Plasmonic Resonant Nanoantennas Induce Changes in the Shape and the Intensity of Infrared Spectra of Phospholipids.

Surface enhanced infrared absorption spectroscopic studies (SEIRAS) as a technique to study biological molecules in extremely low concentrations is greatly evolving. In order to use the technique for identification of the structure and interactions of such biological molecules, it is necessary to identify the effects of the plasmonic electric-field enhancement on the spectral signature. In this study the spectral properties of 1,2-Dipalmitoyl-sn-glycero-3 phosphothioethanol (DPPTE) phospholipid immobilized on gold nanoantennas, specifically designed to enhance the vibrational fingerprints of lipid molecules were studied. An AFM study demonstrates an organization of the DPPTE phospholipid in bilayers on the nanoantenna structure. The spectral data were compared to SEIRAS active gold surfaces based on nanoparticles, plain gold and plain substrate (Si) for different temperatures. The shape of the infrared signals, the peak positions and their relative intensities were found to be sensitive to the type of surface and the presence of an enhancement. The strongest shifts in position and intensity were seen for the nanoantennas, and a smaller effect was seen for the DPPTE immobilized on gold nanoparticles. This information is crucial for interpretation of data obtained for biological molecules measured on such structures, for future application in nanodevices for biologically or medically relevant samples.

Monoclonal antibody 4B1 influences the pKa of Glu325 in lactose permease (LacY) from Escherichia coli: evidence from SEIRAS.

The monoclonal antibody 4B1 binds to a conformational epitope on the periplasmic side of lactose permease (LacY) of Escherichia coli and inhibits H+ /lactose symport and lactose efflux under nonenergized conditions. At the same time, ligand binding and translocation reactions that do not involve net H+ translocation remain unaffected by 4B1. In this study, surface-enhanced infrared absorption spectroscopy applied to the immobilized LacY was used to study the pH-dependent changes in LacY and to access in situ the effect of the 4B1 antibody on the pKa of Glu325, the primary functional H+ -binding site in LacY. A small shift of the pK value from 10.5 to 9.5 was identified that can be corroborated with the inactivation of LacY upon 4B1 binding.

Following the Chemical Immobilization of Membrane Proteins on Plasmonic Nanoantennas Using Infrared Spectroscopy.

Plasmonic nanoantennas are promising sensing platforms for detecting chemical and biological molecules in the infrared region. However, integrating fragile biological molecules such as proteins on plasmonic nanoantennas is an essential requirement in the detection procedure. It is crucial to preserve the structural integrity and functionality of proteins while attaching them. In this study, we attached lactose permease, a large membrane protein, onto plasmonic nanoantennas by means of the nickel-nitrile triacetic acid immobilization technique. We followed the individual steps of the immobilization procedure for different lengths of the nanoantennas. The impact of varying the length of the nanoantennas on the shape of the vibrational signal of the chemical layers and on the protein spectrum was studied. We showed that these large proteins are successfully attached onto the nanoantennas, while the chemical spectra of the immobilization monolayers show a shape deformation which is an effect of the coupling between the vibrational mode and the plasmonic resonance.

Surface-enhanced resonance Raman spectroscopy of heme proteins on a gold grid electrode.

The combination of surface-enhanced resonance Raman spectroscopy (SERRS) and electrochemistry is an ideal tool to study the redox process of the heme proteins and is often performed on silver electrodes. In this manuscript, we present an approach using a microstructured gold surface that serves as the electrochemical working electrode, and at the same time, acts as SERS active substrate. The cell requires a micromolar concentration of sample at the electrode surface. Even if the performance of the gold grid as SERS substrate exhibited a smaller enhancement factor than expected for silver, oxidized and reduced spectra of proteins (Сyt c, Hb and Mb) monolayers could be obtained and the characteristic redox dependent shifts of the marker bands ν19, ν4 and ν10 were seen. The easy modification protocol and the higher stability of the gold electrode towards oxidative currents are the advantages of the present spectroeletrochemical cell. Finally, FDTD simulations confirm that the roughness of the gold grid has an effect on the Raman enhancement of the adsorbed proteins.

SERS discrimination of single DNA bases in single oligonucleotides by electro-plasmonic trapping.

Surface-enhanced Raman spectroscopy (SERS) sensing of DNA bases by plasmonic nanopores could pave a way to novel methods for DNA analyses and new generation single-molecule sequencing platforms. The SERS discrimination of single DNA bases depends critically on the time that a DNA strand resides within the plasmonic hot spot. In fact, DNA molecules flow through the nanopores so rapidly that the SERS signals collected are not sufficient for single-molecule analysis. Here, we report an approach to control the residence time of molecules in the hot spot by an electro-plasmonic trapping effect. By directly adsorbing molecules onto a gold nanoparticle and then trapping the single nanoparticle in a plasmonic nanohole up to several minutes, we demonstrate single-molecule SERS detection of all four DNA bases as well as discrimination of single nucleobases in a single oligonucleotide. Our method can be extended easily to label-free sensing of single-molecule amino acids and proteins.

A universal design to realize a tunable perfect absorber from infrared to microwaves.

We propose a design for an universal absorber, characterized by a resonance frequency that can be tuned from visible to microwave frequencies independently of the choice of the metal and the dielectrics involved. An almost perfect absorption up to 99.8% is demonstrated at resonance for all polarization states of light and for a very wide angular aperture. These properties originate from a magnetic Fabry-Perot mode that is confined in a dielectric spacer of λ/100 thickness by a metamaterial layer and a mirror. An extraordinary large funneling through nano-slits explains how light can be trapped in the structure. Simple scaling laws can be used as a recipe to design ultra-thin perfect absorbers whatever the materials and the desired resonance wavelength, making our design truly universal.