Metabolic phenotyping of human plasma by 1H‐NMR at high and medium magnetic field strengths: a case study for lung cancer

Accurate identification and quantification of human plasma metabolites can be challenging in crowded regions of the NMR spectrum with severe signal overlap. Therefore, this study describes metabolite spiking experiments on the basis of which the NMR spectrum can be rationally segmented into well‐defined integration regions, and this for spectrometers having magnetic field strengths corresponding to ¹H resonance frequencies of 400 MHz and 900 MHz. Subsequently, the integration data of a case–control dataset of 69 lung cancer patients and 74 controls were used to train a multivariate statistical classification model for both field strengths. In this way, the advantages/disadvantages of high versus medium magnetic field strength were evaluated. The discriminative power obtained from the data collected at the two magnetic field strengths is rather similar, i.e. a sensitivity and specificity of respectively 90 and 97% for the 400 MHz data versus 88 and 96% for the 900 MHz data. This shows that a medium‐field NMR spectrometer (400–600 MHz) is already sufficient to perform clinical metabolomics. However, the improved spectral resolution (reduced signal overlap) and signal‐to‐noise ratio of 900 MHz spectra yield more integration regions that represent a single metabolite. This will simplify the unraveling and understanding of the related, disease disturbed, biochemical pathways. Copyright © 2017 John Wiley & Sons, Ltd.     

Phase-Transfer Catalytic Alkylation of Hydroperoxides: A Convenient Route to Mixed Dialkyl Peroxides

The solid-liquid phase transfer catalytic alkylation of hydroperoxides using solid potassium hydroxide as a base and TEBAC as a phase transfer catalyst is reported. When the alkylating agent is a primary bromide, this reaction represents a simple and quick method for the synthesis of mixed dialkyl peroxides in fair yields.     

A Simple Method to Prepare Homoallylic Amines from Secondary Homoallylic Mesylates

The nucleophilic substitution by primary amines of secondary homoallylic mesylates easily obtained from corresponding alcohols offers a convenient way to prepare homoallylic amines. The relative low yields in pure compounds is counterbalanced by the simplicity of the procedure.     

Effect of the synthesis temperature of sodium nonatitanate on batch kinetics of strontium-ion adsorption from aqueous solution

Sodium titanate materials are promising inorganic ion exchangers for the adsorption of strontium from aqueous solutions. Sodium nonatitanate exhibits a layered structure consisting of titanate layers and exchangeable sodium ions between the layers. The materials used in this study include samples synthesized by a hydrothermal method at temperatures between 60 °C and 200 °C. Their structure, composition, and morphology were investigated with X-Ray diffraction measurements; thermogravimetric, compositional and surface area analyses, and scanning electron microscopy. The structure, composition, and morphology depended on the synthesis temperature. Batch kinetics experiments for the removal of strontium from aqueous solutions were performed, and the data were fitted by a pseudo-second-order reaction model and a diffusive model. The strontium extraction capacity also depended on the synthesis temperature and exhibited a maximum for samples synthesized at 100 °C. The sorption process occurs in one or two diffusion-controlled steps that also depend on the synthesis temperature. These diffusion-limited steps are the boundary-layer diffusion and intra-particle diffusion in the case of pure nonatitanate synthesized at temperatures lower than 170 °C, and only intra-particle diffusion in the case of nonatitanate synthesized at 200 °C.     

Structural features and hydrogen-bond properties of galanthamine and codeine: an experimental and theoretical study

Structural features of galanthamine and codeine, two allosteric potentiating ligands of nicotinic acetylcholine receptors (nAChRs), have been investigated through experimental studies in solution by FTIR and NMR spectroscopy and by quantum chemical calculations in the isolated state. The infrared spectra accumulated in solvents of various polarities show that the intramolecular OH···O hydrogen bond in galanthamine is stronger than the corresponding interaction in codeine. Molecular electrostatic potential calculations allow rationalisation of the experimental trends. NOE measurements on the two ligands in the same solvent range show significant differences. In apolar solvents, the NMR spectroscopic data indicate the occurrence of CH···O hydrogen-bond interactions, whereas in the more polar solvents, a trans orientation of the methoxy group with respect to the furanyl oxygen atom is favoured. A natural bond orbital (NBO) analysis provides evidence that these stabilising interactions originate in the hyperconjugation between the lone pairs of the furanyl oxygen atoms, n(O), and the methoxy antibonding σ*(C-H) orbitals within the two molecules. Despite the strong structural similarities between the two allosteric modulators, FTIR equilibrium constants measurements of hydrogen-bond complexation combined with quantum chemistry calculations point out the significant increase of hydrogen-bond accepting strength of galanthamine relative to codeine. This increase is mainly assignable to the stronger hydrogen-bond basicity of the hydroxyl group, and to a lesser extent to the higher hydrogen-bond accepting strength of the amino nitrogen of galanthamine in comparison with the corresponding groups of codeine. An analysis of the interactions that occur between the two ligands and acetylcholine esterase (AChE) suggests significant differences with Trp84, a key component of the AChE catalytic active site. In contrast, both ligands appear to interact similarly with acetylcholine binding protein (AChBP).     

HPLC determination of majdine in Vinca herbacea

A reliable HPLC method coupled with DAD detection was developed and validated for determination of majdine in Vinca herbacea. The chromatographic separation was carried out on a Symmetry C18 column (250 mm x 4.6 mm, 5 microm, Waters) with an isocratic solvent system of 25 mM potassium phosphate buffer (pH = 3.0)-acetonitrile. UV detection was performed at 225 nm. Good linear behavior over the investigated concentration range was observed with the value of r2 > 0.9978. The method was reproducible with intra- and inter-day variations of less than 4.38%. The proposed method was linear, accurate, precise and specific. The validated method was successfully applied to quantify majdine in various parts of V. herbacea, which was collected during the flowering months of April and May. The results indicated that the developed HPLC method could be used for the quality control of V. herbacea and for the standardization of its extracts in majdine.     

Thermophysical properties of polypropylene/aluminum composites

This article is dedicated to the study of the thermal parameters of composite materials. A nonlinear least‐squares criterion is used on experimental transfer functions to identify the thermal conductivity and the diffusivity of aluminum‐polymer composite materials. The density measurements were achieved to deduce the specific heat and thereafter they were compared to values given by differential scanning calorimetry measurement. The thermal parameters of the composite material polypropylene/aluminum were investigated for the two different types of aluminum filler sizes. The experimental data were compared with several theoretical thermal conductivity prediction models. It was found that both the Agari and Bruggeman models provide a good estimation for thermal conductivity. The experimental values of both thermal conductivity and diffusivity have shown a better heat transport for the composite filled with large particles. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 722–732, 2004