Alexandre G. Brolo

A review on the fabrication of substrates for surface enhanced Raman spectroscopy and their applications in analytical chemistry.

This work reviews different types of substrates used for surface-enhanced Raman scattering (SERS) that have been developed in the last 10 years. The different techniques of self-assembly to immobilize metallic nanoparticles on solid support are covered. An overview of SERS platforms developed using nanolithography methods, including electron-beam (e-beam) lithography and focused ion beam (FIB) milling are also included, together with several examples of template-based methodologies to generate metallic nano-patterns. The potential of SERS to impact several aspects of analytical chemistry is demonstrated by selected examples of applications in electrochemistry, biosensing, environmental analysis, and remote sensing. This review shows that highly enhancing SERS substrates with a high degree of reliability and reproducibility can now be fabricated at relative low cost, indicating that SERS may finally realize its full potential as a very sensitive tool for routine analytical applications.

Increased cut-off wavelength for a subwavelength hole in a real metal

A waveguide mode of a subwavelength rectangular hole in a real metal is analyzed. Due to coupling between surface plasmons on the long edges of the hole, the cut-off wavelength increases as the hole-width is reduced. The cut-off wavelength is found to be much larger than Rayleighs criterion for perfect metals - 2.3 times as large for a 15 nm wide hole. The analytical results are verified by finite-difference calculations. The finite difference calculations also show the influence of including material loss.

Nanoholes as nanochannels: flow-through plasmonic sensing.

We combine nanofluidics and nanoplasmonics for surface-plasmon resonance (SPR) sensing using flow-through nanohole arrays. The role of surface plasmons on resonant transmission motivates the application of nanohole arrays as surface-based biosensors. Research to date, however, has focused on dead-ended holes, and therefore failed to harness the benefits of nanoconfined transport combined with SPR sensing. The flow-through format enables rapid transport of reactants to the active surface inside the nanoholes, with potential for significantly improved time of analysis and biomarker yield through nanohole sieving. We apply the flow-through method to monitor the formation of a monolayer and the immobilization of an ovarian cancer biomarker specific antibody on the sensing surface in real-time. The flow-through method resulted in a 6-fold improvement in response time as compared to the established flow-over method.

Probing Dynamic Generation of Hot-Spots in Self-Assembled Chains of Gold Nanorods by Surface-Enhanced Raman Scattering

Further progress in the applications of self-assembled nanostructures critically depends on developing a fundamental understanding of the relation between the properties of nanoparticle ensembles and their time-dependent structural characteristics. Following dynamic generation of hot-spots in the self-assembled chains of gold nanorods, we established a direct correlation between ensemble-averaged surface-enhanced Raman scattering and extinction properties of the chains. Experimental results were supported with comprehensive finite-difference time-domain simulations. The established relationship between the structure of nanorod ensembles and their optical properties provides the basis for creating dynamic, solution-based, plasmonic platforms that can be utilized in applications ranging from sensing to nanoelectronics.

Periodic Metallic Nanostructures as Plasmonic Chemical Sensors

Periodic plasmonic nanostructures are being widely studied, optimized, and developed to produce a new generation of low-cost and efficient chemical sensors and biosensors. The extensive variety of nanostructures, interrogation approaches, and setups makes a direct comparison of the reported performance from different sensing platforms a challenging exercise. In this feature Article, the most common parameters used for the evaluation of plasmonic nanostructures will be reviewed, with particular focus on the advances in periodic plasmonic nanostructures. Recent progress in the fabrication methods that allow for the high-volume production of periodic plasmonic sensors at low cost will be described, together with an assessment of the state of the art in terms of periodic structures employed for chemical sensing.

Attomolar Protein Detection Using in-Hole Surface Plasmon Resonance

An in-hole nanohole surface plasmon resonance sensing scheme is demonstrated. Arrays of periodic nanoholes milled through thin layers of SiO(x) and gold were used to detect the binding of organic and biological molecules inside the nanoholes, while blocking the gold surfaces outside the holes. This new approach is more efficient than the previous nanohole array method, where the response was related to binding events taking place inside of the holes and on the top gold surface. The improved sensitivity to binding events and lower detection limit are related to resonant surface plasmon enhanced transmission through the arrays of nanoholes. The sensitivity was found to be 650 nm/RIU and the detection of three attomoles of proteins was estimated from this scheme.

Hydrogen Peroxide as an Oxidant for Microfluidic Fuel Cells

We demonstrate a microfluidic fuel cell incorporating hydrogen peroxide oxidant. Hydrogen peroxide (H 2 O 2 ) is available at high concentrations, is highly soluble and exhibits a high standard reduction potential. It also enables fuel cell operation where natural convection of air is limited or anaerobic conditions prevail, as in submersible and space applications. As fuel cell performance critically depends on both electrode and channel architecture, several different prototype cells are developed and results are compared. High-surface area electrodeposited platinum and palladium electrodes are evaluated both ex situ and in situ for the combination of direct H 2 O 2 reduction and oxygen reduction via the decomposition reaction. Oxygen gas bubbles produced at the fuel cell cathode introduce an unsteady two-phase flow component that, if not controlled, can perturb the co-laminar flow interface and reduce fuel cell performance. A grooved channel design is developed here that restricts gas bubble growth and transport to the vicinity of the cathodic active sites, enhancing the rate of oxygen reduction, and limiting crossover effects. The proof-of-concept microfluidic fuel cell produced power densities up to 30 mW cm -2 and a maximum current density of 150 mA cm -2 , when operated on 2 M H 2 O 2 oxidant together with formic acid-based fuel at room temperature.

APPLICATIONS OF SURFACE ENHANCED RAMAN SCATTERING TO THE STUDY OF METAL-ADSORBATE INTERACTIONS

Surface enhanced Raman scattering (SERS) is a powerful technique for characterizing adsorbed species and processes at metallic surfaces. The giant signal enhancement (104–106 larger than normal Raman scattering) makes this technique sensitive to even sub-monolayer amounts of adsorbate on a surface. Consequently, the application of SERS to the in situ study of electrochemical processes provides useful mechanistic and structural information. In this review, advantages and limitations of electrochemical SERS techniques are presented along with experimental information about the nature of the metal-adsorbate interactions occurring in various aqueous and non-aqueous systems. Special emphasis is given to experimental results; however, the salient features of the enhancement theories are highlighted. Adsorbate orientation and SERS surface selection rules are discussed.

Flow-Through vs Flow-Over: Analysis of Transport and Binding in Nanohole Array Plasmonic Biosensors

We quantify the efficacy of flow-through nanohole sensing, as compared to the established flow-over format, through scaling analysis and numerical simulation. Nanohole arrays represent a growing niche within surface plasmon resonance-based sensing methods, and employing the nanoholes as nanochannels can enhance transport and analytical response. The additional benefit offered by flow-through operation is, however, a complex function of operating parameters and application-specific binding chemistry. Compared here are flow-over sensors and flow-through nanohole array sensors with equivalent sensing area, where the nanohole array sensing area is taken as the inner-walls of the nanoholes. The footprints of the sensors are similar (e.g., a square 20 μm wide flow-over sensor has an equivalent sensing area as a square 30 μm wide array of 300 nm diameter nanoholes with 450 nm periodicity in a 100 nm thick gold film). Considering transport alone, an analysis here shows that given equivalent sensing area and flow rate the flow-through nanohole format enables greatly increased flux of analytes to the sensing surface (e.g., 40-fold for the case of Q = 10 nL/min). Including both transport and binding kinetics, a computational model, validated by experimental data, provides guidelines for performance as a function of binding time constant, analyte diffusivity, and running parameters. For common binding kinetics and analytes, flow-through nanohole arrays offer ∼10-fold improvement in response time, with a maximum of 20-fold improvement for small biomolecules with rapid kinetics.

Silver Nanoparticles on a Plastic Platform for Localized Surface Plasmon Resonance Biosensing

A cost-effective fabrication method for the preparation of localized surface plasmon resonance (LSPR) biosensors supported on plastics is described. The silver-nanoparticles-on-plastic sensor (SNOPS) was fabricated by chemically modifying the surface of a common plastic, polyethylene terephthalate (PET) to allow the efficient immobilization of Ag NPs. The LSPR of the SNOPS strip showed good sample-to-sample reproducibility. The analytical performance of the sensor strips for monitoring both thiol and protein adsorption, including bioaffinity, was examined. The limit of quantification to the adsorption of 11-mercaptoundecanoic acid was 500 nM and for the detection of streptavidin was approximately 9.5 nM. SNOPS can then be used as a cheap, versatile, and yet sensitive LSPR biosensor.