ABSTRACT
Volatile Organic Compounds (VOC) are a major class of environmental pollutants hazardous to human health, but also highly relevant in other fields including early disease diagnostics and organoleptic perception of aliments. Therefore, accurate analysis of VOC is essential, and a need for new analytical methods is witnessed for rapid on-site detection without complex sample preparation. Surface-Enhanced Raman Spectroscopy (SERS) offers a rapidly developing versatile analytical platform for the portable detection of chemical species. Nonetheless, the need for efficient docking of target analytes at the metallic surface significantly narrows the applicability of SERS. This limitation can be circumvented by interfacing the sensor surface with Metal-Organic Frameworks (MOF). These materials featuring chemical and structural versatility can efficiently pre-concentrate low molecular weight species such as VOC through their ordered porous structure. This review presents recent trends in the development of MOF-based SERS substrates with a focus on elucidating respective design rules for maximizing analytical performance. An overview of the status of the detection of harmful VOC is discussed in the context of industrial and environmental monitoring. In addition, a survey of the analysis of VOC biomarkers for medical diagnosis and emerging applications in aroma and flavor profiling is included.
ABSTRACT
The analysis of low-abundance protein molecules in human serum is reported based on counting of the individual affinity-captured analyte on a solid sensor surface, yielding a readout format similar to digital assays. In this approach, a sandwich immunoassay with rolling circle amplification (RCA) is used for single molecule detection (SMD) through associating the target analyte with spatially distinct bright spots observed by fluorescence microscopy. The unspecific interaction of the target analyte and other immunoassay constituents with the sensor surface is of particular interest in this work, as it ultimately limits the performance of this assay. It is minimized by the design of the respective biointerface and thiol self-assembled monolayer with oligoethylene (OEG) head groups, and a poly[oligo(ethylene glycol) methacrylate] (pHOEGMA) antifouling polymer brush was used for the immobilization of the capture antibody (cAb) on the sensor surface. The assay relying on fluorescent postlabeling of long single-stranded DNA that are grafted from the detection antibody (dAb) by RCA was established with the help of combined surface plasmon resonance and surface plasmon-enhanced fluorescence monitoring of reaction kinetics. These techniques were employed for in situ measurements of conjugating of cAb to the sensor surface, tagging of short single-stranded DNA to dAb, affinity capture of the target analyte from the analyzed liquid sample, and the fluorescence readout of the RCA product. Through mitigation of adsorption of nontarget molecules on the sensor surface by tailoring of the antifouling biointerface, optimizing conjugation chemistry, and by implementing weak Coulombic repelling between dAb and the sensor surface, the limit of detection (LOD) of the assay was substantially improved. For the chosen interleukin-6 biomarker, SMD assay with LOD at a concentration of 4.3 fM was achieved for model (spiked) samples, and validation of the ability of detection of standard human serum samples is demonstrated.