Chiral assemblies of nanoparticles (NPs) are typically constructed with helical or tetrahedral geometries. Simple pairs of NPs are not expected to display chirality due to basic symmetry considerations made under the assumption of their spherical geometry. In this study we demonstrate that assemblies consisting of two metallic NPs do possess chirality and strongly rotate polarization of light. Their chiroplasmonic properties are attributed to the prolate geometry of individual colloidal particles. When bridged by biomolecules, the NP pairs acquire scissor-like geometry, with the long axes of NPs forming an angle of ~9°. This small dihedral angle results in chirality of the NP pair, while the consistency of its sign due to the specific conformation of the bridging biomacromolecules breaks the enantiomeric equivalence of the NP pairs. Strong polarization rotation in these nanoassemblies makes possible their utilization in biological analysis. Heterodimers of gold and silver NPs were made using antibody-antigen bridges. Taking advantage of their chiroplasmonic properties, we investigated their bioanalitical potential for detection of an environmental toxin, microcystin-LR, and a cancer biomarker, prostate-specific antigen. The order-of-magnitude improvements in limits of detection compared to all other analytical techniques are attributed to plasmonic enhancement of intrinsic chirality of biological compounds, strong optical coupling of photons with NP assemblies with twisted geometries, and signal amplification due to the bisignate nature of circular dichroism bands.
An ultrasensitive method for surface enhanced Raman scattering (SERS) detection of prostate-specific antigens (PSAs) was established based on the aptamer directed core-satellite nanostructures. A limit of detection (LOD) of 4.8 aM for PSA was obtained.
In this Letter, gold nanorods (Au NRs) and gold nanoparticles (Au NPs) were assembled into core-satellites (Au NR-NPs) nanostructures using DNA as the linkers. Circular dichroism (CD) measurements of the nanoassemblies displayed two plasmonic CD (PCD) peaks in the vicinity of the surface plasmon resonance (SPR). Interestingly, the number of Au NPs in the assemblies had a significant influence on the shape and intensity of the CD line. The assemblies were enzymatically disassembled by deoxyribonuclease I (DNase I), and the CD responses were simultaneously reversed. With the proof-of-concept design, the PCD response was no change by addding enzyme inhibitor. These experiments suggested that the chirality depended upon the structure of core-satellites nanoassemblies, and the results clarify that the possible origin of the optical activity comes from chiral arrangement of building blocks and Coulomb dipole-dipole interactions. This research also illuminated that the assemblies can be used to develop a new sensor for the sensitive screening of the enzyme inhibitors.
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