We report simultaneous plasmonic scattering and Raman spectroscopic observations of single citrate capped silver nanoparticles (AgNPs) which exhibit surface enhanced Raman scattering (SERS) upon meeting specific conditions induced by laser (532 nm) exposure. We show that nanoparticles which are not initially SERS active become SERS active by laser-induced reshaping/reorientation. A set-up developed for these observations enabled in situ high speed time-lapse characterization using plasmonic and Raman spectroscopies in conjunction with dark-field microscopy (DFM). Changes in the AgNPs were confirmed by monitoring plasmonic scattering spectra and DFM images. Time-lapse observations have shown that laser-induced changes in the plasmonic properties of AgNPs resulted in the appearance of SERS. Spectral matching between plasmon resonance and downward molecular vibronic transitions for molecules adsorbed on the surface of plasmonic nanomaterials is attributed to the nanoparticle SERS. We have further shown that the release of silver ions by silver nanoparticles can be the probable reason for their plasmonic changes. Gold nanoparticles inert to such mild (850 μW, 532 nm) laser-induced changes do not exhibit the appearance of SERS. © The Royal Society of Chemistry.

Pradeep Thalappil

Department Of Chemistry

Kamalesh Chaudhari

Tripti Ahuja

Vasanthanarayan Murugesan

Vidhya Subramanian

Mohd Azhardin Ganayee

Gold Nanoparticles

Metal ions

Metal nanoparticles

Plasmonics

Plasmons

Raman scattering

Raman spectroscopy

Surface scattering

DARK FIELD MICROSCOPY

Plasmon resonances

Plasmonic properties

Raman spectroscopic

Silver nanoparticles (AgNps)

SPECTRAL MATCHINGS

Surface enhanced Raman Scattering (SERS)

VI-BRONIC TRANSITIONS

Silver nanoparticles

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Nanoscale

We introduce a technique called ambient electrospray deposition Raman spectroscopy (AESD RS) for rapid and sensitive surface-enhanced Raman scattering (SERS) based detection of analytes using a miniature Raman spectrometer. Using electrospray, soft landing of preformed silver nanoparticles (AgNPs) was performed for 30-40 seconds for different concentrations of analytes deposited on conducting glass slides. Using AESD RS, SERS signals were collected within 4-6 minutes, including sample preparation. Transmission electron microscopy (TEM) and dark-field microscopy (DFM) were used to characterize the preformed AgNPs before and after electrospray. We achieved the nanomolar and micromolar detection of p-mercaptobenzoic acid (p-MBA) and 2,4-dinitrotoluene (2,4-DNT), respectively. In this work, 0.3 μL of preformed AgNPs were used, which is ∼33 times less in volume than the quantity needed for conventional SERS. Quantitation of unknown concentration of analytes was also possible. A similar amount of electrosprayed AgNPs was utilized to characterize Escherichia coli (E. coli) bacteria of different concentrations. Viability of bacteria was tested using fluorescence microscopic imaging. Besides reduced analysis time and improved reproducibility of the data in every analysis, which is generally difficult in SERS, the amount of AgNPs required is an order of magnitude lower in this method. This method could also be used to probe the real-time changes in molecular and biological species under ambient conditions. © 2019 The Royal Society of Chemistry.

Analyst

Ambient electrospray deposition Raman spectroscopy (AESD RS) using soft landed preformed silver nanoparticles for rapid and sensitive analysis

This article adds a new direction to the functional capability of protein-protected atomically precise gold clusters as sensors. Counting on the extensively researched intense luminescence of these clusters and considering the electron donating nature of select amino acids, we introduce a dual probe sensor capable of sensing changes in luminescence and conductivity, utilizing bovine serum albumin-protected atomically precise gold clusters hosted on nanofibers. To this end, we have also developed a hybrid nanofiber with a conducting core with a porous dielectric shell. We show that clusters in combination with nanofibers offer a highly selective and sensitive platform for the detection of trace quantities of trinitrotoluene, both in solution and in the vapor phase. In the solution phase, trinitrotoluene (TNT) can be detected down to 1 ppt at room temperature, whereas in vapor phase, 4.8 × 109 molecules of TNT can be sensed using a 1 mm fiber. Although the development in electrospinning techniques for fabricating nanofibers as sensors is quite substantial, a hybrid fiber with the dual properties of conductivity and luminescence has not been reported yet. © 2017 American Chemical Society.

Fulltext

ACS Omega

Dual Probe Sensors Using Atomically Precise Noble Metal Clusters

An insight into the intracellular fate of theranostics is important for improving their potential in biological applications. In vivo efficacy of plasmonic theranostics depends on our ability to monitor temporal changes in their size, shape, and state of aggregation, and the identification of molecules adsorbed on their surfaces. We develop a technique which combines plasmonic and Raman scattering microspectroscopy to colocalize plasmonic scattering from metallic nanoparticles with the Raman signatures of biomolecules adsorbed on the surface of the former. Using this technique, we have colocalized biomolecules with the plasmonic scattering from silver nanoparticles in the vicinity of Escherichia coli bacteria. To prove the applicability of this setup for the measurements on mammalian cells, imaging of HEK293 cells treated with gold nanoparticles was performed. We discuss the importance of such correlated measurements over individual techniques, although the latter may lead to misinterpretation of results. Finally, with the above-mentioned examples, we have given criteria to improve the specificity of theranostics. We believe that this methodology will be considered as a prime development in the assessment of theranostics. © 2015 Society of Photo-Optical Instrumentation Engineers.

Journal of Biomedical Optics

In vitro colocalization of plasmonic nano-biolabels and biomolecules using plasmonic and Raman scattering microspectroscopy

Spatiotemporal mapping of the position and orientation of nano-machinery inside complex and dynamic cellular environments is essential for the detailed understanding of many bio-physical processes. For the genuine observation of such biomolecular dynamics with high signal to noise ratio and reduced disturbance from the labeling probes, reduction in the size of nano-bio labels and simplification of techniques for their observation are important. Here we achieve this using polarized dark field scattering micro-spectroscopy (PDFSMS), in its simplest form so that it is deployable in several experiments. We not only locate tiny gold nanorods (GNRs) of size 30 (length) × 10â €..nm (diameter) inside HEK293 cells but also demonstrate mapping of their in-situ polarization patterns using a novel method. Real time observations of rotating GNR with DFSMS and PDFSMS are used to resolve in-plane and out-of-plane rotational modes of GNR. We have shown that PDFSMS itself can provide complete information about the state of GNR. A step ahead, we demonstrate the application of PDFSMS to track three dimensional rotational dynamics of transferrin-conjugated GNRs inside live HEK293 cells. These first-time observations of the three dimensional intracellular rotational dynamics of tiny GNRs using PDFSMS present a new landmark in single particle scattering spectroscopy.

Scientific Reports

Spatiotemporal mapping of three dimensional rotational dynamics of single ultrasmall gold nanorods

Interaction of bacteria with citrate-reduced silver nanoparticles (AgNPs) of size 25 nm ± 8.5 nm is studied using Raman spectroscopy in conjunction with plasmon resonance imaging of single bacterial cells. Distribution of isolated nanoparticles (NPs) inside Escherichia coli (ATCC 25922; E. coli) is observed by hyperspectral imaging (HSI) as a function of incubation time. Time-dependent degradation of bacterial DNA upon incubation of AgNPs with E. coli is proven by Raman spectroscopic studies. While attachment of NPs is evident in HSI, molecular changes are evident from the surface-enhanced Raman spectra of adsorbed DNA and its fragments. Distinct enhancement of DNA features is observed upon interaction of AgNPs and the number of such distinct features increases with incubation time, reaches a maximum, and decreases afterwards. This systematic interaction of DNA with the NPs system and its gradual chemical evolution is proven by investigating isolated plasmid DNA. A comparative Raman study with silver ions has shown that DNA features are observable only when bacteria are incubated with AgNPs. Energetics of interaction examined with microcalorimetry suggests the exothermicity of -1.547 × 1010 cal mol-1 for the NP-bacteria system. Specific interaction of AgNPs with exocyclic nitrogen present in the bases, adenine, guanine, and cytosine, leads to the changes in DNA. The interactions of E. coli with citrate-reduced silver nanoparticles (AgNPs) are studied using Raman spectroscopy and plasmon resonance imaging of single bacterial cells. While attachment of nanoparticles to bacteria is evident in plasmonic hyperspectral imaging, molecular changes of the adsorbed DNA are seen in Raman spectra. Specific interactions of AgNPs with exocyclic nitrogen present in the bases, adenine, guanine, and cytosine leads to time-dependent changes in the DNA. © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Particle and Particle Systems Characterization

Single-cell investigations of silver nanoparticle-bacteria interactions

Journal of the American Chemical Society

Simultaneous Time-Dependent Surface-Enhanced Raman Spectroscopy, Metabolomics, and Proteomics Reveal Cancer Cell Death Mechanisms Associated with Gold Nanorod Photothermal Therapy

Appearance of SERS activity in single silver nanoparticles by laser-induced reshaping

Journal	Data powered by TypesetNanoscale
Publisher	Data powered by TypesetRoyal Society of Chemistry
ISSN	20403364
Open Access	No