Tetracyclines analysis

Oka, H. Ikai, Y. Kawamura, N. Uno, K. Yamada, M. Harada, K. Uchiyama, M. Asukabe, H. Mori, Y. Suzuki, M. Improvement of chemical analysis of antibiotics. IX. A simple method for residual tetracyclines analysis in honey using a tandem cartridge clean-up system. J. Chromatogr. 1987, 389, 417-426. 

Anderson CR, Rupp HS, Wu WH, Complexities in tetracycline analysis—chemistry, matrix extraction, clean-up, and liquid chromatography, J. Chromatogr. A 2005 1075 23-32. 

Kreuzig (1996) de.scribed a TLC separation by a.scending chromatography for 5 cm for the control of penicillin V fermentations using Merck HPTLC silica gel plates and a mobile phase of toluene-ethyl acetate-acetic acid (40 40 20) the dried plates were scanned at 268 nm and the Rf values for 4-hydroxy-penicillin V, penicillin V, and phenoxyacetic acid were 0.34, 0.50, and 0.60, respectively. Kreuzig (1996) reemphasized the fact that because of widespread use of tetracyclines in veterinary medicine (mainly as feed additives) and in agriculture (e.g., in honeybee culture to prevent foul brood of honeybees), numerous TLC procedures for tetracycline analysis are available. 

An on-line concentration, isolation, and Hquid chromatographic separation method for the analysis of trace organics in natural waters has been described (63). Concentration and isolation are accompHshed with two precolumns connected in series the first acts as a filter for removal of interferences the second actually concentrates target solutes. The technique is appHcable even if no selective sorbent is available for the specific analyte of interest. Detection limits of less than 0.1 ppb were achieved for polar herbicides (qv) in the chlorotriazine and phenylurea classes. A novel method for deterrnination of tetracyclines in animal tissues and fluids was developed with sample extraction and cleanup based on tendency of tetracyclines to chelate with divalent metal ions (64). The metal chelate affinity precolumn was connected on-line to reversed-phase hplc column, and detection limits for several different tetracyclines in a variety of matrices were in the 10—50 ppb range. 

The overall biosynthetic pathway to the tetracychnes has been reviewed (74). Studies (75—78) utilising labeled acetate and malonate and nmr analysis of the isolated oxytetracycline (2), have demonstrated the exclusive malonate origin of the tetracycline carbon skeleton, the carboxamide substituent, and the folding mode of the polyketide chain. Feeding experiments using [1- 02] acetate and analysis of the nmr isotope shift effects, led to the location of... 

DeMoss, D.L. and Wright, G.L. 1997 Analysis of whole skeleton 3H-tetracycline loss as a measure ofbone resorption in maturing rats. Calcified Tissue International 61 412 17. 

UV detection, diode-array detector (DAD) and fluorescence have been the detection techniques used, coupled to HPLC for the analysis of OTC. UV detection is set at 355 nm [49-51], 350 nm [40], or at 353 nm [52], Using the diode array detector [49] offers advantages that the target peak can be identified by its retention time and absorption spectrum. Compared to UV detection, fluorescence detection is generally more specific and is less interfered by other compounds in the sample matrix [51]. A HPLC method with electrochemical detection has also been suggested recently. Zhao et al. [53] described HPLC with a coulometric electrode array system for the analysis of OTC, TC, CTC, DC, and methacycline (MC) in ovine milk. An amper-ometric detection coupled with HPLC was developed by Kazemifard and Moore [54] for the determination of tetracyclines in pharmaceutical formulations. 

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. 

OTC can be well separated from TC, DC, and its impurities by means of capillary electrophoresis [25]. However, the use of CE in the analysis of OTC residues is restricted because of the low concentration sensitivity of this technique [28]. HPLC is by far the most widely used method for the analysis of OTC residues in food and fisheries products. Chromatographic analysis of tetracycline including OTC analysis in foods was reviewed by Oka et al. [65] and MacNeil [72]. HPLC methods for the analysis of OTC are summarized in Table 2. 

Tetracycline Reaction with bromine in alkaline medium, flow injection analysis 19 pg/mL (4 X lCT5 M) 5 X 10 5-l X 10 2 M 62... 

A particularly intriguing aspect of the chemistry of the compounds of the tetracycline family is their ability to form metallic complexes. CTC shares in this intensively studied capability, which is very likely related to the therapeutic activity (9). This property is also used in the purification (10) and analysis (11) of CTC. 

Several qualitative and quantitative immunochemical methods for CAP analysis in biological matrices of animal origin have been described [101,102, 104,105] (see Table 3). Van de Water et al. [ 102] described an ELISA that detected CAP in swine muscle tissue with an IC50 value of 3 ng mL1. This immunoassay was improved and subsequently optimized incorporating the streptavidin-biotin amplification system. There are also several commercially available test kits (see Table 4). RIDASCREEN is a competitive enzyme immunoassay for the quantitative analysis of CAP residues in milk, eggs, and meat in a microtiter plate. The measurement is made photometrically, obtaining a LOD of 100 ng L 1 in meat and eggs and 150 ng L 1 in milk. The test has been also applied to the analysis of tetracyclines. 

Immunochemical methods have been developed and placed on the market to analyze tetracycline residues (see Table 4). Thus, a qualitative EIA has been developed and used to analyze tetracyclines in honey samples with a detection level of 20 pg/kg-1 [96]. A microplate-based indirect ELISA has been developed to analyze tetracyclines using polyclonal antibodies. The assay could measure tetracycline in the range between 0.1 and 6 ng mL L Other tetracycline antibiotics such as chlortetracycline, rolitetracycline, or minocycline are also highly recognized in this assay [98]. Several immunoassay kits are commercially available for the analysis of tetracyclines although, to our knowledge, none of them... 

As occurred with the other antibiotics, commercial immunoassay formats, also available as kits for tetracyclines and penicillins such as the Parallux, the LacTek, or the Charm II, have also been placed on the market for the analysis of sulfonamides (see Table 4). Thus, the Parallux detects sulfamethazine and sulfadimethoxine in raw milk with a LOD of 10 pg L1. The Charm II detects almost all sulfonamides in honey and milk with a LOD in the range from 1 to 10 pg L, whereas LacTek is able to detect sulfamethazine. Moreover, the 5101SULlp and 5101SUDAlp tests reach LOD values for sulfamethazine and sulfadiazine of around 0.2 pg L 1 and they have been applied to the analysis of urine, milk, and plasma. These tests have proved to be efficient as a point of care for on-site applications on farms. Moreover, commercially available antibodies can be found from several sources such as Silver Lake Research, US Biological, Cortex Biochem. Inc., Accurate Chemical Scientific, Fitzgerald Industries International Inc., and Biotrend Chemikalien GmbH. 

LC, CZE, and CEC techniques were compared for the analysis of tetracycline and its related substances and it was concluded that CEC might be the ideal technique, which... 

Yang S, Cha J, Carlson K (2005) Simultaneous extraction and analysis of 11 tetracycline and sulphonamide antibiotics in influent and effluent domestic wastewater by solid-phase extraction and liquid chromatography-electrospray ionization tandem mass spectrometry. J Chromatogr A 1097 40-53... 

Juergens, U. 1981. High-pressure liquid chromatographic analysis of residues of drugs in honey. I. Tetracycline. Juergens, Uwe. Z. Lebensm.-Unters. Forsch., 173(5) 356-8. 

An important area of direct biochemical interference is that caused by fluorescent or fluorescent quenching materials in the blood or urine after the administration of a drug. These interferences may be observed during catecholamine analysis in urine from patients receiving -methyldopa, tetracyclines, chlortetracyclines, oxytetracycline, erythromycin, chlorpro-mazine, or quinidine (A2, G5). 

Lindsey M.E., M. Meyer, and E.M. Thurman (2001). Analysis of trace levels of sulfonamide and tetracycline antimicrobials in groundwater and surface water using solid-phase extraction and liquid chromatography/mass spectrometry. Analytical Chemistry 73 4640-4646. 

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