Fingerprinting of propolis by easy ambient sonic-spray ionization mass spectrometry

Chemical profiles of a representative set of 49 propolis ethanolic extracts collected worldwide (North and South America, Europe, Asia and Oceania) were obtained via easy ambient sonic-spray ionization mass spectrometry (EASI-MS). This simple and easily implemented fingerprinting technique analyses directly (without any pre-separation or sample manipulation) a tiny droplet of the ethanolic extract placed on a inert surface under ambient conditions. Data acquisition took about a minute per sample with no substantial sample carry-over. Extraction of propolis with ethanol by using an ultrasonic bath method gave EASI-MS data similar to the traditional maceration method, reducing total analysis time for the crude propolis resin from a week to just ca 1 h. Principal component analysis of the EASI-MS data is shown to group samples according to the plant sources of their resins, which characterizes their geographical origin. © 2009 Elsevier B.V. All rights reserved

GC-MS profiling of diterpene compounds in mediterranean propolis from Greece

The objective of this work is to analyze and identify the diterpene compounds in Mediterranean propolis samples from different Greek regions by GC-MS. The chemical composition of six propolis samples was established using previously isolated diterpenes from Cretan propolis as authentic standards for identification, based on mass spectral fragmentation of the TMS derivatives and retention index. More than 30 diterpenes, among which were new propolis constituents, were identified and characterized by means of authentic standards and interpretation of MS fragmentation as well. This is the first detailed profiling of a new type of propolis, rich in diterpenes. The chromatographic and mass- spectral characteristics of the diterpenes identified could be very useful for rapid GC-MS profiling of this propolis type and for revealing its plant sources. © 2010 American Chemical Society

Terpenes with antimicrobial activity from Cretan propolis

Five terpenes, the diterpenes: 14,15-dinor-13-oxo-8(17)-labden-19-oic acid and a mixture of labda-8(17),13E-dien-19-carboxy-15-yl oleate and palmitate as well as the triterpenes, 3,4-seco-cycloart-12-hydroxy-4(28),24-dien-3-oic acid and cycloart-3,7-dihydroxy-24-en-28-oic acid were isolated from Cretan propolis. Moreover, 18 known compounds were also isolated, seven of them for the first time as propolis components. All structures were established on the basis of spectroscopic analysis and chemical evidence. All isolated compounds were tested for antimicrobial activity against some Gram-positive and Gram-negative bacteria as well as against some human pathogenic fungi showing a broad spectrum of antimicrobial activity. © 2009 Elsevier Ltd. All rights reserved