Normal-Phase TLC and Gradient Reversed-Phase HPLC for the Simultaneous Determination of Enrofloxacin and Bromhexine HCl in Presence of Two of Their Official Impurities.

In this work, two chromatographic methods are developed and validated for the determination of enrofloxacin and bromhexine (BRM) HCl in the presence of two of their specified impurities, ciprofloxacin and BRM impurity C. The suggested chromatographic methods included the use of thin layer chromatography (TLC-densitometry) and high-performance liquid chromatography (HPLC). In case of TLC-densitometry, good separation was achieved by using mobile phase of n.butanol:acetone:water:glacial acetic acid:triethylamine (10:3:1:0.5:0.5, by volume) on silica gel stationary phase at 254-nm detection. The developed HPLC method used BDS HYPERSIL C18 column with a mobile phase of water:acetonitrile:methanol:triflouroacetic acid. A linear gradient elution of 75-10%, 20-50% and 5-40% for water, acetonitrile and methanol, respectively, was applied in 13 min at a flow rate of 1.5 mL min-1. These methods were sufficient to separate the four substances simultaneously, and they are validated as per International Conference on Harmonization guidelines.

Dummy molecularly imprinted membranes based on an eco-friendly synthesis approach for recognition and extraction of enrofloxacin and ciprofloxacin in egg samples.

In this work, novel dummy molecularly imprinted membranes (MIMs) were fabricated using the nylon-66 (NY-66) membranes as the subtracts based on an eco-friendly "sandwich" technology with less consumption of organic reagents at mild conditions for recognition and extraction of enrofloxacin (ENR) and ciprofloxacin (CIP) in egg samples. The prepared MIMs were characterized by SEM, ATR-FTIR and TGA, showing the successful construction of uniform and porous polymers on the surface of membranes. A series of adsorption affinity tests were investigated, indicating the prepared materials had specific recognition capacity and excellent stability as novel sorbents. Furthermore, Box-Benhnken design (BBD) and single factor investigations were applied to optimize pretreatment procedures, coupling with Ultra High Performance Liquid Chromatograph (UHPLC) detection. The method showed a good correlation (r2>0.9999) within the linear range of 5.0~5000.0 µg kg-1, and limit of detection (LOD) of ENR and CIP were 0.3 and 0.7 µg kg-1, respectively. The mean recovery ranged from 84.5% to 97.0% within relative standard deviations (RSDs) of 10.2%. Finally, ENR and CIP were not detected in 3 batches of egg samples. The current study developed the dummy MIMs as sorbents combined with UHPLC analysis for extraction and detection of target analytes in food matrices.

Development of doubly porous composite adsorbent for the extraction of fluoroquinolones from food samples.

A doubly porous microcomposite polyaniline/graphene oxide/octadecyl-bonded silica magnetite (PANI/GOx/C18-SiO2-Fe3O4) alginate adsorbent was developed and employed to extract fluoroquinolones. The Fe3O4 facilitated rapid and convenient for the separation of the adsorbent from sample solutions. The double porosity of the alginate hydrogel enhanced the surface area of the polyaniline coating. The developed method exhibited good linearity of 0.0010-50 µg L-1 for danofloxacin; 0.0050-50 µg L-1 for norfloxacin, ciprofloxacin and enrofloxacin; and 0.010-50 µg L-1 for sarafloxacin and difloxacin. The limits of detection were between 0.001 and 0.010 µg L-1 with RSD below 9.0%. The PANI/GOx/C18-SiO2-Fe3O4 adsorbent was utilized to extract fluoroquinolones from honey, milk and egg samples and satisfactory extraction recoveries were achieved ranged from 80 to 98%. The developed adsorbent has good stability which can be reused up to 7 times, is simple to prepare and convenient to use for the extraction fluoroquinolones.

A high-sensitivity thermal analysis immunochromatographic sensor based on au nanoparticle-enhanced two-dimensional black phosphorus photothermal-sensing materials.

For the first time, a quantitative photothermal-sensing immunochromatographic sensor (PT-ICS) is described using Au nanoparticle-enhanced two-dimensional black phosphorus (BP-Au) as signal component for the photothermal-sensing antibody probe. BP-Au has good photothermal properties at 808 nm, and the photothermal conversion efficiency of the BP-Au nanosheet increased by 12.9% over the black phosphorus nanosheet alone. In addition, the antibody was more easily coupled to this nanosheet due to the good physical adsorption capacity of Au nanoparticles. We used this PT-ICS to detect veterinary antibiotics enrofloxacin (ENR), the photothermal-sensing antibody probe was competitive captured by ENR target and antigen coating on test (T) lines of the sensor. This process was exothermic under an 808 nm laser, and the thermal energy decreased as the ENR in the sample increased. This thermal energy was recorded by an infrared thermal imager or an infrared thermometer, and the concentration of the ENR residues in animal-derived foods was obtained by analyzing the temperature changes in T-lines. Under optimal conditions, the PT-ICS exhibited sensitive and specific detection of ENR from 0.03 µg/L to 10 µg/L with detection limits of 0.023 µg/L. The results agreed well with a commercial enzyme-linked-immunosorbent assay kit. This PT-ICS provided a promising strategy for the detection of ENR residues in animal-derived foods and expected to be used for the detection of other highly sensitive biomacromolecules.