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A method is described for rapid (1 h) synthesis of gold nanoclusters (AuNCs) co-functionalized with serine and 11-mercaptoundecanoic acid. The co-functionalized AuNCs exhibit good stability towards temperature, pH values, and over time. They were characterized by atomic force microscopy, high-resolution transmission electron microscopy, dynamic light scattering, and by fluorescence, IR and X-ray photoelectron spectroscopies. The fluorescence of the AuNCs is quenched by Hg(II) and restored on subsequent addition of aureomycin (CTC) or oxytetracycline (OTC). A fluorescent turn-on assay was worked out for simultaneous detection of CTC and OTC based on recording the change of the restored fluorescence measured at 420 and 500 nm under 340 nm photoexcitation. The detection limits are 20 and 9 nM for CTC and OTC, respectively. The concentrations of CTC and OTC can also be visualized by UV illumination. The nanoprobe was successfully applied to the simultaneous determination of CTC and OTC in spiked human urine. Graphical abstract Schematic of a two-wavelength fluorescence recovery method for the simultaneous determination of aureomycin and oxytetracycline. It is based on the use of gold nanocrystals modified with serine and 11-mercaptoundecanoic acid, and on recording the change of the restored fluorescence measured at 420 and 500 nm.

A simple luminescent methodology for the simultaneous determination of doxycycline and chlortetracycline in pharmaceutical preparations and human urine is proposed. Since the native fluorescence of both analytes is negligible, this method takes advantage of the lanthanide-sensitized luminescence, which provides increased sensitivity. Due to the strong overlapping between the luminescence spectra of both europium complexes, the use of luminescence decay curves to resolve mixtures of the analytes is proposed, particularly as these curves are more selective. A factorial design, with three levels per factor, coupled to a central composite design was selected to obtain a calibration matrix of 13 standards plus one blank sample, which were processed with a partial least-squares analysis. In order to assess the effectiveness of the proposed method, a prediction set of 10 synthetic samples was analyzed, and recovery percentages between 95 and 104% were obtained. Limits of detection, calculated by means of a new criterion, were 3.27 and 1.06 μg L(-1) for doxycycline and chlortetracycline, respectively. The method was tested in three different pharmaceutical preparations containing the analytes, with average recovery percentages of 99.4 ± 1.8 for doxycycline and 100.5 ± 2.1 for chlortetracycline. Moreover, a central composite design was also developed to obtain a calibration matrix that made feasible the simultaneous determination of both tetracyclines in human urine samples. In this case, average recovery percentages were 98.0 ± 4.4 and 97.8 ± 4.6 for doxycycline and chlortetracycline, respectively. No extraction method or prior separation of the analytes was needed.

This paper reports an indirect flow-injection (FI) method for the determination of the tetracycline drugs (TCs), tetracycline (TC), chlortetracycline (CTC) and oxytetracycline (OTC), using copper(II) as a probe ion. The method was based on the inhibition caused by these TCs to the copper(II)-catalysed chemiluminescence (CL) reaction between luminol and H(2)O(2). The CL reaction was induced on-line and injection of the sample produced negative peaks as a result of the copper(II) complexation or displacement by the analytes. The height of the peaks was proportional to the drug concentration in the sample. The choice of the catalyst ion, the concentration of luminol, H(2)O(2) and copper(II) are discussed. The linear range was 3.6 x 10(-8)-1.0 x 10(-5), 1.1 x 10(-7)-1.0 x 10(-5) and 1.9 x 10(-7)-1.0 x 10(-5) mol/L for TC, CTC and OTC, respectively. The detection limit was 5.0 x 10(-9) mol/L for TC, 1.0 x 10(-8) mol/L for CTC and 2.0 x 10(-8) mol/L for OTC (3sigma), respectively. The method was applied to the determination of TCs in pharmaceutical preparations and human urine with recoveries in the range 95-105%.

A highly selective method of chlortetracycline (CTC) is proposed on the basis of the measurements of total internal reflected resonance light scattering (TMR-RLS) at water/tetrachloromethane (H20/CCl4) interfaces. In the pH range of 7.54-8.14, the interaction of the binary complex of Eu(III)/CTC in the presence of trioctyl phosphine oxide (TOPO) occurs at the H20/CCl4 interface, resulting in greatly enhanced TIR-RLS signals with the maximum peak located at 340 nm. The enhanced TIR-RLS intensity is in proportion to the CTC concentration in the range 0.98 to approximately 20.0 x 10(-7) mol/L. The limit of detection is 9.8 x 10(-9) mol/L. Synthetic samples and body fluid samples including human urine, human serum, and fresh milk were determined with the recovery of 95.4-106.4% and RSD of 2.9-3.9%.

The fluorescence system of Eu-chlortetracycline-TOPO-sodium dedecyl sulfonate was studied. It was found that chloretetracycline formed a complex with Eu(III) at pH 8.0-9.0 and then emitted the characteristic fluorescence of Eu(III). TOPO and sodium dodecyl sulfonate greatly enhanced the fluorescence intensity of the system. The experiments indicated that under the optimum determining conditions a linear relationship was obtained between the fluorescence intensity and chlortetracycline concentration in the range of 2.0 x 10(-8)-1.0 x 10(-5) M. The detection limit was 6.0 x 10(-9) M. In addition, the luminescence mechanism of the complex system has been discussed.

The quantitation of oxytetracycline, tetracycline, and chlortetracycline was accomplished by high-pressure liquid chromatography using an anion-exchange column. The tetracyclines were extracted from urine as their calcium complexes. Concentrations as low as 12 microgram of oxytetracycline/ml and 4 microgram of tetracycline and chlortetracycline/ml were quantitated accurately. The relative standard deviation of the method varied from 0 to 5%.

An improved extraction procedure for the determination of oxytetracycline, tetracycline and chlortetracycline in urine, plasma and tissues by high-performance liquid chromatography is described. The addition of phenylbutazone (3,5-dioxo-1,2-diphenyl-4-n-butylpyrazolidine) to water, urine or plasma enhances the extraction of these compounds by ethyl acetate. The recovery of oxytetracycline from plasma is increased six fold and the need for two separate extractions of urine and plasma is eliminated. The formation of phenylbutazone-tetracycline ion pairs and their role in the extraction process is discussed.