A core-satellite self-assembled SERS aptasensor containing a “biological-silent region” Raman tag for the accurate and ultrasensitive detection of histamine

Abstract

Herein, a novel interference-free surface-enhanced Raman spectroscopy (SERS) strategy based on magnetic nanoparticles (MNPs) and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine. A core-satellite SERS aptasensor was constructed by combining aptamer-decorated Fe 3 O 4 @Au MNPs (as the recognize probe for histamine) and complementary DNA-modified silver nanoparticles carrying 4-mercaptobenzonitrile (4-MBN) (Ag@4-MBN@Ag-c-DNA) as the SERS signal probe for the indirect detection of histamine. Under an applied magnetic field in the absence of histamine, the assembly gave an intense Raman signal at "Raman biological-silent" region due to 4-MBN. In the presence of histamine, the Ag@4-MBN@Ag-c-DNA SERS-tag was released from the Fe 3 O 4 @Au MNPs, thus decreasing the SERS signal. Under optimal conditions, an ultra-low limit of detection of 0.65×10 -3 ng mL -1 and a linear range from 10 -2 to 10 5 ng mL -1 on the SERS aptasensor were obtained. The histamine content in four food samples were analyzed using the SERS aptasensor, with the results consistent with those determined by high performance liquid chromatography. The present work highlights the merits of indirect strategies for the ultrasensitive and highly selective SERS detection of small biological molecules in complex matrices.

“One-Pot” Readout Cyano-Programmable SERS-Encoded Platform Enables Ultrasensitive and Interference-Free Detection of Multitarget Bioamines

“…The result demonstrated that the Ag layer coating greatly enhanced the SERS signal of the 4-MBN on the surface of the Au NSs, which was expected due to the coupled electromagnetic "hot spots" generated within the noble metal nanogap structure (i.e., hot spots formed between the Au NSs and Ag coating layer). 10,50 To further demonstrate that the SERS signal enhancement was not simply due to an increase in nanoparticle size (since larger nanoparticles show stronger Raman scattering enhancing effects), 4-MBN was adsorbed on the surface of the Au NSs@ Ag nanostructure. The intensity of the 4-MBN peak in the "biological silent" region was only ∼34.1% of the intensity of Au NSs@4-MBN@Ag (Figure S11, Supporting Information).…”

“…For instance, Chen et al proposed an interference-free SERS strategy based on magnetic-driven component, in which 4-mercaptobenzonitrile (4-MBN) operating in the "biological-silent" region was embedded into Ag NPs as SERS tag. 10 Liu et al showed that the Prussian blue had a strong and sharp band in the "biological-silent" region. 44 Li et al achieved 32 resolvable colors in the "biological-silent" region by studying various biological orthogonal Raman molecules containing C�N and C�C with different electronic properties.…”

“…Over the past decade, the selective and rapid detection of bioamine in foods has received a lot of attention, utilizing technologies such as molecule-imprinting technology, aptamer recognition technology, , and electrochemical sensing technology, with the specific emphasis on the detection of single bioamine with high toxicity, such as histamine or tyramine. However, emerging data suggest that a single bioamine is not sufficient to describe the extent of food spoilage, while toxic synergies may exist among multiple bioamines. , For example, it has been reported that histamine can increase tyramine cytotoxicity at histamine concentrations found in certain foods .…”

“…Cyano-containing tagging molecules with Raman bands at ∼2220 cm –1 have already been used to perform single-cell molecular imaging and as SERS tags. For instance, Chen et al proposed an interference-free SERS strategy based on magnetic-driven component, in which 4-mercaptobenzonitrile (4-MBN) operating in the “biological-silent” region was embedded into Ag NPs as SERS tag . Liu et al showed that the Prussian blue had a strong and sharp band in the “biological-silent” region .…”

Food Safety Issues in the Oltrepò Pavese Area: A SERS Sensing Perspective

“…An indirect SERS-tag strategy, specific for His detection, is described by Chen C. et al [86]. The substrate is made up of magnetic Fe 3 O 4 @Au-aptamer nanoparticles that represent the histamine recognize probe and of a complementary DNA (c-DNA) carrying an Ag@4-MBN@Ag system which is the SERS signal probe.…”