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Application of magnetic solid-phase extraction for sensitive determination of anticancer drugs in urine by means of diamino benzidine tetrachlorohydrate modified magnetic nanoparticles

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Abstract

Background

The analysis of drug active molecules and residues in the treatment of cancer is important for the sustainability of human life and therapeutic effects. For this purpose, a new magnetic sorbent was developed to use in solid phase extraction prior to conventional high-performance liquid chromatography (HPLC) analysis of Paclitaxel (PAC) and Gemcitabine (GEM) molecules.

Methods

In this study, a separation and pre-concentration approach based on magnetic solid phase extraction (MSPE) was proposed for PAC and GEM by means of using a newly synthesized magnetic sorbent. After the MSPE procedure, an HPLC system with a diode array detector (DAD) was used to analyze trace amounts of PAC and GEM anticarcinogenic drugs in urine samples. Surface modification of magnetic Fe3O4 nanoparticles was carried out by diaminobenzidinetetrachloro hydrate (DABTC) for the first time and a useful sorbent was obtained for MSPE experiments.

Results

In the proposed method, PAC and GEM molecules were retained on the c in the presence of a pH 5.0 medium and desorbed to 300 μL of acetonitrile: methyl alcohol (1:1) eluent phase before HPLC–DAD analysis. Under the optimized conditions, the limit of detection (LOD) values for PAC and GEM were 1.38 and 1.44 ng mL−1 while the enhancement factor for PAC and GEM were 139.5 and 145.3, respectively. The relative standard deviations (RSD %) for PAC and GEM were below 3.50% in inter-day repeated experiments by means of model solutions containing 100 ng mL−1 drug active ingredients.

Conclusions

Synthesis and characterization of DABTC-Fe3O4 nanoparticles were performed using suitable methodologies. Optimization of MSPE was done step by step. And finally, the developed method was successfully applied to urine samples with quantitative recoveries in the range of 99.0% and 105.0%.

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Data availability

The data presented in this study are available in the article or supplementary materials.

Abbreviations

3-APTES:

3-Aminopropyl triethoxysilane

ACN:MeOH:

Acenotrile: Methyl Alcohol

BR buffer:

Britton–Robinson buffer

DABTC:

Diaminobenzidinetetrachloro hydrate

DABTC-Fe3O4 NPs:

Diaminobenzidinetetrachlorohydrate modified iron oxide nanoparticles

DAD:

Diode array detector

EDX:

Energy dispersive spectroscopy-energy dispersive X-ray

EF:

Enhancement factor

FE-SEM:

Field emission-scanning electron microscope

FTIR:

Fourier Transformed Infrared Spectroscopy

GEM:

Gemcitabine

LOD:

Limit of detection

LOQ:

Limit of quantification

MSPE/HPLC:

Magnetic solid phase extraction/high-performance liquid chromatography

NPs:

Nanoparticles

PAC:

Paclitaxel

PF:

Pre-concentration factor (PF)

PTFE:

Polytetrafluoroethylene

RSD:

Relative standard deviation

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Funding

This study has been supported by Cumhuriyet University Scientific Research Projects Commission as a research project (Code ECZ-073) and created by using experimental data obtained from Emin Akyol’s master thesis.

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Authors and Affiliations

  1. Department of Analytical Chemistry, Faculty of Pharmacy, Sivas Cumhuriyet University, Sivas, Turkey

    Emin Akyol, Halil İbrahim Ulusoy & Ümmügülsüm Polat

  2. Department of Analytical Chemistry, Faculty of Pharmacy, Erciyes University, Kayseri, Turkey

    Erkan Yilmaz

  3. Department of Chemistry, Faculty of Sciences, Erciyes University, Kayseri, Turkey

    Mustafa Soylak

  4. ERNAM-Nanotechnology Application and Research Center, Ernam Erciyes University, Kayseri, Turkey

    Erkan Yilmaz

Authors
  1. Emin Akyol
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  2. Halil İbrahim Ulusoy
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  3. Erkan Yilmaz
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  4. Ümmügülsüm Polat
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  5. Mustafa Soylak
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Contributions

EA: investigation, formal analysis, HIU: data curation, and writing—original draft; UP: validation and data curation; EY and MS: writing—review and editing, conceptualization.

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Correspondence to Halil İbrahim Ulusoy.

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Akyol, E., Ulusoy, H.İ., Yilmaz, E. et al. Application of magnetic solid-phase extraction for sensitive determination of anticancer drugs in urine by means of diamino benzidine tetrachlorohydrate modified magnetic nanoparticles. Pharmacol. Rep 75, 456–464 (2023). https://doi.org/10.1007/s43440-023-00465-5

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