HPLC-atmospheric pressure chemical ionization

Siluk D, Mager DE, Gronich N, Abernethy D, Wainer IW (2007) HPLC-atmospheric pressure chemical ionization mass spectrometric method for enantioselective determination of R, S-propranolol and R, S-hyoscyamine in human plasma. J Chromatogr B 859 213-221... 

The photodegradation of XII was enhanced by humic substances (10mgL-1) or in a natural water sampled in a dam (Villerest, France) (7.2 mg CL-1). Formation of the photoproducts was measured by HPLC-atmospheric pressure chemical ionization-MS (HPLC-APCI-MS) using se-... 

HG Fouda, RP Schneider. Quantitative determination of the antibiotic azithromycin in human serum by high-performance liquid chromatography (HPLC)-atmospheric pressure chemical ionization mass spectrometry Correlation with a standard HPLC-electrochemical method. Ther Drug Monitor 17 179, 1995. 

Wissiack, R. and Rosenberg, E., Universal screening method for the determination of US environmental protection agency phenols at the lower ng 1 level in water samples by online SPE-HPLC-atmospheric pressure chemical ionization mass spectrometry within a single run, J. Chromatogr. A, 963, 149-157, 2002. 

Haschke, M. Zhang, Y.L. Kahle, C. Klawitter, J. Korecka, M. Shaw, L.M. Christians, U. HPLC atmospheric pressure chemical ionization MS/MS for quantification of 15-F2t-isoprostane inhuman urine and plasma. Clin. Chem. 2007, 53 (3), 489 97. 

Combs, M.T. Ashraf-Khorassani, M. Taylor, L.T. HPLC/atmospheric pressure chemical ionization-mass spectroscopy of eight regulated sulfonamides, J.Pharm.BiomedAncd., 1999, 19, 301-308. [LOD 0.05-6 ng sulfathiazole sulfamethazine sulfamerazine sulfapyridine sulfadimethoxine sulfadiazine sulfaquinoxaline sulfachlorpyridazine]... 

A number of analytical techniques such as FTIR spectroscopy,65-66 13C NMR,67,68 solid-state 13 C NMR,69 GPC or size exclusion chromatography (SEC),67-72 HPLC,73 mass spectrometric analysis,74 differential scanning calorimetry (DSC),67 75 76 and dynamic mechanical analysis (DMA)77 78 have been utilized to characterize resole syntheses and crosslinking reactions. Packed-column supercritical fluid chromatography with a negative-ion atmospheric pressure chemical ionization mass spectrometric detector has also been used to separate and characterize resoles resins.79 This section provides some examples of how these techniques are used in practical applications. 

In the following chapters, the basic principles of HPLC and MS, in as far as they relate to the LC-MS combination, will be discussed and seven of the most important types of interface which have been made available commercially will be considered. Particular attention will be paid to the electrospray and atmospheric-pressure chemical ionization interfaces as these are the ones most widely used today. The use of LC-MS for identification and quantitation will be described and appropriate applications will be discussed. 

The pump must provide stable flow rates from between 10 ttlmin and 2 mlmin with the LC-MS requirement dependent upon the interface being used and the diameter of the HPLC column. For example, the electrospray interface, when used with a microbore HPLC column, operates at the bottom end of this range, while with a conventional 4.6 mm column such an interface usually operates towards the top end of the range, as does the atmospheric-pressure chemical ionization (APCI) interface. The flow rate requirements of the different interfaces are discussed in the appropriate section of Chapter 4. 

Atmospheric-pressure chemical ionization (APCI) is another of the techniques in which the stream of liquid emerging from an HPLC column is dispersed into small droplets, in this case by the combination of heat and a nebulizing gas, as shown in Figure 4.21. As such, APCI shares many common features with ESI and thermospray which have been discussed previously. The differences between the techniques are the methods used for droplet generation and the mechanism of subsequent ion formation. These differences affect the analytical capabilities, in particular the range of polarity of analyte which may be ionized and the liquid flow rates that may be accommodated. 

Atmospheric-pressure chemical ionization (APCI) An ionization memod in which a liquid stream is passed through a heated capillary and a concentric flow of a nebulizing gas. Ions are formed by ion-molecule reactions between me analyte and species derived from me HPLC mobile phase. 

Reversed-phase Cig chromatography column. Keystone Scientific Betasil, 100 x 2.0-mm i.d., 5-pm particle size, 100 A, Part No. 105-701-2-CPF TSQ 7000 LC/MS/MS system with electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) interface and gradient high-performance liquid chromatography (HPLC) unit, or equivalent Vacuum manifold for use with SPE cartridges (Varian Vac Elut 10 or equivalent)... 

Reversed-phase high-performance liquid chromatography (HPLC) column 50 mm x 3.2-mm i.d. with Kromasil 5- um Gig packing High-performance liquid chromatograph coupled to a triple-quadrupole mass spectrometer with an atmospheric pressure chemical ionization (APCI) source Gel permeation chromatograph with a 60 mm x 25-mm i.d. column packed with Bio-Beads SX-3 (50-g)... 

For confirmatory assay, liquid chromatography-tandem mass spectrometry (LC-MS/MS) is becoming more frequently used in the analysis of OTC owing to its high sensitivity and ability. Electrospray ionization (ESI) [55-57] and atmospheric pressure chemical ionization (APCI) [41] methods combined with tandem mass spectrometry are favored because of their higher sensitivity and better reproducibility. Hamscher et al. [58] developed a method for the determination of persistent TC residues in soil fertilized with manure by HPLC tandem mass spectrometry, MS-MS, and confirmation by MS-MS-MS. Zhu et al. [59] developed an LC-tandem mass spectrometry for the analysis of common tetracyclines in water. The detection limit for oxytetracycline was 0.21 pg/L. Lykkeberg et al. [60] used LC-MS/MS for determination of oxytetracycline and its impurities EOTC, TC, ETC, ADOTC, oc-AOTC, and /i-AOTC. 

Figure 2.1 Mass spectrometric approach. Dl, direct inlet GC, gas chromatography HPLC, high performance liquid chromatography CZE, capillary zone electrophoresis El, electron ionization Cl, chemical ionization ESI, electrospray ionization DESI, desorption electrospray ionization APCI, atmospheric pressure chemical ionization MALDI, matrix assisted laser desorption ionization B, magnetic analyzer E, electrostatic analyzer...

Negative atmospheric pressure chemical ionization (APC) low-energy collision activation mss spectrometry has also been employed for the characterization of flavonoids in extracts of fresh herbs. Besides the separation, quantitative determination and identification of flavonoids, the objective of the study was the comparison of the efficacy of the various detection systems in the analysis of flavonoids in herb extracts. Freeze-dried herbs (0.5g of chives, cress, dill, lovage, mint, oregano, parsley, rosemary, tarragon and thyme) were ground and extracted with 20 ml of 62.5 per cent aqueous methanol. After sedimentation the suspension was filtered and used for HPLC analyses. Separations were carried out in an... 

With the development of sophisticated ionization techniques including electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), HPLC-MS techniques have been successfully applied to the online analysis of ginsenosides in extracts and biological fluids (Fuzzati, 2004). In terms of sensitivity and specificity, an MS detector is better than UV or ELSD. Among the various MS methods, the HPLC-MS-MS (or just LC-MS-MS) technique is to date the most sensitive method for detection and quantification of ginsenosides. 

HPLC - Beckman 125 binary gradient pumps, 168 diode-array detector, 507 autosampler MS - Ion-trap mass spectrometer Finnigan LCQ equipped by APCI (atmospheric pressure chemical ionization), data analyzed in negative mode, spectra confirming found compounds were obtained from tandem mass spectromectry (MS/MS). 

Stanaszek R, Piekoszewski W. 2004. Simultaneous determination of eight underivatized amphetamines in hair by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (HPLC-APCI-MS). J Anal Toxicol 28 77. 

LC/MS is the ultimate analytical technique, which combines the versatility of HPLC with the identification power of MS. The weak link in LC/MS has always been the interface which connects the liquid stream at atmospheric pressure to the high vacuum present inside the mass spectrometer. The development of several atmospheric pressure interfaces, electrospray and atmospheric pressure chemical ionization (APCI), has contributed to the tremendous success and popularity of LC/MS and LC/MS/MS in bioresearch, drug discovery, combinatorial analysis and pharmacokinetic assays. This topic is covered in more depth in a later chapter. 

X. Xu, A.M. van der Craats, E.M. Kok and P.C.A.M. de Bruyn, Trace analysis of peroxide explosives by high performance liquid chromatography — atmospheric pressure chemical ionization — tandem mass spectrometry (HPLC-APCl-MS/MS) for forensic applications ,... 

For the determination of organotin compounds (tributyltin, triphenyltin, triethyltin, and tetra-ethyltin) a MAE is proposed before the normal phase (NP) HPLC/UV analysis [35], In organotin and arsenic speciation studies, hydride generation is the most popular derivatization method, combined with atomic absorption and fluorescence spectroscopy or ICP techniques [25,36], Both atmospheric pressure chemical ionization (APCI)-MS and electrospray ionization ESI-MS are employed in the determination of butyltin, phenyltin, triphenyltin, and tributyltin in waters and sediments [37], A micro LC/ESI-ion trap MS method has been recently chosen as the official EPA (Environmental Protection Agency) method (8323) [38] it permits the determination of mono-, di-, and tri- butyltin, and mono-, di-, and tri-phenyltin at concentration levels of a subnanogram per liter and has been successfully applied in the analysis of freshwaters and fish [39], Tributyltin in waters has been also quantified through an automated sensitive SPME LC/ESI-MS method [40],... 

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