Chanda Ranjit Yonzon

Introductory Lecture : Surface enhanced Raman spectroscopy: new materials, concepts, characterization tools, and applications

Surface-enhanced Raman spectroscopy (SERS) is currently experiencing a renaissance in its development driven by the remarkable discovery of single molecule SERS (SMSERS) and the explosion of interest in nanophotonics and plasmonics. Because excitation of the localized surface plasmon resonance (LSPR) of a nanostructured surface or nanoparticle lies at the heart of SERS, it is important to control all of the factors influencing the LSPR in order to maximize signal strength and ensure reproducibility. These factors include material, size, shape, interparticle spacing, and dielectric environment. All of these factors must be carefully controlled to ensure that the incident laser light maximally excites the LSPR in a reproducible manner. This article describes the use of nanosphere lithography for the fabrication of highly reproducible and robust SERS substrates for both fundamental studies and applications. Atomic layer deposition (ALD) is introduced as a novel fabrication method for dielectric spacers to study the SERS distance dependence and control the nanoscale dielectric environment. Wavelength scanned SER excitation spectroscopy (WS SERES) measurements show that enhancement factors approximately 10(8) are obtainable from NSL-fabricated surfaces and provide new insight into the electromagneticfield enhancement mechanism. Tip-enhanced Raman spectroscopy (TERS) is an extremely promising new development to improve the generality and information content of SERS. A 2D correlation analysis is applied to SMSERS data. Finally, the first in vivo SERS glucose sensing study is presented.

Localized surface plasmon resonance biosensors

In this review, the most recent progress in the development of noble metal nano-optical sensors based on localized surface plasmon resonance (LSPR) spectroscopy is summarized. The sensing principle relies on the LSPR spectral shifts caused by the surrounding dielectric environmental change in a binding event. Nanosphere lithography, an inexpensive and simple nanofabrication technique, has been used to fabricate the nanoparticles as the LSPR sensing platforms. As an example of the biosensing applications, the LSPR detection for a biomarker of Alzheimers disease, amyloid-derived diffusable ligands, in human brain extract and cerebrospinal fluid samples is highlighted. Furthermore, the LSPR sensing method can be modified easily and used in a variety of applications. More specifically, a LSPR chip capable of multiplex sensing, a combined electrochemical and LSPR protocol and a fabrication method of solution-phase nanotriangles are presented here.

Towards advanced chemical and biological nanosensors - An overview

This paper reviews recent developments in the design and application of two types of optical nanosensor, those based on: (1) localized surface plasmon resonance (LSPR) spectroscopy and (2) surface-enhanced Raman scattering (SERS). The performance of these sensors is discussed in the context of biological and chemical sensing. The first section addresses the LSPR sensors. Arrays of nanotriangles were evaluated and characterized using realistic protein/ligand interactions. Isolated, single nanoparticles were used for chemosensing and performed comparably to the nanoparticle array sensors. In particular, we highlight the effect of nanoparticle morphology on sensing response. The second section details the use of SERS sensors using metal film over nanosphere (MFON) surfaces. The high SERS enhancements and long-term stability of MFONs were exploited in order to develop SERS-based sensors for two important target molecules: a Bacillus anthracis biomarker and glucose in a serum protein mixture.

Localized surface plasmon resonance immunoassay and verification using surface-enhanced Raman spectroscopy

This work exploits the localized surface plasmon resonance (LSPR) spectroscopy of noble metal nanoparticles to achieve sensitive and selective detection of biological analytes. Noble metal nanoparticles exhibit an LSPR that is strongly dependent on their size, shape, material, and the local dielectric environment. The LSPR is also responsible for the intense signals observed in surface-enhanced Raman scattering (SERS). Ag nanoparticles fabricated using the nanosphere lithography (NSL) technique exploits this LSPR sensitivity as a signal transduction method in biosensing applications. The current work implements LSPR biosensing for the anti dinitrophenyl (antiDNP) immunoassay system. Upon forming the 2,4 dinitrobenzoic acid/antiDNP complex, this system shows a large LSPR shift of 44 nm when exposed to antiDNP concentration of 1.5 x 10-6 M. In addition, due to the unique molecular characteristics of the functional groups on the biosensor, it can also be characterized using SERS. First, the nanoparticles are functionalized with a mixed self-assembled monolayer (SAM) comprised of 2:1 octanethiol and 11-amino undecanethiol. The SAM is exposed to 2,4-dinitrobenzoic acid with the 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC) coupling reagent. Finally, the 2,4-dinitrophenyl terminated SAM is exposed to various concentration of antiDNP. LSPR shifts indicate the occurrence of a binding event. SER spectra confirm binding of 2,4 dinitrobenzoic acid with amine-terminated SAM. This LSPR/SERS biosensing method can be generalized to a myriad of biologically relevant systems.

An electrochemical surface-enhanced Raman spectroscopy approach to anthrax detection

Metal film over nanosphere (MFON) electrodes are excellent substrates for surface-enhanced Raman scattering (SERS) spectroscopy. These surfaces are produced by vapor deposition of a metal film over nanospheres that are assembled in a hexagonally close packed arrangement. The efficiency and reproducibility of AgFON electrode as SERS substrates are confirmed by the repeatability of the electrochemical surface enhanced Raman scattering spectra of pyridine and the Ru(bpy)33+/Ru(bpy)32+ complexes adsorbed on AgFON electrodes. The Raman signal for AgFON electrodes is observed to be extremely stable even at extremely negative potentials in both aqueous and nonaqueous electrolytes. Recent reports have indicated that SERS enhancement factors of up to 14 orders of magnitude can be achieved, providing the sensitivity requisite for ultra trace level detection of target analytes. For this reason, we are developing a method for bacterial endospore SERS detection based on the endospores marker -- dipicolinic acid (DPA). The SERS spectra of dipicolinic acid in aqueous solutions are reported. The dipicolinate vibrational features could be observed in the SERS spectra at the concentration as low as 8 × 10-5 M in 5 minutes. These limits of detection are entirely controlled by the thermodynamics and kinetics of DPA binding to the AgFON surface.

Glucose Sensing with Surface-Enhanced Raman Spectroscopy

Since the discovery of SERS nearly thirty years ago, it has progressed from model-system studies of pyridine to state-of-the-art surface-science studies coupled with real-world applications. We have demonstrated a SERS-based glucose sensor as an example of the latter. A SERS-active surface functionalized with a mixed SAM was shown to partition and departition glucose efficiently. The two components of the SAM, DT and MH, provide the appropriate balance of hydrophobic and hydrophilic groups. The DT/MH-functionalized SERS surface partitioned and departitioned glucose in less than 1 min, which indicates that the sensor can be used in real-time, continuous sensing. Furthermore, quantitative glucose measurements, in the physiological concentration range, in a mixture of interfering analytes and in bovine plasma were also demonstrated. Finally, the DT/MH-functionalized SERS surface showed temporal stability for at least 10 days in bovine plasma, making it a potential candidate for implantable sensing.

Localized and Propagating Surface Plasmon Resonance Sensors: A Study Using Carbohydrate Binding Protein

This work encompasses a comparative analysis of the properties of two optical biosensor platforms: (1) the propagating surface plasmon resonance (SPR) sensor based on a planar, thin film gold surface and (2) the localized surface plasmon resonance (LSPR) sensor based on surface confined Ag nanoparticles fabricated by nanosphere lithography. The binding of Concanavalin A (ConA) to mannose-functionalized self-assembled monolayers (SAMs) is chosen to illustrate the similarities and the differences of these sensors. A comprehensive set of non-specific binding studies demonstrate that the single transduction mechanism is due to the specific binding of ConA to the mannose-functionalized surface. Finally, an elementary (2x1) multiplexed version of a LSPR carbohydrate sensing chip to probe the simultaneous binding of ConA to mannose and galactose-functionalized SAMs is also demonstrated.