Andrea Gorassini

New Heterocycles from the Reaction between Some Natural α-Amino Acid Hydrazides and Formaldehyde

The ring forming condensation between some natural α-amino acid phenylhydrazides (1) and aqueous formaldehyde (2) has opened a novel synthetic route to hexahydro-1,2,4-triazin-6-one derivatives (3). Polycyclic systems were obtained from the same reaction carried out with L-aspartic acid 1,4-bis(2-phenylhydrazide) (1d), L-histidine phenylhydrazide (1e) and L-tryptophan phenylhydrazide (1f) which gave perhydro-4,6-dioxo-2,8-diphenyl[1,2,4]triazino[4,5-d][1,2,4]triazepine (5) perhydro-1-oxo-3-phenylimidazo[5,4-d][1,2,4]triazino[4,5-a]pyridine (7) and 1,2,3-H-3-(2-phenylcarbazoyl)-β-carboline (8), respectively. Substrates 1 were conveniently obtained by direct reaction of phenylhydrazine with L-α-amino acid esters retaining the original chirality.

Rapid determination of cholesterol oxidation products in milk powder based products by reversed phase SPE and HPLC-APCI-MS/MS

A rapid and sensitive HPLC-APCI-MS/MS method for the determination of cholesterol oxidation products (COPs) in milk powder based foods is reported. The method consists in the direct saponification of the sample and purification of oxysterols by reversed phase C18-SPE followed by HPLC-MS/MS analysis. By this procedure, the extraction and enrichment of oxysterols are combined in a unique step, reducing sample manipulation and the possible formation of artifacts. LOD and LOQ were in the concentration ranges of 2-8ngg-1 and 8-30ngg-1, respectively. The precision (CV%) was in the range 10-36% in fresh samples with a total COPs amount from 212 to 645ngg-1 and 6-14% for an oxidized sample with a higher amount (3651ngg-1). The recovery ranged from 74±8% for 7-ketocholesterol to 101±12% for 7α-hydroxycholesterol at 200ngg-1 and from 82±2% for 7-ketocholesterol to 117±10% for 5α,6α-epoxycholesterol at 500ngg-1 spiked levels, respectively.

Surface and bulk reactions of cellulose oxidation by periodate. A simple kinetic model

The kinetics of periodate oxidation of cellulose was followed by exploiting the β-alkoxy degradation of oxidised units in alkaline medium, that brings about a decrease of viscometric degree of polymerisation. The parallel strong weight loss after NaOH treatment indicates a non-random mechanism of oxidation. The obtained results are interpreted on the basis of an appositely derived kinetic model that can be applied to other mechanisms of bulk and surface degradation.

New triterpenic acids produced in callus culture from fruit pulp of Acca sellowiana (O. Berg) Burret

The aim of this work was the study of the best conditions for obtaining a callus culture from the pulp of Acca sellowiana, and to perform a quali-quantitative analysis of the secondary metabolites yielded by the in vitro callus culture. To this end, callus was induced on both Murashige and Skoog and Gamborg B5 media containing various combinations of growth regulators. Three previously undescribed ursane-type triterpenoids, 2α,3β,6α,23-tetrahydroxy-18α,19α-urs-20-en-28-oic acid, 2α,3β,23-trihydroxy-18α,19α-urs-20-en-28-oic acid and 2α,3β,6β,23-tetrahydroxy-18α,19α-urs-20-en-28-oic acid were isolated from the methanolic extract of A. sellowiana culture and characterized by 1D and 2D NMR experiments. Moreover, the quali-quantitative analysis (ESI-MSn and GC-MS) also showed the presence of β-sitosterol, phloridzin, oleanolic, ursolic, 3β-hydroxy-18α,19α-urs-20-en-28-oic, maslinic, corosolic, 2α,3β-dihydroxy-18α,19α-urs-20-en-28-oic, and tormentic acid.