Selective Analysis of Redox Processes at the Electrode Interface with Time-Resolved Raman Spectroscopy.

Simultaneous detection of alkaline phosphatase and β-galactosidase activity using SERRS

We have observed simultaneously temporal fluctuation of surface-enhanced resonance Raman scattering (SERRS) and its background-light emission from single Ag nanoaggregates that were adsorbed with metal-free tetraphenylporphine (H(2)TPP) molecules. We found that temporally stable SERRS spectra showed clearly a SERRS band that is attributed to a stretching mode of a chemical bond between a carbon atom and a non-hydrogenated nitrogen atom (C(alpha)-N). This stretching mode was not observed in regular resonance Raman spectra which are free from surface enhancement. On the other hand, we also found that temporally unstable SERRS spectra did not clearly show a C(alpha)-N stretching mode in SERRS bands. Furthermore, temporally stable SERRS spectra were accompanied by temporally stable background-light emission. Kobayashi et al. [J. Phys. Chem. 1985, 89, 5174] reported that formation of an Ag-N bond between surface Ag atoms and non-hydrogenated N atoms in a pyrrole ring enhances the intensity of a C(alpha)-N stretching mode. Thus, the observed relationship between clear appearance of a C(alpha)-N stretching mode and temporal stability of SERRS plus background-light emission strongly suggests that formation of a stable Ag-N bond suppresses fluctuation of both SERRS and background-light emission. Furthermore, the observed relationship implies that chemical contribution to SERRS is stabilization of H(2)TPP molecules that are adsorbed on SERRS-active sites by formation of Ag-N bonds. Additionally, we attributed background-light emission to luminescence of complexes between H(2)TPP molecules and surface Ag atoms considering possible formation of Ag-N bonds, synchronized SERRS intensity with background-light emission intensity, blue-shifted background-light emission maxima from normal fluorescence maxima, and previous reports related to electronic structures of H(2)TPP molecules on Ag surfaces.

Variations in flavin redox states during extracellular electron transfer and electron conduction in Shewanella oneidensis

Raman spectroscopy is a form of vibrational spectroscopy that is well suited to the molecular identification of a variety of analytes, including both explosives and biological agents. The technique has been gaining more widespread interest due to improvements in instrumentation, sensitivity, and its ease of use, in comparison to other techniques. In this paper, we describe recent advances in Raman spectroscopy with respect to the detection of high-energy explosives and biological materials. In particular, emphasis is placed on the exploitation of enhancement factors that overcome traditional limitations on sensitivity, namely, surface enhancement and resonance enhancement, functionalization of target analytes, and the use of novel lab-on-a-chip technology.

The strong electromagnetic field enhancement, occurring at illuminated metal structures with sub-wavelength dimensions, is exploited to develop Raman spectroscopy with exceedingly high sensitivity and lateral resolution, possibly down to single molecule detection. After reviewing Surface Enhanced Raman Spectroscopy (SERS) on single crystalline surfaces and colloids we present recent results on the Tip Enhanced Raman Spectroscopy (TERS) approach, where a metal tip is used as an external enhancing unit. In this way the electromagnetic and chemical surface enhancement are physically separated: the former is confined to the tip, the latter to the metal-adsorbate system. So far, TERS has been reported only for a few molecules exhibiting large Raman cross sections, such as sulphur or dye molecules. Here, we present combined SERS and TERS studies for the CN- ions and TERS for Brilliant Cresyl Blue adsorbed at smooth thin gold films.

Silver-graphene oxide, Gold–graphene oxide, Silver–Gold–graphene oxide nanocomposites were synthesized from Neem leaves (Azadirachta indica) extract using a bio-green one-pot method. The synthesized bio-green nanocomposites were characterized by UV–visible spectroscopy, x-ray diffractogram, transmission electron microscopy, x-ray photoelectron spectroscopy and Raman spectroscopy. The results indicated the decoration of ∼10 nm of silver, ∼20 nm of gold and ∼15 nm of silver–gold nanoparticles on a graphene oxide sheet. The synthesized nanocomposites showed enhancement in surface enhanced Raman spectroscopy with alizarin and also enhancement in cell viability of Chang liver cell lines which may be due to a synergetic effect of nanoparticles and graphene oxide.

Surface-enhanced resonance Raman scattering (SERRS) spectra are reported for chlorophyll a adsorbed on a silver electrode at 298 and 77 K with 406.7-, 457.9-, 514.5-, and 647.1-nm excitation. Submerging the electrode in degassed water at 298 K was found to improve the spectral quality by minimizing sample heating and photooxidation. Spectral intensities and peak resolutions were greater at all excitation wavelengths at liquid nitrogen temperature. Most significantly, roughened silver at the low temperature quenched the fluorescence accompanying red excitation and minimized sample photooxidation, resulting in richly detailed SERRS spectra of chlorophyll a. The close correspondence between chlorophyll a resonance Raman (RR) and SERRS spectra suggests that an electromagnetic mechanism is the major source of the surface enhancement, rather than a chemical mechanism (e.g. a charge-transfer complex between chlorophyll a and the metal). The spectral similarities, together with the presence of the MgN{sub 4} vibration band in the SERRS spectra, also provide evidence that structural alterations (e.g. cleavage of ring V or loss of Mg) do not occur in chlorophyll a after adsorption at the electrode surface. A distinctive SERRS spectrum was obtained for each excitation wavelength. Selective excitation within the various electronic transitions can thus be utilized to verify assignmentsmore » of the vibrational modes of chlorophyll a and to monitor its interactions and photochemical behavior in biomimetic systems.« less

Chapter 1 - Introduction and overview

In situ electrochemical surface enhanced Raman spectra (SERS) for an immobilized monolayer of a flavin analogue (isoalloxazine) at nanostructured silver surfaces are reported. Unique in the present study, the flavin is not directly adsorbed at the Ag surface but is attached through a chemical reaction between cysteamine adsorbed on the Ag surface and methylformylisoalloxazine. Even though the flavin is held away from direct contact with the metal, strong surface enhancements are observed. The nanostructured silver surfaces are produced by electrodeposition through colloidal templates to produce thin (<1 microm) films containing close-packed hexagonal arrays of uniform 900 nm sphere segment voids. The sphere segment void (SSV) structured silver surfaces are shown to be ideally suited to in situ electrochemical SERS studies at 633 nm, giving stable, reproducible surface enhancements at a range of electrode potentials, and we show that the SER spectra are sensitive to subfemtomole quantities of immobilized flavin. Studies of the SER spectra as a function of the electrode potential show clear evidence for the formation of the flavin semiquinone at the electrode surface at cathodic potentials.

Hot-electron transfer between an electrode surface and an adsorbate is potentially useful in numerous electrochemical technologies, especially those operating at room temperature. Although challenging, estimation of the parameters controlling such a transfer process is fundamentally important to electrode design and utilization. Herein, nanothin Au/SiO2/Si electrodes are fabricated and analyzed for the source, generation, energetic characteristics, and interfacial transfer process of photogenerated surface hot electrons using excitation wavelength- and electron density-dependent Raman spectroscopy with methylene blue (MB) as the target molecule. Although Raman signal intensity exponentially increases with Si doping concentration when illuminated by a green laser, the signal intensification appears constant for a red laser. In both cases, Raman enhancement factors follow catalytic degradation with increasing measurement cycles. In conjunction with the calculated density of state distribution of the MB/Au interface, the observed Raman signals are ascribed to the charge-transfer (CT) surface-enhanced Raman scattering (SERS) mechanism, induced by the indirect and the resonant surface plasmon-enhanced direct interfacial transfers of hot electrons originating from Si and Au when excited by green and red lasers, respectively. Applying the electrodes as a CT SERS platform based on the above information to inspect a reduced graphene oxide/silica (rGO/SiO2) nanocomposite, conducting rGO core/insulating SiO2 shell structure, which implies plasmonic-heating property, is proposed and correlated with its photothermal efficiency. The findings shed light on the applicability of the hot-electron injector not only for molecular analysis but also for relevant technologies such as photoelectrocatalysis.

Keywords: solid-liquid interface, solid-state battery, surface-enhanced Raman spectroscopy (SERS), tip-enhanced Raman spectroscopy (TERS), neutron tomography, sulfide solid-state electrolyte, Raman imagingThe ever-growing needs for energy storage systems require batteries with even higher power and energy density with extended life and enhanced safety beyond the current Li-ion battery technologies. Fulfilling these needs requires new battery chemistries, including high-energy-density electrode materials, solid-state electrolytes, and efficient interphases to mitigate the side reactions between the electrodes and the electrolytes.Charge transport across the electrode and electrolyte interface is believed to be one of the charge/discharge rate-limiting steps. Although the composition, morphology, and structure of solid-electrolyte interphase (SEI) have been extensively studied, probing its evolution at the nanoscale is challenging to a large extent. Plasmon-enhanced Raman spectroscopy (PERS) is promising to solve this challenge. PERS is the resonant oscillation of conduction electrons at the interface between negative and positive permittivity molecules stimulated by incident light. It includes surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS). In the first part of this talk, I will show that gap-mode SERS is ideal to probe salt solvation structure in the immediate vicinity (< 20 nm) of the electrode/electrolyte interface. SERS lacks the nanoscale resolution in the sample plane. This can be compensated by TERS. TERS analysis on cycled high-energy silicon anodes indicates that the nanometer scale SEI "islands" are unevenly distributed. Even for the same SEI "island", the composition is different from point to point with inter-point distance smaller than 10 nm.All-solid-state lithium metal batteries (SSBs) promise specific energy >500 Wh/kg. A solid-state electrolyte (SSE) plays an irreplaceable role in reaching such an energy-density goal. Sulfide-based SSEs have emerged as a prominent class of soft ionic conductors that have comparable room-temperature ionic conductivity to their liquid electrolyte counterparts. However, when paring with a high voltage cathode, such as lithium nickel manganese cobalt oxide (NMC), the (electro)chemical instability of the sulfide SSE at the electrode/SSE interfaces becomes a major challenge. The interfacial instability can result in >50% initial capacity loss in a Li/sulfide SSE/NMC battery, thereby keeping the sulfide SSEs from commercialization. In the second part of this talk, I will show how we synergistically use neutron computed tomography and in situ Raman imaging, with clustering analysis to track lithium displacement at the interface of a sulfide-based SSB. Acknowledgment This research was conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) and is supported by Asst. Secretary, Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program. This research used resources at High Flux Isotope Reactor, a DOE Office of Science User Facilities operated by the Oak Ridge National Laboratory.

Surface-Enhanced Raman Scattering (SERS), Applications

The discovery of surface-enhanced Raman spectroscopy (SERS) presents an opportunity for the development of ultrasensitive biosensors. SERS allows for fingerprint detection of biomolecules at low concentrations and can perform single-molecule detection. The most used SERS substrates are Plasmonic metal nanostructures such as Au and Ag mainly because of their superior electrical conductivity. The Plasmonic metal nanoparticles enhance the Raman signal of the target biomolecules through the electromagnetic field mechanism. Despite the successful use of metal nanostructures, alternative materials have been sought which can exhibit similar or better properties than their metal counterparts. Materials such as graphene which has excellent electrical properties and high surface area are good candidates for SERS applications. Graphene is a 2D nanomaterial consisting of sp2 hybridized carbon atoms. The use of graphene in SERS is termed graphene-enhanced Raman spectroscopy (GERS) and is reported to use a charge transfer mechanism. Both graphene and metal nanostructures can be used together as SERS substrate and the synergistic effect of their mechanism can improve the enhancement factor and the sensitivity of the biosensor, however, the use of graphene as a SERS substrate is still at an early stage. GERS can be applied in disease diagnosis, detection of food additives, and biological species biosensors. The use of GERS in biosensors such as glucose biosensors presents an opportunity for ultrasensitive biosensors which can greatly improve the lives of individuals living with diabetes. In this review insights will be given on how to successfully circumvent the challenges associated with small Raman cross-section of glucose detection for use in medical application.

UV polymerization of self-assembled monolayers of a novel carbazolyl-diacetylene (CDS9) chemisorbed on silver films was demonstrated by surface plasmon resonance (SPR) and surface enhanced Raman scattering (SERS) experiments. SPR tests performed during UV exposure permitted one to observe the growth of the absorption coefficient, associated with the formation of the polymeric backbone. The Raman spectra of polymerized monolayers exhibited the bands associated with the C=C stretching modes of the conjugated backbone, typical of the blue and red polymeric phases usually present in polydiacetylenes, with a clear predominance of the red form. Moreover, the strong surface enhancement of the Raman band corresponding to the aromatic C=C stretching modes suggested that carbazolyl groups arrange nearly perpendicularly to the metal surface. In contrast, the absence of a SERS signal in the region of conjugated C[triple bond]C bond stretchings confirmed a polymerization scheme with conjugated triple bonds nearly parallel to the plane of the metal.

Abstract. Apple is one of the highly consumed fruit items. It is also one of the major carriers of pesticide to human health. This has created a great need for precise detection of pesticide residue in apple fruit. Traditional methods cannot meet current industrial desire of rapid and non-destructive detection of pesticide residue in fruits. Optical methods have recently gained importance in the evaluation of food quality because of their rapid and non-destructive nature. This research focuses on development of Raman spectral instrument for rapid detection of commercially available organophosphorous (chlorpyrifos) pesticide in apple surface by surface enhancement technology. Silver colloid was used for surface-enhanced Raman Spectroscopy (SERS) measurement. Apple samples after contamination with different concentrations of chlorpyrifos pesticide were applied to surface enhancement experiment to detect trace amount of pesticide residue. The surface enhancement was coated at several points in the surface of intact apple and laid to nearly dry at laboratory temperature before collecting Raman spectral signals. The noise signals and fluorescence background were removed by Savitzky-Golay filter and 8th order polynomial fitting respectively. Results show that the SERS can be used to detect chlorpyrifos pesticide in apple surface below 1 mg/kg which is lower than maximum permitted residue limit in apple by Chinese government. The result is promising for detection of pesticide residue rapidly and non-destructively. It is potential to be used for rapid and non-destructive detection of pesticide residues in different fruits and vegetables for industrial application.