The focus of this paper is to present techniques to overcome certain difficulties in quantitative analysis with a time- of-flight mass spectrometer (TOF-MS). The method is based on conventional solid-phase extraction, followed by reversed- phase ultra high performance liquid chromatography of the extract, and mass spectrometric analysis. The target compounds included atenolol, atrazine, caffeine, carbamazepine, diclofenac, estrone, ibuprofen, naproxen, simazine, sucralose, sulfamethox- azole, and triclosan. The matrix effects caused by high concentrations of organic compounds in wastewater are especially signif- icant in electrospray ionization mass spectroscopy. Internal-standard calibration with isotopically labeled standards corrects the results for many matrix effects, but some peculiarities were observed. The problems encountered in quantitation of carbamaze- pine and triclosan, due to nonlinear calibration were solved by changing the internal standard and using a narrower mass win- dow. With simazine, the use of a quadratic calibration curve was the best solution.
An advanced and reliable high performance liquid chromatography (HPLC)/ultraviolet detector (UV)/ion-trap timeof-flight (IT-TOF) mass spectrometry was developed for the simultaneous quantification of 19 marker compounds in Bangpoong-tong-sung-san (BPTS), a traditional oriental prescription. Various parameters affecting HPLC separation and IT-TOFdetection were investigated, and optimized conditions were identified. The separation was achieved on a Capcell PAK C18 column(1.5 mm × 250 mm, 5 μm particle size) using a gradient elution of acetonitrile and water containing 0.1% formic acid at aflow rate of 0.1 mL/min. The column temperature was maintained at 40oC and the injection volume was 2 μL. IT-TOF systemwas equipped with an electrospray ion source (ESI) operating in positive or negative ion mode. The optimized electrospray ionizationparameters were as follows: ion spray voltage, +4.5 kV (positive ion mode), or -3.5 kV (negative ion mode); drying gas(N2), 1.5 L/min; heat block temperature, 200oC. Automatic MSn (n = 1~3) analyses were carried out to obtain structural informationof analytes. Elemental compositions and their mass errors were calculated based on their accurate masses obtained from aformula predictor software. The marker compounds in BPTS were identified by comparisons between MSn spectra from standardsand those from extracts. Moreover, the libraries of MS2 and MS3 spectra and accurate masses of parent and fragment ionsfor marker compounds were constructed. The developed method was successfully applied to the BPTS extracts and identified 17out of 19 marker compounds in the BPTS extracts.
The impurity concentration is a crucial parameter for semiconductor thin films. Evaluating the impurity distribution in silicon thin film is another challenge. In this study, we have investigated the doping concentration of boron in silicon thin film using time of flight secondary ion mass spectrometry in dynamic mode of operation. Boron doped silicon film was grown on i) p-type silicon wafer and ii) borosilicate glass using hot wire chemical vapor deposition technique for possible applications in optoelectronic devices. Using well-tuned SIMS measurement recipe, we have detected the boron counts 10 1 ~10 4 along with the silicon matrix element. The secondary ion beam sputtering area, sputtering duration and mass analyser analysing duration were used as key variables for the tuning of the recipe. The quantitative analysis of counts to concentration conversion was done fol-lowing standard relative sensitivity factor. The concentration of boron in silicon was determined 10 17 ~10 21 atoms/cm 3 . The tech-nique will be useful for evaluating distributions of various dopants (arsenic, phosphorous, bismuth etc.) in silicon thin film efficiently.
The Brazil nut (Bertholletia excelsa - Lecythidaceae) is considered a product with high economic value, being a food widely appreciated for its nutritional qualities. Although previous studies have reported the biochemical composition of Brazil nut oil, the knowledge regarding the phospholipid composition exhibits a disagreement: the composition of fatty acids present in the structures of phospholipids is reported as being different from the composition of the free fatty acids present in the oil. In this work, solid phase extraction (SPE) was employed to provide a fast extraction of the phospholipids from Brazil nuts, in order to compare the phospholipid profile of the in nature nuts and their fatty acids precursor present in the oil. The major phospholipids were characterized by mass spectrometry approach. Their fragmentation pattern through direct infusion electrospray ionization ion-trap tandem mass spectrometry (ESI-IT-MS2) proved to be useful to unequivocal characterization of these substances. High resolution (HR) experiments through ESI using a quadruple time of flight mass spectrometry (QTOF) system were performed to reinforce the identifications.
The effects of trifluoroacetic acid (TFA) were evaluated on the generation of multiply charged ions of cytochrome c in a 2-nitrophloroglucinol (2-NPG) matrix in high-vacuum, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The presence of 1% TFA in the 2-NPG matrix solution was more effective in generating multiply charged protein ions than matrix solutions containing 0.1% or 0% TFA. Regarding the matrix itself, with 1% TFA, 2-NPG was significantly more effective in generating multiply charged ions than 2,5-dihydroxybenzoic acid (2,5-DHB). The maximum charge state of cytochrome c was +8 when using a 2-NPG matrix containing 1% TFA.
C8-functionalized magnetic nanoparticles were synthesized by coating magnetic Fe3O4 nanoparticles with silica–amine groups using 3-aminopropyltriethoxysilane and by subsequently modifying the amine groups with chloro(dimethyl)octylsilaneto produce octyl groups on the surface of the MNPs. The C8-functionalized MNPs were used to enrich peptides from trypticprotein digests of myoglobin and α-casein. The enriched peptides were analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI−ΤΟF−MS). MALDI-MS was also used to investigate desalting of the C8-functionalized MNPs. Sample solutions were prepared in 1.0 M NaCl, and the successful removal of salt was observed. Enrichmentwith C8-functionalized MNPs was very effective for separating and concentrating tryptic peptides.
Myoglobin was hydrolyzed by microwave-assisted weak acid hydrolysis with 2% formic acid at 37 oC, 50 oC, and100 oC for 1 h. The most effective hydrolysis was observed at 100 oC. Hydrolysis products were investigated using matrixassistedlaser desorption/ionization time-of-flight mass spectrometry. Most cleavages predominantly occurred at the C-termini ofaspartyl residues. For comparison, weak acid hydrolysis was also performed in boiling water for 20, 40, 60, and 120 min. A 60-min weak acid hydrolysis in boiling water yielded similar results as a 60-min microwave-assisted weak acid hydrolysis at100 oC. These results strongly suggest that microwave irradiation has no notable enhancement effect on acid hydrolysis of proteinsand that temperature is the major factor that determines the effectiveness of weak acid hydrolysis.
The effectiveness of tertiary matrices composed of the combination of three common matrices (dihydrobenzoic acid(DHB), α-cyano-4-hydroxycinnamic acid (CHCA), and sinapinic acid (SA)) was compared with that of single or binary matricesin the analysis of polyethylene glycol (PEG) polymers ranging from 1400 to 10000 Da using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). A tertiary matrix of 2,5-DHB+CHCA+SA was the mosteffective in terms of S/N ratios. CHCA and CHCA+SA produced the highest S/N ratios among the single matrices and thebinary matrices, respectively. The improvement observed when using a tertiary matrix in analyses of PEG polymers by MALDITOFMS is believed to be due to the uniform morphology of the MALDI sample spots and synergistic effects arising from themixture of the three matrix materials.
Characterization of the various chemical aspects of composite polymers is important for quality control of manufac-tured polymers. In this study, we compared three suitable matrices (α cyano-4-hydroxycinnamic acid [CHCA], 2,5 dihydroxy benzoic acid [2,5-DHB], and dithranol), to characterize various synthetic polymers by matrix-assisted laser desorption/ioniza-tion time-of-flight mass spectrometry. Although the spectra obtained with the CHCA and 2,5-DHB matrices were generally good, in certain samples ghost peaks disappeared only when dithranol was used as the matrix. Furthermore, we examined the use of sodium trifluoroacetate (NaTFA) as an additive to reduce interference by metals and copolymers in the spectra. In conclusion, appropriate selection of a matrix, according to the characteristics of the polymer, and the use of additives to improve sensitivity are important considerations for polymer analysis and development.
Liquid chromatography mass spectrometry is widely employed in proteomics studies. One of such instruments is the Liquid Chromatography (LC)-Matrix-assisted laser desorption ionisation (MALDI)-Time of flight (TOF) or LC-MALDI-TOF/TOF. In this study, this instrument was used to identify the membrane proteins of a protozoan parasite namely Entamoeba histo-lytica. It causes amoebiasis in human. The E. histolytica trophozoites were cultured prior to the membrane protein extraction using the conventional method, ProteoPrep® and ProteoExtract® kits. Then, the membrane protein extracts were tryptic- digested and analysed by LC-MALDI-TOF/TOF. Approximately, 194 proteins were identified and 27.8% (54) were predicted as membrane proteins having 1 to 15 transmembrane regions and signal peptides by combining all three extraction methods. Also, this study has discovered 3 unique proteins as compared to our previous study which merit further investigation.