New approach for the clinical monitoring of 25‐hydroxyvitamin D3 and 25‐hydroxyvitamin D2 by ultra high performance liquid chromatography with MS/MS based on the standard reference material 972

Biomarkers, 25‐hydroxyvitamin D₃ and 25‐hydroxyvitamin D₂, are important indicators of the vitamin D general status and are monitored in several pathophysiological disorders, such as osteoporosis, diabetes, heart disease, etc. A novel ultra‐HPLC with MS/MS methodology for the analysis of 25‐hydroxyvitamin D derivatives coupled with a very simple and highly rapid sample preparation step was developed. Analytical parameters obtained showed linearity (R²) above 0.999 for both vitamins with accuracies between 95.8 and 102%. The LODs were as low as 0.22 and 0.67 nmol/L for 25‐hydroxyvitamin D₃ and 25‐hydroxyvitamin D₂, respectively. Intra‐assay precision (%RSD) was lower than 4.5%, and inter‐assay precision (%RSD) was lower than 6.5%. The feasibility of the developed methodology to be applied in clinical routine analysis has been proved by its application in blood samples from non‐agenarian patients, patients with familial hypercholesterolemia and patients suffering from age‐related macular degeneration.     

Rapid analysis of Na,Mg, Ca,Fe, and Zn in breakfast cereals (granola type) by energy dispersive-X-ray fluorescence

Energy dispersive-X-ray fluorescence (ED-XRF) is a well spread near-line analytical technique, suitable for easy and rapid measurement of major elements and/or trace elements especially in many different food matrices. This study demonstrates the fitness for purpose of this method to ensure the correct addition of minerals during breakfast cereal production. Indeed, variations in process and in raw material compositions may lead to values out of legal tolerance, and thus quality controls need to be regularly performed to meet the release compliance criteria. Using such analytical technique close to production lines can allow controls that are more systematic as well as avoiding the shipment of numerous samples for reference method analyses often done to external laboratories. Thus, ED-XRF allows to ensure finished products compliance with product declarations. A commercial ED-XRF device was used during this study. Within 7 min of analytical time for two replicates/sample, the developed method gave accurate results for the quantification of Na, Mg, Ca, Fe, and Zn in breakfast cereals without any proportional biases between ED-XRF and reference method (inductively coupled plasma-atomic emission spectrometry) results.     

Aqueous solution behavior of comb‐shaped poly(2‐ethyl‐2‐oxazoline)

A series of comb polymers consisting of a methacrylate backbone and poly(2‐ethyl‐2‐oxazoline) (PEtOx) side chains was synthesized by a combination of cationic ring‐opening polymerization and reversible addition–fragmentation chain transfer polymerization. Small‐angle neutron scattering (SANS) studies revealed a transition from an ellipsoidal to a cylindrical conformation in D₂O around a backbone degree of polymerization of 30. Comb‐shaped PEtOx has lowered T_g values but a similar elution behavior in liquid chromatography under critical conditions in comparison to its linear analog was observed. The lower critical solution temperature behavior of the polymers was investigated by turbidimetry, dynamic light scattering, transmission electron microscopy, and SANS revealing decreasing T_cp in aqueous solution with increasing molar mass, the presence of very few aggregated structures below T_cp, a contraction of the macromolecules at temperatures 5 °C above T_cp but no severe conformational change of the cylindrical structure. In addition, the phase diagram including cloud point and coexistence curve was developed showing an LCST of 75 °C of the binary mixture poly[oligo(2‐ethyl‐2‐oxazoline)methacrylate]/water. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Anomalous Proton NMR Deshielding in Anilinopyrazoles

In connection with the synthesis of thienobenzodiazepines and certain heterocyclic analogues¹, a number of anilino heterocycle precursors were prepared. Their proton NMR spectra were generally unexceptional with the exclusion of one of the pyrazole isomers which showed a remarkable deshielding of one proton signal in the aniline ring. Further investigations have inferred that this low field shift can be attributed to through speace deshielding by a proximal pyrazole nitrogen lone pair.     

Dye-coated europium monosulfide

Nanoparticles of EuS were synthesized using europium dithiocarbamate complexes. The resulting nanoparticles were coated with the dye, 1-pyrene carboxylic acid and the resulting material was characterized using X-ray powder diffraction, TEM, and UV-visible spectroscopy. Fluorescence spectroscopy was used to determine the relative energy of the conduction band edge to the excited state energy of the dye.     

Vectorial Slepian Functions on the Ball

Abstract

Due to the uncertainty principle, a function cannot be simultaneously limited in space as well as in frequency. The idea of Slepian functions, in general, is to find functions that are at least optimally spatio-spectrally localized. Here, we are looking for Slepian functions which are suitable for the representation of real-valued vector fields on a three-dimensional ball. We work with diverse vectorial bases on the ball which all consist of Jacobi polynomials and vector spherical harmonics. Such basis functions occur in the singular value decomposition of some tomographic inverse problems in geophysics and medical imaging. Our aim is to find band-limited vector fields that are well-localized in a part of a cone whose apex is situated in the origin. Following the original approach towards Slepian functions, the optimization problem can be transformed into a finite-dimensional algebraic eigenvalue problem. The entries of the corresponding matrix are treated analytically as far as possible. For the remaining integrals, numerical quadrature formulae have to be applied. The eigenvalue problem decouples into a normal and a tangential problem. The number of well-localized vector fields can be estimated by a Shannon number which mainly depends on the maximal radial and angular degree of the basis functions as well as the size of the localization region. We show numerical examples of vectorial Slepian functions on the ball, which demonstrate the good localization of these functions and the accurate estimate of the Shannon number.