Investigation of interfacial processes at tetraruthenated zinc porphyrin films using electrochemical surface plasmon resonance and electrochemical quartz crystal microbalance

In the present work we describe the investigation of interfacial and superficial processes on tetraruthenated zinc porphyrin (ZnTRP) films immobilized on gold electrode surface. In situ and real time measurements employing electrochemical surface plasmon resonance (ESPR)and electrochemical quartz crystal microbalance (EQCM) have given new insights into the electrochemical oxidation of ferrocyanide and phenolic compounds (acetaminophen, dopamine, and catechol) on ZnTRP modified electrodes. The decrease of diode like behavior in the presence of such phenolic species in contrast with ferrocyanide was clearly assigned to the inclusion of those species in the porphyrin film, creating new conduction pathways connecting the gold electrode surface with the film/solution interface. In fact, there are evidences that they can intercalate in the film (catechol > dopamine > acetaminophen), whereas ferrocyanide is completely excluded. Accordingly, the molecular size may play a fundamental role in such a process. (C) 2009 Published by Elsevier Ltd.

Probing the binding of tetraplatinum(pyridyl)porphyrin complexes to DNA by means of surface plasmon resonance

Tetrapyridylporphyrins containing four chloro(2,2`-bipyridine)platinum(II) complexes attached at the meta (3-H(2)TPtPyP) and para (4-H(2)TPtPyP) positions of the peripheral pyridine ligands were synthesized and their interaction with DNA investigated. The compounds were isolated in the solid state and characterized by means of spectroscopic and analytical techniques. According to molecular simulations, the two isomers exhibit contrasting structural characteristics, consistent with a saddle shape configuration for 3-H(2)TPtPyP and a planar geometry for 4-H(2)TPtPyP. Surface plasmon resonance studies were carried out on the interaction of the complexes with calf thymus DNA, revealing a preferential binding of 3-H(2)TPtPyP, presumably at the DNA major grooves. (C) 2008 Elsevier Inc. All rights reserved.

Parameter sensitivity analysis of surface plasmon resonance biosensor through numerical simulation

Surface based analytical tools have gained more importance for rapid, sensitive and label-free monitoring of molecular recognition events. Surface plasmon resonance (SPR) has played a prominent role in real time monitoring of surface binding events. SPR is increasing its significance especially for the study of ultrathin dielectric layer. This paper investigates the role of thin films of gold, silver and aluminium for protein detection in SPR biosensors. It is shown that the sensitivity, which is indicated by the shift of plasmon dip, is not linearly related to the thickness of protein but quadratic over a specific range. The approach involves a plot of a reflectivity curve as a function of the angle of incidence.

Developing lspr design guidelines

Applications of localized surface plasmon resonance (LSPR) such as surface enhanced Raman scattering (SERS) devices, biosensors, and nano-optics are growing. Investigating and understanding of the parameters that affect the LSPR spectrum is important for the design and fabrication of LSPR devices. This paper studies different parameters, including geometrical structures and light attributes, which affect the LSPR spectrum properties such as plasmon wavelength and enhancement factor. The paper also proposes a number of rules that should be considered in the design and fabrication of LSPR devices

Evolution towards a new LSPR particle : Nano-sinusoid

This paper proposes a novel nano-sinusoid particle to be employed in enhanced localized surface plasmon resonance (LSPR) bio-sensing devices. Numerical investigations are carried out to demonstrate advantages offered by the proposed nano-particle on LSPR enhancement over other nano-particles including noble nano-triangles and nano-diamonds. Although nano-triangles exhibit high concentration of the electric field near their tips, when illuminated with a light polarized along the tip axis, they present only one hot spot at the vertex along the polarization direction. To create a structure with two hot spots, which is desired in bio-sensing applications, two nano-triangles can be put back-to-back. Therefore, a nano-diamond particle is obtained which exhibits two hot spots and presents higher enhancements than nano-triangles for the same resonant wavelength. The main drawback of the nano-diamonds is the fluctuation in their physical size-plasmon spectrum relationships, due to a high level of singularity as the result for their four sharp tip points. The proposed nano-sinusoid overcomes this disadvantage while maintaining the benefits of having two hot spots and high enhancements.

Investigating nanoparticle-substrate interaction in LSPR biosensing using the image-charge theory

Localized surface plasmon resonance (LSPR) has been used to develop optical biosensors. Tuning the resonance wavelength to detect target biomolecules with a particular dipolar resonance is essential when designing LSPR biosensors. In this paper, the interaction of nanoparticles (NPs) with glass substrate (SiO2) for LSPR wavelength is investigated using the concept of the image-charge theory. Using the FDTD method, it is shown how the NP and substrate size change the plasmon wavelength. Next, this phenomenon is interpreted using the analytical electrostatic eigenvalue method.

Design and analysis of a multilayer surface plasmon resonance biosensor

Designed a multilayer SPR biosensor to improve the detection sensitivity and accuracy simultaneously. Developed a design procedure to identify optimum design parameters for SPR biosensing. Devised a new detection measurement technique based on S-parameters for SPR biosensing.

Simulation and analysis of a sub-wavelength grating based multilayer surface plasmon resonance biosensor

This paper presents a subwavelength grating based multilayer surface plasmon resonance biosensor (SPRB) which includes a periodic array of subwavelength grating on top of a layer of graphene sheet in the biosensor. The proposed biosensor is named grating-graphene SPRB (GG-SPRB). The aim of the proposed multilayer structure is to improve the sensitivity of the SPRB through monitoring of the biomolecular interactions of DNA hybridization. Significant sensitivity improvement is obtained for the GG-SPRB compared with the conventional SPRB. The result of the numerical investigation of the GG-SPRB is presented and compared with a theoretically developed multilayer matrix formalism, and a good agreement has been observed. In addition, an optimization of the grating dimensions including volume factor, grating depth, grating angle, grating period, and grating geometry (e.g., rectangular, sinusoidal and triangular) is presented. The outcome of the investigation presented in this paper identifies desired functioning conditions corresponding to the best design parameters for the GG-SPRB.

Numerical investigation of a grating and graphene-based multilayer surface plasmon resonance biosensor

A multilayer surface plasmon resonance biosensor (SPRB) incorporating a grating-graphene configuration is investigated for enhanced sensitivity. The numerical analysis of the impact of integrating a periodic array of subwavelength grating on top of a layer of graphene sheet for improving sensitivity is presented. The result of monitoring the biomolecular interactions of DNA hybridization is compared against the outcome of the conventional SPRB, a graphene-based multilayer SPRB, and a multilayer layer grating SPRB, and is mathematically validated. It is demonstrated that the inclusion of a grating and graphene layer on top of the gold thin film is an excellent candidate for a highly sensitive SPRB. To achieve further enhancement of sensitivity, the subwavelength grating is numerically optimized against its geometry including grating configurations (rectangular, sinusoidal, and triangular), grating depth, volume factor, and grating period. © 2014 Taylor & Francis.

Analysis of the serological variability of Lettuce mosaic virus using monoclonal antibodies and surface plasmon resonance technology

A panel of 19 monoclonal antibodies (mAbs) was used to study the immunological variability of Lettuce mosaic virus (LMV), a member of the genus Potyvirus, and to perform a first epitope characterization of this virus. Based on their specificity of recognition against a panel of 15 LMV isolates, the mAbs could be clustered in seven reactivity groups. Surface plasmon resonance analysis indicated the presence, on the LMV particles, of at least five independent recognition/ binding regions, correlating with the seven mAbs reactivity groups. The results demonstrate that LMV shows significant serological variability and shed light on the LMV epitope structure. The various mAbs should prove a new and efficient tool for LIVIV diagnostic and field epidemiology studies.

Advanced schemes for surface plasmon resonance and plasmon-enhanced fluorescence biosensors

Advanced optical biosensor platforms exploiting long range surface plasmons (LRSPs) and responsive N-isopropylacrylamide (NIPAAm) hydrogel binding matrix for the detection of protein and bacterial pathogen analytes were carried out. LRSPs are optical waves that originate from coupling of surface plasmons on the opposite sites of a thin metallic film embedded between two dielectrics with similar refractive indices. LRSPs exhibit orders of magnitude lower damping and more extended profile of field compared to regular surface plasmons (SPs). Their excitation is accompanied with narrow resonance and provides stronger enhancement of electromagnetic field intensity that can advance the sensitivity of surface plasmon resonance (SPR) and surface plasmon-enhanced fluorescence spectroscopy (SPFS) biosensors. Firstly, we investigated thin gold layers deposited on fluoropolymer surface for the excitation of LRSPs. The study indicates that the morphological, optical and electrical properties of gold film can be changed by the surface energy of fluoropolymer and affect the performance of a SPFS biosensor. A photo-crosslinkable NIPAAm hydrogel was grafted to the sensor surface in order to serve as a binding matrix. It was modified with bio-recognition elements (BREs) via amine coupling chemistry and offered the advantage of large binding capacity, stimuli responsive properties and good biocompatibility. Through experimental observations supported by numerical simulations describing diffusion mass transfer and affinity binding of target molecules in the hydrogel, the hydrogel binding matrix thickness, concentration of BREs and the profile of the probing evanescent field was optimized. Hydrogel with a up to micrometer thickness was shown to support additional hydrogel optical waveguide (HOW) mode which was employed for probing affinity binding events in the gel by means of refractometric and fluorescence measurements. These schemes allow to reach limits of detection (LODs) at picomolar and femtomolar levels, respectively. Besides hydrogel based experiments for detection of molecular analytes, long range surface plasmon-enhanced fluorescence spectroscopy (LRSP-FS) was employed for detection of bacterial pathogens. The influence of capture efficiency of bacteria on surfaces and the profile of the probing field on sensor response were investigated. The potential of LRSP-FS with extended evanescent field is demonstrated for detection of pathogenic E. coli O157:H7 on sandwich immunoassays . LOD as low as 6 cfu mL-1 with a detection time of 40 minutes was achieved.rn

New enhancement strategies for plasmon-enhanced fluorescence biosensors

This thesis investigates metallic nanostructures exhibiting surface plasmon resonance for the amplification of fluorescence signal in sandwich immunoassays. In this approach, an analyte is captured by an antibody immobilized on a plasmonic structure and detected by a subsequently bound fluorophore labeled detection antibody. The highly confined field of surface plasmons originates from collective charge oscillations which are associated with high electromagnetic field enhancements at the metal surface and allow for greatly increased fluorescence signal from the attached fluorophores. This feature allows for improving the signal-to-noise ratio in fluorescence measurements and thus advancing the sensitivity of the sensor platform. In particular, the thesis presents two plasmonic nanostructures that amplify fluorescence signal in devices that rely on epifluorescence geometry, in which the fluorophore absorbs and emits light from the same direction perpendicular to the substrate surface.rnThe first is a crossed relief gold grating that supports propagating surface plasmon polaritons (SPPs) and second, gold nanoparticles embedded in refractive index symmetric environment exhibiting collective localized surface plasmons (cLSPs). Finite-difference time-domain simulations are performed in order to design structures for the optimum amplification of established Cy5 and Alexa Fluor 647 fluorophore labels with the absorption and emission wavelengths in the red region of spectrum. The design takes into account combined effect of surface plasmon-enhanced excitation rate, directional surface plasmon-driven emission and modified quantum yield for characteristic distances in immunoassays. Homebuilt optical instruments are developed for the experimental observation of the surface plasmon mode spectrum, measurements of the angular distribution of surface plasmon-coupled fluorescence light and a setup mimicking commercial fluorescence reading systems in epifluorescence geometry.rnCrossed relief grating structures are prepared by interference lithography and multiple copies are made by UV nanoimprint lithography. The fabricated crossed diffraction gratings were utilized for sandwich immunoassay-based detection of the clinically relevant inflammation marker interleukin 6 (IL-6). The enhancement factor of the crossed grating reached EF=100 when compared to a flat gold substrate. This result is comparable to the highest reported enhancements to date, for fluorophores with relatively high intrinsic quantum yield. The measured enhancement factor excellently agrees with the predictions of the simulations and the mechanisms of the enhancement are explained in detail. Main contributions were the high electric field intensity enhancement (30-fold increase) and the directional fluorescence emission at (4-fold increase) compared to a flat gold substrate.rnCollective localized surface plasmons (cLSPs) hold potential for even stronger fluorescence enhancement of EF=1000, due to higher electric field intensity confinement. cLSPs are established by diffractive coupling of the localized surface plasmon resonance (LSPR) of metallic nanoparticles and result in a narrow resonance. Due to the narrow resonance, it is hard to overlap the cLSPs mode with the absorption and emission bands of the used fluorophore, simultaneously. Therefore, a novel two resonance structure that supports SPP and cLSP modes was proposed. It consists of a 2D array of cylindrical gold nanoparticles above a low refractive index polymer and a silver film. A structure that supports the proposed SPP and cLSP modes was prepared by employing laser interference lithography and the measured mode spectrum was compared to simulation results.rn

Collimated Field Emission Beams from Metal Double-Gate Nanotip Arrays Optically Excited via Surface Plasmon Resonance

The generation of collimated electron beams from metal double-gate nanotip arrays excited by near infrared laser pulses is studied. Using electromagnetic and particle tracking simulations, we showed that electron pulses with small rms transverse velocities are efficiently produced from nanotip arrays by laser-induced field emission with the laser wavelength tuned to surface plasmon polariton resonance of the stacked double-gate structure. The result indicates the possibility of realizing a metal nanotip array cathode that outperforms state-of-the-art photocathodes.