[Show abstract][Hide abstract] ABSTRACT: Surface-enhanced laser desorption and ionization time-of-flight mass spectrometry (SELDI-TOF/MS), a laboratory-friendly technique, is used to identify biomarkers for cancer. The aim of the present study was to explore the application of SELDI proteomic patterns in serum for distinguishing between cases of pancreatic cancer, chronic pancreatitis, type 2 diabetes mellitus and healthy controls.
Sera from 12 healthy controls, 24 patients with type 2 diabetes mellitus, 126 with pancreatic cancer, including 84 with diabetes, and 61 with chronic pancreatitis, 32 of which were diabetics, were analyzed using SELDI-TOF/MS. Spectra (IMAC-30) were clustered and classified using Biomarker Wizard and Biomarker Pattern software.
Two decision tree classification algorithms, one with and one without CA 19-9, were constructed. In the absence of CA 19-9, the splitting protein peaks were: m/z 1526, 1211, and 3519; when CA 19-9 was used in the analysis, it replaced the m/z 3519 splitter. The two algorithms performed equally for classifying patients. A classification tree that considered diabetic patients only was constructed; the main splitters were: 1211, CA 19-9, 7903, 3359, 1802. With this algorithm, 100% of patients with type 2 diabetes mellitus, 97% with chronic pancreatitis and 77% of patients with pancreatic cancer were correctly classified. SELDI-TOF/MS features improved the diagnostic accuracy of CA 19-9 (AUC = 0.883 for CA 19-9; AUC = 0.935 for CA 19-9 and SELDI-TOF/MS features combined).
SELDI-TOF/MS allows identification of new peptides which, in addition to CA 19-9, enable the correct classification of the vast majority of patients with pancreatic cancer, which can be distinguished from patients with chronic pancreatitis or type 2 diabetes mellitus.
Clinical Chemistry and Laboratory Medicine 06/2009; 47(6):713-23. DOI:10.1515/CCLM.2009.158 · 2.96 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Baltic amber contains high levels of succinic acid, most of which is part of the polymer framework, and only recently has the presence of microcrystals of free succinic acid been documented by scanning electron microscopy and X-ray diffraction analysis. The determination of succinic acid can be used for an easy identification of Baltic amber among other fossil resins and to distinguish it from imitations, widely diffused on the market, produced with natural or modified recent or sub-fossil resins, such as copals. We report here a simple method, based on negative ion electrospray ionization mass spectrometry, for evaluating the free succinic acid content in water/methanol extracts of ambers from different origin, using a sample of about 20 mg. The limit of quantification is better than 1 ppm and, when applied to a set of amber samples of different origin, it was able to distinguish those of Baltic origin (showing free succinic acid levels in the range 50-400 ppm) from the others (for which succinic acid was undetectable, i.e. at levels lower than 1 ppm).
Rapid Communications in Mass Spectrometry 02/2009; 23(3):403-8. DOI:10.1002/rcm.3886 · 2.64 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The paper presents the application of a method based on coupled gas chromatography-mass spectrometry, using an isotopically labelled internal standard for the quantitative analysis of benzene (B), toluene (T), ethyl benzene (E), and o-, m-, p-xylenes (X). Their atmospheric concentrations were determined based on short-term sampling, in different sites of Cluj-Napoca, a highly populated urban centre in N-W Romania, with numerous and diversified road vehicles with internal combustion engines. The method is relatively inexpensive and simple and shows good precision and linearity in the ranges of 7–60 μg/m3
(B), 13–90 μg/m3
(T), 7–50 μg/m3
(E), 10–70 μg/m3
(X-m,p), and 20–130 μg/m3
(X-o). The limits of quantitation/detection of the method LOQ/LOD are of 10/5 μg/m3
(Xo), 5/3 μg/m3
(B, E, X-m,p), and of 3/1 μg/m3 (T), respectively.
Journal of Environmental and Public Health 01/2009; 2009(1687-9805):148527. DOI:10.1155/2009/148527
[Show abstract][Hide abstract] ABSTRACT: Amber is a fossil resin constituted of organic polymers derived through complex maturation processes of the original plant resin. A classification of eight samples of amber of different geological age (Miocene to Triassic) and geographical origin is here proposed using direct mass spectrometric techniques, i.e. laser desorption ionization (LDI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI), in order to obtain a fingerprint related to the amber origin. Differences and similarities were detected among the spectra with the four methods, showing quite complex spectra, full of ionic species in the mass range investigated (up to m/z 2000). The evaluation required statistical analysis involving multivariate techniques. Cluster analysis or principal component analysis (PCA) generally did not show a clear clustering with respect to the age of samples, except for the APPI method, which allowed a satisfying clustering. Using the total ion current (TIC) obtained by the different analytical approaches on equal quantities of the different amber samples and plotted against the age, the only significant correlation appeared to be that involving APPI. To validate the method, four amber samples from Cretaceous of Spain were analyzed. Also in this case a significant correlation with age was found only with APPI data. PCA obtained with TIC values from all the MS methods showed a fair grouping of samples, according to their age. Three main clusters could be detected, belonging to younger, intermediate and older fossil resins, respectively. This MS analysis on crude amber, either solid or extract, followed by appropriate multivariate statistical evaluation, can provide useful information on amber age. The best results are those obtained by APPI, indicating that the quantity of amber soluble components that can be photoionized decreases with increasing age, in agreement with the formation of highly stable, insoluble polymers.
Rapid Communications in Mass Spectrometry 03/2008; 22(5):630-8. DOI:10.1002/rcm.3404 · 2.64 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: In an investigation devoted to the search for plasma markers for colorectal cancer (CRC), carried out by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry, a series of overexpressed peptides were identified in the plasma of patients. Among them the peptide with molecular weight 903 Da was the most abundant one, with a mean +/- (SD) relative abundance of 37 +/- 17% and a frequency over 60%. Interestingly, also in plasma samples of ten subjects affected by familial adenomatous polyposis (FAP), the peptide with molecular weight 903 was overexpressed. In this investigation, MALDI/MS/MS experiments were carried out on the ion at m/z 904 detected in the MALDI mass spectra of CRC and FAP patients. The data analysis by SwissProt.2007.01.09 indicates that this peptide is due to the sequence RPPGFSPF, found in the kininogen-1 precursor, which is an alpha-2-thiol proteinase inhibitor. In the case of subjects affected by a particular FAP syndrome, the MALDI/MS/MS spectra were quite different from those obtained from CRC and FAP patients. In fact, two sequences have been evidenced: RPPGFSPF belonging to kininogen-1 precursor, and PRKSSSSR belonging to Forkhead box protein 01A.
Journal of Mass Spectrometry 12/2007; 42(12):1606-12. DOI:10.1002/jms.1358 · 2.71 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The behaviour of some N,N'-disubstituted hexahydropyrimidines, a class of naturally occurring compounds of biological and biomedical interest, has been studied in both electron ionization (EI) and electrospray ionization (ESI) modes coupled with collisional experiments (ESI-MSn). In both techniques, the [M-H]+ ions are highly abundant, even if their formation is generated by two different mechanisms, i.e. H. loss from the M+. species in the case of EI and hydride (H-) abstraction from the molecules in the case of ESI. Furthermore, due to the low, step-by-step internal energy deposition typical of collisional experiments performed in an ion trap mass spectrometer, different fragment ions were observed in EI and ESI-MSn collisions. In both cases, the ions can be related to the original structure and allow us to identify the positions in which the different substituents are present.
Rapid Communications in Mass Spectrometry 03/2006; 20(5):823-8. DOI:10.1002/rcm.2375 · 2.64 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A case study of urban air quality assessment was carried along a heavily circulated road, aiming to assess the impact of heavy vehicles traffic on the air quality on adjacent streets. A simple method was used for the collection of volatiles from air, in charcoal filled tubes. The analytes were desorbed in an organic solvent, then separated on a capillary column. The concentration of volatile organic atmospheric contaminants mainly originating from the exhaust gas of internal combustion engines, were then determined by using GC/MS quantitative analysis methods. Particulate matter concentrations in the air along the monitored street, were determined in 9 sampling sites, using a portable detector, and by applying the short time sampling methodology.
[Show abstract][Hide abstract] ABSTRACT: A method is presented, based on coupled gas chromatography-mass spectrometry GC-MS, to determine the atmospheric concentrations of benzene, toluene, ethyl benzene and o-, m-, p-xylenes mainly originating from the exhaust gas of internal combustion engines. Subsequent to preconcentration on active charcoal, the air contaminants were desorbed in dichloromethane, and perdeuterated benzene C6D6 was added as internal standard. The extract solutions were analyzed by GC-MS in the selected ion monitoring mode.