In-tube solid phase microextraction coupled to miniaturized liquid chromatography for both, noble metal nanoparticle assessment and sensitive plasmonic assay development

• Published in: Analytica chimica acta Vol. 1171; p. 338665
• Main Authors: Sanjuan-Navarro, L., Cortés-Bautista, S., Moliner-Martínez, Y., Campíns-Falcó, P.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-08-2021
• Subjects: Acids; In-tube SPME; Miniaturized liquid chromatography; Noble nanoparticle assessment; Plasmonic assay; Spermine; Urine sample; Plasmonic assay; Miniaturized liquid chromatography; Spermine; Acids; Urine sample; Noble nanoparticle assessment; In-tube SPME
• ISSN: 0003-2670; 1873-4324
• DOI: 10.1016/j.aca.2021.338665

Colorimetric localized surface plasmon resonance (LSPR) as analytical response is applied for a wide number of chemical sensors and biosensors. However, the dependence of different factors, such as size distribution of nanoparticles (NPs), shape, dielectric environment, inter-particle distance and matrix, among others, can provide non-reliable results by UV–vis spectrometry in complex matrices if NP assessment is not carried out, particularly at low levels of analyte concentrations. Miniaturized liquid chromatography, capillary (CapLC) and nano (NanoLC), coupled on line with in-tube solid phase microextraction (IT-SPME) is proposed for the first time for both, controlling suitability of used noble metal NP dispersions and developing plasmonic assays. Several capped noble NPs and target analytes were tested from variations in the chromatographic profiles obtained by using diode array detection. The IT-SPME step, which influenced the chromatographic fingerprint provided by noble NP dispersions, was studied by asymmetrical flow field flow fractionation (AF4) too. We monitored NP aggregation induced by interaction with several analytes like acids and spermine (SPN). Assessment of NPs was achieved in less than 10 min and it permitted to develop suitable plasmonic tests. Here, it was also demonstrated that these assays can be followed by IT-SPME-miniaturized LC-DAD and more sensitivity and selectivity than those provided by UV–Vis spectrometry were achieved. Analysing urine samples to determine SPN as a cancer biomarker as a proof of concept is presented.
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•In tube-SPME and Miniaturized LC as a new tool for plasmonic assays.•Assessment of noble NPs from the ratio of two chromatographic peaks in 10 min.•Improved sensitivity and selectivity for spermine and H+ - induced assays.•Urine samples for healthy volunteers and cancer patients were tested.