Role of nanoparticles in analytical solid phase microextraction (SPME)

2013 ◽  
Vol 10 (2) ◽  
pp. 120 ◽  
Author(s):  
Katarzyna Zielińska ◽  
Herman P. van Leeuwen

Environmental context Organic hydrophobic compounds are present in water in low concentrations, and they can be analysed by means of a preconcentration technique called solid phase microextraction. We investigate the role of sorbing nanoparticles in the solid phase microextraction analysis of organic compounds. Our results show that nanoparticles are capable of partitioning between water and the solid phase and aggregate at the interface leading, most probably, to substantial overestimation of the original sample concentration. Abstract Solid phase microextraction (SPME) is commonly used to measure the free concentration of fairly hydrophobic substances in aqueous media on the basis of their partitioning between sample solution and a solid phase. Here we study the role of nanoparticles that may sorb the analyte in the sample medium. As an example case, the solid phase poly(dimethylsiloxane) (PDMS) is exposed to an aqueous dispersion containing silica nanoparticles with 10-nm radius. Confocal laser microscopic data show that these SiO2 nanoparticles do enter the PDMS and partition between the sample solution and solid phase. Moreover, they form aggregates at the surface of the solid phase. The overall partitioning of the SiO2 nanoparticles in the aqueous sample–PDMS system is examined and potential effects on the SPME analysis of organic analytes are indicated.

Bioanalysis ◽  
2021 ◽  
Author(s):  
Sheelan Ahmad ◽  
Daniel Baker ◽  
Darragh Murnane ◽  
Neil Spooner ◽  
Ute Gerhard

Aim: Determination of plasma protein binding ( PPB) is considered vital for better understanding of pharmacokinetic and pharmacodynamic activities of drugs due to the role of free concentration in pharmacological response. Methodology & results: Solid-phase microextraction (SPME) was investigated for measurement of PPB from biological matrices and compared with a gold standard approach (rapid equilibrium dialysis [RED]). Discussion & conclusion: SPME-derived values of PPB correlated well with literature values, and those determined by RED. Respectively, average protein binding across three concentrations by RED and SPME was 33.1 and 31.7% for metoprolol, 89.0 and 86.6% for propranolol and 99.2 and 99.0% for diclofenac. This study generates some evidence for SPME as an alternative platform for the determination of PPB.


2014 ◽  
Vol 11 (1) ◽  
pp. 72 ◽  
Author(s):  
Katarzyna Zielińska

Environmental context Speciation analysis of organic compounds in aquatic media is often performed using solid phase microextraction with the assumption that only the free organic form is accumulated. We show that in the presence of silica nanoparticles, this interpretation is confounded by partitioning of nanoparticulate-bound compounds between water and the solid phase, as well as their aggregation at solid–bulk medium interfaces. Equilibrium measurement of the target analyte is feasible if the solid phase is protected by a suitable membrane. Abstract Solid phase microextraction (SPME) is applied in the speciation analysis of the hydrophobic compound triclosan in an aqueous medium containing sorbing SiO2 nanoparticles (NPs). It is found that these NPs, as well as their complexes with triclosan, partition between the bulk medium and the solid phase poly(dimethylsiloxane) (PDMS). Furthermore, they appear to aggregate at the PDMS–water interface. The total triclosan concentration in the solid phase thus includes both the free and the NP-bound forms. Proper computation of the analyte concentration in the sample medium requires (i) consideration of the speciation of triclosan inside the solid phase and (ii) elimination of the effects of aggregation of NP complexes at the solid phase–bulk medium interface. Possible solutions include application of a protective membrane with pore size smaller than the NP diameter. This allows measurement of the free triclosan concentration, albeit at the cost of longer accumulation times and loss of kinetic information on the triclosan–NP complex.


2010 ◽  
Vol 10 (7) ◽  
pp. 1388-1400 ◽  
Author(s):  
Gesine Witt ◽  
Carina Bartsch ◽  
Gladys A. Liehr ◽  
Rajko Thiele ◽  
Michael S. McLachlan

1996 ◽  
Vol 68 (24) ◽  
pp. 4463-4467 ◽  
Author(s):  
Wouter H. J. Vaes ◽  
Eñaut Urrestarazu Ramos ◽  
Henk J. M. Verhaar ◽  
Willem Seinen ◽  
Joop L. M. Hermens

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