Characterization and determination of the alkaloid metabolites of Evodiae fructus in rat urine by liquid chromatography-tandem mass spectrometry detection

The lack of authentic standards limits the quantitative analysis of herbal drugs in biological samples. This present work demonstrated a practicable assay of herbs and their metabolites independent of the availability of authentic standards. A liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) method for the qualitative and quantitative determination of the metabolites after oral administration of Evodiae fructus and Zuojinwan preparation in rat urine has been developed. Urine samples extracted with a protein precipitation procedure were separated on a C(18) column using a mixture of water (containing 0.1% formic acid) and acetonitrile (30:70, v/v) as mobile phase. The detection was performed by MS with electrospray ionization interface in positive selected reaction monitoring (SRM) mode. One urine sample after administration was selected as 'standard'. The method validation was carried out according to a conventional method that was calibrated by authentic standards. The fully validated method was applied to the pharmacokinetic study of the metabolites in rat urine. The results could provide evidence to explain the combination of Coptidis rhizoma and Evodiae fructus in terms of elimination.     

Synthesis of Densely Functionalised 5‐Halogen‐1,3‐oxazin‐2‐ones by Halogen‐Mediated Regioselective Cyclisation of N‐Cbz‐Protected Propargylic Amines: A Combined Experimental and Theoretical Study

A very efficient synthesis of 5‐halogen‐1,3‐oxazin‐2‐ones has been accomplished by the halocyclisation reaction of chiral nonracemic N‐carbobenzyloxy (N‐Cbz)‐protected propargylic amines by using I₂, Br₂ and Cl₂ as electrophile sources. The nature of the halogen influences the reaction time and yield. However, in all cases the reaction is totally regioselective taking place through a 6‐endo‐dig process regardless of the nature of the halogen and of the substituents in the starting material. To rationalise the experimental results, theoretical studies at the B3LYP/6‐311G* level have been performed.     

Carbon monoxide-assisted synthesis of single-crystalline Pd tetrapod nanocrystals through hydride formation

Carbon monoxide can adsorb specifically on Pd(111) to induce the formation of unique Pd nanostructures. In the copresence of CO and H(2), single-crystalline Pd tetrapod nanocrystals have now been successfully prepared. The Pd tetrapods are enclosed by (111) surfaces and are yielded through hydride formation. Density functional theory calculations revealed that the formation of PdH(x) in the presence of H(2) reduces the binding energy of CO on Pd and thus helps to decrease the CO coverage during the synthesis, which is essential to the formation of the PdH(x) tetrapod nanocrystals. In addition to tetrapod nanocrystals, tetrahedral nanocrystals were also produced in the copresence of CO and H(2) when the reaction temperature was ramped to further lower the CO coverage. Upon aging in air, the as-prepared PdH(x) nanocrystals exhibited a shape-dependent hydrogen releasing behavior. The conversion rate of PdH(x) tetrapod nanocrystals into metallic Pd was faster than that of tetrahedral nanocrystals.     

Supercritical fluid chromatography with photodiode array detection for pesticide analysis in papaya and avocado samples

To improve the analysis of pesticides in complex food matrices with economic importance, alternative chromatographic techniques, such as supercritical fluid chromatography, can be used. Supercritical fluid chromatography has barely been applied for pesticide analysis in food matrices. In this paper, an analytical method using supercritical fluid chromatography coupled to a photodiode array detection has been established for the first time for the quantification of pesticides in papaya and avocado. The extraction of methyl parathion, atrazine, ametryn, carbofuran, and carbaryl was performed through the quick, easy, cheap, effective, rugged, and safe methodology. The method was validated using papaya and avocado samples. For papaya, the correlation coefficient values were higher than 0.99; limits of detection and quantification ranged from 130–380 and 220–640 μg/kg, respectively; recovery values ranged from 72.8–94.6%; precision was lower than 3%. For avocado, limit of detection values were ?450 μg/kg; precision was lower than 11%; recoveries ranged from 50.0–94.2%. Method feasibility was tested for lime, banana, mango, and melon samples. Our results demonstrate that the proposed method is applicable to methyl parathion, atrazine, ametryn, and carbaryl, toxics pesticides used worldwide. The methodology presented in this work could be applicable to other fruits.     

Effects of Mn2+ on the chrome‐free colored Ti/Zr‐based conversion coating on 6063 aluminum alloy

The conversion coating with golden color and improved corrosion resistance had been prepared by adding Mn²⁺ in the Ti/Zr conversion coating solution. Comparing with that of conversion coating without Mn²⁺, the optimal treatment time of this conversion coating was much shorter and the corrosion resistance was obviously improved. The effect of Mn²⁺ on the formation of golden Ti/Zr conversion coating was thoroughly investigated by means of energy dispersive X‐ray spectroscopy, SEM, XPS, and Raman and electrochemical workstation. The results showed that the conversion coating had a double‐layer structure: the outer layer consisted of the metal‐organic complex and the inner layer was mainly made up of Na₃AlF₆. Mn²⁺ was oxidized into MnOOH in solution and precipitated on the substrate surface which provided the nucleus to Na₃AlF₆ crystal and accelerated Na₃AlF₆ crystal formation and also made the microstructure of conversion coating change to the cubic. The mechanism of the formation of the conversion coating can be deemed as nucleation, growth of Na₃AlF₆ crystal, and formation of metal‐organic complex. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of substrate temperature and N2/Ar flow ratio on the stoichiometry,structure and hardness of TaNx coatings deposited by DC reactive sputtering

The effect of substrate temperature and N2/Ar flow ratio on the stoichiometry, structure and hardness of TaN_x coatings prepared on (111) Si substrates by DC reactive sputtering was investigated. For the structural, chemical and morphological analysis, X‐ray diffraction (XRD), Auger electron scanning and atomic force microscopy were respectively used. Hardness values of thin films were determined using the work of indentation model from nanoindentation measurements. TaN stoichiometric coatings were obtained for samples deposited at room temperature. The stoichiometric TaN phase was not obtained by increasing the temperature up to 773 K, even when increasing the N₂/Ar flow ratio. Even when a saturation in nitrogen content was achieved, nitrogen vacancies are still present in those samples. For coatings prepared at 773 K and low N₂/Ar flow ratio, a phase mixture between TaN_x and cubic α‐Ta was observed, while a cubic structure δ‐TaN was formed by increasing the N₂/Ar flow ratio. A maximum in hardness and (38 GPa) was obtained for the sample deposited at 773 K and a N₂/Ar flow ratio of 0.2, which presented a δ‐TaN cubic crystalline structure and a roughness value of 1.6 nm. Copyright © 2015 John Wiley & Sons, Ltd.     

Liquid chromatographic method development for steroids determination (corticoids and anabolics). Application to animal feed samples

A LC isocratic separation study of a complex mixture containing 18 steroids (corticoids and anabolics), used potentially as growth promoters, was carried out. For this purpose, using a Hypersil ODS column at controlled temperature, mobile phases (from binary to quaternary) prepared from water and MeOH, ACN or THF as organic modifiers and UV detection at 245 nm, were employed (dehydroepiandrosterone was detected at 200 nm). The optimum separation was achieved using water/acetonitrile (65:35, v/v) as mobile phase at 30 degrees C, allowing the separation of 16 out of 18 steroids in about 30 min. The retention scale using optimized binary mobile phases was related with steroids hydrophobicity and structure, allowing a classification into three groups for these compounds. To improve the separation several alkyl-silica packings were tested: Type A (Lichrospher C8) and Type B (Luna C18, Kromasil C18, Purospher C18 and Synergy C12). Taking into account resolution, number of separated compounds and run time analysis the Hypersil column was selected as the best choice for further applications. Calibration graphs were obtained using fluorocortisone, fluoxymesterone or methylprednisolone as internal standard. The optimized separation was applied to the analysis of piglet feed samples spiked with steroids. The sample preparation process included solvent extraction using diethyleter and solid phase extraction using silica cartridges. The recoveries were in the range 70-92%. Decision limits and detection capability were in the range 34-198 and 41-249 microg/kg, respectively. Repeatability was also evaluated.     

Water-soluble carbosilane dendrimers protect phosphorothioate oligonucleotides from binding to serum proteins

Treatment of dendriplexes formed between water-soluble carbosilane dendrimers and phosphorothioate oligodeoxynucleotides (ODN) with the anionic detergent sodium dodecyl sulfate disrupted the complexes indicating that the nature of the union in such dendriplexes is merely electrostatic. However, dendriplexes were not dissociated by serum proteins like bovine or human serum albumins, as assessed by gel electrophoresis and fluorescence experiments. This would imply a dendrimer-mediated protective effect able to prevent ODN interactions with serum proteins and additionally could translate into a reduction of the ODN doses needed to achieve the biological effects. The employment of carbosilane dendrimers as carriers may solve the problem of ODN kidnapping by plasmatic proteins as a key drawback for therapeutics involving ODNs. As examples, transfection processes on normal primary peripheral blood cells and diagnosis of HIV infection in the presence of serum have been assayed.     

J-aggregation of a water-soluble tetracationic porphyrin in mixed LB films with a calix[8]arene carboxylic acid derivative

The molecular organization of a mixed film, containing a water-soluble tetracationic porphyrin (TMPyP) and a p-tert-butyl calix[8]arene octacarboxylic acid derivative (C8A), at the air-water interface and on a solid support (LB film), has been investigated. Although the TMPyP aggregation was not detected at the air-water interface, TMPyP J-aggregates have been found in the LB films (Y-type). Unlike tetraanionic porphyrins, for example TSPP, the TMPyP J-aggregates are not induced by a zwitterion formation. The TMPyP J-aggregation is a result of a "double comb" configuration, where porphyrins from opposite layers are interwoven in a linear infinite J-aggregate. Our results confirm that TMPyP molecules tend to self-aggregate strongly, provided the electrostatic repulsions of their peripheral groups are cancelled by the anionic groups of the C8A matrix.