A multiresidual method based on ion-exchange chromatography with conductivity detection for the determination of biogenic amines in food and beverages

In the present work a sensitive and accurate method by ion chromatography and conductimetric detection has been developed for the determination of biogenic amines in food samples at microgram per kilogram levels. The optimized extraction procedure of trimethylamine, triethylamine, putrescine, cadaverine, histamine, agmatine, spermidine, and spermine from real samples, as well as the separation conditions based on a multilinear gradient elution with methanesulfonic acid and the use of a weak ionic exchange column, have provided excellent results in terms of resolution and separation efficiency. Extended calibration curves (up to 200 mg/kg, r?>?0.9995) were obtained for all the analyzed compounds. The method gave detection limits in the range 23–65 μg/kg and quantification limits in spiked blank real samples in the range 65–198 μg/kg. Recovery values ranged from 82 to 103 %, and for all amines, a good repeatability was obtained with precision levels in the range 0.03–0.32 % (n?=?4). The feasibility and potential of the method were tested by the analysis of real samples, such as tinned tuna fish, anchovies, cheese, wine, olives, and salami.

Microwave‐Assisted Solid‐Phase Synthesis of a 1,2‐Disubstituted Benzimidazole Library by Using a Phosphonium Linker

An efficient and rapid microwave‐assisted solid‐phase method for the synthesis of 5‐methyl‐1,2‐disubstituted benzimidazoles derivatives has been developed. The phosphonium linker, obtained by reaction between polymer‐supported triphenylphosphine and 4‐fluoro‐3‐nitrobenzyl iodide, underwent aromatic substitution with primary amines, followed by one‐pot reaction with aldehydes in the presence of SnCl₂·2H₂O, yielded the benzimidazole system under microwave irradiation. The final products were released from the resin with NaOH under microwave irradiation and were obtained in high purity and good overall yield.     

Regiospecific Addition of Alcohols to 9-Hydroxy-and 9-Methoxy-1, 4-Anthraquinone

Conjugated addition of alcohols to 9-hydroxy-and 9-methoxy-1, 4-anthraquinone, in the presence of a strong acid and an oxidant, affords the 2-alkoxy- and 3-alkoxy-substituted regioisomer, respectively.     

Structural Diversity from the Transannular Cyclizations of Natural Germacrone and Epoxy Derivatives: A Theoretical–Experimental Study

Treatment of germacrone ( 1 ) with different electrophiles, and of its epoxy derivatives germacrone‐4,5‐epoxide ( 2 ), germacrone‐1,10‐epoxide ( 3 ) and isogermacrone‐4,5‐epoxide ( 4 ) with Brönsted/Lewis acids and Ti^III, gives rise to a great structural diversity. Thus, by using a maximum of two steps, the production of more than 40 compounds corresponding to 14 skeletons is described. Computational calculations rationalizing the structural divergence produced are also described. Finally, since some of the compounds generated are bioactive natural sesquiterpenes, the mechanisms of formation of these substances will provide new insights in their biosynthesis.     

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.     

Inorganic mercury and methylmercury determination in polluted waters by HPLC coupled to cold vapour atomic fluorescence spectroscopy

A systematic study of Hg²⁺ and CH₃Hg⁺ (MeHg⁺) speciation using hyphenated techniques, was performed for high-performance liquid chromatography coupled to on-line UV irradiation and cold-vapour atomic fluorescence spectroscopy (HPLC-UV-CV-AFS). First, a comparative study of the behaviour of three mobile phase compositions (using tetrabutylammonium bromide (TBAB), L-cysteine and ammonium pyrrolidinedithiocarbamate (APDC)) is presented. The separation and detection system was optimised by considering factors that modify fluorescence signal and the separation such as, the addition of different percentages of an organic modifier (methanol (MeOH) and acetonitrile (ACN)) to the mobile phase, the type of reducing agent used (SnCl₂ and NaBH₄) and the potential memory effects of the material of which the injection system is made (stainless steel, PEEK). The mobile phase selected for its sensitivity was a mixture 80?:?20 MeOH?:?0.0015?mol?l^–1 APDC and 0.01?mol?l^–1 NH₄CH₃COO (pH 5.5). The detection and quantification limits were close to 1.5 and 5?µg?l^?1 for both species (as Hg), respectively. Recoveries obtained using fortified water samples of distinct origin (soft mineral, tap, river, seawater, and wastewater), ranged from 90 to 115% for concentrations about 2 and 20 times over quantification limits. Good repeatability was obtained (about 5%) independently of the concentrations, with reproducibility values about 20% at low concentrations and 5–10% at higher concentrations. Our proposed method proved to be straightforward for use by environmental laboratories for routine Hg²⁺ and MeHg⁺ determinations in polluted water samples.     

Distribution of arsenic species in environmental samples collected in Northern Chile

Gradient ion chromatographic separation coupled with ICP-MS was used to resolve and determine the most common arsenic species in environmental and biological samples of carrots, trout, soil, sediment and river water from Region II of Chile. The carrot and trout samples showed a concentration of 49 and 168 µg g^?1, respectively, of total As. Both concentrations are high considering the basal level. In the carrots, percentage of 45 and 31% of total As were found for As(III) and As(V) species, respectively. In the trout, the higher concentration related to AsB at 39% of the total As. As(III) and DMA were also present in relatively high concentrations. The River Loa and the soil in which the carrots are growing also present very high As(V) concentrations of 100 and 17 µg g^?1, respectively. The ratio between the concentration for the same As species found in the living organisms (carrots and trout) and the environment in which they grow (soil and water) can provide important information about the possible absorption or biotransformation of As species in living beings. As(III) and DMA are the species in which the greatest accumulation occurs with respect to the medium in which they are present, and biotransformation also appears to take place.     

Comparison of membrane assisted liquid–liquid microextraction devices applied to a series of volatile organic compounds in aqueous environmental matrices

An extraction device has been investigated for the separation and preconcentration of a series of volatile organic compounds (CHCl₃, CHCl₂Br, CHClBr₂ and CHBr₃) in aqueous matrices. The device consisted of a microporous membrane system utilising a hollow fibre tube filled with organic solvent directly immersed into the sample solution. The hollow fibre containing 160 µL organic solvent was immersed in a glass vial with 10 mL capacity, and the extraction took place through diffusive transport between the aqueous sample and the small amount of solvent. For validation of the method, some operational conditions, such as extraction solvent, temperature, stirring rate and separation time, were optimised. Limit of detection was at low ppb levels, with GC-MS analysis under selected ion monitoring (SIM), whereas enrichment factors between 22 and 35 were obtained. Good reproducibility with RSDs between 7.2% and 9.8% and large linear dynamic ranges with R ² between 0.996 and 0.998 were also achieved. In addition, the performance of the membrane assisted solvent extraction (MASE) system was compared with two existing configurations: a non-porous membrane separation device, as well as with a comparable microporous configuration. The comparison considered the extraction mechanism and the underlying transport processes. The application to real samples showed a good concordance with classical analytical methods.     

Short stereocontrolled synthesis of trans and cis-tetrahydro-pyrazinoisoquinolinediones

Addition of aldehyde dimethyl acetals (here acetaldehyde) to unisolated O-trimethylsilyl derivatives of 1-acetyl-3-arylmethylpiperazine-2,5-diones (here 2,5-dimethoxyphenyl), in the presence of TMSOTf as the catalyst, gave nearly quantitatively the corresponding N-methoxyalkyl derivatives which, under acidic treatment, gave in very good yield through a Pictet-Spengler-type reaction involving N-acyliminium cations (6S*,11aR*)-2-acetyl-6-alkyl-3,6,11,11a-tetrahydro-2H-pyrazino[1,2-b]isoquinoline-1,4-diones. Epimerization of the 11a-stereocentre was accomplished by radical bromination, spontaneous hydrobromide elimination and catalytic hydrogenation, to give the (6S*,11aS*)-isomers. We propose these compounds as precursors of tetrahydroisoquinoline antitumour antibiotics.