Aggregation of gold nanoparticles (AuNPs) can be utilized in chemical and biomolecular sensing as a sensitive and easy-to-visualize process. However, interpretation of experimental results requires a clear understanding of physicochemical processes that take place upon multiple interactions between an analyte and AuNPs. In this article, interactions between citrate-stabilized AuNPs and organic compounds bearing various functional groups in an aqueous medium were experimentally and theoretically studied using spectrophotometry of the localized surface plasmon resonance (LSPR), transmission electron microscopy (TEM), conductometry, zeta potential measurements, and finite-difference time-domain (FDTD) modeling. As a result, it has been found that organic compounds containing both thiol and amine groups strongly promote the aggregation of AuNPs due to their cooperative functionalities. FDTD modeling has enabled consideration of the light extinction (i.e., LSPR response) properties of nanoparticle aggregates involving single, chain-like, and globular structures. Taking one billion distributions of differently structured aggregates into account, the theoretical light extinction was fitted to that of the experimental result with a root-mean-square deviation of 7%.

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We demonstrate a novel sensor platform with enhanced sensitivity and selectivity for detecting aflatoxin B1 – a common food toxin in cereals. The approach is based on a molecularly imprinted...

This paper attempts to compare the main features of random and highly ordered gold nanostructure arrays (NSA) prepared by thermally annealed island film and nanoimprint lithography (NIL) techniques, respectively. Each substrate possesses different morphology in terms of plasmonic enhancement. Both methods allow such important features as spectral tuning of plasmon resonance position depending on size and shape of nanostructures; however, the time and cost is quite different. The respective comparison was performed experimentally and theoretically for a number of samples with different geometrical parameters. Spectral characteristics of fabricated NSA exhibited an expressed plasmon peak in the range from 576 to 809 nm for thermally annealed samples and from 606 to 783 nm for samples prepared by NIL. Modelling of the optical response for nanostructures with typical shapes associated with these techniques (parallelepiped for NIL and semi-ellipsoid for annealed island films) was performed using finite-difference time-domain calculations. Mathematical simulations have indicated the dependence of electric field enhancement on the shape and size of the nanoparticles. As an important point, the distribution of electric field at so-called ‘hot spots’ was considered. Parallelepiped-shaped nanoparticles were shown to yield maximal enhancement values by an order of magnitude greater than their semi-ellipsoid-shaped counterparts; however, both nanoparticle shapes have demonstrated comparable effective electrical field enhancement values. Optimized Au nanostructures with equivalent diameters ranging from 85 to 143 nm and height equal to 35 nm were obtained for both techniques, resulting in the largest electrical field enhancement. The application of island film thermal annealing method for nanochips fabrication can be considered as a possible cost-effective platform for various surface-enhanced spectroscopies; while the NIL-fabricated NSA looks like more effective for sensing of small-size objects.

3-D quantification of biomolecular covers using surface plasmonpolariton resonance experiment Chegel, V.; Chegel, Yu.; Guiver, Michael; Lopatynskyi, A.; Lopatynska, O.; Lozovski, V. Sensors and Actuators B 134 (2008) The concentration of surface molecules N s and components of molecular susceptibility jl (ω) can both be determined from surface plasmon-polariton resonance (SPPR) experiments, instead of effective layer thickness and index of refraction, which are usually determined. The theoretical consideration of a molecular layer as monolayer of separated 3D-oscillators provides a new perspective for investigating molecules during SPPR experiment. It is shown that SPPR response and the form of the reflective curve depend on the form of a biomolecule and its orientation relative to the surface of the metal-carrier of plasmon oscillations. The experimental data for immunological reaction for the calculation of surface molecular concentration and mass of biomolecular covering are presented.

Sensing explosive taggants such as 3-nitrotoluene (3-NT) and 2,3-dimethyl-2,3-dinitrobutane has become a strategic priority in homeland security. This work reports the synthesis of a solid-state plasmonic sensor based on a nanocomposite of Ag nanoparticles (NPs) embedded in a molecularly imprinted polymer (MIP) for selective detection of 3-NT, an explosive taggant for 2,4,6-trinitrotoluene. In our approach, the in situ synthesis of Ag NPs and the molecular imprinting with 3-NT as a template take place simultaneously inside the polyethyleneimine (PEI) thin film during the baking step after spin coating. The MIP sensor fabrication is done by a low-cost, fast, and scalable one-step procedure. We demonstrate the chemosensing capabilities of Ag-PEI MIP nanocomposites to 3-NT using the localized surface plasmon resonance band intensity decay as a sensing parameter. The molecular imprinting approach results in an enhancement of specific sensor response to 3-NT, with a limit of detection of 54.8 ng for 3-NT and a sensitivity of 24.0% ± 3.0%. We tested the MIP sensor specificity by comparing the sensor response to several NO2-containing molecules. The Ag-PEI MIP sensor demonstrated a robust, specific molecular recognition toward 3-NT. Because the MIP nanocomposite sensor is easy to prepare, easy to use, and inexpensive, these plasmonic sensors can be easily implemented with portable reading platforms into remote explosive detection and bomb disposal robots.

An experimental approach for improving the sensitivity of the surface plasmon resonance (SPR) DNA hybridization sensor using gold nanoparticles (GNPs), modified by specific oligonucleotides, was elaborated. An influence of the ionic strength on the aggregation stability of unmodified GNPs and GNPs modified by the thiolated oligonucleotides was investigated by monitoring a value of light extinction at 520 nm that can be considered as a measure of a quantity of the non-aggregated GNPs. While the unmodified GNPs started to aggregate in 0.2 × saline-sodium citrate (SSC), GNPs modified by the negatively charged oligonucleotides were more stable at increasing ionic strength up to 0.5 × SSC. A bioselective element of the SPR DNA hybridization sensor was formed by immobilization on the gold sensor surface of the thiolated oligonucleotides P2, the sequence of which is a fragment of the rpoB gene of Mycobacterium tuberculosis. The injections into the measuring flow cell of the SPR spectrometer of various concentrations of GNPs modified by the complementary oligonucleotides T2-18m caused the pronounced concentration-dependent sequence-specific sensor responses. The magnitude of the sensor responses was much higher than in the case of the free standing complementary oligonucleotides. According to the obtained experimental data, the usage of GNPs modified by specific oligonucleotides can amplify the sensor response of the SPR DNA hybridization sensor in ~1200 times.

It is shown that the response of a surface plasmon resonance nanosystem designed according to Kretschmann geometry on the application of an external electric potential to the gold-electrolyte interface is well described by the proposed mathematical model, which takes into account the geometric surface imperfection and dependence of optical constants of the surface layer of gold film and capacitance of the electrical double layer on applied voltage. This model allows the appropriate correction for results of electrochemical surface plasmon resonance measurements. The dependence of a value of biomolecules adsorption in a surface plasmon resonance nanosystem on applied electric potential is shown for the first time. It is found that a shift of surface plasmon resonance angular position (Δθ(SPR)) and a change of capacitance of electrical double layer on the surface of gold (ΔC(dl)) for the adsorption of proteins under applied voltage are related to the nonlinear dependence Δθ(SPR) = (a + b x ΔC(dl))(-1). This phenomenon can be exploited in biochemical analysis to monitor the interaction of biomolecules, enhance response of biosensors, block unwanted adsorption, etc.