Sumeet Mahajan

Mimicking the colourful wing scale structure of the Papilio blumei butterfly.

The brightest and most vivid colours in nature arise from the interaction of light with surfaces that exhibit periodic structure on the micro- and nanoscale. In the wings of butterflies, for example, a combination of multilayer interference, optical gratings, photonic crystals and other optical structures gives rise to complex colour mixing. Although the physics of structural colours is well understood, it remains a challenge to create artificial replicas of natural photonic structures. Here we use a combination of layer deposition techniques, including colloidal self-assembly, sputtering and atomic layer deposition, to fabricate photonic structures that mimic the colour mixing effect found on the wings of the Indonesian butterfly Papilio blumei. We also show that a conceptual variation to the natural structure leads to enhanced optical properties. Our approach offers improved efficiency, versatility and scalability compared with previous approaches.

SERS-Melting: A New Method for Discriminating Mutations in DNA Sequences

The reliable discrimination of mutations, single nucleotide polymorphisms (SNPs), and other differences in genomic sequence is an essential part of DNA diagnostics and forensics. It is commonly achieved using fluorescently labeled DNA probes and thermal gradients to distinguish between the matched and mismatched DNA. Here, we describe a novel method that uses surface enhanced (resonance) Raman spectroscopy (SER(R)S) to follow denaturation of dsDNA attached to a structured gold surface. This denaturation is driven either electrochemically or thermally on SERS active sphere segment void (SSV) gold substrates. Using this method, we can distinguish between wild type, a single point mutation (1653C/T), and a triple deletion (DeltaF 508) in the CFTR gene at the 0.02 attomole level, and the method can be used to differentiate the unpurified PCR products of the wild type and DeltaF 508 mutation. Our method has the potential to provide small, rapid, sensitive, reproducible platforms for detecting genetic variations and sequencing genes.

Quantitative SERS using the sequestration of small molecules inside precise plasmonic nanoconstructs

We show how the macrocyclic host, cucurbit[8]uril (CB[8]), creates precise subnanometer junctions between gold nanoparticles while its cavity simultaneously traps small molecules; this enables their reproducible surface-enhanced Raman spectroscopy (SERS) detection. Explicit shifts in the SERS frequencies of CB[8] on complexation with guest molecules provides a direct strategy for absolute quantification of a range of molecules down to 10(-11) M levels. This provides a new analytical paradigm for quantitative SERS of small molecules.

Intracellular SERS nanoprobes for distinction of different neuronal cell types.

Distinction between closely related and morphologically similar cells is difficult by conventional methods especially without labeling. Using nuclear-targeted gold nanoparticles (AuNPs) as intracellular probes we demonstrate the ability to distinguish between progenitor and differentiated cell types in a human neuroblastoma cell line using surface-enhanced Raman spectroscopy (SERS). SERS spectra from the whole cell area as well as only the nucleus were analyzed using principal component analysis that allowed unambiguous distinction of the different cell types. SERS spectra from the nuclear region showed the developments during cellular differentiation by identifying an increase in DNA/RNA ratio and proteins transcribed. Our approach using nuclear-targeted AuNPs and SERS imaging provides label-free and noninvasive characterization that can play a vital role in identifying cell types in biomedical stem cell research.

Surface enhanced coherent anti-Stokes Raman scattering on nanostructured gold surfaces

Coherent anti-Stokes Raman spectroscopy (CARS) is a well-known tool in multiphoton imaging and nonlinear spectroscopy. In this work we combine CARS with plasmonic surface enhancement on reproducible nanostructured surfaces. We demonstrate strong correlation between plasmon resonances and surface-enhanced CARS (SECARS) intensities on our nanostructured surfaces and show that an enhancement of ∼10(5) can be obtained over standard CARS. Furthermore, we find SECARS to be >10(3) times more sensitive than surface-enhanced Raman Spectroscopy (SERS). We also demonstrate SECARS imaging of molecular monolayers. Our work paves the way for reliable single molecule Raman spectroscopy and fast molecular imaging on plasmonic surfaces.

Metal Oxide Nanoparticle Mediated Enhanced Raman Scattering and Its Use in Direct Monitoring of Interfacial Chemical Reactions

Metal oxide nanoparticles (MONPs) have widespread usage across many disciplines, but monitoring molecular processes at their surfaces in situ has not been possible. Here we demonstrate that MONPs give highly enhanced (×10(4)) Raman scattering signals from molecules at the interface permitting direct monitoring of their reactions, when placed on top of flat metallic surfaces. Experiments with different metal oxide materials and molecules indicate that the enhancement is generic and operates at the single nanoparticle level. Simulations confirm that the amplification is principally electromagnetic and is a result of optical modulation of the underlying plasmonic metallic surface by MONPs, which act as scattering antennae and couple light into the confined region sandwiched by the underlying surface. Because of additional functionalities of metal oxides as magnetic, photoelectrochemical and catalytic materials, enhanced Raman scattering mediated by MONPs opens up significant opportunities in fundamental science, allowing direct tracking and understanding of application-specific transformations at such interfaces. We show a first example by monitoring the MONP-assisted photocatalytic decomposition reaction of an organic dye by individual nanoparticles.

Enhancing solar cells with localized plasmons in nanovoids

Localized plasmons in silver nanovoids enhance organic solar cell efficiencies experimentally by a factor of four and similarly in a-Si cells, accounted for by theoretical and computational analysis of absorption at the plasmonic interface.

Reproducible Deep-UV SERRS on Aluminum Nanovoids

Surface-enhanced Raman scattering (SERS) with deep-UV excitation is of particular interest because a large variety of biomolecules such as amino acids exhibit electronic transitions in the UV spectral range and resonant excitation dramatically increases the cross section of the associated vibrational modes. Despite its potential, UV-SERS is still little-explored. We present a novel straightforward scalable route to fabricate aluminum nanovoids for reproducible SERS in the deep-UV without the need of expensive lithographic techniques. We adopt a modified template stripping method utilizing a soluble template and self-assembled polymer spheres to create nanopatterned aluminum films. We observe high surface enhancement of approximately 6 orders of magnitude, with excitation in the deep-UV (244 nm) on structures optimized for this wavelength. This work thus enables sensitive detection of organics and biomolecules, normally nonresonant at visible wavelengths, with deep-UV surface-enhanced resonant Raman scattering on reproducible and scalable substrates.

In Situ SERS Monitoring of Photochemistry within a Nanojunction Reactor

We demonstrate a powerful SERS-nanoreactor concept composed of self-assembled gold nanoparticles (AuNP) linked by the sub-nm macrocycle cucurbit[n]uril (CB[n]). The CB[n] functions simultaneously as a nanoscale reaction vessel, sequestering and templating a photoreaction within, and also as a powerful SERS-transducer through the large field enhancements generated within the nanojunctions that CB[n]s define. Through the enhanced Raman fingerprint, the real-time SERS-monitoring of a prototypical stilbene photoreaction is demonstrated. By choosing the appropriate CB[n] nanoreactor, selective photoisomerism or photodimerization is monitored in situ from within the AuNP-CB[n] nanogap.

Single nanoparticle SERS probes of ion intercalation in metal-oxide electrodes.

Probing ion-intercalating processes in electrodes is hugely important for batteries, supercapacitors, and photovoltaic devices. In this work we use single-nanoparticle (NP) probes to see real-time molecular changes correlated to electrochemically modulated ion-intercalation in metal-oxide electrodes. Using surface-enhanced Raman spectroscopy (SERS) transduced by single NP probes, we observe that the Raman frequencies and spectral intensities of the adsorbed molecules vary on cycling the electrochemical potential on a vanadium-oxide electrode. The potential-dependent frequency shifts in SERS from an electrochemically inert molecule are attributed to a Stark effect induced by chemical and structural changes as a result of ion-intercalation processes in vanadium oxide. Our study opens up a unique strategy to explore adsorbates and molecular reaction pathways on ion-intercalating materials and semiconducting interfaces.