron transfer atom radical polymerization (SI-ARGET-ATRP) of 2-hydroxyethyl methacrylate (HEMA) followed by esterification reaction with fluorinated acyl compound. X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Time-of-Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) highlighted the surface chemical changes after each step. Surface properties were investigated by contact angle measurements and surface energy calculations. Hydrophobic surfaces with low surface energy and good water-repellent properties were obtained using a simple handling polymerization procedure. This is the first study in applying ARGET ATRP to prepare hydrophobic biopolymer films offering potential applications in packaging.

Surface initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA-ATRP) of 4-vinylpyridine on poly(ethylene terephthalate).

Poly(ethylene terephthalate) (PET) substrates were modified by means of surface-initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA-ATRP) of 4-vinylpyridine (4VP). Substrates were pretreated in order to graft chloromethylbenzene (CMB) units capable of initiating the radical polymerization reaction of 4VP units. Surface characterization techniques, including Water Contact Angle (WCA), Attenuated Total Reflection (ATR), X-ray photoelectron spectroscopy (XPS), Atomic Force Microscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) showed a successful grafting of a stable, smooth and homogenous layer of p4VP. This process offers the advantages of a rapid, simplified and low cost strategy to chemically modify polymer substrates with covalently bonded layer of the pH responsive p4VP for different applications. Moreover, by using TOF-SIMS profiling, we were able to track a density gradient along the z-axis generated by the interpenetrating phases of the different layers of the final modified surface. Fact that we correlated to the various positions of initiation sites within the polyethylenimine (PEI) used for PET aminolysis prior to CMB grafting. Our strategy will be used in future work to graft other polymers for different applications where industrial scale viable options are needed.

Toward Cell Selective Surfaces: Cell Adhesion and Proliferation on Breath Figures with Antifouling Surface Chemistry.

We report the preparation of microporous functional polymer surfaces that have been proven to be selective surfaces toward eukaryotic cells while maintaining antifouling properties against bacteria. The fabrication of functional porous films has been carried out by the breath figures approach that allowed us to create porous interfaces with either poly(ethylene glycol) methyl ether methacrylate (PEGMA) or 2,3,4,5,6-pentafluorostyrene (5FS). For this purpose, blends of block copolymers in a polystyrene homopolymer matrix have been employed. In contrast to the case of single functional polymer, using blends enables us to vary the chemical distribution of the functional groups inside and outside the formed pores. In particular, fluorinated groups were positioned at the edges while the hydrophilic PEGMA groups were selectively located inside the pores, as demonstrated by TOF-SIMS. More interestingly, studies of cell adhesion, growth, and proliferation on these surfaces confirmed that PEGMA functionalized interfaces are excellent candidates to selectively allow cell growth and proliferation while maintaining antifouling properties.

Ion beam analysis and PD-MS as new analytical tools for quality control of pharmaceuticals: comparative study from fluphenazine in solid dosage forms.

In order to evaluate the potential of accelerator based analytical techniques ((particle induced X-ray emission (PIXE), particle induced gamma-ray emission (PIGE), and particle desorption mass spectrometry (PD-MS)) for the analysis of commercial pharmaceutical products in their solid dosage form, the fluphenazine drug has been taken as a representative example. It is demonstrated that PIXE and PIGE are by far the best choice for quantification of the active ingredient (AI) (certification with 7% precision) from the reactions induced on its specific heteroatoms fluorine and sulfur using pellets made from original tablets. Since heteroatoms cannot be present in all types of drugs, the PD-MS technique, which makes easily the distinction between AI(s) and excipients, has been evaluated for the same material. It is shown that the quantification of AI is obtained via the detection of its protonated molecule. However, calibration curves have to be made from the secondary ion yield variations since matrix effects of various nature are characteristics of such mixtures of heterogeneous materials (including deposits from soluble components). From the analysis of solid tablets, (either transformed into pellets and even as received), it is strongly suggested that the physical state of the grains in the mixture is a crucial parameter in the ion emission and accordingly for the calibration curves. As a result of our specific (but not optimized) conditions the resulting precision is <17% with an almost linear range extending from 0.04 to 7.87 mg of AI in a tablet made under the manufacturer conditions (the commercial drug product is labeled at 5 mg).