Paper-based Spectroscopy Substrates Research Articles

Highly sensitive plasmonic paper substrate fabricated via amphiphilic polymer self-assembly in microdroplet for detection of emerging pharmaceutical pollutants

We report an innovative and facile approach to fabricating an ultrasensitive plasmonic paper substrate for surface-enhanced Raman spectroscopy (SERS). The approach exploits the self-assembling capability of poly(styrene-b-2-vinyl pyridine) block copolymers to form a thin film at the air-liquid interface within the single microdroplet scale for the first time and the subsequent in situ growth of silver nanoparticles (AgNPs). The concentration of the block copolymer was found to play an essential role in stabilizing the droplets during the mass transfer phase and formation of silver nanoparticles, thus influencing the SERS signals. SEM analysis of the morphology of the plasmonic paper substrates revealed the formation of spherical AgNPs evenly distributed across the surface of the formed copolymer film with a size distribution of 47.5 nm. The resultant enhancement factor was calculated to be 1.2 × 107, and the detection limit of rhodamine 6G was as low as 48.9 pM. The nanohybridized plasmonic paper was successfully applied to detect two emerging pollutants—sildenafil and flibanserin—with LODs as low as 1.48 nM and 3.45 nM, respectively. Thus, this study offers new prospects for designing an affordable and readily available, yet highly sensitive, paper-based SERS substrate with the potential for development as a lab-on-a-chip device.

Layer-by-Layer Biopolymer Assembly for the In Situ Fabrication of AuNP Plasmonic Paper-A SERS Substrate for Food Adulteration Detection.

Here, we introduce an environmentally friendly approach to fabricate a simple and cost-effective plasmonic paper for detecting food additives using surface-enhanced Raman spectroscopy (SERS). The plasmonic paper is fabricated by in situ growth of gold nanoparticles (AuNPs) on filter paper (FP). To facilitate this green fabrication process, we applied a double-layered coating of biopolymers, chitosan (CS) and alginate (ALG), onto the FP using a layer-by-layer (LbL) assembly through electrostatic interactions. Compared to single-layer biopolymer coatings, double-layered biopolymer-coated paper, ALG/CS/FP, significantly improves the reduction properties. Consequently, effective in situ growth of AuNPs can be achieved as seen in high density of AuNP formation on the substrate. The resulting plasmonic paper provides high SERS performance with an enhancement factor (EF) of 5.7 × 1010 and a low limit of detection (LOD) as low as 1.37 × 10-12 M 4-mercaptobenzoic acid (4-MBA). Furthermore, it exhibits spot-to-spot reproducibility with a relative standard deviation (RSD) of 8.2% for SERS analysis and long-term stability over 50 days. This paper-based SERS substrate is applied for melamine (MEL) detection with a low detection limit of 0.2 ppb, which is sufficient for monitoring MEL contamination in milk based on food regulations. Additionally, we demonstrate a simultaneous detection of β-agonists, including ractopamine (RAC) and salbutamol (SAL), exhibiting the multiplexing capability and versatility of the plasmonic paper in food contaminant analysis. The development of this simple plasmonic paper through the LbL biopolymer assembly not only paves the way for novel SERS substrate fabrication but also broadens the application of SERS technology in food contaminant monitoring.

Rapid and non-invasive surface-enhanced Raman spectroscopy (SERS) detection of chlorpyrifos in fruits using disposable paper-based substrates charged with gold nanoparticle/halloysite nanotube composites.

Chlorpyrifos is one of the most widely used organophosphate insecticides in agricultural production. Nevertheless, the residues of chlorpyrifos in agricultural by-product seriously threaten human health. Thus, the ultrasensitive detection of chlorpyrifos residues in agri-food products is of great demand. Herein, an AuNP/HNT-assembled disposable paper SERS substrate was prepared by an electrostatic self-assembly method to detect chlorpyrifos residues. The AuNP/HNT paper substrate exhibited high SERS activity, good reproducibility, and long-term stability, which was successfully used for quantitative detection of chlorpyrifos; the detection limit reached 7.9 × 10-9M. For spiked apple samples the calculated recovery was 87.9% with aRSD value of 6.1%. The excellent detection ability of AuNP/HNT paper-based SERS substrate indicated that it will play an important role in pesticide detection in the future. AuNP/HNT assembled disposable paper SERS substrate was prepared by an electrostatic self-assembly method to detect chlorpyrifos residues in fruits.